Title of Invention

""COMPOUNDS OF THE FORMULA (XXVIII)

Abstract Compounds of the formula (XXVIII) in which X represents halogen, alkyl, alkenyl, alkynyl, alkoxy, alkenyloxy, alkylthio, alkyl-sulphinyl, alkylsulphonyl, haloalkyl, haloalkoxy, haloalkenyloxy, nitro, cyano or in each case optionally substituted phenyl, phenoxy, phenylthio, phenylalkoxy or phenylalkylthio, W and Y independently of one another represent hydrogen, halogen, alkyl, alkenyl, alkynyl, alkoxy, alkenyloxy, haloalkyl, haloalkoxy, haloalkenyloxy, nitro or cyano, Z represents an in each case optionally saturated or unsaturated, optionally substituted heterocycle which is attached to the phenyl ring via a nitrogen atom and which may be interrupted by one or two carbonyl groups.
Full Text The present invention relates to compounds of the formula (XXVIII).
The present invention relates to novel N-heterocyclylphenyl-substituted cyclic ketoenols, to a plurality of processes for their preparation and to their use as pesticides and/or herbicides and/or microbicides.
Moreover, the invention relates to novel selective herbicidal active compound combinations comprising firstly the N-heterocyclylphenyl-substituted cyclic ketoenols and secondly at least one compound which improves crop plant tolerance, which combinations can be used with particularly good results for the selective control of weeds and crops of various useful plants.
Pharmaceutical properties of 3-acylpyrrolidine-2,4-diones have already been described (S. Suzuki et al. Chem. Pharm. Bull. .15 1120 (1967)). Furthermore, N-phenylpyrrolidine-2,4-diones were synthesized by R. Schmierer and H. Mildenberger (Liebigs Ann. Chem. 1985, 1095). A biological activity of these compounds has not been described.
EP-A-0 262 399 and GB-A-2 266 888 disclose compounds of a similar structure (3-arylpyrrolidine-2,4-diones), of which, however, no herbicidal, insecticidal or acaricidal action has been disclosed. Unsubstituted, bicyclic 3-arylpyrrolidine-2,4-dione derivatives (EP-A-355 599, EP-A-415 211 and JP-A-12-053670) and substituted monocyclic 3-arylpyrrolidine-2,4-dione derivatives (EP-A-377 893 and EP-A-442 077) having herbicidal, insecticidal or acaricidal action have been disclosed.
There have also been disclosed polycyclic 3-arylpyrrolidine-2,4-dione derivatives (EP-A-442 073) and 1H-arylpyrrolidinedione derivatives (EP-A-456 063, EP-A-521 334, EP-A-596 298, EP-A-613 884, EP-A-613 885, WO 94/01 997, WO 95/26 954, WO 95/20 572, EP-A-0 668 267, WO 96/25 395, WO 96/35 664, WO 97/01 535, WO 97/02 243, WO 97/36 868, WO 97/43275, WO 98/05638, WO 98/06721, WO 98/25928, WO 99/16748, WO 99/24437, WO 99/43649, WO 99/48869, WO 99/55673, WO 01/17972, WO 01/23354, WO 01/74770, WO 03/062244, DE-A-10 231 333 and DE-A-10 239 479).
It is known that certain substituted A3-dihydrofuran-2-one derivatives have herbicidal properties (cf. DE-A-4 014 420). The synthesis of the tetronic acid derivatives used as starting materials (such as, for example, 3-(2-methylphenyl)-4-hydroxy-5-(4-fluorophenyl)-3-dihydrofuran-2-one) is also described in DE-A-4 014 420. Compounds of a similar structure are known from the publication Campbell et al., J. Chem. Soc, Perkin Trans. 1, 1985, (8) 1567-76, but no insecticidal and/or acaricidal activity is mentioned. 3-Aryl-3-dihydrofuranone derivatives having herbicidal, acaricidal and insecticidal properties are also known from EP-A-528 156, EP-A-0 647 637, WO

95/26 345, WO 96/20 196, WO 96/25 395, WO 96/35 664, WO 97/01 535, WO 97/02 243, WO 97/36 868, WO 98/05638, WO 98/25928, WO 99/16748, WO 99/43649, WO 99/48869, WO 99/55673, WO 01/17972, WO 01/23354, WO 01/74770, WO 03/062244 and DE-A-10 239 479. 3-Aryl-3-dihydrothiophenone derivatives are likewise known (WO 95/26 345, 96/25 395, WO 97/01 535, WO 97/02 243, WO 97/36 868, WO 98/05638, WO 98/25928, WO 99/16748, WO 99/43649, WO 99/48869, WO 99/55673, WO 01/17972, WO 01/23354, WO 01/74770 and WO 03/062244).
Certain phenylpyrone derivatives which are unsubstituted in the phenyl ring are already known (cf. A.M. Chirazi, T. Kappe and E. Ziegler, Arch. Pharm. 309, 558 (1976) and K.-H. Boltze and K. Heidenbluth, Chem. Ber. 91, 2849), but a possible use of these compounds as pesticides has not been mentioned. Phenylpyrone derivatives which are substituted in the phenyl ring and have herbicidal, acaricidal and insecticidal properties are described in EP-A-588 137, WO 96/25 395, WO 96/35 664, WO 97/01 535, WO 97/02 243, WO 97/16 436, IN 184979, WO 97/36 868, WO 98/05638, WO 99/43649, WO 99/48869, WO 99/55673, WO 01/17972, WO 01/74770 and WO 03/062244.
Certain 5-phenyl-l,3-thiazine derivatives which are unsubstituted in the phenyl ring are already known (cf. E. Ziegler and E. Steiner, Monatsh. 95, 147 (1964), R.Ketcham, T. Kappe and E. Ziegler, J. Heterocycl. Chem. 10, 223 (1973)), but a possible use of these compounds as pesticides has not been mentioned. 5-Phenyl-l,3-thiazine derivatives which are substituted in the phenyl ring and have herbicidal, acaricidal and insecticidal action are described in WO 94/14 785, WO 96/02 539, WO 96/35 664, WO 97/01 535, WO 97/02 243, WO 97/02 243, WO 97/36 868, WO 99/05638, WO 99/43649, WO 99/48869, WO 99/55673, WO 01/17972, WO 01/74770 and WO 03/062244.
It is known that certain substituted 2-arylcyclopentanediones have herbicidal and acaricidal properties (cf., for example, US-4 283 348; 4 338 122; 4 436 666; 4 526 723; 4 551 547; 4 632 698; WO 96/01 798; WO 96/03 366, WO 97/14 667 and also WO 98/39281, WO 99/43649, WO 99/48869, WO 99/55673, WO 01/17972, WO 01/74770 and WO 03/062244). Moreover, compounds having similar substitutions are known; 3-hydroxy-5,5-dimethyl-2-phenylcyclopent-2-en-1-one from the publication Micklefield et al., Tetrahedron, (1992), 7519-26, and the natural product involutin (-)-cis-5-(3,4-dihydroxyphenyl)-3,4-dihydroxy-2-(4-hydroxyphenyl)cyclopent-2-enone from the publication Edwards et al., J. Chem. Soc. S, (1967), 405-9. An insecticidal or acaricidal action is not described. Moreover, 2-(2,4,6-trimethylphenyl)-l,3-indanedione is known from the publication J. Economic Entomology, 66, (1973), 584 and the Offenlegungsschrift

(Gennan Published Specification) IN 138958, with herbicidal and acaricidal actions being mentioned.
It is known that certain substituted 2-arylcyclohexanediones have herbicidal and acaricidal properties (US-4 175 135, 4 209 432, 4 256 657, 4 256 658, 4 256 659, 4 257 858, 4 283 348, 4 303 669, 4 351 666, 4 409 153, 4 436 666, 4 526 723, 4 613 617, IN148697,IN150370, and also Wheeler, T.N., J. Org. Chem. 44, 4906 (1979)), WO 99/43649, WO 99/48869, WO 99/55673, WO 01/17972, WO 01/74770 and WO 03/062244).
It is known that certain substituted 4-arylpyrazolidine-3,5-diones have acaricidal, insecticidal and herbicidal properties (cf., for example, WO 92/16 510, EP-A-508 126, WO 96/11574, WO 96/21652, WO 99/43649, WO 99/47525, WO 99/48869, WO 99/55673, WO 01/17 351, WO 01/17 352, WO 01/17 353, WO 01/17 972, WO 01/17 973, WO 03/028446 and WO 03/062244).
However, the activity and/or activity spectrum of these compounds is, in particular at low application rates and concentrations, not always entirely satisfactory. Furthermore, these compounds are not always sufficiently well tolerated by plants.
We have now found novel compounds of the formula (I)
(Formula Removed)
in which
X represents halogen, alkyl, alkenyl, alkynyl, alkoxy, alkenyloxy, alkylthio, alkylsulphinyl, alkylsulphonyl, haloalkyl, haloalkoxy, haloalkenyloxy, nitro, cyano or in each case optionally substituted phenyl, phenoxy, phenylthio, phenylalkoxy or phenylalkylthio,
W and Y independently of one another represent hydrogen, halogen, alkyl, alkenyl, alkynyl, alkoxy, alkenyloxy, haloalkyl, haloalkoxy, haloalkenyloxy, nitro or cyano,
Z represents an in each case optionally saturated or unsaturated, optionally substituted
heterocycle which is attached to the phenyl ring via a nitrogen atom and which may be interrupted by one or two carbonyl groups,
CKE represents one of the .groups
(Figure Removed)
in which
A represents hydrogen, represents in each case optionally halogen-substituted alkyl,
alkenyl, alkoxyalkyl, alkylthioalkyl, saturated or unsaturated, optionally
substituted cycloalkyl in which optionally at least one ring atom is replaced by a
heteroatom, or in each case optionally halogen-, alkyl-, haloalkyl-, alkoxy-, haloalkoxy-,
cyano- or nitro-substituted aryl, arylalkyl or hetaryl,
B represents hydrogen, alkyl or alkoxyalkyl, or
A and B together with the carbon atom to which they are attached represent a saturated or
unsaturated, unsubstituted or substituted cycle which optionally contains at least
one heteroatom,
D represents hydrogen or represents an optionally substituted radical from the group
consisting of alkyl, alkenyl, alkynyl, alkoxyalkyl, saturated or unsaturated
cycloalkyl, in which optionally one or more ring members are replaced by
heteroatoms, arylalkyl, aryl, hetarylalkyl or hetaryl or
A and D together with the atoms to which they are attached represent a saturated or
unsaturated cycle which optionally contains at least one (in the case of CKE=8
further) heteroatom and which is unsubstituted or substituted in the A,D moiety, or
A and Q* together represent optionally halogen- or hydroxy-substituted alkenediyl or
alkanediyl or alkenediyl substituted by in each case optionally substituted alkyl,
alkoxy, alkylthio, cycloalkyl, benzyloxy or aryl or
Q! represents hydrogen or alkyl,
>" independently of one another represent hydrogen or alkyl,
Q represents hydrogen, in each case optionally substituted alkyl, alkoxyalkyl,
alkylthioalkyl, optionally substituted cycloalkyl (in which optionally one
methylene group is replaced by oxygen or sulphur) or optionally substituted
phenyl, or
Q3 and Q4 together with the carbon atom to which they are attached represent a saturated
or unsaturated, unsubstituted or substituted cycle which optionally contains a
heteroatom,
G represents hydrogen (a) or represents one of the groups
(Figure Removed)
in which
E represents a metal ion equivalent or an ammonium ion,
L represents oxygen or sulphur,
M represents oxygen or sulphur,
R.I represents in each case optionally halogen-substituted alkyl, alkenyl,
alkoxyalkyl, alkylthioalkyl, polyalkoxyalkyl or optionally halogen-, alkylor
alkoxy-substituted cycloalkyl which may be interrupted by at least one
heteroatom, in each case optionally substituted phenyl, phenylalkyl,
hetaryl, phenoxyalkyl or hetaryloxyalkyl,
R represents in each case optionally halogen-substituted alkyl, alkenyl, alkoxyalkyl,
polyalkoxyalkyl or represents in each case optionally substituted
cycloalkyl, phenyl or benzyl,
R.3, R and R independently of one another represent in each case optionally
halogen-substituted alkyl, alkoxy, alkylamino, dialkylamino, alkylthio,
alkenylthio, cycloalkylthio and represent in each case optionally substituted
phenyl, benzyl, phenoxy or phenylthio,
R" and R' independently of one another represent hydrogen, in each case
optionally halogen-substituted alkyl, cycloalkyl, alkenyl, alkoxy,
alkoxyalkyl, represent optionally substituted phenyl, represent optionally
substituted benzyl, or together with the N atom to which they are attached
represent a cycle which is optionally interrupted by oxygen or sulphur.
Depending inter alia on the nature of the substituents, the compounds of the formula (I) can be
present as geometrical and/or optical isomers or isomer mixtures of varying composition which, if
appropriate, can be separated in a customary manner. The present invention provides both the pure
isomers and the isomer mixtures, their preparation and use and compositions comprising them.
However, for the sake of simplicity, hereinbelow only, compounds of the formula (I) are referred
to, although what is meant is both the pure compounds and, if appropriate, mixtures having various
proportions of isomeric compounds.
Taking into consideration the meanings (1) to (8) of the group CKE, the following principle
structures (1-1) to (1-8) result:
(Figure Removed)
in which
A, B, D, G, Q1, Q2, Q3, Q4, Q5, Q6, W, X, Y and Z are as defined above.
Talcing into consideration the different meanings (a), (b), (c), (d), (e), (f) and (g) of the group G,
the following principle structures (I-l-a) to (I-l-g) result if CKE represents the group (1)
(Figure Removed)
in which
A, B, D, E, L, M, W, X, Y, Z, R1, R2, R3, R4, R5, R6 and R7 are as defined above.
Taking into consideration the different meanings (a), (b), (c), (d), (e), (f) and (g) of the group G,
the following principle structures (I-2-a) to (I-2-g) result if CKE represents the group (2)
(I-2-a):
(Figure Removed)
in which
A, B, E, L, M, W, X, Y, Z, R1, R2, R3, R4, R^, R6 and R? are as defined above.
Taking into consideration the different meanings (a), (b), (c), (d), (e), (f) and (g) of the group G,
the following principle structures (I-3-a) to (I-3-g) result if CKE represents the group (3)
(I-3-a):
(Figure Removed)
in which
A, B, E, L, M, W, X, Y, Z, R1, R2, R3, R4, R5, R^ and R7 are as defined above.
Depending on the position of the substituent G, the compounds of the formula (1-4) can be present
in the two isomeric forms of the formulae (1-4- A) and (I-4-B)
(Figure Removed)
which is meant to be indicated by the broken line in formula (1-4).
The compounds of the formulae (I-4-A) and (I-4-B) can be present both as mixtures and in the
form of their pure isomers. Mixtures of the compounds of the formulae (I-4-A) and (I-4-B) can, if
appropriate, be separated in a manner known per se by physical methods, for example by
chromatographic methods.
For reasons of clarity, hereinbelow only one of the possible isomers is shown in each case. This
does not exclude that the compounds may, if appropriate, be present in the form of the isomer
mixtures or in the respective other isomeric form.
Taking into consideration the different meanings (a), (b), (c), (d), (e), (f) and (g) of the group G,
the following principle structures (I-4-a) to (I-4-g) result if CKE represents the group (4)
(Figure Removed)
in which
A, D, E, L, M, W, X, Y, Z, R1, R2, R3, R4, R5, R6 and R7 are as defined above.
Taking into consideration the different meanings (a), (b), (c), (d), (e), (f) and (g) of the group G,
the following principle structures (I-5-a) to (I-5-g) result if CKE represents the group (5)
(Figure Removed)
in which
A, E, L, M, W, X, Y, Z, R1, R2, R3, R4, R5, R6 and R7 are as defined above.
Depending on the position of the substituent G, the compounds of the formula (1-6) can be present
in the two isomeric forms of the formulae (I-6-A) and (I-6-B)
(Figure Removed)
which is meant to be indicated by the broken line in formula (1-6).
The compounds of the formulae (I-6-A) and (I-6-B) can be present both as mixtures and in the
form of their pure isomers. Mixtures of the compounds of the formulae (I-6-A) and (I-6-B) can, if
appropriate, be separated by physical methods, for example by chromatographic methods.
For reasons of clarity, hereinbelow only one of the possible isomers is shown in each case. This
does not exclude that the compounds may, if appropriate, be present in the form of the isomer
mixtures or in the respective other isomeric form.
Taking into consideration the different meanings (a), (b), (c), (d), (e), (f) and (g) of the group G,
the following principle structures (I-6-a) to (I-6-g) result:
(Figure Removed)
in which
A, B, Q1, Q2, E, L, M, W, X, Y, Z, R1, R2, R3, R4, R5, R6 and R7 are as defined above.
Depending on the position of the substituent G, the compounds of the formula (1-7) can be present
in the two isomeric forms of the formulae (I-7-A) and (I-7-B), which is meant to be indicated by
the broken line in formula (1-7).
(Figure Removed)
The compounds of the formulae (I-7-A) and (I-7-B) can be present both as mixtures and in the
form of their pure isomers. Mixtures of the compounds of the formulae (I-7-A) and (I-7-B) can, if
appropriate, be separated by physical methods, for example by chromatographic methods.
For reasons of clarity, hereinbelow only one of the possible isomers is shown in each case. This
includes that the relevant compound may, if appropriate, be present in the form of the isomer
mixture or in the respective other isomeric form.
Taking into consideration the different meanings (a), (b), (c), (d), (e), (f) and (g) of the group G,
the following principle structures (I-7-a) to (I-7-g) result:
(Figure Removed)
A, B, E, L, M, Q3, Q4, Q5, Q6, W, X, Y, Z, R1, R2, R3, R4, R5, R6 and R7 are as defined above.
Depending on the position of the substituent G, the compounds of the formula (1-8) can be present
in the two isomeric formulae (I-8-A) and (I-8-B)
(Figure Removed)
which is meant to be indicated by the broken line in formula (1-8).
The compounds of the formulae (I-8-A) and (I-8-B) can be present both as mixtures and in the
form of their pure isomers. Mixtures of the compounds of the formulae (I-8-A) and (I-8-B) can, if
appropriate, be separated in a manner known per se by physical methods, for example by
chromatographic methods.
For reasons of clarity, hereinbelow only one of the possible isomers is shown in each case. This
does not exclude that the compounds may, if appropriate, be present in the form of the isomer
mixtures or in the respective other isomeric form.
Taking into consideration the different meanings (a), (b), (c), (d), (e), (f) and (g) of the group G,
the following principle structures (I-8-a) to (I-8-g) result if Het represents the group (8):
(Figure Removed)
in which
A, D, E, L, M, W, X, Y, Z, R1, R2, R3, R4? R55 R6 and R7 are as defined above.
Furthermore, it has been found that the novel compounds of the formula (I) are obtained by one of
the processes described below:
(A) Substituted 3-(N-heterocyclyl)phenylpyrrolidine-2,4-diones or enols thereof of the formula
(Figure Removed)
in which
A, B, D, W, X, Y and Z are as defined above
are obtained when
N-acylamino acid esters of the formula (II)
in which
A, B, D, W, X, Y and Z are as defined above
and
R.8 represents alkyl (preferably C1-C6-alkyl)
are condensed intramolecularly in the presence of a diluent and in the presence of a base.
(B) Moreover, it has been found that substituted 3-(N-heterocyclyl)phenyl-4-hydroxy-A^-dihydrofuranone
derivatives of the formula (I-2-a)
(Figure Removed)
in which
A, B, W, X, Y and Z are as defined above
are obtained when
carboxylic esters of the formula (ID)
(Figure Removed)
in which
A, B, W, X, Y, Z and R8 are as defined above
are condensed intramolecularly in the presence of a diluent and in the presence of a base.
(C) Furthermore, it has been found that substituted 3-(N-heterocyclyl)phenyl-4-hydroxy-A3-dihydrothiophenone
derivatives of the formula (I-3-a)
(Figure Removed)
in which
A, B, W, X, Y and Z are as defined above
are obtained when
B-ketocarboxylic esters of the formula (IV)
(Figure Removed)
in which
A, B, W, X, Y, Z and R^ are as defined above and
V represents hydrogen, halogen, alkyl (preferably C1-C6-alkyl) or alkoxy (preferably
C1-C6-alkoxy)
are cyclized intramolecularly, if appropriate in the presence of a diluent and in the
presence of an acid.
(D) Furthermore, it has been found that the novel substituted 3-(N-heterocyclyl)phenylpyrone
derivatives of the formula (I-4-a)
(Figure Removed)
in which
A, D, W, X, Y and Z are as defined above
are obtained when
carbonyl compounds of the formula (V)
(Figure Removed)
in which
A and D are as defined above
or silylenol ethers thereof of the formula (Va)
(Figure Removed)
in which
A, D and R.8 are as defined above
are reacted with ketene acid halides of the formula (VI)
(Figure Removed)
in which
W, X, Y and Z are as defined above and
Hal represents halogen (preferably chlorine or bromine),
if appropriate in the presence of a diluent and if appropriate in the presence of an acid
acceptor.
Furthermore, it has been found
(E) that the novel substituted 2-(N-heterocyclyl)phenyl-l,3-thiazine derivatives of the formula
(Figure Removed)
in which
A, W, X, Y and Z are as defined above
are obtained when thioamides of the formula (VH)
(Figure Removed)
in which
A is as defined above
are reacted with ketene acid halides of the formula (VI)
(Figure Removed)
in which
Hal, W, X, Y and Z are as defined above,
if appropriate in the presence of a diluent and if appropriate in the presence of an acid
acceptor.
Furthermore, it has been found
(F) that compounds of the formula (I-6-a)
(Figure Removed)
in which
A, B, Q1, Q2, W, X, Y and Z are as defined above
are obtained when
ketocarboxylic acid esters of the formula (VHI)
(Figure Removed)
in which
A, B, Q1, Q2, W, X, Y and Z are as defined above and
R.8 represents alkyl (in particular C \ -Cg-alkyl)
are cyclized intramolecularly, if appropriate in the presence of a diluent and if appropriate
in the presence of a base.
Moreover, it has been found
(G) that compounds of the formula (I-7-a)
(Figure Removed)
in which
A, B, Q3, Q4, Q5, Q6, W, X, Y and Z are as defined above
are obtained when
6-aryl-5-ketohexanoic esters of the formula (EX)
(Figure Removed)
in which
A, B, Q3, Q4, Q5, Q6, W, X, Y and Z are as defined above
and
R.8 represents alkyl (preferably C i -Cg-alkyl)
are condensed intramolecularly in the presence of a diluent and in the presence of a base.
(H) Furthermore, it has been found that the compounds of the formula (I-8-a)
(Figure Removed)
in which
A, D, W, X, Y and Z are as defined above
are obtained when
compounds of the formula (X)
in which
A and D are as defined above
a) are reacted with compounds of the formula (VI)
(Figure Removed)
in which
Hal, W, X, Y and Z are as defined above,
if appropriate in the presence of a diluent and if appropriate in the presence of an
acid acceptor, or
B) are reacted with compounds of the formula (XI)
(Figure Removed)
in which
W, X, Y and Z are as defined above
and U represents NH2 or O-R8,
where R8 is as defined above,
if appropriate in the presence of a diluent and if appropriate in the presence of a
base, or
y) are reacted with compounds of the formula (XII)
(Figure Removed)
in which
A, D, W, X, Y, Z and R8 are as defined above,
if appropriate in the presence of a diluent and if appropriate in the presence of a
base.
Moreover, it has been found
(I) that the compounds of the formulae (I-l-b) to (I-8-b) shown above in which A, B, D, Q*,
Q2, Q3. Q4, Q5» Q6, R1, W, X, Y and Z are as defined above are obtained when
compounds of the formulae (I-l-a) to (I-8-a) shown above in which A, B, D, Ql, Q, Q3,
Q4 Q Q W, X, Y and Z are as defined above are in each case
(a) reacted with acid halides of the formula (XIII)
(Xffl)
in which
R.1 is as defined above and
Hal represents halogen (hi particular chlorine or bromine)
or
(6) reacted with carboxylic anhydrides of the formula (XTV)
(Figure Removed)
in which
R.1 is as defined above,
if appropriate in the presence of a diluent and if appropriate in the presence of an acid
binder;
(J) that the compounds of the formulae (I-l-c) to (I-8-c) shown above in which A, B, D, Ql,
Q2, Q3, Q4, Q5, Q6, R2, M, W, X, Y and Z are as defined above and L represents oxygen
are obtained when compounds of the formulae (I-l-a) to (I-8-a) shown above in which A,
B, D, Q1, Q2, Q3, Q4, Q5, Q6, W, X, Y and Z are as defined above are in each case
reacted with chloroformic esters or chloroformic thioesters of the formula (XV)
(Figure Removed)
in which
R2 and M are as defined above
if appropriate in the presence of a diluent and if appropriate in the presence of an acid
binder;
(K) that compounds of the formulae (I-l-c) to (I-8-c) shown above in which A, B, D, Q, Q2,
Q3, Q4 Q Q R2 M, W, X, Y and Z are as defined above and L represents sulphur are
obtained when compounds of the formulae (I-l-a) to (I-8-a) shown above in which A, B,
D, Q1, Q2, Q3, Q4, Q5, Q6, W, X, Y and Z are as defined above are in each case
reacted with chloromonothioformic esters or chlorodithioformic esters of the formula
(Figure Removed)
in which
M and R2 are as defined above,
if appropriate in the presence of a diluent and if appropriate in the presence of an acid
binder
and
(L) that compounds of the formulae (I-l-d) to (I-8-d) shown above in which A, B, D, Q1, Q2,
Q3 Q4 Q Q R3, W, X, Y and Z are as defined above are obtained when compounds of
the formulae (I-l-a) to (I-8-a) shown above in which A, B, D, Q1, Q2, Q3, Q4, Q5, Q6, W,
X, Y and Z are as defined above are in each case
reacted with sulphonyl chlorides of the formula (XVII)
(Figure Removed)
in which
R3 is as defined above,
if appropriate in the presence of a diluent and if appropriate in the presence of an acid
binder,
(M) that compounds of the formulae (I-l-e) to (I-8-e) shown above in which A, B, D, L, Ql,
Q2, Q3, Q4, Q5, C& R4, R5, W, X, Y and Z are as defined above are obtained when
compounds of the formulae (I-l-a) to (I-8-a) shown above in which A, B, D, Ql, Q2, Q3,
Q4» Q^> Q^» W, X, Y and Z are as defined above are in each case
reacted with phosphorus compounds of the formula (XVni)
(Figure Removed)
in which
L, R4 and R are as defined above and
Hal represents halogen (in particular chlorine or bromine),
if appropriate in the presence of a diluent and if appropriate in the presence of an acid
binder,
(N) that compounds of the formulae (I-l-f) to (1-8-f) shown above in which A, B, D, E, Q% Q2,
Q3. Q4 Q, Q W, X, Y and Z are as defined above are obtained when compounds of the
formulae (I-l-a) to (I-8-a) shown above in which A, B, D, Q1, Q2, Q3, Q4, Q5, Q6, W, X,
Y and Z are as defined above are in each case
reacted with metal compounds or amines of the formulae (XIX) and (XX), respectively,
(XK) ,2 (XX)
in which
Me represents a mono- or divalent metal (preferably an alkali metal or alkaline earth
metal, such as lithium, sodium, potassium, magnesium or calcium),
t represents the number 1 or 2 and
R.10, R.H, R.12 independently of one another represent hydrogen or alkyl (preferably C1-
C6-alkyl),
if appropriate in the presence of a diluent,
(O) that compounds of the formulae (I-l-g) to (I-8-g) shown above in which A, B, D, L, Q,
Q2, Q3, Q4, Q5, Q6, R6, R7> W, X, Y and Z are as defined above are obtained when
compounds of the formulae (I-l-a) to (I-8-a) shown above in which A, B, D, Q, Q, Q
Q4 Q Q W, X, Y and Z are as defined above are in each case
(a) reacted with isocyanates or isothiocyanates of the formula (XXI)
(Figure Removed)
in which
R.6 and L are as defined above,
if appropriate in the presence of a diluent and if appropriate in the presence of a catalyst,
or
(fi) reacted with carbamoyl chlorides or thiocarbamoyl chlorides of the formula (XXH)
(Figure Removed)
in which
L, R.6 and R7 are as defined above,
if appropriate in the presence of a diluent and if appropriate in the presence of an acid
binder,
(P) that compounds of the formulae (1-1) to (1-8) shown above in which A, B, D, Q1, Q2, Q3,
W, X, Y and Z are as defined above are obtained when compounds of the
formulae (I-l1) to (I-81)
(Figure Removed)
in which
A, B, D, G, Q1, Q2, Q3, Q4, Q5, Q6, W, X and Y are as defined above and
represents chlorine, bromine, iodine, preferably bromine,
are reacted with NH-heterocycles of the formula (XXET)
(Figure Removed)
in which
Z is as defined above
in the presence of a solvent, a base and a catalyst, suitable catalysts being in particular
copper(I) salts.
Furthermore, it has been found that the novel compounds of the formula (I) are highly active as
pesticides, preferably as insecticides and/or acaricides and/or herbicides and/or fungicides.
Surprisingly, it has now also been found that certain substituted cyclic ketoenols, when used
jointly with the compounds which improve crop plant tolerance (safeners/
antidotes) described hereinbelow, are extremely effective in preventing damage of the crop plants
and can be used especially advantageously as combination products with a broad range of activity
for the selective control of undesired plants in crops of useful plants, such as, for example, in
cereals, but also in maize, soybeans and rice.
The invention also relates to selectively herbicidal compositions with an effective content of an
active compound combination comprising, as components,
(a1) at least one substituted cyclic ketoenol of the formula (I) in which CKE, W, X, Y and Z
have the abovementioned meanings
and
(b1) at least one compound which improves crop plant tolerance and which is selected from the
following group of compounds:
4-dichloroacetyl-l-oxa-4-aza-spiro[4.5]-decane (AD-67, MON-4660), 1-dichloroacetyl-hexahydro-
3,3,8a-trimethylpyrrolo[l,2-a]-pyrimidui-6(2H)-one (dicyclonon, BAS-145138), 4-dichloroacetyl-
3,4-dihydro-3-methyl-2H-l,4-benzoxazine (benoxacor), 1-methyl-hexyl 5-chloro-quinolin-8-oxyacetate
(cloquintocet-mexyl - cf. also related compounds in EP-A-86750, EP-A-94349,
EP-A-191736, EP-A-492366), 3-(2-chloro-benzyl)-l-(l-methyl-l-phenyl-ethyl)-urea (cumyluron),
a-(cyanomethoximino)-phenylacetonitrile (cyometrinil), 2,4-dichloro-phenoxyacetic acid (2,4-D),
4-(2,4-dichloro-phenoxy)-butyric acid (2,4-DB), l-(l-methyl-l-phenyl-ethyl)-3-(4-methyl-phenyl)-
urea (daimuron, dymron), 3,6-dichloro-2-methoxy-benzoic acid (dicamba), S-l-methyl-1-phenylethyl
piperidine-1-thiocarboxylate (dimepiperate), 2,2-dichloro-N-(2-oxo-2-(2-propenylamino)-
ethyl)-N-(2-propenyl)-acetamide (DKA-24), 2,2-dichloro-N,N-di-2-propenyl acetamide
(dichlormid), 4,6-dichloro-2-phenyl-pyrimidine (fenclorim), ethyl l-(2,4-dichloro-phenyl)-5-
trichloro-methyl-lH-l,2,4-triazole-3-carboxylate (fenchlorazole-ethyl - cf. also related compounds
in EP-A-174562 and EP-A-346620), phenyl-methyl 2-chloro-4-trifluoromethyl-thiazole-5-
carboxylate (flurazole), 4-chloro-N-(l,3-dioxolan-2-yl-methoxy)-a-trifluoro-acetophenone oxime
(fluxofenim), 3-dichloroacetyl-5-(2-furanyl)-2,2-dimethyl-oxazolidine (furilazole, MON-13900),
ethyl 4,5-dihydro-5,5-diphenyl-3-isoxazolecarboxylate (isoxadifen-ethyl - cf. also related
compounds in WO-A-95/07897), l-(ethoxycarbonyl)-ethyl-3,6-dichloro-2-methoxybenzoate
(lactidichlor), (4-chloro-o-tolyloxy)-acetic acid (MCPA), 2-(4-chloro-o-tolyloxy)-propionic acid
(mecoprop), diethyl 1 -(2,4-dichloro-phenyl)-4,5-dihydro-5-methyl-lH-pyrazole-3,5-dicarboxylate
(mefenpyr-diethyl - cf. also related compounds in WO-A-91/07874), 2-dichloromethyl-2-methyl-
1,3-dioxolane (MG-191), 2-propenyl-l-oxa-4-azaspiro[4.5]decane 4-carbodithioate (MG-838), 1,8-
naphthalic anhydride, a-(l,3-dioxolan-2-yl-methoximino)-phenylacetonitrile (oxabetrinil), 2,2-
dichloro-N-(l,3-dioxolan-2-yl-methyl)-N-(2-propenyl)-acetamide (PPG-1292), 3-dichloroacetyl-
2,2-dimethyl-oxazolidine (R-28725), 3-dichloroacetyl-2,2,5-rrimethyl-oxazolidine (R-29148), 4-(4-
chloro-o-tolyl)-butyric acid, 4-(4-chloro-phenoxy)-butyric acid, diphenylmethoxyacetic acid,
methyl diphenyhnethoxyacetate, ethyl diphenylmethoxyacetate, methyl l-(2-chloro-phenyl)-5-
phenyl-lH-pyrazole-3-carboxylate, ethyl l-(2,4-dichloro-phenyl)-5-methyl-lH-pyrazole-3-
carboxylate, ethyl l-(2,4-aichloro-phenyl)-5-isopropyl-lH-pyrazole-3-carboxylate, ethyl l-(2,4-
dichloro-phenyl)-5-( 1,1 -dimethyl-ethyl)-!H-pyrazole-3-carboxylate, ethyl 1 -(2,4-dichloro-phenyl)-
5-phenyl-lH-pyrazole-3-carboxylate (cf. also related compounds in EP-A-269806 and
EP-A-333131), ethyl 5-(2)4-dichloro-ben2yl)-2-isoxazoline-3-carboxylate) ethyl 5-phenyl-2-
isoxazoline-3-carboxylate, ethyl 5-(4-fluoro-phenyl)-5-phenyl-2-isoxazoline-3-carboxylate (cf. also
related compounds in WO-A-91/08202), 1,3-dimethyl-but-l-yl 5-chloro-quinolin-8-oxy-acetate, 4-
allyloxy-butyl 5-chloro-quinolin-8-oxy-acetate, l-allyloxy-prop-2-yl 5-chloro-quinolin-8-oxyacetate,
methyl 5-chloro-quinoxalin-8-oxy-acetate, ethyl 5-chloro-quinolin-8-oxy-acetate, allyl
5-chloro-quinoxalin-8-oxy-acetate, 2-oxo-prop-l-yl 5-chloro-quinolin-8-oxy-acetate, diethyl 5-
chloro-quinolin-8-oxy-malonate, diallyl 5-chloro-quinoxalin-8-oxy-malonate, diethyl 5-chloroquinolin-
8-oxy-malonate (cf. also related compounds in EP-A-582198), 4-carboxy-chroman-4-ylacetic
acid (AC-304415, cf. EP-A-613618), 4-chloro-phenoxy-acetic acid, 3,3'-dimethyl-4-
methoxy-benzophenone, 1 -bromo-4-chloromethylsulphonyl-benzene, 1 -[4-(N-2-methoxybenzoylsulphamoyl)-
phenyl]-3-methyl-urea (alias N-(2-methoxy-benzoyl)-4-[(methylamino-carbonyl)-
amino]-benzenesulphonamide), l-[4-(N-2-methoxybenzoylsulphamoyl)-phenyl]-3,3-dimethyl-urea,
l-[4-(N-4,5-dunethylbenzoylsulphamoyl)-phenyl]-3-methyl-urea, l-[4-(N-naphthylsulphamoyl)-
phenyl]-3,3-dimethyl-urea, N-(2-methoxy-5-methyl-benzoyl)-4-(cyclopropylaminocarbonyl)-
benzenesulphonamide,
and/or one of the following compounds (defined by general formulae)
of the general formula (Ha)
(Figure Removed)
or of the general formula (lib)
(Figure Removed)
or of the formula (He)
(Figure Removed)
where
n represents a number of between 0 and 5,
A1 represents one of the divalent heterocyclic groups outlined hereinbelow,
(Figure Removed)
n represents a number of between 0 and 5,
A2 represents alkanediyl having 1 or 2 carbon atoms which is optionally substituted by C1-C4-
alkyl and/or C1-C4-alkoxy-carbonyl,
represents hydroxyl, mercapto, amino, C1-C6-alkoxy, C1-C6-alkylthio, C1-C6-alkylamino or
di-(C1-C4-alkyl)amino,
represents hydroxyl, mercapto, amino, C1-C6-alkoxy, C1-C6-alkylthio, C1-C6-alkylamino or
di-(C1-C4-alkyl)amino,
represents C1-C4-alkyl which is optionally substituted in each case by fluorine, chlorine
and/or bromine,
represents hydrogen, or represents C1-C6-alkyl, C2-C6-alkenyl or d-Q-alkynyl,
C1-C4-alkoxy-C1-C4-alkyl, dioxolanyl-C1-C4-alkyl, furyl, furyl-C1-C4-alkyl, thienyl,
thiazolyl, piperidinyl, each of which is optionally substituted by fluorine, chlorine and/or
bromine, or represents phenyl which is optionally substituted by fluorine, chlorine and/or
bromine or C1-C4-alkyl,
represents hydrogen, or represents C1-C6-alkyl, drCe-alkenyl or C2-Ce-alkynyl,
C1-C4-alkoxy-C!-C4-alkyl, dioxolanyl-C1-C4-alkyl, furyl, furyl-C1-C4-alkyl, thienyl,
thiazolyl, piperidinyl, each of which is optionally substituted by fluorine, chlorine and/or
bromine, or represents phenyl which is optionally substituted by fluorine, chlorine and/or
bromine or C1-C4-alkyl, or together with R24 represents C1-C6-alkanediyl or C2-C5-
oxaalkanediyl, each of which is optionally substituted by C1-C4-alkyl, phenyl, furyl, a
fused benzene ring or by two substituents which, together with the C atom to which they
are bonded, form a 5- or 6-membered carbocycle,
represents hydrogen, cyano, halogen, or represents C1-C4-alkyl, C3-C6-cycloalkyl or
phenyl, each of which is optionally substituted by fluorine, chlorine and/or bromine,
R27 represents hydrogen, or represents CpCs-alky!, Cs-Ce-cycloalkyl or tri(C1-C4-alkyl)silyl,
optionally substituted by hydroxyl, cyano, halogen or C1-C4-alkoxy,
R28 represents hydrogen, cyano, halogen, or represents C1-C4-alkyl, C3-C6-cycloalkyl or
phenyl, each of which is optionally substituted by fluorine, chlorine and/or bromine,
X1 represents nitro, cyano, halogen, C1-C4-alkyl, C1-C4-haloalkyl, C1-C4-alkoxy or C1-C4-
haloalkoxy,
X2 represents hydrogen, cyano, nitro, halogen, C1-C4-alkyl, C1-C4-haloalkyl, C1-C4-alkoxy or
C1-C4-haloalkoxy,
X3 represents hydrogen, cyano, nitro, halogen, C1-C4-alkyl, C1-C4-haloalkyl, C1-C4-alkoxy or
C1-C4-haloalkoxy,
and/or the following compounds (defined by general formulae)
of the general formula (Ed)
(Figure Removed)
or of the general formula (He)
(Figure Removed)where
represents a number of between 0 and 5,
represents hydrogen .or d -C4-alkyl,
represents hydrogen or C1-C4-alkyl,
R31 represents hydrogen, or represents C1-C6-alkyl, C1-C6-alkoxy, CrC6-alkylthio, CrC6-
alkylamino or di-(C1-C4-alkyl)amino, each of which is optionally substituted by cyano,
halogen or C1-C4-alkoxy, or represents C3-C6-cycloalkyl, C3-C6-cycloalkyloxy, C3-C6-
cycloalkylthio or C3-C6-cycloalkylamino, each of which is optionally substituted by cyano,
halogen or C1-C4-alkyl,
R3 represents hydrogen, or represents C1-C6-alkyl which is optionally substituted by cyano,
hydroxyl, halogen or C1-C4-alkoxy, or represents Cj-C6-alkenyl or Cj-Cs-alkynyl, each of
which is optionally substituted by cyano or halogen, or represents C3-C6-cycloalkyl which
is optionally substituted by cyano, halogen or C1-C4-alkyl,
R33 represents hydrogen, or represents C1-C6-alkyl which is optionally substituted by cyano,
hydroxyl, halogen or C1-C4-alkoxy, or represents C3-C6-alkenyl or C3-C6-alkynyl, each of
which is optionally substituted by cyano or halogen, or represents C3-C6-cycloalkyl which
is optionally substituted by cyano, halogen or C1-C4-alkyl, or represents phenyl which is
optionally substituted by nitro, cyano, halogen, C1-C4-alkyl, C1-C4-haloalkyl, C1-C4-alkoxy
or C1-C4-haloalkoxy, or together with R32 represents C2-C6-alkanediyl or C2-C5-
oxaalkanediyl, each of which is optionally substituted by C1-C4-alkyl,
X4 represents nitro, cyano, carboxyl, carbamoyl, formyl, sulphamoyl, hydroxyl, amino,
halogen, C1-C4-alkyl, C1-C4-haloalkyl, C1-C4-alkoxy or C1-C4-haloalkoxy, and
X5 represents nitro, cyano, carboxyl, carbamoyl, formyl, sulphamoyl, hydroxyl, amino,
halogen, C1-C4-alkyl, C1-C4-haloalkyl, C1-C4-alkoxy or C1-C4-haloalkoxy.
Formula (I) provides a general definition of the compounds according to the invention. Preferred
substituents or ranges of the radicals given in the formulae mentioned hereinabove and
hereinbelow are illustrated in the following text:
X preferably represents halogen, C3-C6-alky!, C1-C6-alkenyl,C1-C6-alkynyl,
haloalkyl, C1-C6-alkoxy, C3-C6-alkenyloxy, C1-C6-alkylthio, C1-C6-alkylsulphinyl, C\-
Cg-alkylsulphonyl,C1-C6-haloalkoxy, C3-C6-haloalkenyloxy, nitro, cyano or represents
phenyl, phenoxy, phenylthio, benzyloxy or benzylthio, each of which is optionally monoor
disubstituted by halogen, C1-C6-alkyl, C1-C6-alkoxy, C1-C4-haloalkyl,
haloalkoxy, nitro or cyano,
W and Y independently of one another preferably represent hydrogen, halogen, C1-C6-alkyl, C\-
Cg-alkenyl, C1-C6-alkynyl, C}-C6-haloalkyl, C1-C6-alkoxy, C1-C6-haloalkoxy, nitro or
cyano,
Z preferably represents optionally substituted pyrazolyl, triazolyl, tetrazolyl, pyrrolyl,
indolyl, benzimidazolyl, benzpyrazolyl, benztriazolyl, pyrrolidinyl, piperidinyl,
piperazddinyl, morpholinyl or thiomorpholinyl which is attached via a nitrogen atom to the
phenyl ring,
CKE preferably represents one of the groups
(Figure Removed)
preferably represents hydrogen or represents C^-C^-alkyl, C3-Cg-alkenyl,
alkoxy-C1-C6-alkyl, Ci-CiQ-alkylthio-Ci-Cg-alkyl, each of which is optionally mono- to
pentasubstituted by halogen, represents C3-Cg-cycloalkyl which is optionally mono- to
trisubstituted by halogen, C1-C6-alkyl,C1-C2-haloallQrl or C1-C6-alkoxy and in which
optionally one or two not directly adjacent ring members are replaced by oxygen and/or
sulphur or represents phenyl, naphthyl, hetaryl having 5 or 6 ring atoms (for example
furanyl, pyridyl, imidazolyl, triazolyl, pyrazolyl, pyrimidyl, thiazolyl or thienyl), phenyl-
C1-C6-alkyl or naphthyl-C1-C6-alkyl, each of which is optionally mono- to trisubstituted
by halogen, C1-C6-alkyl,C1-C6-haloalkyl, C1-C6-alkoxy,C1-C6-haloalkoxy, cyano or
nitro,
B preferably represents hydrogen, C \ -C j 2-alkyl or C i -Cg-alkoxy-C j -Cg-alkyl, or
A, B and the carbon atom to which they are attached preferably represent saturated C3-Cjocycloalkyl
or unsaturated Cs-CjQ-cycloalkyl in which optionally one ring member is
replaced by oxygen or sulphur and which are optionally mono- or disubstituted by C1-C6alkyl,
C3-C10-cydoalkyl, C1-C6-haloalkyl,C1-C6-alkoxy, C1-C6-alkylthio, halogen or
phenyl or
A, B and the carbon atom to which they are attached preferably represent C3-C6-cycloalkyl
which is substituted by an alkylenediyl group which optionally contains one or two not
directly adjacent oxygen and/or sulphur atoms and which is optionally mono- to
tetrasubstituted by C1-C4-alkyl or by an alkylenedioxyl or by an alkylenedithioyl group
which, together with the carbon atom to which it is attached, forms a further five- to eightmember
ring or
A, B and the carbon atom to which they are attached preferably represent C3-Cg-cycloalkyl or
C5-Cg-cycloalkenyl in which two substituents together with the carbon atoms to which
they are attached represent C2-C6-alkanediyl, C2-Cg-alkenediyl or C^Cg-alkanediendiyl,
each of which is optionally mono- to disubstituted by C1-C6-alkyl, C1-C6-alkoxy or
halogen and in which optionally one methylene group is replaced by oxygen or sulphur,
D preferably represents hydrogen, representsC1-C6-alkyU C3-Cg-alkenyl, C3-Cg-alkynyl,
Ci-Cio-alkoxy-C1-C6-alkyl, each of which is optionally mono- to pentasubstituted by
halogen, represents C3-Cg-cycloalkyl which is optionally mono- to trisubstituted by
halogen, Cj^-alkyl, C1-C4-alkoxy or C1-C4-haloalkyl and in which optionally one ring
member is replaced by oxygen or sulphur or represents phenyl, hetaryl having 5 or 6 ring
atoms (for example furanyl, imidazolyl, pyridyl, thiazolyl, pyrazolyl, pyrimidyl, pyrrolyl,
thienyl or triazolyl), phenyl-C1-C6-alkyl or hetaryl-C1-C6-alkyl having 5 or 6 ring atoms
(for example furanyl, imidazolyl, pyridyl, thiazolyl, pyrazolyl, pyrimidyl, pyrrolyl, thienyl
or triazolyl), each of which radicals is optionally mono- to trisubstituted by halogen, C\-
C6-alkyl, C1-C6-haloalkyl, C1-C6-alkoxy, C1-C6-haloalkoxy, cyano or nitro, or
-41-
A and D together preferably represent in each case optionally mono- or disubstituted €3-05-
alkanediyl or C3-C6-alkenediyl in which optionally one methylene group is replaced by a
carbonyl group, oxygen or sulphur,
possible substituents being in each case:
halogen, hydroxyl, mercapto or Ci-Cjo-alkyl, Cj^-alkoxy, C1-C6-alkylthio, C-^-C^-
cycloalkyl, phenyl or benzyloxy, each of which is optionally mono- to trisubstituted by
halogen, or a further C3-Cg-alkanediyl grouping, C3-C6-alkenediyl grouping or butadienyl
grouping which is optionally substituted by C1-C6-alkyl or in which optionally two
adjacent substituents together with the carbon atoms to which they are attached form a
further saturated or unsaturated cycle having 5 or 6 ring atoms (in the case of the
compound of the formula (1-1), A and D together with the atoms to which they are attached
then represent, for example, the groups mentioned further below (AD-1 to AD-10)) which
can contain oxygen or sulphur, or which optionally contains one of the following groups
(Figure Removed)
A and Ql together preferably represent C3-C6-alkanediyl or C^Cg-alkenediyl, each of which is
optionally mono- or disubstituted by identical or different substituents from the group
consisting of halogen, hydroxyl, of Ci-Cjo-alkyl,C1-C6-alkoxy,C1-C6-alkylthio, C^-C'jcycloalkyl,
each of which is optionally mono- to trisubstituted by identical or different
halogen, and of benzyloxy and phenyl, each of which is optionally mono- to trisubstituted
by identical or different substituents from the group consisting of halogen,
and C1-C6-alkoxy, which C3-C6-alkanediyl or C4-C6-alkenediyl moreover optionally
contains one of the groups below
(Figure Removed)
or
or is bridged by a C}-C2-alkanediyl group or by an oxygen atom or
Q1 preferably represents hydrogen or C j -C4-alkyl,
Q Q Q aod Q" independently of one another preferably represent hydrogen or C1-C4-alkyl,
Q preferably represents hydrogen, representsC1-C6-alkyl, C1-C6-alkoxy-Ci^-alkyl, Cj-
C6-alkylthio-C1-C2-alkyl, each of which is optionally mono- to pentasubstituted by
halogen, represents C3-Cg-cycloalkyl which is optionally substituted by C1-C4-alkyl or
C1-C4-alkoxy and in which optionally one methylene group is replaced by oxygen or
sulphur or represents phenyl which is optionally mono- or disubstituted by halogen, Cj-
C4-alkyl, Cj^-alkoxy, Cj^-haloalkyl, Ci^-haloalkoxy, cyano or nitro, or
Q3 and Q^ together with the carbon atom to which they are attached preferably represent a 03-67-
ring which is optionally mono- to trisubstituted by C-alkyl, C1-C4-alkoxy or C\-C2~
haloalkyl and in which optionally one ring member is replaced by oxygen or sulphur,
G preferably represents hydrogen (a) or represents one of the groups
E (0 or (g), in particular (a), (b),(c) or (g)
in which
E represents a metal ion equivalent or an ammonium ion,
L represents oxygen or sulphur and
M represents oxygen or sulphur,
preferably representsC1-C2Q-aO/yl, C2-C2Q-alkenyl,C1-C6-alkoxy-C1-C6-alkyl,
alkylthio-Ci-Cg-alkyl, poly-Ci-Cg-alkoxy-C1-C6-alkyl, each of which is optionally monoto
pentasubstituted by halogen, or represents C3-Cg-cycloalkyl which is optionally monoto
trisubstituted by halogen, C1-C6-alkyl or C^-Cg-alkoxy and in which optionally one or
more (preferably not more than two) not directly adjacent ring members are replaced by
oxygen and/or sulphur,
preferably represents phenyl which is optionally mono- to trisubstituted by halogen, cyano,
nitro,C1-C6-alkyl, C1-C6-alkoxy,C1-C6-haloalkyl, C1-C6-haloalkoxy, C1-C6-alkylthio
or C1-C6-alkylsulphonyl,
preferably represents phenyl-Ci-Cg-alkyl which is optionally mono- to trisubstituted by
halogen, nitro, cyano,C1-C6-alkyl, C1-C6-alkoxy,C1-C6-haloalkyl orC1-C6-haloalkoxy,
preferably represents 5- or 6-membered hetaryl which is optionally mono- or disubstituted
by halogen orC1-C6-alkyl (for example pyrazolyl, thiazolyl, pyridyl, pyrimidyl, furanyl or
thienyl),
preferably represents phenoxy Cj^-alkyl which is optionally mono- or disubstituted by
halogen or C1-C6-alkyl or
preferably represents 5- or 6-membered hetaryloxy C1-C6-alkyl which is optionally monoor
disubstituted by halogen, amino or C1-C6-alkyl (for example pyridyloxy-C1-C6-alkyl,
pyrimidyloxy-C1-C6-alkyl or thiazolyloxy-Ci-Cg-alkyl),
R2 preferably represents Cj^Q-alkyl, C2-C2()-alkenyl,C1-C6-alkoxy-C2-Cg-alkyl, Ply-Ci-
Cg-alkoxy-C2-Cg-alkyl, each of which is optionally mono- to pentasubstituted by halogen,
preferably represents C3-Cg-cycloalkyl which is optionally mono- or disubstituted by
halogen,C1-C6-alkyl or C1-C6-alkoxy or
preferably represents phenyl or benzyl, each of which is optionally mono- to trisubstituted
by halogen, cyano, nitro, C1-C6-aUcyl, C1-C6-alkoxy,C1-C6-haloalkyl orC1-C6-haloalkoxy,
R3 preferably represents C1-C6-alkyl which is optionally mono- to nonasubstituted by
halogen or represents phenyl or benzyl, each of which is optionally mono- to trisubstituted
by halogen, C1-C6-alky!, C1-C6-alkoxy, C1-C4-haloalkyl, C1-C4-haloalkoxy, cyano or
nitro,
R and R independently of one another preferably represent C1-C6-alkyl, C1-C6-alkoxy, C1-C6alkylamino,
di-(C1-C6-alkyl)amino, C1-C6-alkylthio, C2-C6-alkenylthio, C--Cycloalkylthio,
each of which is optionally mono- to pentasubstituted by halogen, or represent
phenyl, phenoxy or phenylthio, each of which is optionally mono- to trisubstituted by
halogen, nitro, cyano, C1-C4-alkoxy, C1-C4-haloalkoxy, C1-C4-alkylthio, C1-C4-haloalkylthio,
C1-C4-alkyl or C1-C4-haloalkyl,
R and R independently of one another preferably represent hydrogen, represent C\-Cg-alkyl,
C3-C6-cycloalkyl, C1-C6-alkoxy, C3-Cg-alkenyl, C1-C6-alkoxy-C1-C6-alkyl, each of
which is optionally mono- to pentasubstituted by halogen, represent phenyl which is
optionally mono- to trisubstituted by halogen, C1-C6-haloalkyl, C1-C6-alkyl or C1-C6alkoxy,
represent benzyl which is optionally mono- to trisubstituted by halogen, C\-Cgalkyl,
C1-C6-haloalkyl orC1-C6-alkoxy or together represent a C3-Cg-alkylene radical
which is optionally mono- or disubstituted by C1-C4-alkyl and in which optionally one
carbon atom is replaced by oxygen or sulphur,
preferably represents hydrogen, preferably represents C1-C6-alkyl or C1-C6-alkoxy, each
of which is optionally mono- to trisubstituted by halogen, represents C3-Cg-cycloalkyl
which is optionally mono- to trisubstituted by halogen, C1-C4-alkyl or C1-C4-alkoxy and
in which optionally one methylene group is replaced by oxygen or sulphur, or represents
phenyl, phenyl-C-aUcyl or phenyl-C-alkoxy, each of which is optionally mono- or
disubstituted by halogen, C1-C6-alkyl, C1-C6-alkoxy, C1-C4-haloalkyl,
haloalkoxy, nitro or cyano,
preferably represents. hydrogen or C4-C6-alkyl or
R13 and R14 together preferably represent C1-C6-alkanediyl,
and R^ are identical or different and preferably represent C1-C6-alkyl or
and R together preferably represent a C2-C4-alkanediyl radical which is optionally monoor
disubstituted by C1-C6-alkyl, C1-C6-haloalkyl or by phenyl which is optionally monoor
disubstituted by halogen, C1-C6-alkyl, C1-C4-haloalkyl, C1-C6-alkoxy, C1-C4-haloalkoxy,
nitro or cyano,
and R independently of one another preferably represent hydrogen, represent optionally
halogen-substituted C1-C6-alkyl or represent phenyl which is optionally mono- or
disubstituted by halogen, C1-C6-alkyl, C1-C6-alkoxy, C1-C4-haloalkyl, C1-C4-haloalkoxy,
nitro or cyano or
and R together with the carbon atom to which they are attached preferably represents
carbonyl group or represent Cs-Cy-cycloalkyl which is optionally mono- or disubstituted
by halogen, C1-C4-alkyl or C1-C4-alkoxy and in which optionally one methylene group is
replaced by oxygen or sulphur,
and R independently of one another preferably represent Cj-CiQ-alkyl, C2-Cio-alkenyl,
Cj-Cjo-alkoxy, Cj-Cio-alkylamino, C3-C10-alkenylamino, di-(Ci-Cio-alkyl)amino or
di-(C3-CjQ-alkenyl)amino.
In the radical definitions mentioned as being preferred, halogen represents fluorine, chlorine,
bromine and iodine, in particular fluorine, chlorine and bromine.
X particularly preferably represents fluorine, chlorine, bromine, C1-C4-alkyl, C1-C4-alkoxy,
C1-C4-haloalkyl, C1-C4-haloalkoxy, nitro or cyano,
W and Y independently of one another particularly preferably represent hydrogen, fluorine,
chlorine, bromine, C1-C4-alkyl, Cj^-haloalkyl, Cj^-alkoxy, C1-C4-haloalkoxy,
Z particularly preferably represents one of the radicals
(Figure Removed)
V* particularly preferably represents hydrogen, fluorine, chlorine, bromine, iodine,
C1-C6-alkyl, C1-C4-aSao\y, C1-C4haloalkyl, C1-C4-haloalkoxy, cyano or nitro,
V particularly preferably represents hydrogen, fluorine, chlorine, bromine,C1-C6
alkyl or C-haloalkyl,
V^ and V^ together particularly preferably represent C3-C4-alkanediyl which is optionally
mono- to tetrasubstituted by fluorine and which may optionally be interrupted once
or twice by oxygen or represent butadienyl which is optionally mono- or
disubstituted by fluorine, chlorine, bromine, C-Calky!,C1-C6alkoxy,
haloalkyl, C1-C2-haloalkoxy, cyano or nitro,
CKE particularly preferably represents one of the groups
(Figure Removed)
A particularly preferably represents hydrogen, representsC1-C6-alkyl, C ] -C4-alkoxy-C1-C6-
alkyl, each of which is optionally mono- to trisubstituted by fluorine or chlorine, represents
C3-C(-cycloalkyl which is optionally mono- or disubstituted by fluorine, chlorine, C1-C2-
alkyl, trifluoromethyl or C1-C2-alkoxy or (but not in the case of the compounds of the
formulae (1-3), (1-4), (1-6) and (1-7)) represents phenyl or benzyl, each of which is
optionally mono- or disubstituted by fluorine, chlorine, bromine, C^-C^alky!, Ci~C2-
haloalkyl, C-Calkoxy, C1-C2-haloalkoxy, cyano or nitro,
B particularly preferably represents hydrogen, C^-C^alky! orC1-C2-alkoxyl-C1-C2-alkyl or
A, B and the carbon atom to which they are attached particularly preferably represent saturated
C3-C7-cycloalkyl or unsaturated C5-C7-cycloalkyl in which optionally one ring member is
replaced by oxygen or sulphur and which is optionally mono- or disubstituted by C1-C6alkyl,
trifluoromethyl orC1-C6-alkoxy, with the proviso that in this case Q^ particularly
preferably represents hydrogen or methyl, or
A, B and the carbon atom to which they are attached particularly preferably represent 05 -Cgcycloalkyl
which is substituted by an alkylenediyl group which optionally contains one or
two not directly adjacent oxygen or sulphur atoms and which is optionally mono- or
disubstituted by methyl or ethyl, or by an alkylenedioxyl or by an alkylenedithiol group
which, together with the carbon atom to which it is attached, forms a further five- or sixmembered
ring, with the proviso that in this case particularly preferably represents
hydrogen or methyl,
A, B and the carbon atom to which they are attached particularly preferably represent
cycloalkyl or C5-Cg-cycloalkenyl in which two substituents together with the carbon
atoms to which they are attached represent C2-C4-alkanediyl, C2-C4-alkenediyl or butadienediyl,
each of which is optionally substituted by C1-C2-alkyl orC1-C2-alkoxy, with
the proviso that in this case Q^ particularly preferably represents hydrogen or methyl,
D particularly preferably represents hydrogen, represents C1-C6-alkyl, C3-C(j-alkenyl, Cj-
C4-alkoxy-C2-C3-alkyl, each of which is optionally mono- to trisubstituted by fluorine,
represents C3-Cg-cycloalkyl which is optionally mono- or disubstituted by C1-C4-alkyl,
C1-C4-alkoxy or C1-C2-haloalkyl and in which optionally one methylene group is
replaced by oxygen or (but not in the case of the compounds of the formula (I-l))
represents phenyl or pyridyl, each of which is optionally mono- or disubstituted by
fluorine, chlorine, bromine,C1-C6alkyl, C1-C4-haloalkyl, C1-C4-alkoxy or C1-C4-haloalkoxy,
or
A and D together particularly preferably represent C3-C5-alkanediyl which is optionally mono- or
disubstituted and in which one methylene group may be replaced by a carbonyl group,
oxygen or sulphur, possible substituents being C1-C2-alkyl or C^-C2-alkoxy, or
A and D (in the case of the compounds of the formula (I-l)) together with the atoms to which they
are attached represent one of the groups AD-1 to AD-10:
(Figure Removed)
or
A and Q* together particularly preferably represent C3-C4-alkanediyl or C4-alkenediyl, each of
which is optionally mono- or disubstituted by identical or different substituents from the
group consisting of fluorine, chlorine, hydroxyl and C1-C6-alkyl and Cj^-alkoxy, each
of which is optionally mono- to trisubstituted by fluorine, or
Q1 particularly preferably represents hydrogen,
Q2 particularly preferably represents hydrogen,
Q, Q and Q" independently of one another particularly preferably represent hydrogen or C1-C3-
alkyl,
Q-* particularly preferably represents hydrogen, C1-C4-alkyl, trifiuoromethyl or represents C3-
Cg-cycloalkyl which is optionally mono- or disubstituted by methyl or methoxy, or
Q3 and Q^ together with the carbon to which they are attached particularly preferably represent a
saturated C5-C6-ring which is optionally mono- or disubstituted by C1-C2-alkyl or C\-C2~
alkoxy and in which optionally one ring member is replaced by oxygen or sulphur, with the
proviso that in this case A particularly preferably represents hydrogen or methyl, or
G particularly preferably represents hydrogen (a) or represents one of the groups
(Figure Removed)
in which
E represents a metal ion equivalent or an ammonium ion,
L represents oxygen or sulphur and
M represents oxygen or sulphur,
R1 particularly preferably representsC1-C6-alkyl, C2-Cg-alkenyl, C \ -C4-alkoxy-C \ -C2-alkyl,
C1-C4-alkylthio-C1-C2-alkyl, each of which is optionally mono- to trisubstituted by
fluorine or chlorine, or represents C3-C6-cycloalkyl which is optionally mono- or
disubstituted by fluorine, chlorine, Cj^-alkyl orC1-C2-alkoxy and in which optionally
one or two not directly adjacent ring members are replaced by oxygen,
particularly preferably represents phenyl which is optionally mono- or disubstituted by
fluorine, chlorine, bromine, cyano, nitro, C-Calky!, C1-C4-alkoxy, C1-C2-haloalkyl or
C 1 -C2-haloalkoxy,
R.2 particularly preferably represents C1-C6-alkyl, C2-C6-alkenyl or C1-C4-alkoxy-C2-C4-
alkyl, each of which is optionally mono- to trisubstituted by fluorine,
particularly preferably represents C3-C6-cycloalkyl which is optionally monosubstituted
byC1-C2-alkyl orC1-C2-alkoxy or
particularly preferably represents phenyl or benzyl, each of which is optionally mono- or
disubstituted by fluorine, chlorine, bromine, cyano, nitro, C1-C4-alkyl, Cj-C3-alkoxy,
trifluoromethyl or trifluoromethoxy,
R.3 particularly preferably representsC1-C6-alkyl which is optionally mono- to trisubstituted
by fluorine or represents phenyl or benzyl, each of which is optionally monosubstituted by
fluorine, chlorine, bromine, C-alkyl, C-alkoxy, trifluoromethyl, trifluoromethoxy,
cyano or nitro,
particularly preferably represents C1 –C6-alkyl, C1-C6-alkoxy,C1-C6-alkylamino,
C6-alkytyamino, C1-C6-alkylthio, C3-C4-alkenylthio, C3-C6-cycloalkylthio, each of which
is optionally mono- to trisubstituted by fluorine, or represents phenyl, phenoxy or
phenylthio, each of which is optionally mono- or disubstituted by fluorine, chlorine,
bromine, nitro, cyano, Cj-C3-alkoxy, C1-C3-haloalkoxy, C1-C3-alkylthio, C1-C3-haloalkylthio,
C1-C3-alkyl or trifluoromethyl,
particularly preferably represents C1-C6-alkoxy or C1-C6-alkylthio,
particularly preferably represents hydrogen, represents C1-C6-alkyl, C3-C6-cycloalkyl,
C1-C6-alkoxy, C3-C6-alkenyl,C1-C6-alkoxy-C-alkyl, each of which is optionally
mono- to trisubstituted by fluorine, represents phenyl which is optionally mono- or
disubstituted by fluorine, chlorine, bromine, trifluoromethyl, C-alkyl or
alkoxy, represents benzyl which is optionally monosubstituted by fluorine, chlorine,
bromine,C1-C6alkyl, trifluoromethyl or C1-C4-alkoxy,
R7 particularly preferably represents CrC6-alkyl, C3-C6-alkenyl or CrC6-alkoxy-C1-C4-alkyl,
R^ and R7 together particularly preferably represent a C4-C5-alkylene radical which is optionally
mono- or disubstituted by methyl or ethyl and in which optionally a methylene group is
replaced by oxygen or sulphur.
In the radical definitions mentioned as being particularly preferred, halogen represents fluorine,
chlorine, bromine and iodine, in particular fluorine, chlorine and bromine.
W very particularly preferably represents hydrogen, methyl, ethyl or chlorine,
X very particularly preferably represents chlorine, methyl, ethyl, propyl, methoxy, ethoxy,
propoxy, trifluoromethyl, difluoromethoxy or trifluoromethoxy,
Y very particularly preferably represents hydrogen or methyl,
Z very particularly preferably represents one of the radicals
Vl very particularly preferably represents hydrogen, fluorine, chlorine, bromine, methyl,
ethyl, methoxy, ethoxy, trifluoromethyl or cyano,
CKE very particularly preferably represents one of the groups
(Figure Removed)
A very particularly preferably represents hydrogen, represents C-alkyl or C-alkoxy-
C1-C2-alkyl, each of which is optionally mono- to trisubstituted by fluorine, represents
cyclopropyl, cyclopentyl or cyclohexyl and, only in the case of the compounds of the
formula (1-5), represents phenyl which is optionally mono- or disubstituted by fluorine,
chlorine, bromine, methyl, ethyl, n-propyl, isopropyl, methoxy, ethoxy, trifluoromethyl,
trifluoromethoxy, cyano or nitro,
B very particularly preferably represents hydrogen, methyl or ethyl or
A, B and the carbon atom to which they are attached very particularly preferably represent
saturated C5-C6-cycloalkyl in which optionally one ring member is replaced by oxygen or
sulphur and which is optionally monosubstituted by methyl, ethyl, propyl, isopropyl,
trifluoromethyl, methoxy, ethoxy, propoxy, butoxy or isobutoxy, with the proviso that in
this case Q^ very particularly preferably represents hydrogen, or
A, B and the carbon atom to which they are attached very particularly preferably represent Cgcycloalkyl
which is substituted by an alkylenedioxyl group containing two not directly
adjacent oxygen atoms, with the proviso that in this case Q^ very particularly preferably
represents hydrogen, or
A, B and the carbon atom to which they are attached very particularly preferably represent C5-
C6-cycloalkyl or C5-C6-cycloalkenyl in which two substituents together with the carbon
atoms to which they are attached represent C2-C4-alkanediyl or C2-C4-alkenediyl or
butadienediyl, with the proviso that in this case Q3 very particularly preferably represents
hydrogen,
D very particularly preferably represents hydrogen, represents C1-C4-alkyl, C3-C4-alkenyl,
C1-C4-alkoxy-C1-C3-alkyl, each of which is optionally mono- to trisubstituted by fluorine,
represents cyclopropyl, cyclopenryl or cyclohexyl or (but not in the case of the compounds
of the formula (1-1)) represents pyridyl or phenyl which is optionally monosubstituted by
fluorine, chlorine, methyl, ethyl, n-propyl, isopropyl, methoxy, ethoxy or trifluoromethyl,
or
A and D together very particularly preferably represent C3-C5-alkanediyl which is optionally
mono- or disubstituted by methyl or methoxy and in which optionally one carbon atom is
replaced by oxygen or sulphur or represent the group AD-1
A and Q* together very particularly preferably represent C3-C4-alkanediyl which is optionally
mono- or disubstituted by methyl or methoxy, or
Q 1 very particularly preferably represents hydrogen,
Q2 very particularly preferably represents hydrogen,
Q4, Q5 and Q6 independently of one another very particularly preferably represent hydrogen or
methyl,
Q3 very particularly preferably represents hydrogen, methyl, ethyl, propyl or isopropyl, or
Q3 and Q4 together with the carbon to which they are attached very particularly preferably
represent a saturated C5-C6-ring which is optionally monosubstituted by methyl or
methoxy, with the proviso that in this case A very particularly preferably represents
hydrogen,
G very particularly preferably represents hydrogen (a) or represents one of the groups
(Figure Removed)
in particular (a), (b) or (c)
in which
E represents a metal ion equivalent or an ammonium ion,
L represents oxygen or sulphur and
M represents oxygen or sulphur,
R1 very particularly preferably representsC1-C6-alkyl, C2-Cg-alkenyl,C1-C2-alkoxy-Cjalkyl,
C1-C2-alkylthio-Ci-alkyl, each of which is optionally mono- to trisubstituted by
fluorine, or represents cyclopropyl or cyclohexyl, each of which is optionally
monosubstituted by fluorine, chlorine, methyl or methoxy,
very particularly preferably represents phenyl which is optionally monosubstituted by
fluorine, chlorine, bromine, cyano, nitro, methyl, methoxy, trifluoromethyl or trifluoromethoxy,
R2 very particularly preferably represents C1-C6-alkyl, C2-C6-alkenyl or C1-C4-alkoxy-C2-
C3-alkyl, each of which is optionally monosubstituted by fluorine,
or very particularly preferably represents phenyl or benzyl, each of which is optionally
monosubstituted by fluorine, chlorine, cyano, nitro, methyl, ethyl, n-propyl, i-propyl,
methoxy, ethoxy, trifluoromethyl or trifluoromethoxy,
R^ very particularly preferably represents methyl, ethyl, n-propyl, isopropyl, each of which is
optionally mono- to trisubstituted by fluorine, or represents phenyl or benzyl, each of
which is optionally monosubstituted by fluorine, chlorine, bromine, methyl, tert-butyl,
methoxy, trifluoromethyl, trifluoromethoxy, cyano or nitro,
R4 very particularly preferably representsC1-C6alkyl, C1-C4-alkoxy, C1-C4-alkylamino, di-
(C1-C4-alkyl)amino, C-alkylthio, each of which is optionally mono- to trisubstituted
by fluorine, or represents phenyl, phenoxy or phenylthio, each of which is optionally
monosubstituted by fluorine, chlorine, bromine, nitro, cyano,C1-C2-alkoxy,
fluoroalkoxy,C1-C2-alkylthio, C-fiuoroalkylthio or C
R very particularly preferably represents methoxy, ethoxy, propoxy, butoxy, methylthio,
ethylthio, propylthio or butylthio,
R very particularly preferably represents hydrogen, represents Cj^-alkyl, C$ -Cgcycloalkyl,
C-alkoxy, C3-C4-alkenyl, C1-C4-alkoxy-C1-C4-alkyl, each of which is
optionally mono- to trisubstituted by fluorine, represents phenyl which is optionally
monosubstituted by fluorine, chlorine, bromine, trifluoromethyl, methyl or methoxy,
represents benzyl which is optionally monosubstituted by fluorine, chlorine, bromine,
methyl, trifluoromethyl or methoxy,
R very particularly preferably represents methyl, ethyl, propyl, isopropyl, butyl, isobutyl or
allyl,
R and R7 very particularly preferably represent a C4-C5-alkylene radical in which optionally one
methylene group is replaced by oxygen or sulphur.
W most preferably represents hydrogen, methyl or ethyl,
X most preferably represents chlorine, methyl or ethyl,
Y most preferably represents hydrogen,
Z most preferably represents, in the 4- or 5-position, the radical
V most preferably represents chlorine or methoxy,
CKE most preferably represents one of the groups
(Figure Removed)
A most preferably represents hydrogen, C \ -C4-alkyl or cyclopropyl,
B most preferably represents hydrogen or methyl, or
A, B and the carbon atom to which they are attached most preferably represent saturated
cycloalkyl in which optionally one ring member is replaced by oxygen and which is
optionally monosubstituted by methyl or methoxy, with the proviso that in this case Q^
most preferably represents hydrogen,
D most preferably represents hydrogen,
or
A and D together most preferably represent C3-C5-alkanediyl in which optionally one carbon atom
is replaced by oxygen,
Q * most preferably represents hydrogen,
Q most preferably represents hydrogen,
Q3 most preferably represents methyl,
Q most preferably represents methyl, or
Q3 and Q together with the carbon to which they are attached most preferably represent a
saturated Cf-Cg-ring, with the proviso that in this case A most preferably represents
hydrogen,
most preferably represents hydrogen,
Q most preferably represents hydrogen,
G most preferably represents hydrogen (a) or represents one of the groups
(Figure Removed)
in which
L represents oxygen and
M represents oxygen or sulphur,
R.1 most preferably represents C1-C6-alkyl orC1-C2-alkoxy-Ci-alkyl,
R.2 most preferably represents C \ -Cg-alkyl or benzyl.
The general or preferred radical definitions or illustrations given above can be combined with one
another as desired, i.e. including combinations between the respective ranges and preferred ranges.
They apply both to the end product and, correspondingly, to precursors and intermediates.
Preference according to the invention is given to the compounds of the formula (I) which contain a
combination of the meanings given above as being preferred (preferable).
Particular preference according to the invention is given to the compounds of the formula (I) which
contain a combination of the meanings given above as being particularly preferred.
Very particular preference according to the invention is given to the compounds of the formula (I)
which contain a combination of the meanings given above as being very particularly preferred.
Most preference according to the invention is given to the compounds of the formula (I) which
contain a combination of the meanings given above as being most preferred.
Saturated or unsaturated hydrocarbon radicals, such as alkyl or alkenyl, can in each case be
straight-chain or branched as far as this is possible, including in combination with heteroatoms,
such as, for example, in alkoxy.
Optionally substituted radicals can, unless stated otherwise, be mono- or polysubstituted, where in
the case of polysubstitution the substituents can be identical or different.
In addition to the compounds mentioned in the Preparation Examples, the following
compounds of the formula (I-l-a) may be specifically mentioned:
(Figure Removed)
Table 1:
(Table Removed)
In addition to the compounds mentioned in the Preparation Examples, the following
compounds of the formula (I-2-a) may be specifically mentioned:
(Figure Removed)
Table 8:
(Table Removed)
In addition to the compounds mentioned in the Preparation Examples, the following
compounds of the formula (I-8-a) may be specifically mentioned:
(Figure Removed)
Table 15; W, X, Y and Z are as shown in Table 1.
(Table Removed)
Table 16; A and D are as shown in Table 15
W, X, Y and Z are as shown in Table 2.
Table 17: A and Dare as shown in Table 15
W, X, Y and Z are as shown in Table 3.
Table 18; A and Dare as shown in Table 15
W, X, Y and Z are as shown in Table 4.
Table 19; A and Dare as shown in Table 15
W, X, Y and Z are as shown in Table 5.
Table 20; A and D are as shown in Table 15
W, X, Y and Z are as shown in Table 6.
Table 21; A and D are as shown in Table 15
W, X, Y and Z are as shown in Table 7.
Preferred meanings of the groups mentioned above in connection with the compounds
improving crop plant tolerance ("herbicide safeners") of the formulae (Ha), (lib), (He), (Ed)
and (He) are defined hereinbelow.
n preferably represents the numbers 0,1,2, 3 or 4.
A1 preferably represents one of the divalent heterocyclic groups outlined hereinbelow
O—N
A2 preferably represents methylene or ethylene, each of which is optionally substituted
by methyl, ethyl, methoxycarbonyl or ethoxycarbonyl.
R21 preferably represents hydroxyl, mercapto, amino, methoxy, ethoxy, n- or i-propoxy,
n-, i-, s- or t-butoxy, methylthio, ethylthio, n- or i-propylthio, n-, i-, s- or t-butylthio,
methylamino, ethylamino, n- or i-propylamino, n-, i-, s- or t-butylamino,
dimethylamino or diethylamino.
R22 preferably represents hydroxyl, mercapto, amino, methoxy, ethoxy, n- or i-propoxy, n-,
i-, s- or t-butoxy, methylthio, ethylthio, n- or i-propylthio, n-, i-, s- or t-butylthio,
methylamino, ethylamino, n- or i-propylamino, n-, i-, s- or t-butylamino,
dimethylamino or diethylamino.
R23 preferably represents methyl, ethyl, n- or i-propyl, each of which is optionally
substituted by fluorine, chlorine and/or bromine.
R24 preferably represents hydrogen, or represents methyl, ethyl, n- or i-propyl, n-, i-, s- or
t-butyl, propenyl, butenyl, propynyl or butynyl, methoxymethyl, ethoxymethyl,
methoxyethyl, ethoxyethyl, dioxolanylmethyl, furyl, furylmethyl, thienyl, thiazolyl,
piperidinyl, each of which is optionally substituted by fluorine and/or chlorine, or
represents phenyl which is optionally substituted by fluorine, chlorine, methyl, ethyl,
n- or i-propyl, n-, i-, s- or t-butyl.
R25 preferably represents hydrogen, or represents methyl, ethyl, n- or i-propyl, n-, i-, s- or
t-butyl, propenyl, butenyl, propynyl or butynyl, methoxymethyl, ethoxymethyl,
methoxyethyl, ethoxyethyl, dioxolanylmethyl, furyl, furylmethyl, thienyl, thiazolyl,
piperidinyl, each of which is optionally substituted by fluorine and/or chlorine, or
represents phenyl which is optionally substituted by fluorine, chlorine, methyl, ethyl,
n- or i-propyl, n-, i-, s- or t-butyl or together with R represents one of the radicals
-CH2-O-CH2-CH2- and -CH2-CH2-O-CH2-CH2- which are optionally substituted
by methyl, ethyl, furyl, phenyl, a fused benzene ring or by two substituents which,
together with the.carbon atom to which they are bonded, form a 5- or 6-membered
carbocycle.
R26 preferably represents hydrogen, cyano, fluorine, chlorine, bromine, or represents
methyl, ethyl, n- or i-propyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl or
phenyl, each of which is optionally substituted by fluorine, chlorine and/or bromine.
R27 preferably represents hydrogen, or represents methyl, ethyl, n- or i-propyl, n-, i-, s- or
t-butyl, optionally substituted by hydroxyl, cyano, fluorine, chlorine, methoxy, ethoxy,
n- or i-propoxy.
R28 preferably represents hydrogen, cyano, fluorine, chlorine, bromine, or represents
methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, cyclopropyl, cyclobutyl, cyclopentyl,
cyclohexyl or phenyl, each of which is optionally substituted by fluorine, chlorine
and/or bromine.
X1 preferably represents nitro, cyano, fluorine, chlorine, bromine, methyl, ethyl, n- or ipropyl,
n-, i-, s- or t-butyl, difluoromethyl, dichloromethyl, trifluoromethyl,
trichloromethyl, chlorodifluoromethyl, fluorodichloromethyl, methoxy, ethoxy, n- or ipropoxy,
difluoromethoxy or trifluoromethoxy.
X2 preferably represents hydrogen, nitro, cyano, fluorine, chlorine, bromine, methyl,
ethyl, n- or i-propyl, n-, i-, s- or t-butyl, difluoromethyl, dichloromethyl,
trifluoromethyl, trichloromethyl, chlorodifluoromethyl, fluorodichloromethyl,
methoxy, ethoxy, n- or i-propoxy, difluoromethoxy or trifluoromethoxy.
X3 preferably represents hydrogen, nitro, cyano, fluorine, chlorine, bromine, methyl,
ethyl, n- or i-propyl, n-, i-, s- or t-butyl, difluoromethyl, dichloromethyl,
trifluoromethyl, trichloromethyl, chlorodifluoromethyl, fluorodichloromethyl,
methoxy, ethoxy, n- or i-propoxy, difluoromethoxy or trifluoromethoxy.
R29 preferably represents hydrogen, methyl, ethyl, n- or i-propyl.
R30 preferably represents hydrogen, methyl, ethyl, n- or i-propyl.
R31 preferably represents hydrogen, or represents methyl, ethyl, n- or i-propyl, n-, i-, s- or
t-butyl, methoxy, ethoxy, n- or i-propoxy, n-, i-, s- or t-butoxy, methylthio, ethylthio, nor
i-propylthio, n-, i-, s- or t-butylthio, methylamino, ethylamino, n- or i-propylamino,
n-, i-, s- or t-butylamino, dimethylamino or diethylamino, each of which is optionally
-70-
substituted by cyano, fluorine, chlorine, methoxy, ethoxy, n- or i-propoxy, or
represents cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclopropyloxy,
cyclobutyloxy, cyclopentyloxy, cyclohexyloxy, cyclopropylthio, cyclobutylthio,
cyclopentylthio, cyclohexylthio, cyclopropylamino, cyclobutylamino,
cyclopentylamino or cyclohexylamino, each of which is optionally substituted by
cyano, fluorine, chlorine, bromine, methyl, ethyl, n- or i-propyl.
R32 preferably represents hydrogen, or represents methyl, ethyl, n- or i-propyl, n-, i- or
s-butyl, each of which is optionally substituted by cyano, hydroxyl, fluorine, chlorine,
methoxy, ethoxy, n- or i-propoxy, or represents propenyl, butenyl, propynyl or butynyl,
each of which is optionally substituted by cyano, fluorine, chlorine or bromine, or
represents cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl, each of which is
optionally substituted by cyano, fluorine, chlorine, bromine, methyl, ethyl, n- or ipropyl.
R33 preferably represents hydrogen, or represents methyl, ethyl, n- or i-propyl, n-, i- or
s-butyl, each of which is optionally substituted by cyano, hydroxyl, fluorine, chlorine,
methoxy, ethoxy, n- or i-propoxy, or represents propenyl, butenyl, propynyl or butynyl,
each of which is optionally substituted by cyano, fluorine, chlorine or bromine, or
represents cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl, each of which is
optionally substituted by cyano, fluorine, chlorine, bromine, methyl, ethyl, n- or ipropyl,
or represents phenyl which is optionally substituted by nitro, cyano, fluorine,
chlorine, bromine, methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, trifluoromethyl,
methoxy, ethoxy, n- or i-propoxy, difluoromethoxy or trifluoromethoxy, or together
with R32 represents butane-l,4-diyl(trimethylene), pentane-l,5-diyl, l-oxabutane-1,4-
diyl or 3-oxapentane-l,5-diyl, each of which is optionally substituted by methyl or
ethyl.
X4 preferably represents nitro, cyano, carboxyl, carbamoyl, formyl, sulphamoyl, hydroxyl,
amino, fluorine, chlorine, bromine, methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl,
trifluoromethyl, methoxy, ethoxy, n- or i-propoxy, difluoromethoxy or
trifluoromethoxy.
X5 preferably represents nitro, cyano, carboxyl, carbamoyl, formyl, sulphamoyl, hydroxyl,
amino, fluorine, chlorine, bromine, methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl,
trifluoromethyl, methoxy, ethoxy, n- or i-propoxy, difluoromethoxy or
trifluoromethoxy.
Examples of the compounds of the formula (Ha) which are very particularly preferred as
herbicide safeners according to the invention are listed in the table which follows.
Table Examples of the compounds of the formula (Ha)
(Table Removed)
Examples of the compounds of the formula (Kb) which are very particularly preferred as
herbicide safeners according to the invention are listed in the table which follows.
(Figure Removed)
Table Examples of the compounds of the formula (nb)
(Table Removed)
Examples of the compounds of the formula (He) which are very particularly preferred as
herbicide safeners according to the invention are listed in the table which follows.
(Figure Removed)
Table Examples of the compounds of the formula (He)
(Table Removed)
Examples of the compounds of the formula (Ed) which are very particularly preferred as
herbicide safeners according to the invention are listed in the table which follows.
(Ed)
Table Examples of the compounds of the formula (Ed)
(Table Removed)
Examples of the compounds of the formula (He) which are very particularly preferred as
herbicide safeners according to the invention are listed in the table which follows.
(Figure Removed)
Table Examples of the compounds of the formula (He)
(Table Removed)
Cloquintocet-mexyl, fenchlorazol-ethyl, isoxadifen-ethyl, mefenpyr-diethyl, furiiazole,
fenclorim, cumyluron, dymron, dimepiperate and the compounds IIe-5 and IIe-11 are most
preferred as the compound which improves crop plant tolerance [component (b')], with
cloquintocet-mexyl and mefenpyr-diethyl being especially preferred.
The compounds of the general formula (Ha) to be used in accordance with the invention as
safeners are known and/or can be prepared by methods known per se (cf. WO-A-91/07874,
WO-A-95/07897).
The compounds of the general formula (Kb) to be used in accordance with the invention as
safeners are known and/or can be prepared by methods known per se (cf. EP-A-191736).
The compounds of the general formula (He) to be used in accordance with the invention as
safeners are known and/or can be prepared by methods known per se (cf. DE-A-2218097, DEA-
2350547).
The compounds of the general formula (Ed) to be used in accordance with the invention as
safeners are known and/or can be prepared by methods known per se (cf. DE-A-19621522/USA-
6235680).
The compounds of the general formula (He) to be used in accordance with the invention as
safeners are known and can be prepared by methods known per se (cf. WO-A-99/66795/US-A-
6251827).
Examples of the selectively herbicidal combinations according to the invention of in each case
one active compound of the formula (I) and in each case one of the above-defined safeners are
listed in the table which follows.
Table Examples of the combinations according to the invention
Active compounds of the formula
(Table Removed)
Surprisingly, it has now been found that the above-defined active compound combinations of
N-heterocyclylphenyl-substituted cyclic ketoenols of the general formula (I) and safeners
(antidotes) from the above group (b') are not only very well tolerated by useful plants, but also
have a particularly high herbicidal activity and can be used in a variety of crops, in particular in
cereals (mainly wheat), but also in soybeans, potatoes, maize and rice, for the selective control
of weeds.
It must be considered as surprising that, from a multiplicity of known safeners or antidotes
which are capable of antagonizing the damaging effect of a herbicide on the crop plants, it is
precisely the abovementioned compounds of group (b') which are capable of virtually
completely compensating for the harmful effect of N-heterocyclylphenyl-substituted cyclic
ketoenols on the crop plants without adversely affecting the herbicidal activity towards the
weeds to a substantial degree.
What must be emphasized in this context is the particularly advantageous activity of the
particularly and most preferred components from group (b'), in particular with regard to
leaving cereal plants, such as, for example, wheat, barley and rye, but also maize and rice, as
crop plants unharmed.
Using, for example, according to process (A) ethyl N-[6-methyl-3-(N-4-chloropyrazolyl)-
phenylacetyl]-l-aminocyclohexanecarboxylate as starting material, the course of the process
according to the invention can be represented by the following equation:
(Figure Removed)
Using, for example, according to process (B) ethyl O-[2-chloro-5-(N-4-chloropyrazolyl)-
phenylacetyl]-2-hydroxyisobutyrate, the course of the process according to the invention can
be represented by the following equation:
(Figure Removed)
Using, for example, according to process (C) ethyl 2-[6-methyl-3-(N-4-chloropyrazolyl)-
phenyl]-4-(4-methoxy)benzyhnercapto-4-methyl-3-oxovalerate, the course of the process
according to the invention can be represented by the following equation:
CH,
Using, for example, according to process (D) chlorocarbonyl 2-[2,6-dimethyl-4-(N-4-
chloropyrazolyl)phenyl] ketene and acetone as starting materials, the course of the process
according to the invention can be represented by the following equation:
(Figure Removed)
Using, for example, according to process (E) chlorocarbonyl 2-[2,6-dimethyl-4-(N-4-
chloropyrazolyl)phenyl] ketene and thiobenzamide as starting materials, the course of the
process according to the invention can be represented by the following equation:
base
=0
-85-
Using, for example, according to process (F) ethyl 5-[2,6-dimethyl-(N-4-chloropyrazolylphenyl)]-
2,3-tetramethylene-4-oxovalerate, the course of the process according to the
invention can be represented by the following equation:
(Figure Removed)
Using, for example, according to process (G) ethyl 5-[2,6-dimethyl-4-(N-4-chloropyrazolyl)
phenyl]-2,2-dimethyl-5-oxohexanoate, the course of the process according to the
invention can be represented by the following equation:
0 CH
Using, for example, according to process (Ha) hexahydropyridazine and chlorocarbonyl 2-
[2,6-dimethyl-4-(N-4-chloropyrazolyl)phenyl] ketene as starting materials, the course of the
reaction of the process according to the invention can be represented by the following
equation:
Using, for example, according to process (HP) hexahydropyridazine and dimethyl 2,6-
dimethyl-4-(N-4-chloropyrazolyl)phenyhnalonate as starting materials, the course of the
process according to the invention can be represented by the following equation:
(Figure Removed)
Using, for example, according to process (Hy) l-ethoxycarbonyl-2-[2,6-dimethyl-4-(N-4-
chloropyrazolyl)phenylacetyl]hexahydropyrida2ine as starting material, the course of the
reaction can be represented by the following equation:
Using, for example, according to process (la) 3-[2,6-dimethyl-4-(N-4-chloropyrazolyl)-
phenyl]-5,5-dimethylpyrrolidine-2,4-dione and pivaloyl chloride as starting materials, the
course of the process according to the invention can be represented by the following
equation:
3.CH
Using, for example, according to process (I) (variant 6) 3-[2,6-dimethyl-4-(N-4-chloropyrazolyl)
phenyl]-4-hydroxy-5-phenyl-A^-dihydroruran-2-one and acetic anhydride as
starting materials, the course of the process according to the invention can be represented by
the following equation:
Using, for example, according to process (J) 8-[2,6-dimethyl-4-(N-4-chloropyrazolyl)-
phenyl]-l,6-dia2abicyclo-(4,3,Ol'6)-nonane-7)9-dione and ethoxyethyl chloroformate as
starting materials, the course of the process according to the invention can be represented by
the following equation:
(Figure Removed)
Using, for example, according to process (K) 3-[2,6-dimethyl-4-(N-4-chloropyrazolyl)-
phenyl]-4-hydroxy-5-methyl-6-(3-pyridyl)pyrone and methyl chloromonothioformate as
starting materials, the course of the reaction can be represented by the following equation:
Using, for example, according to process (L) 2-[2,6-dimethyl-4-(N-4-chloropyrazolyl)-
phenyl]-5,5-pentamethylenepyrrolidine-2,4-dione and methanesulphonyl chloride as starting
materials, the course of the reaction can be represented by the following equation:
(Figure Removed)
Using, for example, according to process (M) 2-[2,6-dimethyl-4-(N-4-chloropyrazolyl)-
phenyl]-4-hydroxy-5,5-dimethyl-A3-dihydrofuran-2-one and 2,2,2-trifluoroethyl methanethiophosphonyl
chloride as starting materials, the course of the reaction can be represented
by the following equation:
Using, for example, according to process (N) 3-[2-chloro-5-(N-4-chloropyrazolyl)phenyl]-5-
cyclopropyl-5-methylpyrrolidine-2,4-dione and NaOH as components, the course of the
process according to the invention can be represented by the following equation:
Using, for example, according to process (O) (variant a) 3-[6-methyl-3-(N-4-
chloropyrazolyl)phenyl]-4-hydroxy-5-tetramethylene-A3-dihydrofuran-2-one and ethyl isocyanate
as starting materials, the course of the reaction can be represented by the following
equation:
(Figure Removed)
Using, for example, according to process (O) (variant 8) 3-[2-chloro-5-(N-4-chloropyrazolyl)
phenyl]-5-methylpyrrolidine-2,4-dione and dimethylcarbamoyl chloride as starting
materials, the course of the reaction can be represented by the following equation:
(Figure Removed)
Using, for example, according to process (P) 3-[(2,6-dimethyl-4-bromo)phenyl]-4,4-(pentamethylene)
pyrrolidine-2,4-dione and 4-chloropyrazole as starting materials, the course of
the reaction can be represented by the following equation:
(Figure Removed)
The compounds, required as starting materials in the process (a) according to the invention,
of the formula (H)
(Figure Removed)
in which
A, B, D, W, X, Y, Z and R8 are as defined above
are novel.
The acylamino acid esters of the formula (II) are obtained, for example, when amino acid
derivatives of the formula (XXIV)
(Figure Removed)
in which
A, B, R8 and D are as defined above
are acylated with substituted phenylacetic acid derivatives of the formula (XXV)
(Figure Removed)
in which
W, X, Y and Z are as defined above and
T represents a leaving group introduced by reagents that activate carboxylic acids,
such as carbonyldiimidazole, carbodiimides (such as, for example,
dicyclohexylcarbodiimide), phosphorylating reagents (such as, for example, POC13,
BOP-C1), halogenating agents, for example thionyl chloride, oxalyl chloride,
phosgene, sulphonyl chlorides (for example toluenesulphonyl chloride) or
chloroformic esters,
(Chem. Reviews 52,237-416 (1953); Bhattacharya, Indian J. Chem. 6, 341-5,1968)
or when acylamino acids of the formula (XXVI)
(Figure Removed)
in which
A, B, D, W, X, Y and Z are as defined above
are esterified (Chem. Ind. (London) 1568 (1968)).
The compounds of the formula (XXVI)
(Figure Removed)
in which
A, B, D, W, X, Y and Z are as defined above
are novel.
The compounds of the formula (XXVT) are obtained when amino acids of the formula
(Figure Removed)
in which
A, B and D are as defined above
are acylated with substituted phenylacetic acid derivatives of the formula (XXV)
(Figure Removed)
in which
W, X, Y and Z are as defined above and
T is as defined above,
for example according to Schotten-Baumann (Organikum, VEB Deutscher Verlag der
Wissenschaften, Berlin 1977, p. 505).
The compounds of the formula (XXV) are novel. They can be prepared by processes known
in principle and as shown in the Preparation Examples (see, for example, H. Henecka,
Houben-Weyl, Methoden der Organischen Chemie [Methods of Organic Chemistry], Vol. 8,
pp. 467-469 (1952)).
The compounds of the formula (XXV) are obtained, for example, by reacting substituted
phenylacetic acids of the formula (XXVHI)
(Figure Removed)
in which
W, X ,Y and Z are as defined above
with halogenating agents (for example thionyl chloride, thionyl bromide, oxalyl chloride,
phosgene, phosphorus trichloride, phosphorus tribromide or phosphorus pentachloride),
phosphorylating reagents (such as, for example, POC13, BOP-C1), carbonyldiimidazole,
carbodiimides (for example dicyclohexylcarbodiimide), if appropriate in the presence of a
as
diluent (for example, optionally chlorinated aliphatic or aromatic hydrocarbons, such
toluene or methylene chloride, or ethers, for example tetrahydrofuran, dioxane, methyl tertbutyl
ether), at temperatures of from -20°C to 150°C, preferably from -10°C to 100°C.
Some of the compounds of the formulae (XXTV) and (XXVII) are known and/or can be
prepared by known processes (see, for example, Compagnon, Miocque Ann. Chim. (Paris)
[14] 5, p. 11-22,23-27(1970)).
The substituted cyclic aminocarboxylic acids of the formula (XXVII) in which A and B.
form a ring are generally obtained by means of a Bucherer-Bergs synthesis or a Strecker
synthesis, where they are obtained in each case in different isomeric forms. Thus, the
conditions of the Bucherer-Bergs synthesis give predominantly the isomers (for simplicity
reasons referred to as 6 hereinbelow) in which the radicals R and the carboxyl group are in
equatorial positions, while the conditions of the Strecker synthesis give predominantly the
isomers (for simplicity reasons referred to as a hereinbelow) where the amino group and the
radical R are in equatorial positions.
(Figure Removed)
Bucherer-Bergs synthesis
(B-isomer)
H
Strecker synthesis
(a-isomer)
(L. Munday, J. Chem. Soc. 4372 (1961); J.T. Eward, C. Jitrangeri, Can. J. Chem. 53, 3339
(1975).
Furthermore, the starting materials, used in process (A) above, of the formula (II)
(Figure Removed)
in which
A, B, D, W, X, Y, Z and R8 are as defined above
can be prepared by reacting aminonitriles of the formula (XXEX)
(Figure Removed)
in which
A, B and D are as defined above
with substituted phenylacetic acid derivatives of the formula (XXV)
(Figure Removed)
in which
T, W, X, Y and Z are as defined above
to give compounds of the formula (XXX)
(Figure Removed)
in which
A, B, D, W, X, Y and Z are as defined above
which are then subjected to an acidic alcoholysis.
The compounds of the formula (XXX) are also novel.
The compounds, required as starting materials for the process (B) according to the
invention, of the formula (HI)
(Figure Removed)
in which
A, B, W, X, Y, Z and R8 are as defined above
are novel.
They can be prepared by methods known in principle.
Thus, the compounds of the formula (IE) are obtained, for example, when
2-hydroxycarboxylic esters of the formula (XXXI-A)
(Figure Removed)
wn
in which
A, B and R8 are as defined above
are acylated with substituted phenylacetic acid derivatives of the formula (XXV)
(Figure Removed)
in which
T, W, X, Y and Z are as defined above
(Chem. Reviews 52, 237-416 (1953)).
Furthermore, compounds of the formula (HI) are obtained when
substituted phenylacetic acids of the formula (XXVffl)
(Figure Removed)
in which
W, X, Y and Z are as defined above
are alkylated with a-halocarboxylic esters of the formula (XXXI-B)
(Figure Removed)
in which
A, B and R.8 are as defined above and
Hal represents chlorine or bromine.
The compounds of the formula (XXVin) are novel.
The compounds of the fonnula (XXXI-B) are commercially available.
The compounds of the formula (XXVin)
(Figure Removed)
in which
W, X, Y and Z are as defined above
are obtained, for example, when phenylacetic esters of the formula (XXXII)
(Figure Removed)
in which
W, X, Y, Z and are as defined above
are hydrolyzed in the presence of acids or bases in the presence of a solvent under generally
known standard conditions.
The compounds of the formula (XXXIT) are novel.
The compounds of the formula (XXXII)
(Figure Removed)
in which
W, X, Y, Z and R.8 are as defined above
are obtained, for example, by the process (Q) described in the examples
when phenylacetic esters of the formula (XXXII-a)
(Figure Removed)
in which
R.S, W, X and Y are as defined above and
Z' represents halogen (in particular bromine)
are reacted in the presence of an HN-containing heterocycle of the formula (XXIII) in which
Z is as defined above in the presence of a base and, if appropriate, in the presence of a
catalyst (preferably copper salts, such as, for example, copper(I) iodide) (S. Buchwald et. al.
JACS 123. 7727, 2001).
Some of the phenylacetic esters of the formula (XXXII-a) are known from the applications
WO 96/35 664 and WO 97/02 243, or they can be prepared by the processes described
therein.
The compounds, required as starting materials in the above process (C), of the formula (IV)
(Figure Removed)
in which
A, B, V, W, X, Y, Z and R8 are as defined above
are novel.
They can be prepared by methods known in principle.
The compounds of the formula (IV) are obtained, for example, when
substituted phenylacetic esters of the formula (XXXII)
(Figure Removed)
in which
W, X, Y, Z and are as defined above
are acylated with 2-benzylthiocarbonyl halides of the formula (XXXHI)
(Figure Removed)
in which
A, B and V are as defined above and
Hal represents halogen (in particular chlorine or bromine)
in the presence of strong bases (see, for example, M.S. Chambers, E.J. Thomas,
D.J. Williams, J. Chem. Soc. Chem. Commun., (1987), 1228).
Some of the benzylthiocarbonyl halides of the formula (XXXHI) are known, and/or they can
be prepared by known processes (J. Antibiotics (1983), 26. 1589).
The halocarbonyl ketenes of the formula (VI) required as starting materials for the above
processes (D), (E) and (H-a) are novel. They can be prepared in a simple manner by
methods known in principle (cf, for example, Org. Prep. Proced. Int., 7, (4), 155-158, 1975
and DE 1 945 703). Thus, for example, the compounds of the formula (VI)
(Figure Removed)
in which
W, X, Y and Z are as defined above and
Hal represents chlorine or bromine
are obtained when
substituted phenylmalonic acids of the formula (XXXTV)
(Figure Removed)
in which
W, X, Y and Z are as defined above
are reacted with acid halides, such as, for example, thionyl chloride, phosphorus(V)
chloride, phosphorus(in) chloride, oxalyl chloride, phosgene or thionyl bromide, if
appropriate in the presence of catalysts, such as, for example, diethylformamide, methylsteryl
formamide or triphenylphosphine and, if appropriate, in the presence of bases, such
as, for example, pyridine or triethylamine.
The substituted phenylmalonic acids of the formula (XXXIV) are novel. They can be
prepared in a simple manner by known processes (cf., for example, Organikum, VEB
Deutscher Verlag der Wissenschaften, Berlin 1977, p. 517 ff, EP-A-528 156, WO
96/35 664, WO 97/02 243, WO 97/01535, WO 97/36868 and WO 98/05638).
Thus, phenylmalonic acids of the formula (XXXIV)
(Figure Removed)
in which
W, X ,Y and Z are as defined above
are obtained when phenyhnalonic acid derivatives of the formula (XI) where U = OR°
(XI)
in which

U, W, X, Y and Z are as defined above
are initially hydrolyzed in the presence of a base and a solvent and then carefully acidified
(EP-A-528 156, WO 96/35 664, WO 97/02 243).
The malonic esters of the formula (XI) where U =
(Figure Removed)
in which
U, W, X, Y and Z are as defined above
are novel.
They can be prepared by generally known methods of organic chemistry (cf., for example,
Tetrahedron Lett. 27, 2763 (1986), Organikum VEB Deutscher Verlag der Wissenschaften,
Berlin 1977, p. 587 ff., WO 96/35664, WO 97/02243, WO 97/01535, WO 97/36868, WO
98/05638 and WO 99/47525).
The carbonyl compounds, required as starting materials for the process (D) according to the
invention, of the formula (V)
(Figure Removed)
in which
A and D are as defined above
or their silyl enol ethers of the formula (Va)
(Figure Removed)
in which
A, D and R8 are as defined above
are compounds which are commercially available, generally known or obtainable by known
processes.
The preparation of the ketene acid chlorides of the formula (VI) required as starting
materials for carrying out the process (E) according to the invention has already been
described above. The thioamides, required for carrying out the process (E) according to the
invention, of the formula (VII)
(Figure Removed)
in which
A is as defined above
are compounds which are generally known in organic chemistry.
The compounds, required as starting materials for the above process (F), of the formula
(Figure Removed)
in which
A, B, Q1, Q2, W, X, Y, Z and R8 are as defined above
are novel.
They can be prepared by methods known hi principle.
The 5-aryl-4-ketocarboxylic esters of the formula (VIE) are obtained, for example, when 5-
aryl-4-ketocarboxylic acids of the formula (XXXV)
(Figure Removed)
in which
W, X, Y, Z, A, B, Q1 and Q2 are as defined above
are esterified (cf., for example, Organikum, 15th Edition, Berlin, 1977, page 499) or
alkylated (see Preparation Example).
The 5-aryl-4-ketocarboxylic acids of the formula (XXXV)
(Figure Removed)
in which
A, B, Q1, Q2, W, X, Y and Z are as defined above
are novel, but can be prepared by methods known in principle (WO 96/01 798,
WO 97/14667, WO 98/3928 1).
The 5-aryl-4-ketocarboxylic acids of the formula (XXXV) are obtained, for example, when
2-phenyl-3-oxoadipic esters of the formula (XXXVI)
(Figure Removed)
in which
A, B, Q1, Q2, W, X, Y and Z are as defined above and
R.8 and R.8' represent alkyl (in particular C i -Cg-alkyl) and
when the compound of the formula (XXXVm) is used, R8 represents hydrogen,
are decarboxylated, if appropriate in the presence of a diluent and if appropriate in the
presence of a base or an acid (cf, for example, Organikum, 15th Edition, Berlin, 1977,
pages 519 to 521).
The compounds of the formula (XXXVI)
(Figure Removed)
in which
A, B, Q1, Q2, W, X, Y, Z, R8, R8' are as defined above and in which
if the compound of the formula (XXXVni) is used, R8 also represents hydrogen,
are novel.
The compounds of the formula (XXXVI) are obtained, for example,
when dicarboxylic semiester chlorides of the formula (XXXVII),
(Figure Removed)
in which
A, B, Oj , Q2 and R8 are as defined above and
Hal represents chlorine or bromine
or carboxylic anhydrides of the formula (XXXVin)
(Figure Removed)
in which
A, B, Q! and Q^ are as defined above
are acylated with a phenylacetic ester of the formula (XXXII)
(Figure Removed)
in which
W, X, Y, Z and R8' are as defined above
in the presence of a diluent and in the presence of a base (cf., for example, M.S. Chambers,
E. J. Thomas, D.J. Williams, J. Chem. Soc. Chem. Common., (1987), 1228, cf. also the
Preparation Examples).
Some of the compounds of the formulae (XXXVH) and (XXXVIII) are known compounds
of organic chemistry, and/or they can be prepared in a simple manner by methods known in
principle.
The compounds, required as starting materials for the above process (G), of the formula (DC)
(Figure Removed)
in which
A, B, Q3, Q4, Q5, Q6, W, X, Y, Z and R8 are as defined above
are novel.
They can be prepared by methods known in principle.
The 6-aryl-5-ketocarboxylic esters of the formula (DC) are obtained, for example, when 6-
aryl-5-ketocarboxylic acids of the formula (XXXDC)
(Figure Removed)
in which
A, B, Q3, Q4, Q5, Q6, W, X, Y and Z are as defined above
are esterified (cf., for example, Organikum, 15th Edition, Berlin, 1977, page 499).
The 6-aryl-5-ketocarboxylic acids of the formula (XXXDC)
(Figure Removed)
in which
A, B, Q3, Q4, Q5, Q6, W, X, Y and Z are as defined above
are novel. They can be prepared by methods known in principle (WO 99/43649, WO
99/48869), for example by
hydrolyzing and decarboxylating substituted 2-phenyl-3-oxoheptanedioic esters of the
formula (XL)
(Figure Removed)
in which
A, B, Q3, Q4, Q5, Q6, W, X, Y and Z are as defined above and
R8 and R8' represent alkyl (preferably C j -Cg-alkyl) and,
if the compound of the formula (XLII) is used, R8 represents hydrogen,
if appropriate in the presence of a diluent and if appropriate in the presence of a base or an
acid (cf., for example, Organikum, 15th Edition, Berlin, 1977, pages 519 to 521).
The compounds of the formula (XL)
(Figure Removed)
in which
A, B, Q3, Q4, Q5, Q6, W, X, Y, Z, R8 and R8' are as defined above
are novel and can be obtained
by condensing dicarboxylic esters of the formula (XLI),
(Figure Removed)
in which
A, B, Q3, Q4, Q55 Q6 ^4 R8 are as defined above
or carboxylic anhydrides of the formula (XLII)
in which
A, B, Q3, Q4, Q5, Q6 are as defined above
with a substituted phenylacetic ester of the formula (XXXII)
(Figure Removed)
in which
W, X, Y, Z and R.8 are as defined above
in the presence of a diluent and in the presence of a base.
Some of the compounds of the formulae (XLI) and (XLII) are known, and/or they can be
prepared by known processes.
Some of the hydrazines, required as starting materials for the processes (H-a) and (H-6)
according to the invention, of the formula (X)
(Figure Removed)
in which
A and D are as defined above
are known, and/or they can be prepared by methods known from literature (cf., for example,
Liebigs Arm. Chem. 585. 6 (1954); Reaktionen der organischen Synthese [Reaction of
organic synthesis], C. Ferri, pages 212, 513; Georg Thieme Verlag Stuttgart, 1978; Liebigs
Ann. Chem. 443. 242 (1925); Chem. Ber. 98, 2551 (1965), EP-A-508 126, WO 92/16510,
WO 99/47 525, WO 01/17 972).
The compounds, required for the process (H-y) according to the invention, of the formula
(Figure Removed)
in which
A, D, W, X, Y, Z and R8 are as defined above
are novel.
The acylcarbazates of the formula (XII) are obtained, for example, when carbazates of the
formula (XLHT)
(Figure Removed)
in which
A, R8 and D are as defined above
are acylated with substituted phenylacetic acid derivatives of the formula (XXV)
(Figure Removed)
in which
T, W, X, Y and Z are as defined above
(Chem. Reviews 52, 231-416 (1953); Bhattacharya, Indian J. Chem. 6, 341-5, 1968).
Some of the carbazates of the formula (XLIQ) are commercially available and some are
known compounds, or they can be prepared by processes of organic chemistry known in
principle.
Some of the compounds, required as starting materials for the above process (P), of the
formulae (I-l1) to (I-81) in which A, B, D, G, Q1, Q2, Q3, Q4, Q5, Q6, W, X and Y are as
defined above and Z1 represents chlorine or bromine, preferably bromine, are known from
the patent applications cited at the outset (for example WO 96/35 664, WO 97/02 243), or
they can be prepared by the processes described therein.
Some of the compounds of the formula
(Figure Removed)
in which
Z is as defined above
are commercially available, or they can be prepared by general processes known in
principle.
The acid halides of the formula (Xm), carboxylic anhydrides of the formula (XTV),
chloroformic esters or chloroformic thioesters of the formula (XV), chloromonothioformic
esters or chlorodithioformic esters of the formula (XVI), sulphonyl chlorides of the formula
(XVU), phosphorus compounds of the formula (XVID) and metal hydroxides, metal
alkoxides or amines of the formulae (XIX) and (XX) and isocyanates of the formula (XXI)
and carbamoyl chlorides of the formula (XXH) furthermore required as starting materials for
carrying out the processes (I), (J), (K), (L), (M), (N) and (O) according to the invention are
generally known compounds of organic or inorganic chemistry.
In addition, the compounds of the formulae (V), (VII), (Xm) to (XXII), (XXTV), (XXVH),
(XXEX), (XXXI-A), (XXXI-B), (XXXm), (XXXVH), (XXXVm), (XLI) and (XLII) are
known from the patent applications cited at the outset, and/or they can be prepared by the
methods given therein.
The process (A) is characterized in that compounds of the formula (II) in which A, B, D, W,
X, Y, Z and R° are as defined above are, in the presence of a base, subjected to an
intramolecular condensation.
Suitable diluents for the process (A) according to the invention are all inert organic solvents.
Preference is given to using hydrocarbons, such as toluene and xylene, furthermore ethers,
such as dibutyl ether, tetrahydrofuran, dioxane, glycol dimethyl ether and diglycol dimethyl
ether, moreover polar solvents, such as dimethyl sulphoxide, sulpholane,
dimethylformamide, dimethylacetamide and N-methylpyrrolidone, and also alcohols, such
as methanol, ethanol, propanol, isopropanol, butanol, isobutanol and tert-butanol.
Suitable bases (deprotonating agents) for carrying out the process (A) according to the
invention are all customary proton acceptors. Preference is given to using alkali metal and
alkaline earth metal oxides, hydroxides and carbonates, such as sodium hydroxide,
potassium hydroxide, magnesium oxide, calcium oxide, sodium carbonate, potassium
carbonate and calcium carbonate, which can also be used in the presence of phase-transfer
catalysts, such as, for example, triethylbenzylammonium chloride, tetrabutylammonium
bromide, Adogen 464 (= methyltrialkyl(Cg-Cio)animonium chloride) or TDA 1 (=
tris(methoxyethoxyethyl)amine). It is furthermore possible to use alkali metals such as
sodium or potassium. Also suitable are alkali metal and alkaline earth metal amides and
hydrides, such as sodium amide, sodium hydride and calcium hydride, and additionally also
alkali metal alkoxides, such as sodium methoxide, sodium ethoxide and potassium tertbutoxide.
When carrying out the process (A) according to the invention, the reaction temperatures can
be varied within a relatively large range. In general, the process is carried out at
temperatures between 0°C and 250°C, preferably between 50°C and 150°C.
The process (A) according to the invention is generally carried out under atmospheric
pressure.
When carrying out the process (A) according to the invention, the reaction components of
the formula (H) and the deprotonating bases are generally employed in approximately
doubly equimolar amounts. However, it is also possible to use a relatively large excess (up
to 3 mol) of one component or the other.
The process (B) is characterized in that compounds of the formula (ffl) in which A, B, W, X,
Y, Z and R° are as defined above are, in the presence of a diluent and in the presence of a
base, subjected to an intramolecular condensation.
Suitable diluents for the process (B) according to the invention are all inert organic solvents.
Preference is given to using hydrocarbons, such as toluene and xylene, furthermore ethers,
such as dibutyl ether, tetrahydrofuran, dioxane, glycol dimethyl ether and diglycol dimethyl
ether, moreover polar solvents, such as dimethyl sulphoxide, sulpholane,
dimethylformamide and N-methylpyrrolidone. It is furthermore possible to use alcohols,
such as methanol, ethanol, propanol, isopropanol, butanol, isobutanol and tert-butanol.
Suitable bases (deprotonating agents) for carrying out the process (B) according to the
invention are all customary proton acceptors. Preference is given to using alkali metal and
alkaline earth metal oxides, hydroxides and carbonates, such as sodium hydroxide,
potassium hydroxide, magnesium oxide, calcium oxide, sodium carbonate, potassium
carbonate and calcium carbonate, which can also be used hi the presence of phase-transfer
catalysts, such as, for example, triethylbenzylammonium chloride, tetrabutylammonium
bromide, Adogen 464 (= memyltrialkyl(Cg-Ci0)animonium chloride) or IDA 1 (= tris-
(methoxyethoxyethyl)amine). It is furthermore possible to use alkali metals, such as sodium
or potassium. Also suitable are alkali metal and alkaline earth metal amides and hydrides,
such as sodium amide, sodium hydride and calcium hydride, and additionally also alkali
metal alkoxides, such as sodium methoxide, sodium ethoxide and potassium tert-butoxide.
When carrying out the process (B) according to the invention, the reaction temperatures can
be varied within a relatively wide range, hi general, the process is carried out at
temperatures between 0°C and 250°C, preferably between 50°C and 150°C.
The process (B) according to the invention is generally carried out under atmospheric
pressure.
When carrying out the process (B) according to the invention, the reaction components of
the formula (HI) and the deprotonating bases are generally employed in approximately
equimolar amounts. However, it is also possible to use a relatively large excess (up to 3 mol)
of one component or the other.
The process (C) is characterized in that compounds of the formula (IV) in which A, B, V,
W, X, Y, Z and R^ are as defined above are, in the presence of an acid and, if appropriate, hi
the presence of a diluent, subjected to intramolecular cyclization.
Suitable diluents for the process (C) according to the invention are all inert organic solvents.
Preference is given to using hydrocarbons, such as toluene and xylene, furthermore
halogenated hydrocarbons, such as dichloromethane, chloroform, ethylene chloride,
chlorobenzene, dichlorobenzene, moreover polar solvents, such as dimethyl sulphoxide,
sulpholane, dimethylformamide and N-methylpyrrolidone. It is furthermore possible to use
alcohols, such as methanol, ethanol, propanol, isopropanol, butanol, isobutanol, tert-butanol.
If appropriate, the acid used can also serve as diluent.
Suitable acids for the process (C) according to the invention are all customary inorganic and
organic acids, such as, for example, hydrohalic acids, sulphuric acid, alkyl-, aryl- and
haloalkylsulphonic acids, in particular halogenated alkylcarboxylic acids, such as, for
example, trifluoroacetic acid.
When carrying out the process (C) according to the invention, the reaction temperatures can
be varied within a relatively wide range. In general, the process is carried out at
temperatures between 0°C and 250°C, preferably between 50°C and 150°C.
The process (C) according to the invention is generally carried out under atmospheric
pressure.
When carrying out the process (C) according to the invention, the reaction components of
the formula (IV) and the acids are employed, for example, in equimolar amounts. However,
it is, if appropriate, also possible to use the acid as solvent or as catalyst.
The process (D) according to the invention is characterized in that carbonyl compounds of
the formula (V) or enol ethers thereof of the formula (V-a) are reacted with ketene acid
halides of the formula (VI) in the presence of a diluent and, if appropriate, in the presence of
an acid acceptor.
Suitable diluents for the process (D) according to the invention are all inert organic solvents.
Preference is given to using optionally halogenated hydrocarbons, such as toluene, xylene,
mesirylene, chlorobenzene and dichlorobenzene, furthermore ethers, such as dibutyl ether,
glycol dimethyl ether, diglycol dimethyl ether and diphenyl ether, moreover polar solvents,
such as dimethyl sulphoxide, sulpholane, dimethylformamide or N-methylpyrrolidone.
Suitable acid acceptors for carrying out the process variant (D) according to the invention
are all customary acid acceptors.
Preference is given to .using tertiary amines, such as triethylamine, pyridine, diazabicyclooctane
(DABCO), diazabicycloundecane (DBU), diazabicyclononene (DBN), Hiinig
base and N,N-dimethylaniline.
When carrying out the process variant (D) according to the invention, the reaction
temperatures can be varied within a relatively wide range. The process variant is expediently
carried out at temperatures between 0°C and 250°C, preferably between 50°C and 220°C.
The process (D) according to the invention is expediently carried out under atmospheric
pressure.
When carrying out the process (D) according to the invention, the reaction components of
the formulae (V) and (VI) in which A, D, W, X, Y and Z are as defined above and Hal
represents halogen and, if appropriate, the acid acceptors are generally employed in
approximately equimolar amounts. However, it is also possible to use a relatively large
excess (up to 5 mol) of one component or the other.
The process (E) according to the invention is characterized in that thioamides of the formula
(VII) are reacted with ketene acid halides of the formula (VI) in the presence of a diluent
and, if appropriate, in the presence of an acid acceptor.
Suitable diluents for the process variant (E) according to the invention are all inert organic
solvents. Preference is given to using hydrocarbons, such as toluene and xylene, furthermore
ethers, such as dibutyl ether, glycol dimethyl ether and diglycol dimethyl ether, moreover
polar solvents, such as dimethyl sulphoxide, sulpholane, dimethylformamide and Nmethylpyrrolidone.
Suitable acid acceptors for carrying out the process (E) according to the invention are all
customary acid acceptors.
Preference is given to using tertiary amines, such as triethylamine, pyridine, diazabicyclooctane
(DABCO), diazabicycloundecane (DBU), diazabicyclononene (DBN), Hiinig base
and N,N-dimethylaniline.
When carrying out the process (E) according to the invention, the reaction temperatures can
be varied within a relatively wide range. Expediently, the process is carried out at
temperatures between 0°C and 250°C, preferably between 20°C and 220°C.
The process (E) according to the invention is expediently carried out under atmospheric
pressure.
When carrying out the process (E) according to the invention, the reaction components of
the formulae (VH) and (VI) in which A, W, X, Y and Z are as defined above and Hal
represents halogen and, if appropriate, the acid acceptors are generally employed in
approximately equimolar amounts. However, it is also possible to use a relatively large
excess (up to 5 mol) of one component or the other.
The process (F) is characterized in that compounds of the formula (VET) in which A, B, Ql,
Q2, W, X, Y, Z and R^ are as defined above are, in the presence of a base, subjected to an
intramolecular condensation.
Suitable diluents for the process (F) according to the invention are all organic solvents
which are inert towards the reactants. Preference is given to using hydrocarbons, such as
toluene and xylene, furthermore ethers, such as dibutyl ether, tetrahydrofuran, dioxane,
glycol dimethyl ether and diglycol dimethyl ether, moreover polar solvents, such as dimethyl
sulphoxide, sulpholane, dimethylformamide and N-methylpyrrolidone. It is furthermore
possible to use alcohols, such as methanol, ethanol, propanol, isopropanol, butanol,
isobutanol, tert-butanol.
Suitable bases (deprotonating agents) for carrying out the process (F) according to the
invention are all customary proton acceptors. Preference is given to using alkali metal and
alkaline earth metal oxides, hydroxides and carbonates, such as sodium hydroxide,
potassium hydroxide, magnesium oxide, calcium oxide, sodium carbonate, potassium
carbonate and calcium carbonate, which can also be used in the presence of phase transfer
catalysts, such as, for example, triethylbenzylammonium chloride, tetrabutylammonium
bromide, Adogen 464 (methyltrialkyl(Cg-Cio)animonium chloride) or IDA 1 (tris-
(methoxyethoxyethyl)amine). It is furthermore possible to use alkali metals, such as sodium
or potassium. Also suitable are alkali metal and alkaline earth metal amides and hydrides,
such as sodium amide, sodium hydride and calcium hydride, and additionally also alkali
metal alkoxides, such as sodium methoxide, sodium ethoxide and potassium tert-butoxide.
When carrying out the process (F) according to the invention, the reaction temperatures can
be varied within a relatively wide range. In general, the process is carried out at
temperatures between -75°C and 250°C, preferably between -50°C and 150°C.
The process (F) according to the invention is generally carried out under atmospheric
pressure.
When carrying out the process (F) according to the invention, the reaction components of
the formula (VIII) and the deprotonating bases are generally employed in approximately
equimolar amounts. However, it is also possible to use a relatively large excess (up to 3 mol)
of one component or the other.
The process (G) is characterized in that compounds of the formula (EX) in which A, B, Q,
Q Q Q W, X, Y, Z and R are as defined above are, in the presence of bases, subjected
to an intramolecular condensation.
Suitable diluents for the process (G) according to the invention are all organic solvents
which are inert towards the reactants. Preference is given to using hydrocarbons, such as
toluene and xylene, furthermore ethers, such as dibutyl ether, tetrahydrofuran, dioxane,
glycol dimethyl ether and diglycol dimethyl ether, moreover polar solvents, such as dimethyl
sulphoxide, sulpholane, dimethylformamide and N-methylpyrrolidone. It is furthermore
possible to use alcohols, such as methanol, ethanol, propanol, isopropanol, butanol,
isobutanol, tert-butanol.
Suitable bases (deprotonating agents) for carrying out the process (G) according to the
invention are all customary proton acceptors.
Preference is given to using alkali metal and alkaline earth metal oxides, hydroxides and
carbonates, such as sodium hydroxide, potassium hydroxide, magnesium oxide, calcium
oxide, sodium carbonate, potassium carbonate and calcium carbonate, which can also be
used in the presence of phase transfer catalysts, such as, for example,
triethylbenzylammonium chloride, tetrabutylammonium bromide, Adogen 464
(methyltrialkyl(C8-Cio)arnmonium chloride) or IDA 1 (tris(methoxyethoxyethyl)amine). It
is furthermore possible to use alkali metals, such as sodium or potassium. Also suitable are
alkali metal and alkaline earth metal amides and hydrides, such as sodium amide, sodium
hydride and calcium hydride, and additionally also alkali metal alkoxides, such as sodium
methoxide, sodium ethoxide and potassium tert-butoxide.
When carrying out the process (G) according to the invention, the reaction temperatures can
be varied within a relatively wide range. In general, the process is carried out at
temperatures between 0°C and 250°C, preferably between 50°C and 150°C.
The process (G) according to the invention is generally carried out under atmospheric
pressure.
When carrying out the process (G) according to the invention, the reaction components of
the formula (EX) and the deprotonating bases are generally employed in approximately equimolar
amounts. However, it is also possible to use a relatively large excess (up to 3 mol) of
one component or the other.
The process (H-a) according to the invention is characterized in that hydrazines of the
formula (X) or salts of these compounds are reacted with ketene acid halides of the formula
(VI) in the presence of a diluent and, if appropriate, in the presence of an acid acceptor.
Suitable diluents for the process (H-a) according to the invention are all inert organic
solvents. Preference is given to using optionally chlorinated hydrocarbons, such as, for
example, mesitylene, chlorobenzene and dichlorobenzene, toluene, xylene, furthermore
ethers, such as dibutyl ether, glycol dimethyl ether, diglycol dimethyl ether and diphenyl
ether, moreover polar solvents, such as dimethyl sulphoxide, sulpholane,
dimethylformamide or N-methylpyrrolidone.
Suitable acid acceptors for carrying out the process variant (H-a) according to the invention
are all customary acid acceptors.
Preference is given to using tertiary amines, such as triethylamine, pyridine, diazabicyclooctane
(DABCO), diazabicycloundecane (DBU), diazabicyclononene (DBN), Hunig base
and N,N-dimethylaniline.
When carrying out the process variant (H-a) according to the invention, the reaction
temperatures can be varied within a relatively wide range. The process variant is expediently
carried out at temperatures between 0°C and 250°C, preferably between 50°C and 220°C.
The process (H-a) according to the invention is expediently carried out under atmospheric
pressure.
When carrying out the process (H-a) according to the invention, the reaction components of
the formulae (VI) and (X) in which A, D, W, X, Y and Z are as defined above and Hal
represents halogen and, if appropriate, the acid acceptors are generally employed in
approximately equimolar amounts. However, it is also possible to use a relatively large
excess (up to 5 mol) of one component or the other.
The process (H-fi) is characterized in that hydrazines of the formula (X) or salts of this
compound in which A and D are as defined above are, in the presence of a base, subjected to
a condensation with melodic esters or malonamides of the formula (XI) in which U, W, X,
Y, Z and R are as defined above.
Suitable diluents for the process (H-B) according to the invention are all inert organic
solvents. Preference is given to using optionally halogenated hydrocarbons, such as toluene,
xylene, mesitylene, chlorobenzene and dichlorobenzene, furthermore ethers, such as dibutyl
ether, tetrahydrofuran, dioxane, diphenyl ether, glycol dimethyl ether and diglycol dimethyl
ether, moreover polar solvents, such as dimethyl sulphoxide, sulpholane,
dimethylformamide, dimethylacetamide and N-methylpyrrolidone, and also alcohols, such
as methanol, ethanol, propanol, isopropanol, butanol, isobutanol and tert-butanol.
Suitable bases (deprotonating agents) for carrying out the process (H-B) according to the
invention are all customary proton acceptors. Preference is given to using alkali metal and
alkaline earth metal oxides, hydroxides and carbonates, such as sodium hydroxide,
potassium hydroxide, magnesium oxide, calcium oxide, sodium carbonate, potassium
carbonate and calcium carbonate, and which can also be used in the presence of phase
transfer catalysts, such as, for example, triethylbenzylammonium chloride, tetrabutylammonium
bromide, Adogen 464 (= memyltrialkyl(Cg-Ci0)aiimionium chloride) or TDA 1
(= tris(methoxyethoxyethyl)amine). It is furthermore possible to use alkali metals, such as
sodium or potassium. Also suitable are alkali metal and alkaline earth metal amides and
hydrides, such as sodium amide, sodium hydride and calcium hydride, and additionally also
alkali metal alkoxides, such as sodium methoxide, sodium ethoxide and potassium tertbutoxide.
It is also possible to use tertiary amines, such as triethylamine, pyridine, diazabicyclooctane
(DABCO), diazabicycloundecane (DBU), diazabicyclononene (DBN), Hunig base and N,Ndimethylaniline.
When carrying out the process (H- B) according to the invention, the reaction temperatures
can be varied within a relatively wide range, hi general, the process is carried out at
temperatures between 0°C and 280°C, preferably between 50°C and 180°C.
The process (H-B) according to the invention is generally carried out under atmospheric
pressure.
When carrying out the process (H-6) according to the invention, the reaction components of
the formulae (XI) and (X) are generally employed in approximately equimolar amounts.
However, it is also possible to use a relatively large excess (up to 3 mol) of one component
or the other.
The process (H-y) is characterized in that compounds of the formula (XII) in which A, D, W,
X, Y, Z and R° are as defined above are, in the presence of a base, subjected to an
intramolecular condensation.
Suitable diluents for the process (H-y) according to the invention are all inert organic
solvents. Preference is given to using hydrocarbons, such as toluene and xylene, furthermore
ethers such as dibutyl ether, tetrahydrofuran, dioxane, glycol dimethyl ether and diglycol
dimethyl ether, moreover polar solvents, such as dimethyl sulphoxide, sulpholane,
dimethylformamide and N-methylpyrrolidone, and also alcohols, such as methanol, ethanol,
propanol, isopropanol, butanol, isobutanol and tert-butanol.
Suitable bases (deprotonating agents) for carrying out the process (H-y) according to the
invention are all customary proton acceptors. Preference is given to using alkali metal and
alkaline earth metal oxides, hydroxides and carbonates, such as sodium hydroxide,
potassium hydroxide, magnesium oxide, calcium oxide, sodium carbonate, potassium
carbonate and calcium carbonate, and which can also be used in the presence of phase transfer
catalysts, such as, for example, triethylbenzylammonium chloride, tetrabutylammonium
bromide, Adogen 464 (= memyltrialkyl(Cg-CiQ)ammonium chloride) or TDA 1 (=
tris(methoxyethoxyethyl)amine). It is furthermore possible to use alkali metals, such as
sodium or potassium. Also suitable are alkali metal and alkaline earth metal amides and
hydrides, such as sodium amide, sodium hydride and calcium hydride, and additionally also
alkali metal alkoxides, such as sodium methoxide, sodium ethoxide and potassium tertbutoxide.
When carrying out the process (H-y) according to the invention, the reaction temperatures
can be varied within a relatively wide range, hi general, the process is carried out at
temperatures between -20°C and 250°C, preferably between 50°C and 150°C.
The process (H-y) according to the invention is generally carried out under atmospheric
pressure.
When carrying out the process (H-y) according to the invention, the reaction components of
the formula (XII) and the deprotonating bases are generally employed in approximately
doubly equimolar amounts. However, it is also possible to use a relatively large excess (up
to 3 mol) of one component or the other.
The process (I-a) is characterized in that compounds of the formulae (I-l-a) to (I-8-a) are in
each case reacted with carbonyl halides of the formula (XIH), if appropriate in the presence
of a diluent and if appropriate in the presence of an acid binder.
Suitable diluents for the process (I-a) according to the invention are all solvents which are
inert towards the acid halides. Preference is given to using hydrocarbons, such as benzine,
benzene, toluene, xylene and tetraline, furthermore halogenated hydrocarbons, such as
methylene chloride, chloroform, carbon tetrachloride, chlorobenzene and o-dichlorobenzene,
moreover ketones, such as acetone and methyl isopropyl ketone, furthermore ethers, such as
diethyl ether, tetrahydrofuran and dioxane, additionally carboxylic esters, such as ethyl
acetate, and also strongly polar solvents, such as dimethyl sulphoxide and sulpholane. The
hydrolytic stability of the acid halide permitting, the reaction can also be carried out in the
presence of water.
Suitable acid binders for the reaction according to the process (I-a) according to the
invention are all customary acid acceptors. Preference is given to using tertiary amines, such
as triethylamine, pyridine, diazabicyclooctane (DABCO), diazabicycloundecene (DBU),
diazabicyclononene (DBN), Hiinig base and N,N-dimethylaniline, furthermore alkaline earth
metal oxides, such as magnesium oxide and calcium oxide, moreover alkali metal and
alkaline earth metal carbonates, such as sodium carbonate, potassium carbonate and calcium
carbonate, and also alkali metal hydroxides, such as sodium hydroxide and potassium
hydroxide.
In the process (I-a) according to the invention, the reaction temperatures can be varied
within a relatively wide range. In general, the process is carried out at temperatures between
-20°C and +150°C, preferably between 0°C and 100°C.
When carrying out the process (I-a) according to the invention, the starting materials of the
formulae (I-l-a) to (I-8-a) and the carbonyl halide of the formula (Xin) are generally each
employed in approximately equivalent amounts. However, it is also possible to use a
relatively large excess (up to 5 mol) of the carbonyl halide. Work-up is carried out by
customary methods.
The process (I-fi) is characterized in that compounds of the formulae (I-l-a) to (I-8-a) are
reacted with carboxylic anhydrides of the formula (XTV), if appropriate in the presence of a
diluent and if appropriate in the presence of an acid binder.
Suitable diluents for the process (1-6) according to the invention are, preferably, those
diluents which are also preferred when using acid halides. Besides, it may also be possible
for excess carboxylic anhydride to act simultaneously as diluent.
In process (1-6), suitable acid binders, which are added, if appropriate, are preferably those
acid binders which are also preferred when using acid halides.
The reaction temperatures in the process (1-6) according to the invention can be varied
within a relatively wide range. In general, the process is carried out at temperatures between
-20°C and +150°C, preferably between 0°C and 100°C.
When carrying out the process (1-6) according to the invention, the starting materials of the
formulae (I-l-a) to (I-8-a) and the carboxylic anhydride of the formula (XIV) are generally
each employed in approximately equivalent amounts. However, it is also possible to use a
relatively large excess (up to 5 mol) of the carboxylic anhydride. Work-up is carried out by
customary methods.
In general, diluent and excess carboxylic anhydride and the carboxylic acid formed are
removed by distillation or by washing with an organic solvent or with water.
The process (J) is characterized in that compounds of the formulae (I-l-a) to (I-8-a) are in
each case reacted with chloroformic esters or chloroformic thioesters of the formula (XV), if
appropriate in the presence of a diluent and if appropriate in the presence of an acid binder.
Suitable acid binders for the reaction according to the process (J) according to the invention
are all customary acid acceptors. Preference is given to using tertiary amines, such as triethylamine,
pyridine, DABCO, DBU, DBA, Hunig base and N.N-dimethylaniline,
furthermore alkaline earth metal oxides, such as magnesium oxide and calcium oxide,
moreover alkali metal and alkaline earth metal carbonates, such as sodium carbonate,
potassium carbonate and calcium carbonate, and also alkali metal hydroxides, such as
sodium hydroxide and potassium hydroxide.
Suitable diluents for the process (J) according to the invention are all solvents which are
inert towards the chloroformic esters or chloroformic thioesters. Preference is given to using
hydrocarbons, such as benzine, benzene, toluene, xylene and tetraline, furthermore
halogenated hydrocarbons, such as methylene chloride, chloroform, carbon tetrachloride,
chlorobenzene and o-dichlorobenzene, moreover ketones, such as acetone and methyl
isopropyl ketone, furthermore ethers, such as diethyl ether, tetrahydrofuran and dioxane,
additionally carboxylic esters, such as ethyl acetate, and also strongly polar solvents, such as
dimethyl sulphoxide and sulpholane.
When carrying out the process (J) according to the invention, the reaction temperatures can
be varied within a relatively wide range. If the process is carried out in the presence of a
diluent and an acid binder, the reaction temperatures are generally between -20°C and
+100°C, preferably between 0°C and 50°C.
The process (J) according to the invention is generally carried out under atmospheric
pressure.
When carrying out the process (J) according to the invention, the starting materials of the
formulae (I-l-a) to (I-8-a) and the appropriate chloroformic ester or chloroformic thioester
of the formula (XHI) are generally each employed in approximately equivalent amounts.
However, it is also possible to use a relatively large excess (up to 2 mol) of one component
or the other. Work-up is carried out by customary methods, hi general, precipitated salts are
removed and the reaction mixture that remains is concentrated by removing the diluent
under reduced pressure.
The process (K) according to the invention is characterized hi that compounds of the
formulae (I-l-a) to (I-8-a) are in each case reacted with compounds of the formula (XVI), in
the presence of a diluent and, if appropriate, in the presence of an acid binder.
In Preparation Process (K), about 1 mol of chloromonothioformic ester or chlorodithioformic
ester of the formula (XVI) is reacted per mole of starting material of the formulae (I-
1-a) to (I-8-a), at from 0 to 120°C, preferably from 20 to 60°C.
Suitable diluents, which are added, if appropriate, are all inert polar organic solvents, such
as ethers, amides, sulphones, sulphoxides, and also halogenated alkanes.
Preference is given to using dimethyl sulphoxide, tetrahydrofuran, dimethylformamide or
methylene chloride.
If, in a preferred embodiment, the enolate salt of the compounds (I-l-a) to (I-8-a) is prepared
by the addition of strong deprotonating agents, such as, for example, sodium hydride or
potassium tert-butoxide, the further addition of acid binders can be dispensed with.
If acid binders are used, these are customary inorganic or organic bases, for example sodium
hydroxide, sodium carbonate, potassium carbonate, pyridine, triethylamine.
The reaction can be carried out under atmospheric pressure or under elevated pressure and is
preferably carried out under atmospheric pressure. Work-up is carried out by customary
methods.
The process (L) according to the invention is characterized in that compounds of the
formulae (I-l-a) to (I-8-a) are in each case reacted with sulphonyl chlorides of the formula
(XVH), if appropriate in the presence of a diluent and if appropriate in the presence of an
acid binder.
hi the Preparation Process (L), about 1 mol of sulphonyl chloride of the formula (XVII) is
reacted per mole of starting material of the formula (I-l-a to I-8-a), at from -20 to 150°C,
preferably from 20 to 70°C.
Suitable diluents, which are added, if appropriate, are all inert polar organic solvents, such
as ethers, amides, nitriles, sulphones, sulphoxides or halogenated hydrocarbons, such as
methylene chloride.
Preference is given to using dimethyl sulphoxide, tetrahydrofuran, dimethylformamide,
methylene chloride.
If, in a preferred embodiment, the enolate salt of the compounds (I-l-a) to (I-8-a) is prepared
by adding strong deprotonating agents (such as, for example, sodium hydride or potassium
tert-butoxide), the further addition of acid binders can be dispensed with.
If acid binders are used, these are customary inorganic or organic bases, for example sodium
hydroxide, sodium carbonate, potassium carbonate, pyridine, triethylamine.
The reaction can be carried out under atmospheric pressure or under elevated pressure and is
preferably carried out under atmospheric pressure. Work-up is carried out by customary
methods.
The process (M) according to the invention is characterized in that compounds of the
formulae (I-l-a) to (I-8-a) are in each case reacted with phosphorus compounds of the
formula (XVIII), if appropriate in the presence of a diluent and if appropriate in the presence
of an acid binder.
In the Preparation Process (M), to obtain compounds of the formulae (I-l-e) to (I-8-e), 1 to
2, preferably 1 to 1.3 mol of the phosphorus compound of the formula (XVffl) are reacted to
1 mol of the compounds (I-l-a) to (I-8-a), at temperatures between -40°C and 150°C,
preferably between -10 and 110°C.
Suitable diluents, which are added, if appropriate, are all inert polar organic solvents, such
as ethers, amides, nitriles, alcohols, sulphides, sulphones, sulphoxides, etc.
Preference is given to using acetonitrile, dimethyl sulphoxide, tetrahydrofuran, dimethylformamide,
methylene chloride.
Suitable acid binders, which are added, if appropriate, are customary inorganic or organic
bases, such as hydroxides, carbonates or amines. Examples are sodium hydroxide, sodium
carbonate, potassium carbonate, pyridine, triethylamine.
The reaction can be carried out under atmospheric pressure or under elevated pressure and is
preferably carried out under atmospheric pressure. Work-up is carried out by customary
methods of organic chemistry. The end products obtained are preferably purified by
crystallization, chromatographic purification or by "incipient distillation", i.e. removal of
the volatile components under reduced pressure.
The process (N) is characterized in that compounds of the formulae (I-l-a) to (I-8-a) are
reacted with metal hydroxides or metal alkoxides of the formula (XIX) or amines of the
formula (XX), if appropriate in the presence of a diluent.
Suitable diluents for the process (N) according to the invention are, preferably, ethers, such
as tetrahydrofuran, dioxane, diethyl ether, or else alcohols, such as methanol, ethanol,
isopropanol, and also water.
The process (N) according to the invention is generally carried out under atmospheric
pressure.
The reaction temperatures are generally between -20°C and 100°C, preferably between 0°C
and50°C.
The process (O) according to the invention is characterized in that compounds of the
formulae (I-l-a) to (I-8-a) are in each case reacted with (O-ct) compounds of the formula
(XXI), if appropriate in the presence of a diluent and if appropriate in the presence of a
catalyst, or with (O-6) compounds of the formula (XXII), if appropriate in the presence of a
diluent and if appropriate in the presence of an acid binder.
In Preparation Process (O-a), about 1 mol of isocyanate of the formula (XXI) is reacted per
mole of starting material of the formulae (I-l-a) to (I-8-a), at from 0 to 100°C, preferably at
from 20 to 50°C.
Suitable diluents, which are added, if appropriate, are all inert organic solvents, such as
ethers, amides, nitriles, sulphones, sulphoxides.
If appropriate, catalysts may be added to accelerate the reaction. Suitable catalysts are, very
advantageously, organotin compounds, such as, for example, dibutyltin dilaurate. The
reaction is preferably carried out under atmospheric pressure.
hi the Preparation Process (O-6), about 1 mol of carbamoyl chloride of the formula (XXII) is
reacted per mole of starting material of the formulae (I-l-a) to (I-8-a), at from -20 to 150°C,
preferably from 0 to 70°C.
Suitable diluents, which are added, if appropriate, are all inert polar organic solvents, such
as ethers, amides, sulphones, sulphoxides or halogenated hydrocarbons.
Preference is given to using dimethyl sulphoxide, tetrahydrofuran, dimethylfonnamide or
methylene chloride.
If, in a preferred embodiment, the enolate salt of the compound (I-l-a) to (I-8-a) is prepared
by adding strong deprotonating agents (such as, for example, sodium hydride or potassium
tert-butoxide), the further addition of acid binders can be dispensed with.
If acid binders are used, these are customary inorganic or organic bases, for example sodium
hydroxide, sodium carbonate, potassium carbonate, triethylamine or pyridine.
The reaction can be carried out under atmospheric pressure or under elevated pressure and is
preferably carried out under atmospheric pressure. Work-up is carried out by customary
methods.
The process (P) is characterized in that compounds of the formula (I-l1) to (I-81) in which A,
B, D, Ql, Q2, Q3, Q4, Q5> Q6, w> X, Y, Rl, R2, R3, R4 R5j R6 md R7 ^ M defmed
above and Z1 represents halogen, particularly preferably bromine, are, in the presence of a
copper salt and in the presence of a base, subjected to a coupling reaction with HNheterocycles
of the formula (XXffl) in which Z is as defined above (J. Am. Chem. Soc.
2001, 123. 7729-29; WO 02-85 838; Synlett 2002, 3,423-30).
Suitable solvents for the process (P) according to the invention are, for example, optionally
halogenated aliphatic, alicyclic or aromatic hydrocarbons, such as, for example, benzine,
benzene, toluene, xylene, petroleum ether, hexane, cyclohexane, chlorobenzene,
dichlorobenzene, ethers, such as diethyl ether, diisopropyl ether, dioxane, tetrahydrofuran or
ethylene glycol dimethyl ether or ethylene glycol diethyl ether; amides, such as, for
example, N,N-dirnethylformamide, N,N-dimethylacetamide, N-methylformanilide, Nmethylpyrrolidone
or hexamethylphosphoric triamide; esters, such as methyl acetate or ethyl
acetate, or mixtures of such solvents. Preference is given to using N,N-dimethylformamide.
Suitable bases for the process (P) according to the invention are alkali metal and/or alkaline
earth metal carbonates, alkoxides, phosphates, fluorides and/or hydroxides, and particular
preference is given to potassium carbonate, sodium carbonate, caesium carbonate, caesium
bicarbonate, sodium methoxide, potassium tert-butoxide, potassium amylate, caesium
fluoride, potassium phosphate and barium hydroxide. Especially preferred are potassium
carbonate, sodium carbonate, caesium carbonate and/or caesium bicarbonate. Potassium
carbonate is very especially preferred.
The bases can also be employed in the presence of phase transfer catalysts, such as, for
example, triethylbenzylammonium chloride, tetrabutylammonium bromide or TDA 1 (=
tris(methoxy-ethoxyethyl)amine).
The copper salts used in the process (P) according to the invention are copper(I) salts, such
as, for example, Cul.
The process (P) can furthermore also be carried out in the presence of additional auxiliary
bases, such as diamines, such as, for example, ethylenediamine, propylenediamine, 1,2-
diaminocyclohexane.
When carrying out the process (P), the reaction temperatures can be varied within a
relatively wide range, hi general, the process is carried out at temperatures of from 0 to
250°C, preferably from 30 to 200°C; with very particular preference from 50 to 150°C.
The process (P) according to the invention is generally carried out under atmospheric
pressure.
When carrying out the process (P) according to the invention, the reaction components of
the formulae (I-l1) to (I-81) and (XXffl) are generally employed in equimolar amounts.
However, it is also possible to use a relatively large excess (up to 3 mol) of one component
or the other. The bases are generally employed in a molar ratio of from 1:1 to 10:1,
preferably from 2:1 to 5:1. The copper salts are generally employed in a molar ratio of from
0.01:1 to 1:1, preferably from 0.05:1 to 0.5:1.
The process Q is characterized in that compounds of the formula (XXXtt-a) in which W, X,
Y and R^ are as defined above and Z' represents halogen, particularly preferably bromine,
are, in the presence of a base and in the presence of a copper salt, subjected to a coupling
reaction with HN-containing heterocycles of the formula (XXIII) in which Z is as defined
above (J. Am. Chem. Soc. 2001,123. 7727-29; WO 02-85 838, Synlett 2002, 3,427-30).
Suitable solvents for the process (Q) according to the invention are optionally halogenated
aliphatic, alicyclic or aromatic hydrocarbons, such as, for example, benzine, benzene,
toluene, xylene, petroleum ether, hexane, cyclohexane, chlorobenzene, dichlorobenzene,
ethers, such as diethyl ether, diisopropyl ether, dioxane, tetrahydrofuran or ethylene glycol
dimethyl ether or ethylene glycol diethyl ether; amides, such as, for example, N,N-dimethylfbrmamide,
N,N-dimethylacetamide, N-methylformanilide, N-methylpyrrolidone or hexamethylphosphoric
triamide; esters, such as methyl acetate or ethyl acetate, or mixtures of
such solvents. Preference is given to using N,N-dimethylformamide.
Suitable bases for the process (Q) according to the invention are alkali metal and/or alkaline
earth metal carbonates, alkoxides, phosphates, fluorides and/or hydroxides, and particular
preference is given to potassium carbonate, sodium carbonate, caesium carbonate, caesium
bicarbonate, sodium methoxide, potassium tert-butoxide, potassium amylate, caesium
fluoride, potassium phosphate and barium hydroxide. Especially preferred are potassium
carbonate, sodium carbonate, caesium carbonate and/or caesium bicarbonate. Potassium
carbonate is very especially preferred.
The bases can also be employed in the presence of phase-transfer catalysts, such as, for
example, triethylbenzylammonium chloride, tetrabutylammonium bromide or TDA 1
(= tris(methoxy-ethoxyethyl)amine).
The copper salts in the process (Q) according to the invention are copper(I) salts, such as,
for example, Cul.
The process (Q) can furthermore also be carried out in the presence of additional auxiliary
bases, such as diamines, such as, for example, ethylenediamine, propylenediamine, 1,2-
diaminocyclohexane.
When carrying out the process (Q), the reaction temperatures can be varied within a
relatively wide range. In general, the process is carried out at temperatures of from 0 to
250°C, preferably from 30 to 200°C; very particularly preferably from 50 to 150°C.
The process (Q) according to the invention is generally carried out under atmospheric
pressure.
When canying out the process (Q) according to the invention, the reaction components of
the formulae (XXXH-a) and (XXffi) are generally employed in equimolar amounts.
However, it is also possible to use a relatively large excess (up to 3 mol) of one component
or the other. The bases are generally employed in a molar ratio of from 1:1 to 10:1,
preferably from 2:1 to 5:1. The copper salts are generally employed in a molar ratio of from
0.001:1 to 1:1, preferably from 0.05:1 to 0.5:1.
The active compounds are well tolerated by plants and have advantageous toxicity to warmblooded
species; they can be employed for controlling animal pests, in particular insects,
arachnids and nematodes encountered in agriculture, forests, in the protection of stored
products and materials and in the hygiene sector. They are preferably used as crop protection
agents. They are active against normally sensitive and resistant species and against all or some
stages of development. The abovementioned pests include:
From the order of the Isopoda, for example, Oniscus asellus, Armadillidium vulgare and
Porcellio scaber.
From the order of the Diplopoda, for example, Blaniulus guttulatus.
From the order of the Chilopoda, for example, Geophilus carpophagus and Scutigera spp.,
From the order of the Symphyla, for example, Scutigerella immaculata.
From the order of the Thysanura, for example, Lepisma saccharina.
From the order of the Collembola, for example, Onychiurus armatus.
From the order of the Orthoptera, for example, Acheta domesticus, Gryllotalpa spp., Locusta
migratoria migratorioides, Melanoplus spp. and Schistocerca gregaria.
From the order of the Blattaria, for example, Blatta orientalis, Periplaneta americana,
Leucophaea maderae and Blattella germanica.
From the order of the Dermaptera, for example, Forficula auricularia.
From the order of the Isoptera, for example, Reticulitermes spp..
From the order of the Phthiraptera, for example, Pediculus humanus corporis, Haematopinus
spp., Linognathus spp., Trichodectes spp., Damalinia spp..
From the order of the Thysanoptera, for example, Hercinothrips femoralis, Thrips tabaci,
Thrips palmi, Frankliniella occidentalis.
From the order of the Heteroptera, for example, Eurygaster spp., Dysdercus intermedius,
Piesma quadrata, Cimex lectularius, Rhodnius prolixus and Triatoma spp..
From the order of the Homoptera, for example, Aleurodes brassicae, Bemisia tabaci,
Trialeurodes vaporariorum, Aphis gossypii, Brevicoryne brassicae, Cryptomyzus ribis, Aphis
fabae, Aphis pomi, Eriosoma lanigerum, Hyalopterus arundinis, Phylloxera vastatrix,
Pemphigus spp., Macrosiphum avenae, Myzus spp., Phorodon humuli, Rhopalosiphum padi,
Empoasca spp., Euscelis bilobatus, Nephotettix cincticeps, Lecanium corni, Saissetia oleae,
Laodelphax striatellus, Nilaparvata lugens, Aonidiella aurantii, Aspidiotus hederae,
Pseudococcus spp. and Psylla spp..
From the order of the Lepidoptera, for example, Pectinophora gossypiella, Bupalus piniarius,
Cheimatobia brumata, Lithocolletis blancardella, Hyponomeuta padella, Plutella xylostella,
Malacosoma neustria, Euproctis chrysorrhoea, Lymantria spp., Bucculatrix thurberiella,
Phyllocnistis citrella, Agrotis spp., Euxoa spp., Feltia spp., Earias insulana, Heliothis spp.,
Mamestra brassicae, Panolis flammea, Spodoptera spp., Trichoplusia ni, Carpocapsa
pomonella, Pieris spp., Chilo spp., Pyrausta nubilalis, Ephestia kuehniella, Galleria mellonella,
Tineola bisselliella, Tinea pellionella, Hofinannopbila pseudospretella, Cacoecia podana,
Capua reticulana, Choristoneura rumiferana, Clysia ambiguella, Homona magnanima, Tortrix
viridana, Cnaphalocerus spp. and Oulema oryzae.
From the order of the Coleoptera, for example, Anobium punctatum, Rhizopertha dominica,
Bruchidius obtectus, Acanthoscelides obtectus, Hylotrupes bajulus, Agelastica alni,
Leptinotarsa decemlineata, Phaedon cochleariae, Diabrotica spp., Psylliodes chrysocephala,
Epilachna varivestis, Atomaria spp., Oryzaephilus surinamensis, Anthonomus spp., Sitopbilus
spp., Otiorrhynchus sulcatus, Cosmopolites sordidus, Ceuthorrhynchus assimilis, Hypera
postica, Dermestes spp., Trogoderma spp., Anthrenus spp., Attagenus spp., Lyctus spp.,
Meligethes aeneus, Ptinus spp., Niptus hololeucus, Gibbium psylloides, Tribolium spp.,
Tenebrio molitor, Agriotes spp., Conoderus spp., Melolontha melolontha, Amphimallon
solstitialis, Costeiytra zealandica and Lissorphoptms oryzophilus.
From the order of the Hymenoptera, for example, Diprion spp., Hoplocampa spp., Lasius spp.,
Monomorium pharaonis and Vespa spp..
From the order of the Diptera, for example, Aedes spp., Anopheles spp., Culex spp.,
Drosophila melanogaster, Musca spp., Fannia spp., Calliphora erythrocephala, Lucilia spp.,
Chrysomyia spp., Cuterebra spp., Gastrophilus spp., Hyppobosca spp., Stomoxys spp., Oestrus
spp., Hypoderma spp., Tabanus spp., Tannia spp., Bibio hortulanus, Oscinella frit, Phorbia
spp., Pegomyia hyoscyami, Ceratitis capitata, Dacus oleae, Tipula paludosa, Hylemyia spp.
and Liriomyza spp..
From the order of the Siphonaptera, for example, Xenopsylla cheopis and Ceratophyllus spp..
From the order of the Arachnida, for example, Scorpio maurus, Latrodectus mactans, Acarus
siro, Argas spp., Omithodoros spp., Dermanyssus gallinae, Eriophyes ribis, Phyllocoptruta
oleivora, Boophilus spp., Rhipicephalus spp., Amblyomma spp., Hyalomma spp., Ixodes spp.,
Psoroptes spp., Chorioptes spp., Sarcoptes spp., Tarsonemus spp., Bryobia praetiosa,
Panonychus spp., Tetranychus spp., Hemitarsonemus spp. and Brevipalpus spp..
The plant-parasitic nematodes include, for example, Pratylenchus spp., Radopholus similis,
Ditylenchus dipsaci, Tylenchulus semipenetrans, Heterodera spp., Globodera spp.,
Meloidogyne spp., Aphelenchoides spp., Longidorus spp., Xiphinema spp., Trichodorus spp.
and Bursaphelenchus spp..
If appropriate, the compounds or active compound combinations according to the invention
may also be used in certain concentrations or application rates to act as herbicides. If
appropriate, they can also be employed as intermediates or precursors for the synthesis of
further active compounds.
All plants and plant parts can be treated in accordance with the invention. Plants are to be
understood as meaning in the present context all plants and plant populations such as desired
and undesired wild plants or crop plants (including naturally occurring crop plants). Crop
plants can be plants which can be obtained by conventional plant breeding and optimization
methods or by biotechnplogical and recombinant methods or by combinations of these
methods, including the transgenic plants and inclusive of the plant cultivars protectable or
not protectable by plant breeders' rights. Plant parts are to be understood as meaning all
parts and organs of plants above and below the ground, such as shoot, leaf, flower and root,
examples which may be mentioned being leaves, needles, stalks, stems, flowers, fruit bodies,
fruits, seeds, roots, tubers and rhizomes. The plant parts also include harvested material, and
vegetative and generative propagation material, for example cuttings, tubers, rhizomes,
offsets and seeds.
The treatment according to the invention of the plants and plant parts with the active
compounds or active compound combinations is carried out directly or by allowing the
compounds to act on the surroundings, environment or storage space by the customary
treatment methods, for example by immersion, spraying, evaporation, fogging, scattering,
painting on or injection and, in the case of propagation material, in particular in the case of
seeds, also by applying one or more coats.
The active compounds or active compound combinations can be converted into the
customary formulations such as solutions, emulsions, wettable powders, suspensions,
powders, dusts, pastes, soluble powders, granules, suspension-emulsion concentrates,
natural and synthetic materials impregnated with active compound, and microencapsulations
in polymeric materials.
These formulations are produced in a known manner, for example by mixing the active
compounds with extenders, that is, liquid solvents and/or solid carriers, optionally with the
use of surfactants, that is, emulsifiers and/or dispersants, and/or foam formers.
If the extender used is water, it is also possible, for example, to use organic solvents as
cosolvents. The following are essentially suitable as liquid solvents: aromatics such as
xylene, toluene or alkylnaphthalenes, chlorinated aromatics or chlorinated aliphatic
hydrocarbons such as chlorobenzenes, chloroethylenes or methylene chloride, aliphatic
hydrocarbons such as cyclohexane or paraffins, for example mineral oil fractions, mineral
and vegetable oils, alcohols such as butanol or glycol and their ethers and esters, ketones
such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, strongly
polar solvents such as dimethylformamide and dimethyl sulphoxide, or else water.
Suitable solid carriers are:
for example ammonium salts and ground natural minerals such as kaolins, clays, talc, chalk,
quartz, attapulgite, montmorillonite or diatomaceous earth, and ground synthetic materials
such as highly-disperse silica, alumina and silicates; suitable solid carriers for granules are:
for example crushed and fractionated natural rocks such as calcite, marble, pumice, sepiolite
and dolomite, or else synthetic granules of inorganic and organic meals, and granules of
organic material such as sawdust, coconut shells, maize cobs and tobacco stalks; suitable
emulsifiers and/or foam formers are: for example nonionic and anionic emulsifiers such as
polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers, for example
alkylaryl polyglycol ethers, alkylsulphonates, alkyl sulphates, arylsulphonates, or else
protein hydrolysates; suitable dispersants are: for example lignin-sulphite waste liquors and
methylcellulose.
Tackifiers such as carboxymethylcellulose and natural and synthetic polymers hi the form of
powders, granules or latices, such as gum arabic, polyvinyl alcohol and polyvinyl acetate, or
else natural phospholipids such as cephalins and lecithins and synthetic phospholipids can
be used hi the formulations. Other additives can be mineral and vegetable oils.
It is possible to use colorants such as inorganic pigments, for example iron oxide, titanium
oxide and Prussian Blue, and organic colorants such as alizarin colorants, azo colorants and
metal phthalocyanine colorants, and trace nutrients such as salts of iron, manganese, boron,
copper, cobalt, molybdenum and zinc.
The formulations generally comprise between 0.1 and 95% by weight of active compound,
preferably between 0.5 and 90%.
The active compounds according to the invention, as such or in their formulations, can also
be used as a mixture with known fungicides, bactericides, acaricides, nematicides or
insecticides, for example in order to widen the spectrum of action or to prevent the
development of resistances in this way. In many cases, synergistic effects result, i.e. the
activity of the mixture exceeds the activity of the individual components.
Compounds which are suitable as components in the mixtures are, for example, the
following:
Fungicides:
2-phenylphenol; 8-hydroxyquinoline sulphate; acibenzolar-S-methyl; aldimorph; amidoflumet;
ampropylfos; ampropylfos-potassium; andoprim; anilazine; azaconazole;
azoxystrobin; benalaxyl; benodanil; benomyl; benthiavalicarb-isopropyl; benzamacril;
benzamacril-isobutyl; bilanafos; binapacryl; biphenyl; bitertanol; blasticidin-S;
bromuconazole; bupirimate; butbiobate; butylamine; calcium polysulphide; capsimycin;
captafol; captan; carbendazim; carboxin; carpropamid; carvone; quinomethionate;
chlobenthiazone; chlorfenazole; chloroneb; chlorothalonil; chlozolinate; clozylacon;
cyazofamid; cyflufenamid; cymoxanil; cyproconazole; cyprodinil; cyprofuram; Dagger G;
debacarb; dichlofluanid; dichlone; dichlorophen; diclocymet; diclomezine; dicloran;
diethofencarb; difenoconazole; diflumetorim; dimethirimol; dimethomorph; dimoxystrobin;
diniconazole; diniconazole-M; dinocap; diphenylamine; dipyrithione; ditalimfos; dithianon;
dodine; drazoxolon; edifenphos; epoxiconazole; ethaboxam; ethirimol; etridiazole;
famoxadone; fenamidone; fenapanil; fenarimol; fenbuconazole; fenfuram; fenhexamid;
fenitropan; fenoxanil; fenpiclonil; fenpropidin; fenpropimorph; ferbam; fluazinani;
flubenzunine; fludioxonil; flumetover; flumorph; fluoromide; fluoxastrobin;
fluquinconazole; flurprimidol; flusilazole; flusulfamide; flutolanil; flutriafol; folpet; fosetyl-
Al; fosetyl-sodium; fuberidazole; furalaxyl; furametpyr; furcarbanil; furmecyclox;
guazatine; hexachlorobenzene; hexaconazole; hymexazol; imazalil; imibenconazole;
iminoctadine triacetate;. iminoctadine tris(albesilate); iodocarb; ipconazole; iprobenfos;
iprodione; iprovalicarb; irumamycin; isoprothiolane; isovaledione; kasugamycin; kresoximmethyl;
mancozeb; maneb; meferimzone; mepanipyrim; mepronil; metalaxyl; metalaxyl-M;
metconazole; methasulfocarb; methfiiroxam; metiram; metominostrobin; metsulfovax;
mildiomycin; myclobutanil; myclozolin; natamycin; nicobifen; nitrothal-isopropyl;
noviflumuron; nuarimol; ofurace; orysastrobin; oxadixyl; oxolinic acid; oxpoconazole;
oxycarboxin; oxyfenthiin; paclobutrazol; pefiirazoate; penconazole; pencycuron;
phosdiphen; phthalide; picoxystrobin; piperalin; polyoxins; polyoxorim; probenazole;
prochloraz; procymidone; propamocarb; propanosine-sodium; propiconazole; propineb; proquinazid;
prothioconazole; pyraclostrobin; pyrazophos; pyrifenox; pyrimethanil; pyroquilon;
pyroxyfur, pyrrolnitrin; quinconazole; quinoxyfen; quintozene; simeconazole; spiroxamine;
sulphur; tebuconazole; tecloftalam; tecnazene; tetcyclacis; tetraconazole; thiabendazole;
thicyofen; thifluzamide; thiophanate-methyl; thiram; tioxymid; tolclofos-methyl;
tolylfluanid; triadimefon; triadimenol; triazbutil; triazoxide; tricyclamide; tricyclazole;
tridemorph; trifloxystrobin; triflumizole; triforine; triticonazole; uniconazole; validamycin
A; vinclozolin; zineb; ziram; zoxamide; (2S)-N-[2-[4-[[3-(4-chlorophenyl)-2-propynyl]oxy]-
3-methoxyphenyl]ethyl]-3-methyl-2-[(methylsulphonyl)amino]-butanamide; 1-(1-
naphthalenyl)-1 H-pyrrole-2,5-dione; 2,3,5,6-tetrachloro-4-(methylsulphonyl)-pyridine; 2-
amino-4-methyl-N-phenyl-5-thiazolecarboxamide; 2-chloro-N-(2,3-dihydro-l,l,3-trimethyllH-
inden-4-yl)-3-pyridinecarboxamide; 3,4,5-trichloro-2,6-pyridinedicarbonitrile;
Actinovate; cis-l-(4-chlorophenyl)-2-(lH-l,2,4-triazole-l-yl)-cycloheptanol; methyl l-(2,3-
dihydro-2,2-dimethyl-lH-inden-l-yl)-lH-imidazole-5-carboxylate; monopotassium
carbonate; N-(6-methoxy-3-pyridinyl)-cyclopropanecarboxamide; N-butyl-8-( 1,1-
dimethylethyl)-l-oxaspiro[4.5]decan-3-amine; sodium tetrathiocarbonate;
and copper salts and preparations such as Bordeaux mixture; copper hydroxide; copper
naphthenate; copper oxychloride; copper sulphate; cufraneb; cuprous oxide; mancopper;
oxine-copper.
Bactericides:
bronopol, dichlorophen, nitrapyrin, nickel dimethyldithiocarbamate, kasugamycin, octhilinone,
furancarboxylic acid, oxytetracyclin, probenazole, streptomycin, tecloftalam, copper sulphate
and other copper preparations.
Insecticides/Acaricides/Nematicides:
abamectin, ABG-9008, acephate, acequinocyl, acetamiprid, acetoprole, acrinathrin, AKD-
1022, AKD-3059, AKD-3088, alanycarb, aldicarb, aldoxycarb, allethrin, alpha-cypermethrin
(alphamethrin), amidoflumet, aminocarb, amitraz, avermectin, AZ-60541, azadirachtin, azamethiphos,
azinphos-methyl, azinphos-ethyl, azocyclotin,
Bacillus popilliae, Bacillus sphaericus, Bacillus subtilis, Bacillus thuringiensis, Bacillus
thuringiensis strain EG-2348, Bacillus thuringiensis strain GC-91, Bacillus thuringiensis
strain NCTC-11821, baculoviruses, Beauveria bassiana, Beauveria tenella, benclothiaz,
bendiocarb, benfuracarb, bensultap, benzoximate, beta-cyfluthrin, beta-cypermethrin,
bifenazate, bifenthrin, binapacryl, bioallethrin, bioallethrin S-cyclopentyl isomer,
bioethanomethrin, biopermethrin, bioresmethrin, bistrifluron, BPMC, brofenprox,
bromophos-ethyl, bromopropylate, bromfenvinfos (-methyl), BTG-504, BTG-505,
bufencarb, buprofezin, butathiofos, butocarboxim, butoxycarboxim, butylpyridaben,
cadusafos, camphechlor, carbaryl, carbofuran, carbophenothion, carbosulfan, cartap, CGA-
50439, quinomethionate, chlordane, chlordimeform, chloethocarb, chlorethoxyfos,
chlorfenapyr, chlorfenvinphos, chlorfluazuron, chlormephos, chlorobenzilate, chloropicrin,
chlorproxyfen, chlorpyrifos-methyl, chlorpyrifos (-ethyl), chlovaporthrin, chromafenozide,
cis-cypermethrin, cis-resmethrin, cis-permethrin, clocythrin, cloethocarb, clofentezine,
clothianidin, clothiazoben, codlemone, coumaphos, cyanofenphos, cyanophos, cycloprene,
cycloprothrin, Cydia pomonella, cyfluthrin, cyhalothrin, cyhexatin, cypermethrin,
cyphenothrin (IR-trans isomer), cyromazine,
DDT, deltamethrin, demeton-S-methyl, demeton-S-methylsulphone, diafenthiuron, dialifos,
diazinon, dichlofenthion, dichlorvos, dicofol, dicrotophos, dicyclanil, diflubenzuron,
dimefluthrin, dimethoate, dimethylvinphos, dinobuton, dhiocap, dinotefuran, diofenolan,
disulfoton, docusate-sodium, dofenapyn, DOWCO-439,
eflusilanate, emamectin, emamectin benzoate, empenthrin (IR isomer), endosulfan, Entomophthora
spp., EPN, esfenvalerate, ethiofencarb, ethiprole, ethion, ethoprophos, etofenprox,
etoxazole, etrimfos,
famphur, fenamiphos, fenazaquin, fenbutatin oxide, fenfluthrin, fenitrothion, fenobucarb,
fenothiocarb, fenoxacrim, fenoxycarb, fenpropathrin, fenpyrad, fenpyrithrin, fenpyroximate,
fensulfothion, fenthion, fentrifanil, fenvalerate, fipronil, flonicamid, fluacrypyrim,
fluazuron, flubenzimine, flubrocythrinate, flucycloxuron, flucythrinate, flufenerim,
flufenoxuron, flufenprox, flumethrin, flupyrazofos, flutenzin (flufenzine), fluvalinate,
fonofos, formetanate, formothion, fosmethilan, fosthiazate, fubfenprox (fluproxyfen),
furathiocarb,
gamma-cyhalothrin, gamma-HCH, gossyplure, grandlure, granulosis viruses,
halfenprox, halofenozide, HCH, HCN-801, heptenophos, hexaflumuron, hexythiazox, hydramethylnone,
hydroprene,
DCA-2002, imidacloprid, imiprothrin, indoxacarb, iodofenphos, iprobenfos, isazofos, isofenphos,
isoprocarb, isoxathion, ivermectin,
japonilure,
kadethrin, nuclear polyhedrosis viruses, kinoprene,
lambda-cyhalothrin, lindane, lufenuron,
malathion, mecarbam, mesulfenfos, metaldehyde, metam-sodium, methacrifos,
methamidophos, Metarhizium anisopliae, Metarhizium flavoviride, methidathion,
methiocarb, methomyl, methoprene, methoxychlor, methoxyfenozide, metofluthrin,
metolcarb, metoxadiazone, mevinphos, milbemectin, milbemycin, MKI-245, MON-45700,
monocrotophos, moxidectin, MTI-800,
naled, NC-104, NC-170, NC-184, NC-194, NC-196, niclosamide, nicotine, nitenpyram,
nithiazine, ISfNI-OOOl, NNI-0101, NNI-0250, NNI-9768, novaluron, noviflumuron,
OK-5101, OK-5201, OK-9601, OK-9602, OK-9701, OK-9802, omethoate, oxamyl,
oxydemeton-methyl,
Paecilomyces fumosoroseus, parathion-methyl, parathion (-ethyl), permethrin (cis-, trans-),
petroleum, PH-6045, phenothrin (IR-trans isomer), phenthoate, phorate, phosalone,
phosmet, phosphamidon, phosphocarb, phoxim, piperonyl butoxide, pirimicarb, pirimiphosmethyl,
pirimiphos-ethyl, potassium oleate, prallethrin, profenofos, profluthrin, promecarb,
propaphos, propargite, propetamphos, propoxur, prothiofos, prothoate, protrifenbute,
pymetrozine, pyraclofos, pyresmethrin, pyrethmm, pyridaben, pyridalyl, pyridaphenthion,
pyridathion, pyrimidifen, pyriproxyfen,
quinalphos,
resmethrin, RH-5849, ribavirin, RU-12457, RU-15525,
S-421, S-1833, salithion, sebufos, SI-0009, silafluofen, spinosad, spirodiclofen,
spiromesifen, sulfluramid, sulfotep, sulprofos, SZI-121,
tau-fluvalinate, tebufenozide, tebufenpyrad, tebupirimfos, teflubenzuron, tefluthrin,
temephos, Temivinphos, Terbam, Terbufos, Tetrachlorvinphos, Tetradifon, Tetramethrin,
Tetramethrin (1R isomer), tetrasul, theta-cypermethrin, thiacloprid, thiamethoxam,
thiapronil, thiatriphos, thiocyclam hydrogen oxalate, thiodicarb, thiofanox, thiometon,
thiosultap-sodium, thuringiensin, tolfenpyrad, tralocythrin, tralomethrin, transfluthrin,
triarathene, triazamate, triazophos, triazuron, trichlophenidine, trichlorfon, Trichoderma
atroviride, triflumuron, trimethacarb,
vamidothion, vaniliprole, verbutin, Verticillium lecanii,
WL-108477, WL-40027,
YI-5201, YI-5301, YI-5302,
XMC, xylylcarb,
ZAr3274, zeta-cypermethrin, zolaprofos, ZXI-8901,
the compound 3-methylphenyl propylcarbamate (Tsumacide Z),
the compound 3-(5-chloro-3-pyridinyl)-8-(2,2,2-trifluoroethyl)-8-azabicyclo[3.2.1]octane-3-
carbonitrile (CAS Reg. No. 185982-80-3) and the corresponding 3-endo isomer (CAS Reg. No.
185984-60-5) (cf. WO 96/37494, WO 98/25923),
and preparations which contain insecticidally active plant extracts, nematodes, fungi or viruses.
A mixture with other known active compounds, such as herbicides, or with fertilizers and
growth regulators is also possible.
When used as insecticides in their commercially available formulations and in the use forms
prepared with these formulations, the active compounds according to the invention can
furthermore exist in the form of a mixture with synergists. Synergists are compounds by which
the activity of the active compounds is increased without it being necessary for the synergist
added to be active itself.
The active compound content of the use forms prepared from the commercially available
formulations can vary within broad ranges. The active compound concentration of the use
forms can be from 0.0000001 up to 95% by weight of active compound, preferably between
0.0001 and 1% by weight.
They are applied in a customary manner adapted to suit the use forms.
When used against hygiene pests and pests of stored products, the active compound or
active compound combination is distinguished by excellent residual action on wood and clay
as well as good stability to alkali on limed substrates.
As already mentioned above, it is possible to treat all plants or their parts in accordance with
the invention, hi a preferred embodiment, wild plant species or plant varieties and plant
cultivars which have been obtained by traditional biological breeding methods, such as
hybridization or protoplast fusion, and the parts of these varieties and cultivars are treated. In a
further preferred embodiment, transgenic plants and plant cultivars which have been obtained
by recombinant methods, if appropriate in combination with conventional methods (genetically
modified organisms), and their parts are treated. The term "parts" or "parts of plants" or "plant
parts" has been explained above.
Plants which are treated particularly preferably in accordance with the invention are those of
the plant cultivars which are in each case commercially available or in use. Plant cultivars are
understood as meaning plants with new traits which have been bred either by conventional
breeding, by mutagenesis or by recombinant DNA techniques. They may take the form of
cultivars, biotypes and genotypes.
Depending on the plant species or plant cultivars, their location and growth conditions (soils,
climate, vegetation period, nutrition), the treatment according to the invention may also result
in superadditive ("synergistic") effects. Thus, for example, reduced application rates and/or a
widened activity spectrum and/or an increase in the activity of the substances and compositions
which can be used in accordance with the invention, better plant growth, increased tolerance to
high or low temperatures, increased tolerance to drought or to salinity in the water or soil,
increased flowering performance, facilitated harvesting, accelerated maturation, higher yields,
higher quality and/or better nutritional value of the harvested products, better storage
characteristics and/or processability of the harvested products are possible which exceed the
effects which were actually to be expected.
The preferred transgenic plants or plant cultivars (those obtained by recombinant methods) to
be treated in accordance with the invention include all those plants which, owing to the process
of recombinant modification, were given genetic material which confers particular,
advantageous, valuable traits to these plants. Examples of such properties are better plant
growth, increased tolerance to high or low temperatures, increased tolerance to drought or to
salinity in the water or soil, increased flowering performance, facilitated harvesting,
accelerated maturation, higher yields, higher quality and/or higher nutritional value of the
harvested products, better storage characteristics and/or better processability of the harvested
products. Further examples of such traits, examples which must be mentioned especially, are
better defence of the plants against animal and microbial pests, such as against insects, mites,
phytopathogenic fungi, bacteria and/or viruses and an increased tolerance of the plants to
certain herbicidal active compounds. Examples of transgenic plants which may be mentioned
are the important crop plants, such as cereals (wheat, rice), maize, soybeans, potato, cotton,
oilseed rape, beet, sugar cane and fruit plants (with the fruits apples, pears, citrus fruits and
grapes), with particular emphasis on maize, soybeans, potatoes, cotton and oilseed rape. Traits
which are especially emphasized are the increased defence of the plants against insects, owing
to toxins being formed in the plants, in particular toxins which are generated in the plants by
the genetic material of Bacillus thuringiensis (for example by the genes CrylA(a), CryIA(b),
CryIA(c), CryllA, CrymA, CrymB2, Cry9c Cry2Ab, CrySBb and CrylF and their
combinations; hereinbelow "Bt plants"). Other traits which are particularly emphasized are the
increased defence of plants against fungi, bacteria and viruses by the systemic acquired
resistance (SAR), systemin, phytoalexins, elicitors and resistance genes and correspondingly
expressed proteins and toxins. Other traits which are especially emphasized are the increased
tolerance of the plants to certain herbicidal active compounds, for example imidazolinones,
sulphonylureas, glyphosate or phosphinotricin (for example "PAT" gene). The genes which
confer the desired traits in each case may also be present in the transgenic plants in
combination with one another. Examples of "Bt plants" which may be mentioned are maize
cultivars, cotton cultivars, soybean cultivars and potato cultivars which are commercially
available under the trade names YIELD GARD® (for example maize, cotton, soybeans),
KnockOut® (for example maize), StarLink® (for example maize), Bollgard® (cotton),
Nucotn® (cotton) and NewLeaf® (potato). Examples of herbicide-tolerant plants which may
be mentioned are maize cultivars, cotton cultivars and soybean cultivars which are
commercially available under the trade names Roundup Ready® (tolerance to glyphosate, for
example maize, cotton, soybean), Liberty Link® (tolerance to phosphinotricin, for example
oilseed rape), IMI® (tolerance to imidazolinones) and STS® (tolerance to sulphonylureas, for
example maize). Herbicide-resistant plants (plants bred in a conventional manner for herbicide
tolerance) which may be mentioned include also the varieties commercially available under the
name Clearfield® (for example maize). Naturally, these statements also apply to plant cultivars
having these genetic traits or genetic traits still to be developed, which plant cultivars will be
developed and/or marketed in the future.
The plants listed can be treated particularly advantageously with the compounds according to
the invention or the active compound mixtures according to the invention. The preferred
ranges stated above for the active compounds and mixtures also apply to the treatment of these
plants. Particular emphasis may be given to the treatment of plants with the compounds or
mixtures specifically mentioned in the present text.
The active compounds or active compound combinations according to the invention are not
only active against plant, hygiene and stored-product pests, but also, in the veterinary medicine
sector, against animal parasites (ectoparasites), such as ixodid ticks, argasid ticks, scab mites,
trombi-culid mites, flies (stinging and sucking), parasitic fly larvae, lice, hair lice, bird lice and
fleas. These parasites include:
From the order of the Anoplurida, for example, Haematopinus spp., Linognathus spp.,
Pediculus spp., Phtirus spp., Solenopotes spp..
From the order of the Mallophagida and the sub-orders Amblycerina and Ischnocerina, for
example, Trimenopon spp., Menopon spp., Trinoton spp., Bovicola spp., Werneckiella spp.,
Lepikentron spp., Damalina spp., Trichodectes spp., Felicola spp..
From the order of the Diptera and the sub-orders Nematocerina and Brachycerina, for
example, Aedes spp., Anopheles spp., Culex spp., Simulium spp., Eusimulium spp.,
Phlebotomus spp., Lutzomyia spp., Culicoides spp., Chrysops spp., Hybomitra spp.,
Atylotus spp., Tabanus spp., Haematopota spp., Philipomyia spp., Braula spp., Musca spp.,
Hydrotaea spp., Stomoxys spp., Haematobia spp., Morellia spp., Fannia spp., Glossina spp.,
Calliphora spp., Lucilia spp., Chrysomyia spp., Wohlfahrtia spp., Sarcophaga spp., Oestrus
spp., Hypoderma spp., Gasterophilus spp., Hippobosca spp., Lipoptena spp. and Melophagus
spp..
From the order of the Siphonapterida, for example, Pulex spp., Ctenocephalides spp.,
Xenopyslla spp. and Ceratophyllus spp..
From the order of the Heteropterida, for example, Cimex spp., Triatoma spp., Rhodnius spp.
and Panstrongylus spp..
From the order of the Blattarida, for example, Blatta orientalis, Periplaneta americana,
Blattella germanica and Supella spp..
From the sub-class of the Acaria (Acarida) and the orders of the Meta- and Mesostigmata,
for example, Argas spp., Ornithodorus spp., Otobius spp., Ixodes spp., Amblyomma spp.,
Boophilus spp., Dermacentor spp., Haemophysalis spp., Hyalomma spp., Rhipicephalus
spp., Dermanyssus spp., Raillietia spp., Pneumonyssus spp., Sternostoma spp. and Varroa
spp..
From the order of the Actinedida (Prostigmata) and Acaridida (Astigmata), for example,
Acarapis spp., Cheyletiella spp., Ornithocheyletia spp., Myobia spp., Psorergates spp.,
Demodex spp., Trombicula spp., Listrophorus spp., Acarus spp., Tyrophagus spp.,
Caloglyphus spp., Hypodectes spp., Pterolichus spp., Psoroptes spp., Chorioptes spp.,
Otodectes spp., Sarcoptes spp., Notoedres spp., Knemidocoptes spp., Cytodites spp. and
Laminosioptes spp..
The active compounds or active compound combinations according to the invention are also
suitable for controlling arthropods which attack agricultural livestock, such as, for example,
cattle, sheep, goats, horses, pigs, donkeys, camels, buffaloes, rabbits, chickens, turkeys,
ducks, geese, honeybees, other domestic animals, such as, for example, dogs, cats, cage
birds, aquarium fish, and so-called experimental animals, such as, for example,, hamsters,
guinea-pigs, rats and mice. By combating these arthropods, it is intended to reduce deaths
and decreased performances (in meat, milk, wool, hides, eggs, honey and the like), so that
more economical and simpler animal keeping is made possible by using the active
compounds according to the invention.
In the veterinary sector, the active compounds or active compound combinations according
to the invention are used in a known manner by enteral administration, for example in the
form of tablets, capsules, drinks, drenches, granules, pastes, boli, the feed-through method,
suppositories, by parenteral administration, such as, for example, by means of injections
(intramuscular, subcutaneous, intravenous, intraperitoneal and the like), implants, by nasal
application, by dermal administration, for example in the form of dipping or bathing,
spraying, pouring-on and spotting-on, washing, dusting, and with the aid of shaped articles
which comprise active compound, such as collars, ear tags, tail marks, limb bands, halters,
marking devices and the like.
When administered to livestock, poultry, domestic animals and the like, the active
compounds or active compound combinations can be used as formulations (for example
powders, emulsions, flowables) which comprise the active compounds in an amount of 1 to
80% by weight, either directly or after dilution by a factor of 100 to 10 000, or they may be
used in the form of a chemical bath.
Furthermore, it has been found that the compounds or active compound combinations
according to the invention have a potent insecticidal action against insects which destroy
industrial materials.
The following insects may be mentioned by way of example and as being preferred, but
without any limitation:
Beetles, such as
Hylotrupes bajulus, Chlorophorus pilosis, Anobium punctatum, Xestobium rufovillosum,
Ptilinus pecticornis, Dendrobium pertinex, Ernobius mollis, Priobium carpini, Lyctus
brunneus, Lyctus africanus, Lyctus planicollis, Lyctus linearis, Lyctus pubescens,
Trogoxylon aequale, Minthes rugicollis, Xyleborus spec., Tryptodendron spec., Apate
monachus, Bostrychus capucins, Heterobostrychus brunneus, Sinoxylon spec., Dinoderus
minutus.
Dermapterans, such as Sirex juvencus, Urocerus gigas, Urocerus gigas taignus, Urocerus
augur.
Termites, such as Kalotermes flavicollis, Cryptotermes brevis, Heterotermes indicola,
Reticulitermes flavipes, Reticulitermes santonensis, Reticulitermes lucifugus, Mastotermes
darwiniensis, Zootermopsis nevadensis, Coptotermes formosanus.
Bristletails, such as Lepisma saccharina.
Industrial materials are to be understood as meaning, in the present context, non-live
materials, such as, preferably, synthetic materials, glues, sizes, paper and board, leather,
wood and timber products, and paint. The materials to be very particularly preferably
protected against attack by insects are wood and timber products.
Wood and timber products which can be protected by the composition according to the
invention or mixtures comprising such a composition are to be understood as meaning, for
example:
construction timber, wooden beams, railway sleepers, bridge components, jetties, wooden
vehicles, boxes, pallets, containers, telephone poles, wood cladding, windows and doors
made of wood, plywood, particle board, joiner's articles, or wood products which, quite
generally, are used in the construction of houses or in joinery.
The active compounds or active compound combinations can be used as such, in the form of
concentrates or generally customary formulations, such as powders, granules, solutions,
suspensions, emulsions or pastes.
The formulations mentioned can be prepared in a manner known per se, for example by
mixing the active compounds with at least one solvent or diluent, emulsifier, dispersant
and/or binder or fixative, water repellent, if appropriate desiccants and UV stabilizers and, if
appropriate, colorants and pigments and other processing auxiliaries. The insecticidal
compositions or concentrates used for the protection of wood and wooden materials
comprise the active compound according to the invention in a concentration of 0.0001 to
95% by weight, in particular 0.001 to 60% by weight.
The amount of the compositions or concentrates employed depends on the species and the
occurrence of the insects and on the medium. The optimum rate of application can be
determined upon use in each case by a test series. However, in general, it suffices to employ
0.0001 to 20% by weight, preferably 0.001 to 10% by weight, of the active compound, based
on the material to be protected.
The solvent and/or diluent used is an organochemical solvent or solvent mixture and/or an
oily or oil-type organochemical solvent or solvent mixture of low volatility and/or a polar
organochemical solvent or solvent mixture and/or water and, if appropriate, an emulsifier
and/or wetting agent.
Organochemical solvents .which are preferably employed are oily or oil-type solvents having
an evaporation number of above 35 and a flashpoint of above 30°C, preferably above 45°C.
Substances which are used as such oily and oil-type solvents which have low volatility and
are insoluble in water are suitable mineral oils or their aromatic fractions, or mineral-oilcontaining
solvent mixtures, preferably white spirit, petroleum and/or alkylbenzene.
Substances which are advantageously used are mineral oils with a boiling range of 170 to
220°C, white spirit with a boiling range of 170 to 220°C, spindle oil with a boiling range of
250 to 350°C, petroleum or aromatics of boiling range 160 to 280°C, essence of terpentine
and the like.
In a preferred embodiment, liquid aliphatic hydrocarbons with a boiling range of 180 to
210°C or high-boiling mixtures of aromatic and aliphatic hydrocarbons with a boiling range
of 180 to 220°C and/or spindle oil and/or monochloronaphthalene, preferably
a-monochloronaphthalene, are used.
The organic oily or oil-type solvents of low volatility having an evaporation number of
above 35 and a flashpoint of above 30°C, preferably above 45°C, can be partially replaced
by organochemical solvents of high or medium volatility, with the proviso that the solvent
mixture also has an evaporation number of above 35 and a flashpoint of above 30°C,
preferably above 45°C, and that the insecticide/fungicide mixture is soluble or emulsifiable
in this solvent mixture.
In a preferred embodiment, part of the organochemical solvent or solvent mixture is
replaced by an aliphatic polar organochemical solvent or solvent mixture. Substances which
are preferably used are aliphatic organochemical solvents having hydroxyl and/or ester
and/or ether groups, such as, for example, glycol ethers, esters and the like.
The organochemical binders used within the scope of the present invention are the synthetic
resins and/or binding drying oils which are known per se and can be diluted with water
and/or are soluble or dispersible or emulsifiable in the organochemical solvents employed,
in particular binders composed of, or comprising, an acrylate resin, a vinyl resin, for
example polyvinyl acetate, polyester resin, polycondensation or polyaddition resin,
polyurethane resin, alkyd resin or modified alkyd resin, phenol resin, hydrocarbon resin,
such as indene/cumarone resin, silicone resin, drying vegetable and/or drying oils and/or
physically drying binders based on a natural and/or synthetic resin.
The synthetic resin used as the binder can be employed in the form of an emulsion,
dispersion or solution. Up to 10% by weight of bitumen or bituminous substances can also
be used as binders. In addition, colorants, pigments, water repellents, odour-masking
substances and inhibitors or anticorrosives known per se and the like can also be employed.
The composition or the concentrate preferably comprises, in accordance with the invention,
at least one alkyd resin or modified alkyd resin and/or a drying vegetable oil as the
organochemical binder. Preferably used according to the invention are alkyd resins with an
oil content of over 45% by weight, preferably 50 to 68% by weight.
All or some of the abovementioned binder can be replaced by a fixative (mixture) or a
plasticizer (mixture). These additives are intended to prevent volatilization of the active
compounds and crystallization or precipitation. They preferably replace 0.01 to 30% of the
binder (based on 100% of binder employed).
The plasticizers are from the chemical classes of the phthalic esters, such as dibutyl
phthalate, dioctyl phthalate or benzyl butyl phthalate, the phosphoric esters, such as tributyl
phosphate, the adipic esters, such as di-(2-ethylhexyl) adipate, the stearates, such as butyl
stearate or amyl stearate, the oleates, such as butyl oleate, the glycerol ethers or relatively
high-molecular-weight glycol ethers, glycerol esters and p-toluenesulphonic esters.
Fixatives are chemically based on polyvinyl alkyl ethers, such as, for example, polyvinyl
methyl ether, or ketones, such as benzophenone or ethylenebenzophenone.
Particularly suitable as a solvent or diluent is also water, if appropriate as a mixture with one
or more of the abovementioned organochemical solvents or diluents, emulsifiers and
dispersants.
Particularly effective protection of wood is achieved by large-scale industrial impregnation
processes, for example vacuum, double-vacuum or pressure processes.
If appropriate, the ready-to-use compositions can additionally comprise other insecticides
and, if appropriate, additionally one or more fungicides.
Suitable additional components which may be admixed are, preferably, the insecticides and
fungicides mentioned in WO 94/29 268. The compounds mentioned in that document are
expressly part of the present application.
Very particularly preferred components which may be admixed are insecticides, such as
chlorpyriphos, phoxim, silafluofin, alphamethrin, cyfluthrin, cypermethrin, deltamethrin,
permethrin, imidacloprid, NI-25, flufenoxuron, hexaflumuron, transfluthrin, thiacloprid,
methoxyphenoxid and triflumuron,
and fungicides, such as epoxyconazole, hexaconazole, azaconazole, propiconazole,
tebuconazole, cyproconazole, metconazole, imazalil, dichlofluanid, tolylfluanid, 3-iodo-2-
propynylbutyl carbamate, N-octyl-isothiazolin-3-one and 4,5-dichloro-N-octylisothiazolin-3-
one.
The compounds or active compound combinations according to the invention can at the
same time be employed for protecting objects which come into contact with salt water or
brackish water, in particular hulls, screens, nets, buildings, moorings and signalling systems,
against fouling.
Fouling by sessile Oligochaeta, such as Serpulidae, and by shells and species from the
Ledamorpha group (goose barnacles), such as various Lepas and Scalpellum species, or by
species from the Balanomorpha group (acorn barnacles), such as Balanus or Pollicipes
species, increases the frictional drag of ships and, as a consequence, leads to a marked
increase in operation costs owing to higher energy consumption and additionally frequent
residence in the dry dock.
Apart from fouling by algae, for example Ectocarpus sp. and Ceramium sp., fouling by
sessile Entomostraka groups, which come under the generic term Cirripedia (cirriped
crustaceans), is of particular importance.
Surprisingly, it has now been found that the compounds according to the invention, alone or
in combination with other active compounds, have an outstanding antifouling action.
Using the compounds according to the invention, alone or in combination with other active
compounds, allows the use of heavy metals such as, for example, in bis(trialkyltin)
sulphides, tri-n-butyltin laurate, tri-w-butyltin chloride, copper(I) oxide, triethyltin chloride,
tri-«-butyl-(2-phenyl-4-chlorophenoxy)tin, tributyltin oxide, molybdenum disulphide,
antimony oxide, polymeric butyl titanate, phenyl-(bispyridine)-bismuth chloride, tri-nbutyltin
fluoride, manganese ethylenebisthiocarbamate, zinc dimethyldithiocarbamate, zinc
ethylenebisthiocarbamate, zinc salts and copper salts of 2-pyridinethiol 1-oxide, bisdimethyldithiocarbamoylzinc
ethylene-bisthiocarbamate, zinc oxide, copper(I) ethylene-bisdithiocarbamate,
copper thiocyanate, copper naphthenate and tributyltin halides to be
dispensed with, or the concentration of these compounds to be substantially reduced.
If appropriate, the ready-to-use antifouling paints can additionally comprise other active
compounds, preferably algicides, fungicides, herbicides, molluscicides, or other antifouling
active compounds.
Preferably suitable components in combination with the antifouling compositions according
to the invention are:
algicides such as
2-terf-butylamino-4-cyclopropylamino-6-methylthio-l ,3,5-triazine, dichlorophen, diuron,
endothal, fentin acetate, isoproturon, methabenzthiazuron, oxyfluorfen, quinoclamine and
terbutryn;
fungicides such as
benzo[6]thiophenecarboxylic acid cyclohexylamide S,S-dioxide, dichlofluanid, fluorfolpet,
3-iodo-2-propinyl butylcarbamate, tolylfluanid and azoles such as
azaconazole, cyproconazole, epoxyconazole, hexaconazole, metconazole, propiconazole and
tebuconazole;
molluscicides such as
fentin acetate, metaldehyde, methiocarb, niclosamid, thiodicarb and trimethacarb;
Fe chelates;
or conventional antifouling active compounds such as
4,5-dichloro-2-octyl-4-isothiazolin-3-one, diiodomethylparatryl sulphone, 2-(N,Ndimethylthiocarbamoylthio)-
5-nitrothiazyl, potassium, copper, sodium and zinc salts of 2-
pyridinethiol 1-oxide, pyridine-triphenylborane, tetrabutyldistannoxane, 2,3,5,6-tetrachloro-
4-(methylsulphonyl)-pyridine, 2,4,5,6-tetrachloroisophthalonitrile, tetramethylthiuram
disulphide and 2,4,6-trichlorophenyhnaleimide.
The antifouling compositions used comprise the active compound according to the invention
of the compounds according to the invention in a concentration of 0.001 to 50% by weight,
in particular 0.01 to 20% by weight.
Moreover, the antifouling compositions according to the invention comprise the customary
components such as, for example, those described in Ungerer, Chem. Ind. 1985, 37, 730-732
and Williams, Antifouling Marine Coatings, Noyes, Park Ridge, 1973.
Besides the algicidal, fungicidal, molluscicidal active compounds and insecticidal active
compounds according to the invention, antifouling paints comprise, in particular, binders.
Examples of recognized binders are polyvinyl chloride in a solvent system, chlorinated
rubber in a solvent system, acrylic resins in a solvent system, in particular in an aqueous
system, vinyl chloride/vinyl acetate copolymer systems in the form of aqueous dispersions
or in the form of organic solvent systems, butadiene/sryrene/acrylonitrile rubbers, drying
oils such as linseed oil, resin esters or modified hardened resins in combination with tar or
bitumens, asphalt and epoxy compounds, small amounts of chlorine rubber, chlorinated
polypropylene and vinyl resins.
If appropriate, paints also comprise inorganic pigments, organic pigments or colorants which
are preferably insoluble in salt water. Paints may furthermore comprise materials such as
rosin to allow controlled release of the active compounds. Furthermore, the paints may
comprise plasticizers, modifiers which affect the rheological properties and other
conventional constituents. The compounds according to the invention or the
abovementioned mixtures may also be incorporated into self-polishing antifouling systems.
The active compounds or active compound combinations are also suitable for controlling
animal pests, in particular insects, arachnids and mites, which are found in enclosed spaces
such as, for example, dwellings, factory halls, offices, vehicle cabins and the like. They can
be employed in domestic insecticide products for controlling these pests alone or in
combination with other active compounds and auxiliaries. They are active against sensitive
and resistant species and against all development stages. These pests include:
From the order of the Scorpionidea, for example, Buthus occitanus.
From the order of the Acarina, for example, Argas persicus, Argas reflexus, Bryobia ssp.,
Dermanyssus gallinae, Glyciphagus domesticus, Omithodorus moubat, Rhipicephalus
sanguineus, Trombicula alfreddugesi, Neutrombicula autumnalis, Dermatophagoides
pteronissimus, Dermatophagoides forinae.
From the order of the Araneae, for example, Aviculariidae, Araneidae.
From the order of the Opiliones, for example, Pseudoscorpiones chelifer, Pseudoscorpiones
cheiridium, Opiliones phalangium.
From the order of the Isopoda, for example, Oniscus asellus, Porcellio scaber.
From the order of the Diplopoda, for example, Blaniulus guttulatus, Polydesmus spp..
From the order of the Chilopoda, for example, Geophilus spp..
From the order of the Zygentoma, for example, Ctenolepisma spp., Lepisma saccharina,
Lepismodes inquilinus.
From the order of the Blattaria, for example, Blatta orientalis, Blattella germanica, Blattella
asahinai, Leucophaea maderae, Panchlora spp., Parcoblatta spp., Periplaneta australasiae,
Periplaneta americana, Periplaneta brunnea, Periplaneta fuliginosa, Supella longipalpa.
From the order of the Saltatoria, for example, Acheta domesticus.
From the order of the Dermaptera, for example, Forficula auricularia.
From the order of the Isoptera, for example, Kalotermes spp., Reticulitermes spp..
From the order of the Psocoptera, for example, Lepinatus spp., Liposcelis spp..
From the order of the Coleptera, for example, Anthrenus spp., Attagenus spp., Dermestes
spp., Latheticus oryzae, Necrobia spp., Ptinus spp., Rhizopertha dominica, Sitophilus
granarius, Sitophilus oryzae, Sitophilus zeamais, Stegobium paniceum.
From the order of the Diptera, for example, Aedes aegypti, Aedes albopictus, Aedes
taeniorhynchus, Anopheles spp., Calliphora erythrocephala, Chrysozona pluvialis, Culex
quinquefasciatus, Culex pipiens, Culex tarsalis, Drosophila spp., Fannia canicularis, Musca
domestica, Phlebotomus spp., Sarcophaga camaria, Simulium spp., Stomoxys calcitrans,
Tipula paludosa.
From the order of the Lepidoptera, for example, Achroia grisella, Galleria mellonella, Plodia
interpunctella, Tinea cloacella, Tinea pellionella, Tineola bisselliella.
From the order of the Siphonaptera, for example, Ctenocephalides cam's, Ctenocephalides
felis, Pulex irritans, Tunga penetrans, Xenopsylla cheopis.
From the order of the Hymenoptera, for example, Camponotus herculeanus, Lasius
fuliginosus, Lasius niger, Lasius umbratus, Monomorium pharaonis, Paravespula spp.,
Tetramorium caespitum.
From the order of the Anoplura, for example, Pediculus humanus capitis, Pediculus
humanus corporis, Phthirus pubis.
From the order of the Heteroptera, for example, Cimex hemipterus, Cimex lectularius,
Rhodinus prolixus, Triatoma infestans.
They are used in the household insecticides sector alone or in combination with other
suitable active compounds such as phosphoric esters, carbamates, pyrethroids, growth
regulators or active compounds from other known classes of insecticides.
They are used in aerosols, pressure-free spray products, for example pump and atomizer
sprays, automatic fogging systems, foggers, foams, gels, evaporator products with
evaporator tablets made of cellulose or polymer, liquid evaporators, gel and membrane
evaporators, propeller-driven evaporators, energy-free, or passive, evaporation systems,
moth papers, moth bags and moth gels, as granules or dusts, in baits for spreading or in bait
stations.
The active compounds or active compound combinations according to the invention can also
be used as defoliants, desiccants, haulm killers and, in particular, as weed killers. Weeds in
the broadest sense are understood as meaning all plants which grow at locations where they
are undesired. Whether the substances according to the invention act as nonselective or
selective herbicides depends essentially on the application rate.
The active compounds or active compound combinations according to the invention can be
used for example in the following plants:
Dicotyledonous weeds of the genera: Abutilon, Amaranthus, Ambrosia, Anoda, Anthemis,
Aphanes, Atriplex, Bellis, Bidens, Capsella, Carduus, Cassia, Centaurea, Chenopodium,
Cirsium, Convolvulus, Datura, Desmodium, Emex, Erysimum, Euphorbia, Galeopsis,
Galinsoga, Galium, Hibiscus, Ipomoea, Kochia, Lamium, Lepidium, Lindernia, Matricaria,
Mentha, Mercurialis, Mullugo, Myosotis, Papaver, Pharbitis, Plantago, Polygonum,
Portulaca, Ranunculus, Raphanus, Rorippa, Rotala, Rumex, Salsola, Senecio, Sesbania,
Sida, Sinapis, Solanurn, Sonchus, Sphenoclea, Stellaria, Taraxacum, Thlaspi, Trifolium,
Urtica, Veronica, Viola, Xanthium.
Dicotyledonous crops of the genera: Arachis, Beta, Brassica, Cucumis, Cucurbita,
Helianthus, Daucus, Glycine, Gossypium, Ipomoea, Lactuca, Linum, Lycopersicon,
Nicotiana, Phaseolus, Pisum, Solanurn, Vicia.
Monocotyledonous weeds of the genera: Aegilops, Agropyron, Agrostis, Alopecurus, Apera,
Avena, Brachiaria, Bromus, Cenchrus, Commelina, Cynodon, Cyperus, Dactyloctenium,
Digitaria, Echinochloa, Eleocharis, Eleusine, Eragrostis, Eriochloa, Festuca, Fimbristylis,
Heteranthera, Imperata, Ischaemum, Leptochloa, Lolium, Monochoria, Panicum, Paspalum,
Phalaris, Phleum, Poa, Rottboellia, Sagittaria, Scirpus, Setaria, Sorghum.
Monocotvledonous crops of the genera: Allium, Ananas, Asparagus, Avena, Hordeum,
Oryza, Panicum, Saccharum, Secale, Sorghum, Triticale, Triticum, Zea.
However, the use of the active compounds or active compound combinations according to
the invention is hi no way restricted to these genera, but extends in the same manner to other
plants.
Depending on the concentration, the active compounds or active compound combinations
according to the invention are suitable for the nonselective weed control on, for example,
industrial terrains and railway tracks and on paths and locations with and without trees.
Likewise the active compounds according to the invention can be employed for controlling
weeds in perennial crops, for example forests, ornamental tree plantings, orchards,
vineyards, citrus groves, nut orchards, banana plantations, coffee plantations, tea
plantations, rubber plantations, oil palm plantations, cocoa plantations, soft fruit plantings
tobacco stalks; suitable emulsifiers and/or foam-formers are: for example non-ionic and
anionic emulsifiers, such as polyoxyethylene fatly acid esters, polyoxyethylene fatty alcohol
ethers, for example alkylaryl polyglycol ethers, alkylsulphonates, alkyl sulphates, arylsulphonates
and protein hydrolysates; suitable dispersants are: for example lignosulphite waste
liquors and methylcellulose.
Tackifiers such as carboxymethylcellulose and natural and synthetic polymers in the form of
powders, granules or latices, such as gum arabic, polyvinyl alcohol and polyvinyl acetate, and
also natural phospholipids, such as cephalins and lecithins, and synthetic phospholipids, can be
used in the formulations. Other possible additives are mineral and vegetable oils.
It is possible to use colorants such as inorganic pigments, for example iron oxide, titanium
oxide and Prussian Blue, and organic dyestuffs, such as alizarin dyestuffs, azo dyestuffs and
metal phthalocyanine dyestuffs, and trace nutrients such as salts of iron, manganese, boron,
copper, cobalt, molybdenum and zinc.
The formulations generally comprise between 0.1 and 95 per cent by weight of active
compound, preferably between 0.5 and 90%.
The active compounds according to the invention, as such or in their formulations, can also
be used for weed control purposes as a mixture with known herbicides and/or with
substances which improve crop plant tolerance ("safeners"), ready mixes or tank mixes
being possible. Mixtures with herbicide products which contain one or more known
herbicides and a safener are hence also possible.
Herbicides which are suitable for the mixtures are known herbicides, for example
acetochlor, acifluorfen (-sodium), aclonifen, alachlor, alloxydim (-sodium), ametryne, amicarbazone,
amidochlor, amidosulfuron, anilofos, asulam, atrazine, azafenidin, azimsulfuron,
beflubutamid, benazolin (-ethyl), benfuresate, bensulfuron (-methyl), bentazone, benzfendizone,
benzobicyclon, benzofenap, benzoylprop (-ethyl), bialaphos, bifenox, bispyribac
(-sodium), bromobutide, bromofenoxim, bromoxynil, butachlor, butafenacil (-allyl),
butroxydim, butylate, cafenstrole, caloxydim, carbetamide, carfentrazone (-ethyl), chlomethoxyfen,
chloramben, chloridazon, chlorimuron (-ethyl), chlornitrofen, chlorsulfuron,
chlortoluron, cinidon (-ethyl), cinmethylin, cinosulfuron, clefoxydim, clethodim, clodinafop
(-propargyl), clomazone, clomeprop, clopyralid, clopyrasulfuron (-methyl), cloransulam
(-methyl), cumyluron, cyanazine, cybutryne, cycloate, cyclosulfamuron, cycloxydim, cyhalofop
(-butyl), 2,4-D, 2,4-DB, desmedipham, diallate, dicamba, dichlorprop (-P), diclofop
(-methyl), diclosulam, diethatyl (-ethyl), difenzoquat, diflufenican, diflufenzopyr, dimefuron,
dimepiperate, dimethachlor, dimethametryn, dimethenamid, dimexyflam, dinitramine,
diphenamid, diquat, dithiopyr, diuron, dymron, epropodan, EPIC, esprocarb, ethalfluralin,
ethametsulfuron(-methyl), ethofumesate, ethoxyfen, ethoxysulfiiron, etobenzanid, fenoxaprop
(-P-ethyl), fentrazamide, flamprop (-isopropyl, -isopropyl-L, -methyl), flazasulfuron,
florasulam, fluazifop (-P-butyl), fluazolate, flucarbazone (-sodium), flufenacet, flumetsulam,
flumiclorac (-pentyl), flumioxazin, flumipropyn, flumetsulam, fluometuron, fluorochloridone,
fluoroglycofen (-ethyl), flupoxam, flupropacil, flurpyrsulfuron (-methyl,
-sodium), flurenol (-butyl), fluridone, fluroxypyr (-butoxypropyl, -meptyl), flurprimidol,
flurtamone, fluthiacet (-methyl), fiuthiamide, fomesafen, foramsulfuron, glufosinate
(-ammonium), glyphosate (-isopropylammonium), halosafen, haloxyfop (-ethoxyethyl, -Pmethyl),
hexazinone, imazamethabenz (-methyl), imazamethapyr, imazamox, imazapic,
imazapyr, imazaquin, imazethapyr, imazosulfuron, iodosulfuron (-methyl, -sodium), ioxynil,
isopropalin, isoproturon, isouron, isoxaben, isoxachlortole, isoxaflutole, isoxapyrifop, lactofen,
lenacil, linuron, MCPA, mecoprop, mefenacet, mesosulfurone, mesotrione, metamitron,
metazachlor, methabenzthiazuron, metobenzuron, metobromuron, (alpha-) metolachlor,
metosulam, metoxuron, metribuzin, metsulfuron (-methyl), molinate, monolinuron, naproanilide,
napropamide, neburon, nicosulfuron, norflurazon, orbencarb, oryzalin, oxadiargyl,
oxadiazon, oxasulfuron, oxaziclomefone, oxyfluorfen, paraquat, pelargonic acid, pendimethalin,
pendralin, pentoxazone, phenmedipham, picolinafen, pinoxaden, piperophos,
pretilachlor, primisulfuron (-methyl), profluazol, prometryn, propachlor, propanil, propaquizafop,
propisochlor, propoxycarbazone (-sodium), propyzamide, prosulfocarb, prosulfuron,
pyraflufen (-ethyl), pyrazogyl, pyrazolate, pyrazosulfuron (-ethyl), pyrazoxyfen, pyribenzoxim,
pyributicarb, pyridate, pyridatol, pyriftalide, pyriminobac (-methyl), pyrithiobac
(-sodium), quinchlorac, quinmerac, quinoclamine, quizalofop (-P-ethyl, -P-tefuryl), rimsulfuron,
sethoxydim, simazine, simetryn, sulcotrione, sulfentrazone, sulfometuron (-methyl),
sulfosate, sulfosulfuron, tebutam, tebutbiuron, tepraloxydim, terbuthylazine, terbutryn,
thenylchlor, thiafluamide, thiazopyr, thidiazimin, thifensulfuron (-methyl), thiobencarb, tiocarbazil,
tralkoxydim, triallate, triasulfuron, tribenuron (-methyl), triclopyr, tridiphane, trifluralin,
trifloxysulfuron, triflusulfuron (-methyl), tritosulfuron.
A mixture with other known active compounds, such as fungicides, insectides, acaricides,
nematicides, bird repellents, plant nutrients and soil conditioners, is also possible.
The active compounds or. active compound combinations can be applied as such, in the form
of their formulations or the use forms prepared therefrom by further dilution, such as readyto-
use solutions, suspensions, emulsions, powders, pastes and granules. They are applied in
the customary manner, for example by pouring, spraying, atomizing, spreading.
The active compounds or active compound combinations according to the invention can be
applied both before and after plant emergence. They can also be incorporated into the soil
prior to planting.
The application rate of active compound can vary within a substantial range. Essentially, it
depends on the nature of the desired effect. In general, the application rates are between 1 g
and 10 kg of active compound per hectare of soil area, preferably between 5 g and 5 kg per
ha.
The advantageous effect of the compatibility with crop plants of the active compound
combinations according to the invention is particularly pronounced at certain concentration
ratios. However, the weight ratios of the active compounds in the active compound
combinations can be varied within relatively wide ranges. In general, from 0.001 to 1000
parts by weight, preferably from 0.01 to 100 parts by weight, particularly preferably 0.05 to
20 parts by weight, of one of the compounds which improves crop plant compatibility
(antidotes/safeners) mentioned above under (b1) are present per part by weight of active
compound of the formula (I).
The active compound combinations according to the invention are generally applied in the
form of finished formulations. However, the active compounds contained in the active
compound combinations can, as individual formulations, also be mixed during use, i.e. be
applied in the form of tank mixes.
For certain applications, in particular by the post-emergence method, it may furthermore be
advantageous to include, as further additive in the formulations, mineral or vegetable oils
which are tolerated by plants (for example commercial preparation "Rako Binol"), or
ammonium salts, such as, for example, ammonium sulphate or ammonium thiocyanate.
The novel active compound combinations can be used as such, in the form of their
formulations or the use forms prepared therefrom by further dilution, such as ready-to-use
solutions, suspensions, emulsions, powders, pastes and granules. Application is in the
customary manner, for example by watering, spraying, atomizing, dusting or scattering.
The application rates of the active compound combinations according to the invention can
be varied within a certain range; they depend, inter alia, on the weather and on soil factors.
In general, the application rates are between 0.001 and 5 kg per ha, preferably between
0.005 and 2 kg per ha, particularly preferably between 0.01 and 0.5 kg per ha.
The active compound combinations according to the invention can be applied before and
after emergence of the plants, that is to say by the pre-emergence and post-emergence
method.
Depending on their properties, the safeners to be used according to the invention can be
used for pretreating the seed of the crop plant (seed dressing) or can be introduced into the
seed furrows prior to sowing or be used separately prior to the herbicide or together with the
herbicide, before or after emergence of the plants.
Examples of plants which may be mentioned are important crop plants, such as cereals
(wheat, rice), maize, soybeans, potatoes, cotton, oil seed rape, beet, sugarcane and also fruit
plants (with the fruits apples, pears, citrus fruits and grapevines), greater emphasis being
given to maize, soybeans, potatoes, cotton and oil seed rape.
The substances according to the invention have potent microbicidal activity and can be
employed for controlling unwanted microorganisms, such as fungi and bacteria, in crop
protection and in the protection of materials.
Fungicides can be employed in crop protection for controlling Plasmodiophoromycetes,
Oomycetes, Chytridiomycetes, Zygomycetes, Ascomycetes, Basidiomycetes and
Deuteromycetes.
Bactericides can be employed in crop protection for controlling Pseudomonadaceae,
Rhizobiaceae, Enterobacteriaceae, Corynebacteriaceae and Streptomycetaceae.
Some pathogens causing fungal and bacterial diseases which come under the generic names
listed above may be mentioned as examples, but not by way of limitation:
Xanthomonas species, such as, for example, Xanthomonas campestris pv. oryzae;
Pseudomonas species, such as, for example, Pseudomonas syringae pv. lachrymans;
Erwinia species, such as, for example, Erwinia amylovora;
Pythium species, such as, for example, Pythium ultimum;
Phytophthora species, such as, for example, Phytophthora infestans;
Pseudoperonospora species, such as, for example, Pseudoperonospora humuli or
Pseudoperonospora cubensis;
Plasmopara species, such as, for example, Plasmopara viticola;
Brernia species, such as, for example, Bremia lacrucae;
Peronospora species, such as, for example, Peronospora pisi or P. brassicae;
Erysiphe species, such as, for example, Erysiphe graminis;
Sphaerotheca species, such as, for example, Sphaerotheca fuliginea;
Podosphaera species, such as, for example, Podosphaera leucotricha;
Venturia species, such as, for example, Venturia inaequalis;
Pyrenophora species, such as, for example, Pyrenophora teres or P. graminea
(conidia form: Drechslera, syn: Helminthosporium);
Cochliobolus species, such as, for example, Cochliobolus sativus
(conidia form: Drechslera, syn: Hehninthosporium);
Uromyces species, such as, for example, Uromyces appendiculatus;
Puccinia species, such as, for example, Puccinia recondita;
Sclerotinia species, such as, for example, Sclerotinia sclerotiorum;
Tilletia species, such as, for example, Tilletia caries;
Ustilago species, such as, for example, Ustilago nuda or Ustilago avenae;
Pellicularia species, such as, for example, Pellicularia sasakii;
Pyricularia species, such as, for example, Pyricularia oryzae;
Fusarium species, such as, for example, Fusarium culmorum;
Botrytis species, such as, for example, Botrytis cinerea;
Septoria species, such as, for example, Septoria nodorum;
Leptosphaeria species, such as, for example, Leptosphaeria nodorum;
Cercospora species, such as, for example, Cercospora canescens;
Alternaria species, such as, for example, Alternaria brassicae; and
Pseudocercosporella species, such as, for example, Pseudocercosporella herpotrichoides.
The active compounds according to the invention also have very good fortifying action in
plants. Accordingly, they can be used for mobilizing the defences of the plant against attack
by unwanted microorganisms.
hi the present context, plant-fortifying (resistance-inducing) substances are to be understood
as meaning those substances which are capable of stimulating the defence system of plants
such that, when the treated plants are subsequently inoculated with unwanted
microorganisms, they show substantial resistance against these microorganisms.
In the present case, undesirable microorganisms are to be understood as meaning
phytopathogenic fungi, bacteria and viruses. Accordingly, the substances according to the
invention can be used to protect plants for a certain period after the treatment against attack
by the pathogens mentioned. The period for which protection is provided generally extends
over 1 to 10 days, preferably 1 to 7 days, after the treatment of the plants with the active
compounds.
The fact that the active compounds are well tolerated by plants at the concentrations
required for controlling plant diseases permits the treatment of above-ground parts of plants,
of propagation stock and seeds, and of the soil.
The active compounds according to the invention are also suitable for increasing the yield of
crops, hi addition, they show reduced toxicity and are well tolerated by plants.
At certain concentrations and application rates, the active compounds according to the
invention can also be used as herbicides, for influencing plant growth and for controlling
animal pests. If appropriate, they can also be used as intermediates and precursors for the
synthesis of further active compounds.
In the protection of materials, the compounds according to the invention can be employed
for protecting industrial materials against infection with, and destruction by, unwanted
microorganisms.
Industrial materials in the present context are understood as meaning non-living materials
which have been prepared for use in industry. For example, industrial materials which are
intended to be protected by active compounds according to the invention from microbial
change or destruction can be adhesives, sizes, paper and board, textiles, leather, wood,
paints and plastic articles, cooling lubricants and other materials which can be infected with,
or destroyed by, microorganisms. Parts of production plants, for example cooling-water
circuits, which may be impaired by the proliferation of microorganisms may also be
mentioned within the scope of the materials to be protected. Industrial materials which may
be mentioned within the scope of the present invention are preferably adhesives, sizes, paper
and board, leather, wood, paints, cooling lubricants and heat-transfer liquids, particularly
preferably wood.
Microorganisms capable of degrading or changing the industrial materials which may be
mentioned are, for example, bacteria, fungi, yeasts, algae and slime organisms. The active
compounds according to the invention preferably act against fungi, in particular moulds,
wood-discolouring and wood-destroying fungi (Basidiomycetes), and against slime
organisms and algae.
Microorganisms of the following genera maybe mentioned as examples:
Altemaria, such as Alternaria tenuis,
Aspergillus, such as Aspergillus niger,
Chaetomium, such as Chaetomium globosum,
Coniophora, such as Coniophora puetana,
Lentinus, such as Lentinus tigrinus,
Penicillium, such as Penicillium glaucum,
Polyporus, such as Polyporus versicolor,
Aureobasidium, such as Aureobasidium pullulans,
Sclerophoma, such as Sclerophoma pityophila,
Trichoderma, such as Trichoderma viride,
Escherichia, such as Escherichia coli,
Pseudomonas, such as Pseudomonas aeruginosa, and
Staphylococcus, such as Staphylococcus aureus.
Depending on their particular physical and/or chemical properties, the active compounds can
be converted into the customary formulations, such as solutions, emulsions, suspensions,
powders, foams, pastes, granules, aerosols and microencapsulations in polymeric substances
and in coating compositions for seeds, and ULV cool and warm fogging formulations.
These formulations are produced in a known manner, for example by mixing the active
compounds with extenders, that is liquid solvents, liquefied gases under pressure, and/or
solid carriers, optionally with the use of surfactants, that is emulsifiers and/or dispersants,
and/or foam formers. If the extender used is water, it is also possible to employ, for
example, organic solvents as auxiliary solvents. Essentially, suitable liquid solvents are:
aromatics such as xylene, toluene or alkylnaphthalenes, chlorinated aromatics or chlorinated
aliphatic hydrocarbons such as chlorobenzenes, chloroethylenes or methylene chloride,
aliphatic hydrocarbons such as cyclohexane or paraffins, for example petroleum fractions,
alcohols such as butanol or glycol and their ethers and esters, ketones such as acetone,
methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, strongly polar solvents such
as dimethylformamide and dimethyl sulphoxide, or else water. Liquefied gaseous extenders
or carriers are to be understood as meaning liquids which are gaseous at standard
temperature and under atmospheric pressure, for example aerosol propellants such as
halogenated hydrocarbons, or else butane, propane, nitrogen and carbon dioxide. Suitable
solid carriers are: for example ground natural minerals such as kaolins, clays, talc, chalk,
quartz, attapulgite, montmorillonite or diatomaceous earth, and ground synthetic minerals
such as finely divided silica, alumina and silicates. Suitable solid carriers for granules are:
for example crushed and fractionated natural rocks such as calcite, marble, pumice, sepiolite
and dolomite, or else synthetic granules of inorganic and organic meals, and granules of
organic material such as sawdust, coconut shells, maize cobs and tobacco stalks. Suitable
emulsifiers and/or foam formers are: for example nonionic and anionic emulsifiers, such as
polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers, for example
alkylaryl polyglycol ethers, alkylsulphonates, alkyl sulphates, arylsulphonates, or else
protein hydrolysates. Suitable dispersants are: for example lignosulphite waste liquors and
methylcellulose.
Tackifiers such as carboxymethylcellulose and natural and synthetic polymers in the form of
powders, granules or latices, such as gum arabic, polyvinyl alcohol and polyvinyl acetate, or
else natural phospholipids such as cephalins and lecithins and synthetic phospholipids can
be used in the formulations. Other possible additives are mineral and vegetable oils.
It is possible to use colorants such as inorganic pigments, for example iron oxide, titanium
oxide and Prussian Blue, and organic dyestuffs such as alizarin dyestuffs, azo dyestuffs and
metal phthalocyanine dyestuffs, and trace nutrients such as salts of iron, manganese, boron,
copper, cobalt, molybdenum and zinc.
The formulations generally comprise between 0.1 and 95% by weight of active compound,
preferably between 0.5 and 90%.
The active compounds according to the invention can be used as such or in their
formulations, also in a mixture with known fungicides, bactericides, acaricides, nematicides
or insecticides, to broaden, for example, the activity spectrum or to prevent development of
resistance. In many cases, synergistic effects are obtained, i.e. the activity of the mixture is
greater than the activity of the individual components.
Examples of suitable mixing components are the following:
Fungicides:
2-phenylphenol; 8-hydroxyquinoline sulphate; acibenzolar-S-methyl; aldimorph;
amidoflumet; ampropylfos; ampropylfos-potassium; andoprim; anilazine; azaconazole;
azoxystrobin; benalaxyl; benodanil; benomyl; benthiavalicarb-isopropyl; benzamacril;
benzamacril-isobutyl; bilanafos; binapacryl; biphenyl; bitertanol; blasticidin-S;
bromuconazole; bupirimate; buthiobate; butylamine; calcium polysulphide; capsimycin;
captafol; captan; carbendazim; carboxin; carpropamid; carvone; chinomethionat;
chlobenthiazone; chlorfenazole; chloroneb; chlorothalonil; chlozolinate; clozylacon;
cyazofamid; cyflufenamid; cymoxanil; cyproconazole; cyprodinil; cyprofuram; Dagger G;
debacarb; dichlofiuanid; dichlone; dichlorophen; diclocymet; diclomezine; dicloran;
diethofencarb; difenoconazole; diflumetorim; dimethirimol; dimethomorph; dimoxystrobin;
diniconazole; diniconazole-M; dinocap; diphenylamine; dipyrithione; ditalimfos; dithianon;
dodine; drazoxolon; edifenphos; epoxiconazole; ethaboxam; ethirimol; etridiazole;
famoxadone; fenamidone; fenapanil; fenarimol; fenbuconazole; fenruram; fenhexamid;
fenitropan; fenoxanil; fenpiclonil; fenpropidin; fenpropimorph; ferbam; fluazinam;
fiubenzimine; fludioxonil; flumetover; flumorph; fluoromide; fluoxastrobin;
fluquinconazole; flurprimidol; flusilazole; flusulfamide; flutolanil; flutriafol; folpet; fosetyl-
Al; fosetyl-sodium; fuberidazole; furalaxyl; furametpyr; furcarbanil; furmecyclox;
guazatine; hexachlorobenzene; hexaconazole; hymexazole; imazalil; imibenconazole;
iminoctadine triacetate; iminoctadine tris(albesil); iodocarb; ipconazole; iprobenfos;
iprodione; iprovalicarb; irumamycin; isoprothiolane; isovaledione; kasugamycin; kresoximmethyl;
mancozeb; maneb; meferimzone; mepanipyrim; mepronil; metalaxyl; metalaxyl-M;
metconazole; methasulfocarb; methfuroxam; metiram; metominostrobin; metsulfovax;
mildiomycin; myclobutanil; myclozolin; natamycin; nicobifen; nitrothal-isopropyl;
noviflumuron; nuarimol; ofurace; orysastrobin; oxadixyl; oxolinic acid; oxpoconazole;
oxycarboxin; oxyfenthiin; paclobutrazole; pefurazoate; penconazole; pencycuron;
phosdiphen; phthalide; picoxystrobin; piperalin; polyoxins; polyoxorim; probenazole;
prochloraz; procymidone; propamocarb; propanosine-sodium; propiconazole; propineb;
proquinazid; prothioconazole; pyraclostrobin; pyrazophos; pyrifenox; pyrimethanil;
pyroquilon; pyroxyfur; pyrrolenitrine; quinconazole; quinoxyfen; quintozene; simeconazole;
spiroxamine; sulphur; tebuconazole; tecloftalam; tecnazene; tetcyclacis; tetraconazole;
thiabendazole; thicyofen; thifluzamide; thiophanate-methyl; thiram; tioxymid; tolclofosmethyl;
tolylfluanid; triadimefon; triadimenol; triazbutil; triazoxide; tricyclamide;
tricyclazole; tridemorph; trifloxystrobin; triflumizole; triforine; triticonazole; uniconazole;
validamycin A; vinclozolin; zineb; ziram; zoxamide; (2S)-N-[2-[4-[[3-(4-chlorophenyl)-2-
propynyl]oxy]-3-methoxyphenyl]ethyl]-3-rnethyl-2-[(methylsulphonyl)arnino]butanamide;
l-(l-naphthalenyl)-lH-pyrrole-2,5-dione; 2,3,5,6-tetrachloro-4-(methylsulphonyl)pyridine;
2-amino-4-methyl-N-phenyl-5-thiazolecarboxamide; 2-chloro-N-(2,3-dihydro-1,1,3-
trimethyl-lH-inden-4-yl)-3-pyridinecarboxamide; 3,4,5-trichloro-2,6-pyridinedicarbonitrile;
actinovate; cis-l-(4-chlorophenyl)-2-(lH-l,2,4-triazol-l-yl)cycloheptanol; methyl l-(2,3-
dihydro-2,2-dimethyl-lH-inden-l-yl)-lH-imidazole-5-carboxylate; monopotassium
carbonate; N-(6-methoxy-3 -pyridinyl)cyclopropanecarboxamide; N-butyl-8-( 1,1-
dimethylethyl)-l-oxaspiro[4.5]decane-3-amine; sodium tetrathiocarbonate;
and copper salts and preparations, such as Bordeaux mixture; copper hydroxide; copper
naphthenate; copper oxychloride; copper sulphate; cufraneb; cuprous oxide; mancopper;
oxine-copper.
Bactericides:
bronopol, dichlorophen, nitrapyrin, nickel dimethyldithiocarbamate, kasugamycin,
octhilinone, rurancarboxylic acid, oxytetracyclin, probenazole, streptomycin, tecloftalam,
copper sulphate and other copper preparations.
Insecticides/acaricides/nematicides:
abamectin, ABG-9008, acephate, acequinocyl, acetamiprid, acetoprole, acrinathrin, AKD-
1022, AKD-3059, AKD-3088, alanycarb, aldicarb, aldoxycarb, allethrin, allethrin 1Risomers,
alpha-cypermethrin (alphamethrin), amidoflumet, aminocarb, amitraz, avermectin,
AZ-60541, azadirachtin, azamethiphos, azinphos-methyl, azinphos-ethyl, azocyclotin,
Bacillus popilliae, Bacillus sphaericus, Bacillus subtilis, Bacillus thuringiensis, Bacillus
thuringiensis strain EG-2348, Bacillus thuringiensis strain GC-91, Bacillus thuringiensis
-164-
strain NCTC-11821, baculoviruses, Beauveria bassiana, Beauveria tenella, benclothiaz,
bendiocarb, benfuracarb, bensultap, benzoximate, beta-cyfluthrin, beta-cypermethrin,
bifenazate, bifenthrin, binapacryl, bioallethrin, bioallethrin-S-cyclopentyl-isomer,
bioethanomethrin, biopermethrin, bioresmethrin, bistrifluron, BPMC, brofenprox,
bromophos-ethyl, bromopropylate, bromfenvinfos (-methyl), BTG-504, BTG-505,
bufencarb, buprofezin, butathiofos, butocarboxim, butoxycarboxim, butylpyridaben,
cadusafos, camphechlor, carbaryl, carbofuran, carbophenothion, carbosulfan, cartap, CGA-
50439, chinomethionat, chlordane, chlordimeform, chloethocarb, chlorethoxyfos,
chlorfenapyr, chlorfenvinphos, chlorfluazuron, chlormephos, chlorobenzilate, chloropicrin,
chlorproxyfen, chlorpyrifos-methyl, chlorpyrifos (-ethyl), chlovaporthrin, chromafenozide,
cis-cypermethrin, cis-resmethrin, cis-permethrin, clocythrin, cloethocarb, clofentezine,
clothianidin, clothiazoben, codlemone, coumaphos, cyanofenphos, cyanophos, cycloprene,
cycloprothrin, Cydia pomonella, cyfluthrin, cyhalothrin, cyhexatin, cypermethrin,
cyphenothrin (IR-trans-isomer), cyromazine,
DDT, deltamethrin, demeton-S-methyl, demeton-S-methylsulphone, diafenthiuron, dialifos,
diazinon, dichlofenthion, dichlorvos, dicofol, dicrotophos, dicyclanil, diflubenzuron,
dimeflurhrin, dimethoate, dimethylvinphos, dinobuton, dinocap, dinotefuran, diofenolan,
disulfoton, docusat-sodium, dofenapyn, DOWCO-439,
eflusilanate, emamectin, emamectin-benzoate, empenthrin (IR-isomer), endosulfan,
Entomopthora spp., EPN, esfenvalerate, ethiofencarb, ethiprole, ethion, ethoprophos,
etofenprox, etoxazole, etrimfos,
famphur, fenamiphos, fenazaquin, fenbutatin oxide, fenfluthrin, fenitrothion, fenobucarb,
fenothiocarb, fenoxacrim, fenoxycarb, fenpropathrin, fenpyrad, fenpyrithrin, fenpyroximate,
fensulfothion, fenthion, fentrifanil, fenvalerate, fipronil, flonicamid, fluacrypyrim,
fluazuron, flubenzimine, flubrocythrinate, flucycloxuron, flucythrinate, flufenerim,
flufenoxuron, flufenprox, flumethrin, flupyrazofos, flutenzin (flufenzine), fluvalinate,
fonofos, formetanate, fonnothion, fosmethilan, fosthiazate, fubfenprox (fluproxyfen),
furathiocarb,
gamma-cyhalothrin, gamma-HCH, gossyplure, grandlure, granulosis viruses,
halfenprox, halofenozide, HCH, HCN-801, heptenophos, hexaflumuron, hexythiazox,
hydramethylnone, hydroprene,
IKA-2002, imidacloprid, imiprothrin, indoxacarb, iodofenphos, iprobenfos, isazofos,
isofenphos, isoprocarb, isoxathion, ivermectin,
japonilure,
kadethrin, nuclear polyhedrosis viruses, kinoprene,
lambda-cyhalothrin, lindane, lufenuron,
malatbion, mecarbam, mesulfenfos, metaldehyde, metam-sodium, methacrifos,
methamidophos, Metharhizium anisopliae, Metharhizium flavoviride, methidathion,
methiocarb, methomyl, methoprene, methoxychlor, methoxyfenozide, metofluthrin,
metolcarb, metoxadiazone, mevinphos, milbemectin, milbemycin, MKI-245, MON-45700,
monocrotophos, moxidectin, MTI-800,
naled, NC-104, NC-170, NC-184, NC-194, NC-196, niclosamide, nicotine, nitenpyram,
nithiazine, NNI-0001, NNI-0101, NNI-0250, NNI-9768, novaluron, noviflumuron,
OK-5101, OK-5201, OK-9601, OK-9602, OK-9701, OK-9802, omethoate, oxamyl,
oxydemeton-methyl,
Paecilomyces fumosoroseus, parathion-methyl, parathion (-ethyl), permethrin (cis-, trans-),
petroleum, PH-6045, phenothrin (IR-trans isomer), phenthoate, phorate, phosalone,
phosmet, phosphamidon, phosphocarb, phoxim, piperonyl butoxide, pirimicarb, pirimiphosmethyl,
pirimiphos-ethyl, potassium oleate, prallethrin, profenofos, profluthrin, promecarb,
propaphos, propargite, propetamphos, propoxur, prothiofos, prothoate, protrifenbute,
pymetrozine, pyraclofos, pyresmethrin, pyrethrum, pyridaben, pyridalyl, pyridaphenthion,
pyridathion, pyrimidifen, pyriproxyfen,
quinalphos,
resmethrin, RH-5849, ribavirin, RU-12457, RU-15525,
S-421, S-1833, salithion, sebufos, SI-0009, silafluofen, spinosad, spirodiclofen,
spiromesifen, sulfluramid, sulfotep, sulprofos, SZI-121,
tau-fluvalinate, tebufenozide, tebufenpyrad, tebupirimfos, teflubenzuron, tefluthrin,
temephos, temivinphos, terbam, terbufos, tetrachlorvinphos, tetradifon, tetramethrin,
tetramethrin (IR-isomer), tetrasul, theta-cypermethrin, thiacloprid, thiamethoxam,
thiapronil, thiatriphos, thiocyclam hydrogen oxalate, thiodicarb, thiofanox, thiometon,
thiosultap-sodium, thuringiensin, tolfenpyrad, tralocythrin, tralomethrin, transfluthrin,
triarathene, triazamate, triazophos, triazuron, trichlophenidine, trichlorfon, trichoderma
atroviride, triflumuron, trimethacarb,
vamidothion, vaniliprole, verbutin, Verticillium lecanii,
WL-108477, WL-40027,
YI-5201, YI-5301, YI-5302,
XMC, xylylcarb,
ZA-3274, zeta-cypermethrin, zolaprofos, ZXI-8901,
the compound 3-methylphenyl propylcarbamate (tsumacide Z),
the compound 3-(5-chloro-3-pyridinyl)-8-(2,2,2-trifluoroethyl)-8-azabicyclo[3.2.1]octane-3-
carbonitrile (CAS-Reg. No. 185982-80-3) and the corresponding 3-endo-isomer (CAS-Reg.
No. 185984-60-5) (cf. WO-96/37494, WO-98/25923),
and preparations which comprise insecticidally active plant extracts, nematodes, fungi or
viruses.
A mixture with other known active compounds, such as herbicides, or with fertilizers and
growth regulators, is also possible.
In addition, the compounds of the formula (I) according to the invention also have very good
antimycotic activity. They have a very broad antimycotic activity spectrum in particular
against dermatophytes and yeasts, moulds and diphasic fungi (for example against Candida
species, such as Candida albicans, Candida glabrata), and Epidermophyton floccosum,
Aspergillus species, such as Aspergillus niger and Aspergillus fumigatus, Trichophyton
species, such as Trichophyton mentagrophytes,
Microsporon species such as Microsporon cards and audouinii. The list of these fungi by no
means limits the mycotic spectrum covered, but is only for illustration.
The active compounds can be used as such, in the form of their formulations or the use
forms prepared therefrom, such as ready-to-use solutions, suspensions, wettable powders,
pastes, soluble powders, dusts and granules. Application is carried out in a customary
manner, for example by watering, spraying, atomizing, broadcasting, dusting, foaming,
spreading, etc. It is furthermore possible to apply the active compounds by the ultra-lowvolume
method, or to inject the active compound preparation or the active compound itself
into the soil. It is also possible to treat the seeds of the plants.
When using the active compounds according to the invention as fungicides, the application
rates can be varied within a relatively wide range, depending on the kind of application. For
the treatment of parts of plants, the active compound application rates are generally between
0.1 and 10,000 g/ha, preferably between 10 and lOOOg/ha. For seed dressing, the active
compound application rates are generally between 0.001 and 50 g per kilogram of seed,
preferably between 0.01 and 10 g per kilogram of seed. For the treatment of the soil, the
active compound application rates are generally between 0.1 and 10,000 g/ha, preferably
between 1 and 5000 g/ha.
The preparation and the use of the active compounds according to the invention is illustrated
by the examples below.
Preparation Examples
Example I-l-a-1
0 H3Q
At 40-50°C, 3.15 g of the compound of Example II-l in 7 ml of anhydrous dimethylformamide
(DMF) are added to 1.95 g (0.042 mol) of potassium tert-butoxide in 6 ml of anhydrous DMF, and
the mixture is stirred at 60°C for 1 hour.
The reaction mixture is stirred into ice-water and, at 0-10°C, acidified to pH 4 using concentrated
hydrochloric acid. The precipitate is washed with ice-water and dried. This is followed by columnchromatographic
purification on silica gel (dichloromethane:methanol, 20:1).
Yield: 190 mg (6% of theory). M.p.: 265°C.
Analogously to Example (I-l-a-1) and in accordance with the general statements on the preparation, the following compounds of the formula (I-l-a) are
obtained
(Table Removed)
Example I-l-b-1
(Figure Removed)
Under argon, 0.6 g of the compound of Example I-l-a-1 is initially charged in 30 ml of anhydrous
ethyl acetate and 0.15 g of triethylamine (1.5 mmol) = 0.21 ml. The reaction is catalyzed using
10 mg of Steglich base, 0.16 g (0.0015 mol) of isobutyl chloride in 2 ml of anhydrous dichloromethane
is added under reflux. The reaction is monitored by thin-layer chromatography. The
solvent is evaporated and the residue is chromatographed on silica gel using the mobile phase
dichloromethane/ethyl acetate 3:1.
Yield: 0.25 g (34% of theory), m.p. 217°C.
Analogously to Example (I-l-b-1) and in accordance with the general statements on the preparation, the following compounds of the formula (I-l-b) are
obtained
(Table Removed)
Example I-l-c-1
(Figure Removed)
At 10-20°C, 0.14 ml (1 mmol) of triethylamine and 0.1 ml (1 mmol) of ethyl chloroformate in 5 ml
of anhydrous dichloromethane are added to 0.48 g of the compound of Example I-l-a-1 in 10 ml of
anhydrous dichloromethane.
The mixture is stirred at room temperature and the reaction is monitored by thin-layer
chromatography.
The solvent is distilled off and the residue is taken up in dichloromethane, washed twice with 5 ml
of 0.5 N NaOH solution and dried. The solvent is distilled off. The product is then purified by
column chromatography on silica gel (dichloromethanerethyl acetate 3:1).
Yield: 0.3 g (65% of theory), m.p. 240°C.
Analogously to Example (I-l-c-1) and in accordance with the general statements on the preparation, the following compounds of the formula (I-l-c) are
obtained
(Table Removed)
Example 11-16
(Figure Removed)

1.29 g of the compound of Example XXX-1 in 10 ml of dichloromethane are added to 1 ml of
sulphuric acid. The mixture is stirred at 35°C for 2 h. 6 ml of methanol are added. The mixture is
stirred at 60°C for 6 h. The mixture is extracted with dichloromethane, the extract is dried over
magnesium sulphate and the solvent is distilled off. The product is purified by column
chromatography on silica gel (ethyl acetate/n-heptane: 1/4 —»• 1/1).
Yield: 1 g (69% of theory), m.p. 136-137°C.
Example II-l
(Figure Removed)
4ml of triethylamine are added to 3.04 g of methyl l-amino-4-methoxycyclohexanecarboxylate x
HC1 in 40 ml of anhydrous tetrahydrofuran (THF), and the mixture is stirred for 5 minutes. 2.51 g
of 2-methyl-5-[l-(4-chloro)pyrazolyl]phenylacetic acid are then added, and the mixture is stirred at
room temperature for 15 minutes. 2.2 ml of triethylamine are then added, followed immediately by
the dropwise addition of 0.56 ml of phosphorus oxychloride such that the solution boils gently.
The mixture is stirred under reflux for 30 minutes.
The reaction solution is poured into 200 ml of ice-water, made alkaline using 3.5 ml of
triethylamine and extracted with dichloromethane, and the extract is dried. The solvent is then
distilled off and the product is purified by column chromatography on silica gel
(dichloromethane:ethyl acetate 3:1).
Yield: 3.15 g (75% of theory). m.p.: 153°C.
Analogously to Example (II-l) and in accordance with the general statements on the preparation, the following compounds of the formula (II) are obtained
(Table Removed)
Example XXX-1
0.38 g of 2-amino-2-cyclopropylpropionitrile and 0.48 ml of triethylamine are initially charged in
20 ml of tetrahydrofuran. At 0°C, 0.97 g of 4-(4-chloro-pyrazolyl)-2-ethyl-6-methylphenylacetyl
chloride in 20 ml of tetrahydrofuran is added dropwise over a period of 1 h. The mixture is stirred
at room temperature for another 6 h. The reaction solution is filtered off with suction through a frit
and washed, and the solvent is distilled off. The product is purified by column chromatography on
silica gel (ethyl acetate/n-heptane = 1/4 —»1/1).
Yield: 910 mg (62% of theory) m.p. 65-70°C
Example I-2-a-l
1 g of KOtBu is initially charged in 10 ml of DMF and cooled to 0°C, and 2.1 g of the compound
of Example m-1 are dissolved in DMF and added dropwise at 0-10°C. The mixture is stirred at
room temperature for 8 h. The solvent is distilled off and the residue is taken up in water. The
mixture is extracted with ethyl acetate. The aqueous phase is acidified with HC1, the precipitate is
filtered off with suction and the filtrate is dried.
Yield 0.25 g (10% of theory)
!H-NMR (400 MHz, d6-DMSO): 8 = 1.50 (s, 6H, C(CH3)2), 7.5 -8.9 (m, 5H, Ar-H, pyrazole-H)
ppm
Analogously to Example (I-2-a-l) and in accordance with the general statements on the preparation, the following compounds of the formula (I-2-a) are
obtained
(Table Removed)
"iH-NMR (400 MHz, dg-DMSO): 6 in ppm V separation by column chromatography on silica gel using the mobile phase methylene chloride
Example I-2-b-l
(Figure Removed)
0.12 g of the compound of Example I-2-a-l is initially charged in 10 ml of dichloromethane and
0.05 ml of triethylamine, and 0.04 g of isobutyl chloride is added with ice-cooling. The mixture is
stirred at room temperature for 8 h. The mixture is then washed with 10% strength citric acid, and
the phases are separated. The organic phase is dried and the solvent is distilled off.
Yield: 0.04 g (28% of theory), m.p. 150-152°C
JH-NMR (CD3CN): 8= 1.1 (d, 6H), 1.5 (s, 6H), 2.8 (m, 1H), 7.5 - 8.2 (m, 5H) ppm.
Analogously to Example (I-2-b-l) and in accordance with the general statements on the preparation, the following compounds of the formula (I-2-b) are
obtained
(Table Removed)
**H-NMR (400 MHz, dg-DMSO): 6 in ppm 0 separation by column chromatography on silica gel using the mobile phase methylene chloride
(Figure Removed)
sly to Example (III-l) and in accordance with the general statements on the preparation, the following compounds of the formula (III) are obtained
(Table Removed)
Example XXV-1
At room temperature, 2.3 g of oxayl chloride are added dropwise to 4 g of 2-chloro-5-N-(4-
chloropyrazolyl)phenylacetic acid in 100 ml of dichloromethane. The mixture is stirred at room
temperature for 8 h. The mixture is then boiled under reflux until the evolution of gas has ceased.
The solvent is distilled off and the residue is degassed.
Yield: 4.25 g (99% of theory), GC/MS: IvT 285 m/e.
Analogously to Example (I-6-a-l) and in accordance with the general statements on the preparation, the following compound of the formula (I-6-a) is
obtained
(Table Removed)
Analogously to Example (I-6-c-1) and in accordance with the general statements on the preparation, the following compounds of the formula (I-6-c) are
obtained
(Table Removed)
Example VTII-1
3.2 g (22.9 mmol) of potassium carbonate and 8.1 g (57.3 mmol) = 3.6 ml of methyl iodide are
added to 8.6 g (22.9 mmol) of crude product of Example XXXV-1 in 100 ml of anhydrous acetone.
The mixture is stirred under reflux for 16 hours.
The reaction solution is cooled and the precipitate is filtered off with suction and washed with
acetone.
The product is purified by column chromatography on silica gel (dichloromethane:petroleum ether,
2:1 -» 4:1 —» 8:1 —* dichloromethane).
Yield: 3 g (34% of theory).
1H-NMR (400 MHz , dg-DMSO): 5 = 1.30-1.78 (m, 10H, cyclohexyl-H), 2.10 (s, 3H, CH3-aryl),
3.51 (s, 3H, CO2Me), 7.28 (d, 1H, aryl-H), 7.54-7.60 (m, 2H, aryl-H), 7.82, 8.72 (2s, 1H each, 2
pyrazolyl-H) ppm
Analogously to Example (VIII- 1) and in accordance with the general statements on the preparation, the following compound of the formula (VIII) is obtained
(Table Removed)
Example XXXV-1
,
At -15°C, a solution of 5.0 g (18.9 mmol) of methyl 2-methyl-5-[l-(4-
chioropyrazolyl)phenyl]acetate in 10 ml of THF is added dropwise to a solution of 9.44 ml of a
solution (2 molar) of LDA in 30 ml of anhydrous THF, and the mixture is stirred at 0°C for 60
minutes.
At -15°C, a solution of 4.13 g (18.9 mmol) of methyl 3,3-pentamethylenesuccinyl chloride in
10 ml of anhydrous THF and simultaneously 14.2 ml of LDA solution (2.0 molar; 1.5 eq) are then
added dropwise. The mixture is stirred at room temperature for two hours and then poured into
150 ml of ice-cold 10% strength ammonium chloride solution.
The intermediate is extracted with MTB ether and the solvents are distilled off. The residue is
boiled under reflux with 10 g of KOH and 100 ml of water for 3 hours.
The reaction solution is cooled, acidified with concentrated HC1 and extracted with 200 ml of
CH2C12, the extract is dried and the solvent is distilled off.
Yield: 8.6 g (66.8% of theory).
Analogously to Example (XXXV-1) and in accordance with the general statements on the preparation, the following compound of the formula (XXXV) is
obtained
(Table Removed)
* Was converted directly, as crude product, into the compound of the formula (VIII-2)
Example I-7-a-l
Cl
0.80 g (2.2 mmol) of the compound of Example K-l in 2 ml of DMF is added to 0.49 g (4.4 mmol,
2.0 eq) of potassium tert-butoxide in 5 ml of DMF.
The mixture is stirred at 50°C for 3 hours. 20 ml of ice-water are added, cooled 1 N HCI solution is
added to make a volume of 250 ml and the mixture is extracted with dichloromethane. The organic
phase is dried and concentrated.
The residue is purified by column chromatography on silica gel (petroleum etherethyl acetate 2:1).
Yield: 0.15 g (21% of theory). m.p.: 172°C
Analogously to Example (I-7-a-l) and in accordance with the general statements on the preparation, the following compound of the formula (I-7-a) is
obtained
(Table Removed)
1.58 g of potassium carbonate and 4.07 g (2.5 eq) = 1.79 ml of methyl iodide are added to 4.0 g of
the crude product of Example XXXEX-1 in 50 ml of anhydrous acetone. The mixture is stirred
under reflux for 16 hours. The reaction solution is cooled and the precipitate is filtered off with
suction and washed with acetone.
The product is purified by column chromatography on silica gel using a gradient (methylene
chloride:ethyl acetate 50:1 —> 5:1).
Yield: 0.8 g (15% of theory).
'H-NMR (400 MHz, dg-DMSO): 8 = 1.03 (s, 6H, CH3), 2.18 (s, 3H, CH3-aryl), 3.57 (s, 3H,
C02Me), 7.30 (d, 1H, aryl-H), 7.57-7.61 (m, 2H, aryl-H), 7.83, 8.72 (2s, 1H each, 2 pyrazolyl-H)
ppm
Analogously to Example (IX-1) and in accordance with the general statements on the preparation, the following compound of the formula (IX) is obtained
(Table Removed)
*1H-NMR (86-400 MHz DMSO): 8 = 1.05-1.50 (m, 8H, cyclopentyl-H), 2.13 (s, 3H, CH3-aryl),
3.52 (s, 3H, CO2Me), 7.28 (d, 1H, aryl-H), 7.82, 8.70 (2s, 1H each, 2 pyrazolyl-H) ppm
Example XXXIX-1
A solution of 3.0 g (11.3 mmol; 1 eq) of methyl 2-methyl-5-[l-(4-chloropyrazolyl)phenyl]acetate
in 5 ml of anhydrous THF, is, at -15°C, added dropwise to a solution of 5.7 ml of LDA solution
(2 molar; 1.0 eq) in 20 ml of anhydrous THF, and the mixture is stirred at 0°C for 60 minutes.
At -15°C, a solution of 1.61 g (11.3 mmol; 1.0 eq) of 3,3-dimethylglutaric anhydride in 10 ml of
anhydrous THF and simultaneously 8.52 ml of LDA solution (2.0 molar; 1.5 eq) are then added
dropwise. The mixture is stirred at room temperature for 2 hours and then poured into 150 ml of
ice-cold 10% strength ammonium chloride solution. The mixture is acidified with concentrated
HC1.
The intermediate is extracted with MTBE and the solvents are distilled off. The residue is boiled
under reflux with 7 g of KOH and 70 ml of water for 4 hours.
The reaction solution is cooled, acidified with concentrated HC1 and extracted with 200 ml of
MTBE, and the extract is dried and the solvent is distilled off.
Yield: 4 g.
Analogously to Example (XXXIX-1) and in accordance with the general statements on the preparation, the following compound of the formula (XXXIX) is
obtained
(Table Removed)
* The compound was used as crude product for preparing Ex. No. IX-2
Example I-8-a-l
0.85 g of potassium tert-butoxide is initially charged in 36 ml of N,N-dimethylacetamide, 1.6 g of
the compound of Example (XII-1) in N,N-dimethylacetamide are slowly added dropwise at 60°C
and the mixture is stirred for 1 hour. After cooling, the solution is added dropwise to ice-cooled
hydrochloric acid, and the precipitate is filtered off with suction.
Yield: 1.1 g (81% of theory). m.p. 258°C
Analogously to Example (I-8-a-l) and in accordance with the general statements on the preparation, the following compound of the formula (I-8-a) is
obtained
(Table Removed)
Example I-8-b-7
0.2 g of the compound of Example I-8-a-l is initially charged in 30 ml of dichloromethane, 0.067 g
of triethylamine is added, followed by 0.054 g of 2-methylpropionyl chloride, and the mixture is
stirred for 3 h.
The mixture is diluted with water and extracted. The organic phase is dried and the solvent is
distilled off. n-Heptane and a little dichloromethane are added to the residue. The product
crystallizes out and is filtered off with suction.
Yield: 0.19 g (81% of theory), rap.: 161.4°C
Analogously to Example (I-8-b-l) and in accordance with the general statements on the preparation, the following compounds of the formula (I-8-b) are
obtained
(Table Removed)
Example I-8-c-l
0.25 g of the compound of Example (I-8-a-l) is initially charged in 36 ml of dichloromethane,
0.12 ml of triethylamine is added, 0.06 ml of ethyl chloroformate, dissolved in dichloromethane, is
added dropwise at room temperature and the mixture is stirred for 1 hour. The mixture is then
diluted with water and extracted. The organic phase is dried and the solvent is distilled off. n-
Heptane and a little dichloromethane are added to the residue. The product crystallizes out and is
filtered off with suction.
Yield: 0.2 g (71% of theory). m.p. 172°C
Analogously to Example (I-8-b-l) and in accordance with the general statements on the preparation, the following compound of the formula (I-8-c-l) is obtained
(Table Removed)
Example (XII-ll
4-([4-Chloropyrazolyl)-2-ethyl-6-methylphenylacetic acid is initially charged in 35ml of
dichloromethane, and 1.28 g of oxalyl chloride is added. The mixture is stirred under reflux, and
once the evolution of gas ceases, 1 ml of dimethylformamide is added. The mixture is stirred
further under reflux and then cooled under an atmosphere of protective gas. The solvent is distilled
off. The residue is taken up in dichloromethane and added dropwise to a solution of 1.2 g of 1-
ethoxycarbonylhexahydropyridazine in 35 ml of dichloromethane and 1.6 ml of triethylamine. The
mixture is stirred at room temperature for 3 h and then extracted with water and dichloromethane.
The organic phase is separated off and dried, and the solvent is distilled off.
Yield: 2 g (63% of theory).
-NMR-data (300 MHz, CDC13): 8=2.6 (q, 2H, Ar-CH2CH3), 4.3 (q, 2H, O-CH2CH3), 7.3, 7.35
(2s, 2H, ArH), 7.6, 7.9 (2s, 2H, Pyr H) ppm
Analogously to Example (XII- 1) and in accordance with the general statements on the preparation, the following compound of the formula (XII) is obtained
(Table Removed)
Examples according to process O
Example XXXII-1
Methyl (4-N-[4-chloropyrazolyl]-2,6-dimethyl)phenylacetate
Under an atmosphere of argon, 16.6 g (162mmol) of 4-chloropyrazole, 10.3 g (54mmol) of
copper(I) iodide and 56 g (405 mmol) of potassium carbonate (dry) are initially charged in 350 ml
of absolute DMF, and the mixture is stirred for 5 minutes. 34.7 g (135 mmol) of methyl (4-bromo-
2,6-dimethyl)phenylacetate are then slowly added dropwise. The reaction mixture is stirred at
105°C for four days. During this time, the progress of the reaction is monitored by GC, and in each
case after 24 hours (three times in total) 2.6 g (13.5 mmol) of copper(I) iodide and 4.15g
(40.5 mmol) of 4-chloropyrazole are added. The reaction mixture is allowed to cool and the
solvent is then removed under reduced pressure and the residue is filtered through a short frit with
silica gel and then purified chromatographically.
Yield: 17.2 g (46%).
iH-NMR {400 MHz, CDC13}: 2.38 (s, 6H, CH3); 3.70 (s, 3H, OCH3); 3.71 (s, 2H, CH2); 7.31 (s,
2H, Ph-H); 7.61 (s, 1H, pyrazolyl-H); 7.88 (s, 1H, pyrazolyl-H).
Analogously to Example (XXXII-1) and in accordance with the general statements on the
preparation, the following compounds of the formula (XXXII) are obtained.
Example XXXII-2
Methyl (2-ethyl-4-N-[4-raethoxypyrazoIyI]-6-methyl)phenylacetate
OCH3
!H-NMR {400MHz, DMSO-dg}: 1.15 (t, 3jffij= 7Hz, 3H, CH3); 2.28 (s, 3H, CH3); 2.64 (q,
3JHH= 7 Hz, 2H, CH2); 3.62 (s, 3H, OCH3); 3.73 (s, 2H, CH2); 3.76 (s, 3H, OCH3); 7.46 (m, 2H,
Ph-H); 7.50 (s, IH, pyrazolyl-H); 8.24 (s, IH, pyrazolyl-H).
MS/CI: 289 (M+l).
Example XXXII-3
Methyl (2,6-dimethyl-4-N-[4-methoxypyrazolyl])phenylacetate
OCH3
{400 MHz, DMSO-dg}: 2.30 (s, 6H, CH3); 3.62 (s, 3H, OCH3); 3.71 (s, 2H, CH2); 3.76
(s, 3H, OCH3); 7.46 (s, 2H, Ph-H); 7.50 (s, IH, pyrazolyl-H); 8.22 (s, IH, pyrazolyl-H).
MS/CI: 275 (M+l).
Example XXXII-4
Methyl (2,6-diethyl-4-N-[4-chloropyrazolyl])phenylacetate
OCH3
{400MHz, DMSO-dg}: 1.18 (t, 3JHH= 7Hz> 6H> CH3); 2-61 fa. 3jHH= 7 *&> 4H>
CH2); 3.57 (s, 3H, OCH3); 3.79 (s, 2H, CH2); 7.50 (m, 2H, Ph-H); 7.84 (s, IH, pyrazolyl-H); 8.79
(s, IH, pyrazolyl-H).
MS/CI: 307(M+1).
Example XXXII-5
Methyl (2,6-dimethyl-4-N-[4-cyanopyrazoIyl])phenylacetate
!H-NMR {400 MHz, DMSO-d6}: 2.31 (s, 6H, CH3); 3.62 (s, 2H, CH2); 3.74 (s, 3H, OCH3); 7.52
(s, 2H, Ph-H); 8.05 (s, IH, pyrazolyl-H); 8.82 (s, IH, pyrazolyl-H).
MS/CI: 270 (M+l).
Examplc XXXII-6
Methyl (2,6-dimethyl-4-N-[3-chlorotriazolyl])phenylacetate
(Figure Removed)
(400 MHz, DMSO-d6}: 2.26 (s, 6H, CH3; 3.55 (s, 2H, CH2); 3.79 (s, 3H, OCH3); 7.44
(s, 2H, Ph-H); 9.22 (s, IH, triazolyl-H).
MS/CI: 280 (M+l).
Example XXXII-7
Methyl [(3-N-[4-chloropyrazolyl])-6-methyl]phenylacetate
OCH
iH-NMR {400MHz, CDC13}: 2.32 (s, 3H, CH3); 3.67 (s, 2H, CH2); 3.70 (s, 3H, OCH3); 7.22
(m, IH, Ph-H); 7.40 (m, IH, Ph-H); 7.50 (m, IH, Ph-H); 7.60 (s, IH, pyrazolyl-H); 7.95 (s, IH,
pyrazolyl-H).
GC-MS/CI: 265 (M+l).
Example XXXII-8
Methyl (2-chLoro-6-ethyl-4-[4-chloropyrazoIyl])phenylacetate
CO2CH3
iH-NMR {400 MHz, DMSO-d6}: 1.18 (t, 3JHH = 7 Hz, 3H, CH3); 2.72 (q, 3JHH = 7 Hz, 2H,
CH2); 3.64 (s, 3H, OCH3); 3.89 (s, 2H, CH2); 7.69 (m, IH, Ph-H); 7.81 (m, IH, Ph-H); 7.89 (s,
IH, pyrazolyl-H); 8.88 (s, IH, pyrazolyl-H).
MS/CI:313(M+1).
Example XXXH-9
Methyl (2-chloro-6-ethyl-4-[4-chloropyrazolyl])phenylacetate
(Figure Removed)
1H-NMR{400MHz, DMSO-d6}: 1.18 (t, 3;^, = 7 Hz, 3H, CH3); 2.72 (q, 3JnH = 7 Hz, 2H,
CH2); 3.64 (s, 3H, OCH3): 3.89 (s, 2H, CH2); 7.69 (m, IH, Ph-H); 7.81 (m, IH, Ph-H); 7.89 (s,
IH, pyrazolyl-H); 8.88 (s, IH, pyrazolyl-H).
MS/CI: 313 (M+l).
Example XXXII-10
Methyl (2-ethyl-6-methyI-4-[4-chloropyrazolyl])phenylacetate
(Figure Removed)
iH-NMR {400 MHz, DMSO-dg}: 1.18 (t, 3JnH = 7 Hz, 3H, CH3): 2.59 (q, 3JHH = 7 Hz, 2H,
CH2); 3.59 (s, 3H, OCH3); 3.72 (s, 2H, CH2); 7.51 (m, 2H, Ph-H); 7.89 (s, 1H, pyrazolyl-H); 8.78
(s, 1H, pyrazolyl-H).
MS/CI: 313 (M+l).
Example XXVIII-1
(4-N-[4-Chloropyrazolyl]-2,6-dimethyl)phenylaceticacid
17.2g (61.7mmol) of (4-[4-chloropyrazolyl]-2,6-dimethyl)phenylacetic acid are dissolved in
160 ml of methanol and then, with 4.2 g (74 mmol) of potassium hydroxide in 160 ml of water,
heated at 80°C for 12 hours. The methanol is removed using a rotary evaporator, the residue is
adjusted to pH 3 and the precipitated product is filtered off and dried.
Yield: 16.2 g (99%)
{400MHz, CDC13}: 2.38 (s, 6H, CH3); 3.73 (s, 2H, CH2); 7.32 (s, 2H, Ph-H); 7.61 (s,
1H, pyrazolyl-H); 7.86 (s, 1H, pyrazolyl-H); acid-OH not detected.
Analogously to Example (XXVIII-1), the following compounds of the formula (XXVIII) are
obtained.
Example XXVIII-2
(2-Ethyl-4-N-[4-methoxypyrazolyl]-6-methyl)phenylaceticacid
*H-NMR {400MHz, DMSO-d6}: l.l? (t, 3JHH= 7 Hz, 3H, CH3); 2.30 (s, 3H, CH3); 2.65 (q,
3JHH= 7 Hz, 2H, CH2); 3.63 (s, 2H, CH2); 3.77 (s, 3H, OCH3); 7.45 (m, 2H, Ph-H); 7.50 (s, IH,
pyrazolyl-H); 8.23 (s, IH, pyrazolyl-H); 12.5 (s, IH, OH).
MS/CI: 275 (M+l).
Example XXVHI-3
(2,6-Dimethyl-4-N-[4-methoxypyrazoIyl])phenylaceticacid
(Figure Removed)
!H-NMR {400 MHz, DMSO-dg}: 2.30 (s, 6H, CH3); 3.61 (s, 2H, CH2); 3.82 (s, 3H, OCH3); 7.44
(s, 2H, Ph-H); 7.50 (s, IH, pyrazolyl-H); 8.21 (s, IH, pyrazolyl-H); 12.4 (s, IH, OH).
Example XXVIII-4
(2,6-Diethyl-4-N-[4-chIoropyrazolylJ)phenylaceticacid
*H-NMR {400MHz, DMSO-d^}: 1.18 (t, 3JHH= 8 Hz, 6H, CH3); 2.63 (q, 3JHH= 8 Hz, 4H,
CH2); 3.67 (s, 2H, CH2); 7.50 (s, 2H, Ph-H); 7.85 (s, IH, pyrazolyl-H); 8.79 (s, IH, pyrazolyl-H);
12.5 (s, IH, OH).
MS/CI: 293 (M+l).
Example XXVIII-5
(2,6-Dimethyl-4-N-[4-carboxylatopyrazolyl])phenylaceticacid
(Figure Removed)
iH-NMR {400 MHz, DMSO-d6}: 2.32 (s, 6H, CH3); 3.64 (s, 2H, CH2); 7.52 (s, 2H, Ph-H); 8.09
(s, IH, pyrazolyl-H); 8.87 (s, IH, pyrazolyl-H); 12.3 (s, 2H, OH).
MS/CI: 275 (M+l).
Example XXVIII-6
(2,6-Dimethyl-4-N-[3-chlorotriazolyI])phenylaceticacid
(Figure Removed)
!H-NMR {400 MHz, DMSO-d6}: 2.26 (s, 6H, CH3); 3.56 (s, 2H, CH2); 7.44 (s, 2H, Ph-H); 9.22
(s, IH, triazolyl-H); 12.2 (s, IH, OH).
MS/CI: 266 (M+l).
Example XXVIII-7
(3-N-[4-ChIoropyrazolyl]-6-methyl)phenylacetic acid
(Figure Removed)
iH-NMR {400 MHz, CDC13}: 2.34 (s, 3H, CH3); 3.71 (s, 2H, CH2); 7.26 (m, IH, Ph-H); 7.40 (m,
IH, Ph-H); 7.52 (m, IH, Ph-H); 7.62 (s, IH, pyrazolyl-H); 7.85 (s, IH, pyrazolyl-H); acid-OH not
detected.
Example XXVIII-8
(2-Chloro-6-ethyl-4-[4-chloropyrazolyl])phenylacetic acid
(Figure Removed)
{400 MHz, DMSO-de): 1.17 (t, ^HH = 7 Hz, 3H, CH3); 2.71 (q, 3JHH = 7 Hz, 2H,
CH2); 3.79 (s, 2H, CH2); 7.69 (m, IH, Ph-H); 7.79 (m, IH, Ph-H); 7.91 (s, IH, pyrazolyl-H); 8.88
(s, IH, pyrazolyl-H); 12.6 (s, IH, OH).
MS/CI: 299 (M+l).
Exatnple XXVIII-9
(2-ChIoro-6-ethyl-4-[4-chloropyrazolyl])phenylaceticacid
(400MHz, DMSO-dg}: 1.17 (t, 3JHH = 7 Hz, 3H, CH3); 2.71 (q, 3JHH= 7 Hz, 2H,
CH2); 3.79 (s, 2H, CH2); 7.69 (m, IH, Ph-H); 7.79 (m, IH, Ph-H); 7.91 (s, IH, pyrazolyl-H); 8.88
(s, IH, pyrazolyl-H); 12.6 (s, IH, OH).
MS/CI: 299 (M+l).
Example XXVIII-10
(2-Ethyl-6-methyl-4-[4-chloropyrazolyl] )phenylacetic acid
iH-NMR (400 MHz, DMSO-dg}: 1.19 (t, 3JHH = 7 Hz, 3H, CH3); 2.60 (q, 3JnH = 7 Hz, 2H,
CH2); 3.81 (s, 2H, CH2); 7.52 (m, 2H, Ph-H); 7.83 (s, IH, pyrazolyl-H); 8.62 (s, IH, pyrazolyl-H);
OH not detected.
MS/CI: 279 (M+l).
Use examples
Example A
Meloidogyne test
Solvent: 7 parts by weight of dimethylformamide
Emulsifier: 2 parts by weight of alkylaryl polyglycol ether
To produce a suitable preparation of active compound, 1 part by weight of active compound is
mixed with the stated amounts of solvent and emulsifier, and the concentrate is diluted with water
to the desired concentration.
Containers are filled with sand, solution of active compound, Meloidogyne incognita egg/larvae
suspension and lettuce seeds. The lettuce seeds germinate and the plants develop. On the roots,
galls are formed.
After the desired period of time, the nematicidal action is determined in % by gall formation.
100% means that no galls are formed; 0% means that the number of galls in the treated plants
corresponds to that of the untreated control.
In this test, for example, the following compounds of the Preparation Examples show good
activity:
Table A
Plant-damaging nematodes
M eloidogyne test
Active compounds Concentration of active Efficacy
compound in ppm ino/oafterl4d
Ex. I-l-a-2 20 100
Ex.I-6-a-2 20 100
Example B
Myzus test (spray treatment)
Solvents: 78 parts by weight of acetone
1.5 parts by weight of dimethylformamide
Emulsifier: 0.5 part by weight of alkylaryl polyglycol ether
To produce a suitable preparation of active compound, 1 part by weight of active compound is
mixed with the stated amounts of solvent and emulsifier, and the concentrate is diluted with
emulsifier-containing water to the desired concentration.
Discs of Chinese cabbage (Brassica pekinensis) infested by the green peach aphid (Myzus
persicae) are sprayed with a preparation of active compound of the desired concentration.
After the desired period of time, the kill in % is determined. 100% means that all aphids have been
killed; 0% means that none of the aphids have been killed.
hi this test, for example, the following compound of the Preparation Examples shows good
activity:
Table B
Plant-damaging insects
Myzus test
Active compounds Concentration of active Kill rate
compound in g/ha in % after 4 Ex. I-l-a-3 100 80
Example C
Phaedon larvae test
Solvent: 7 parts by weight of dimethylformamide
Emulsifier: 2 parts by weight of alkylaryl polyglycol ether
To produce a suitable preparation of active compound, 1 part by weight of active compound is
mixed with the stated amounts of solvent and emulsifier, and the concentrate is diluted with
emulsifier-containing water to the desired concentration.
Cabbage leaves (Brassica oleracea) are treated by being dipped into the preparation of active
compound of the desired concentration and are populated with larvae of the mustard beetle
(Phaedon cochleariae) while the leaves are still moist.
After the desired period of time, the kill in % is determined. 100% means that all beetle larvae
have been killed; 0% means that none of the beetle larvae have been killed.
In this test, for example, the following compounds of the Preparation Examples show good
activity:
Table C
Plant-damaging insects
Phaedon larvae test
Active compounds Concentration of active Kill rate
compound in ppm in % after 7"
Ex. I-6-a-l 500 90
Ex. I-7-a-l 500 100
Ex. I-7-a-2 500 100
ExampleD
Spodoptera frugiperda test
Solvent: 7 parts by weight of dimethylformamide
Emulsifier: 2 parts by weight of alkylaryl polyglycol ether
To produce a suitable preparation of active compound, 1 part by weight of active compound is
mixed with the stated amounts of solvent and emulsifier, and the concentrate is diluted with
emulsifier-containing water to the desired concentration.
Cabbage leaves (Brassica oleracea) are treated by being dipped into the preparation of active
compound of the desired concentration and are populated with caterpillars of the army worm
(Spodoptera frugiperda) while the leaves are still moist.
After the desired period of time, the kill in % is determined. 100% means that all caterpillars have
been killed; 0% means that none of the caterpillars have been killed.
In this test, for example, the following compound of the Preparation Examples shows good
activity:
Table D
Plant-damaging insects
Spodoptera frugiperda test
Active compounds Concentration of active Kill rate
compound in ppm in % after 7
Ex. I-l-a-1 100 85
Example E
Tetranychus test (OP-resistant/spray treatment)
Solvents: 78 parts by weight of acetone
1.5 parts by weight of dimethylformamide
Emulsifier: 0.5 part by weight of alkylaryl polyglycol ether
To produce a suitable preparation of active compound, 1 part by weight of active compound is
mixed with the stated amounts of solvent and emulsifier, and the concentrate is diluted with
emulsifier-containing water to the desired concentration.
Discs of bean leaves (Phaseolus vulgaris) infested by all stages of the greenhouse red spider mite
(Tetranychus urticae) are sprayed with a preparation of active compound of the desired
concentration.
After the desired period of time, the effect in % is determined. 100% means that all spider mites
have been killed; 0% means that none of the spider mites have been killed.
In this test, for example, the following compound of the Preparation Examples shows good
activity:
Table E
Plant-damaging mites
Tetranychus test (OP-resistant/spray treatment)
Active compounds Concentration of active Kill rate
compound in ppm in % after 4"
Ex. I-l-a-2 20 90
Example F
Sphaerotheca test (cucumber)/protective
Solvents: 24.5 parts by weight of acetone
24.5 parts by weight of dimethylacetamide
Emulsifier: 1 part by weight of alkylaryl polyglycol ether
To produce a suitable preparation of active compound, 1 part by weight of active compound is
mixed with the stated amounts of solvent and emulsifier, and the concentrate is diluted with water
to the desired concentration.
To test for protective activity, the young plants are sprayed with the preparation of active
compound at the stated application rate. After the spray coating has dried on, the plants are
inoculated with an aqueous spore suspension of Sphaerotheca fuliginea. The plants are then
placed in a greenhouse at about 23°C and a relative atmospheric humidity of about 70%.
Evaluation is carried out 7 days after the inoculation. 0% means an efficacy which corresponds to
that of the control, whereas an efficacy of 100% means that no infection is observed.
Table F
Sphaerotheca test (cucumber)/protective
Active compound
Ex. I-6-a-2
Application rate of
active compound in
g/ha
100
Efficacy in %
Example G
In vitro test for the EDs0 determination in microorganisms
A methanolic solution of the active compound to be tested, mixed with Emulsifier PS 16, is
pipetted into the wells of microtitre plates. After the solvent has evaporated, 200ul of
potato/dextrose medium are added to each well.
Beforehand, a suitable concentration of spores or mycelium of the fungus to be tested was added to
the medium.
The resulting concentrations of the active compound are 0.1, 1, 10 and lOOppm. The resulting
concentration of the emulsifier is 300 ppm.
The plates are then incubated on a shaker at a temperature of 22°C for 3-5 days, until sufficient
growth can be observed in the untreated control.
Evaluation is carried out photometrically at a wavelength of 620 nm. The dose of active compound
which causes 50% inhibition of fungal growth compared to the untreated control (ED50) is
calculated from the data measured at different concentrations.
Table G
In vitro test for the ED50 determination in microorganisms
Active compound Microorganism ED50 value
Ex. I-6-a-2 Botrytis cinerea Ex. I-6-c-l Botrytis cinerea Example H
Post-emergence test
Solvent: 5 parts by weight of acetone
Emulsifier: 1 part by weight of alkylaryl polyglycol ether
To produce a suitable preparation of active compound, 1 part by weight of active compound is
mixed with the stated amount of solvent, the stated amount of emulsifier is added and the
concentrate is diluted with water to the desired concentration.
Test plants of a height of 5-15 cm are sprayed with the preparation of active compound such that
the particular amounts of active compound desired are applied per unit area. The concentration of
the spray liquor is chosen such that the particular amounts of active compound desired are applied
in 10001 of water/ha.
After three weeks, the degree of damage to the plants is rated in % damage in comparison to the
development of the untreated control.
The figures denote:
0% = no effect (like untreated control)
100% = total destruction
Example I
Pre-emergence test
Solvent: 5 parts by weight of acetone
Emulsifier: 1 part by weight of alkylaryl polyglycol ether
To produce a suitable preparation of active compound, 1 part by weight of active compound is
mixed with the stated amount of solvent, the stated amount of emulsifier is added and the
concentrate is diluted with water to the desired concentration.
Seeds of the test plants are sown in normal soil. After about 24 hours, the soil is sprayed with the
preparation of active compound such that the particular amounts of active compound desired are
applied per unit area. The concentration of the spray liquor is chosen such that the particular
amounts of active compound desired are applied in 10001 of water/ha.
After three weeks, the degree of damage to the plants is rated in % damage in comparison to the
development of the untreated control.
The figures denote:
0% = no effect (like untreated control)
100% = total destruction
Pre-emergence Greenhouse gofa.i./ha Alopecurus A vena fatua Echinochloa Setaria Amaranthus Sinapis
Ex. I-l-a-2 250 100 100 100 100 100 80~
(Figure Removed)
J. Herbicidal pre-emergence action
Seeds of monocotyledonous and dicotyledonous weed and crop plants are placed into sandy
loam in wood fibre pots and covered with soil. The test compounds, formulated in the form
of wettable powders (WP) or emulsifiable concentrates (EC) are then, in various dosages as
aqueous suspension or emulsion with a water application rate of 600 1/ha (converted), with
0.2% of wetting agent added, applied to the surface of the covering soil.
After the treatment, the pots are placed in a greenhouse and kept under good growth
conditions for the test plants. The visual assessment of the emergence damage on the test
plants is carried out after a trial period of 3 weeks by comparison with untreated controls
(herbicidal effect in percent (%): 100% effect = the plants have died, 0% effect = like
controlled plants).
-249-
K. Herbicidal post-emergence action
Seeds of monocotyledonous and dicotyledonous weed and crop plants are placed into sandy
loam in wood fibre pots, covered with soil and cultivated in a greenhouse under good
growth conditions. 2-3 weeks after sowing, the test plants are treated at the one-leaf stage.
The test compounds, formulated as wettable powders (WP) or emulsifiable concentrates
(EC), are, in various dosages with a water application rate of 600 1/ha (converted), with
0.2% of wetting agent added, sprayed onto the green parts of the plants. After the test plants
were kept in a greenhouse under optimum growth conditions for about 3 weeks, the effect of
the preparations is rated visually in comparison to untreated controls (herbicidal effect in
percent (%): 100% effect = the plants have died, 0% effect = like controlled plants).
Post-emergence Greenhouse gofa.i./ha Sugar beet Echinochloa Setaria Sorghum
Ex. I-l-a-1 (EC) 320 0 100 100 90
(Figure Removed)
Test description for profiling tests
L. Herbicidal post-emergence action
Seeds of monocotyledonous and dicotyledonous weed and crop plants are placed into sandy
loam in wood fibre pots or in plastic pots, covered with soil and cultivated in a greenhouse
and during the vegetation period also outdoors, outside the greenhouse, under good growth
conditions. 2-3 weeks after sowing, the test plants are treated in the one- to three-leaf stage.
The test compounds, formulated as wettable powders (WP) or liquid (EC), are, at various
dosages with a water application rate of 300 1/ha (converted), with added wetting agent (0.2
to 0.3%), sprayed onto the plants and the surface of the soil. 3 to 4 weeks after the treatment
of the test plants, the effect of the preparations is rated visually in comparison to untreated
controls (herbicidal effect in percent (%): 100% effect = the plants have died, 0% effect =
like controlled plants).
Use of safeners
Prior to the application of the test substances, the crop plants are sprayed with the safener
using a certain application rate per hectare (usually 1 day before the application of the test
substances).
By comparison with the effect of test substances on crop plants treated with and without
safener, it is possible to assess the effect of the safener substance.
Container trials with cereals in the greenhouse
Table
(Table Removed)
mefenpyr 1 day before the application of herbicide
Example L
Critical concentration test/soil insects-treatment of transgenic plants
Test insect: Diabrotica balteata - Larvae in soil
Solvent: 7 parts by weight of acetone
Emulsifier: 1 part by weight of alkylaryl polyglycol ether
To produce a suitable preparation of active compound, 1 part by weight of active compound
is mixed with the stated amount of solvent, the stated amount of emulsifier is added and the
concentrate is diluted with water to the desired concentration.
The preparation of active compound is poured onto the soil. Here, the concentration of
active compound in the preparation is virtually immaterial, only the amount by weight of
active compound per volume unit of soil, which is stated in ppm (mg/1), matters. The soil is
filled in to 0.25 1 pots, and these are allowed to stand at 20°C.
Immediately after the preparation, 5 pregerminated maize corns of the cultivar YIELD
GUARD (trade mark of Monsanto Domp., USA) are placed into each pot. After 2 days, the
appropriate test insects are placed into the treated soil. After a further 7 days, the efficacy of
the active compound is determined by counting the maize plants that emerged (1 plant =
20% activity).
Example M
Heliothis virescens test - Treatment of transgenic plants
Solvent: 7 parts by weight of acetone
Emulsifier: 1 part by weight of alkylaryl polyglycol ether
To produce a suitable preparation of active compound, 1 part by weight of active compound
is mixed with the stated amount of solvent and the stated amount of emulsifier, and the
concentrate is diluted with water to the desired concentration.
Soybean shoots (Glycine max) of the cultivar Roundup Ready (trade mark of Monsanto
Comp. USA) are treated by being dipped into the preparation of active compound of the
desired concentration and are populated with the tobacco budworm Heliothis virescens
while the leaves are still moist.
After the desired period of time, the kill of the insects is determined.








We Claim:
1. Compounds of the formula (XXVIII)
(Formula Removed)
in which
X represents halogen, alkyl, alkenyl, alkynyl, alkoxy, alkenyloxy, alkylthio, alkyl-sulphinyl, alkylsulphonyl, haloalkyl, haloalkoxy, haloalkenyloxy, nitro, cyano or in each case optionally substituted phenyl, phenoxy, phenylthio, phenylalkoxy or phenylalkylthio,
W and Y independently of one another represent hydrogen, halogen, alkyl, alkenyl, alkynyl, alkoxy, alkenyloxy, haloalkyl, haloalkoxy, haloalkenyloxy, nitro or cyano,
Z represents an in each case optionally saturated or unsaturated, optionally
substituted heterocycle which is attached to the phenyl ring via a nitrogen atom and which may be interrupted by one or two carbonyl groups.
2. Compounds of the formula (XXXII)
(Formula Removed)
in which
W, X, Y, Z are as defined above and R8 represents alkyl.

Documents:

830-DEL-2006-Abstract-(25-10-2010).pdf

830-DEL-2006-Claims-(25-10-2010).pdf

830-del-2006-claims.pdf

830-DEL-2006-Correspondence-Others-(25-10-2010).pdf

830-del-2006-correspondence-others-1.pdf

830-del-2006-correspondence-others.pdf

830-DEL-2006-Description (Complete)-(25-10-2010).pdf

830-del-2006-description (complete).pdf

830-DEL-2006-Form-1-(25-10-2010).pdf

830-del-2006-form-1.pdf

830-del-2006-form-18.pdf

830-DEL-2006-Form-2-(25-10-2010).pdf

830-del-2006-form-2.pdf

830-DEL-2006-Form-3-(25-10-2010).pdf

830-del-2006-form-3.pdf

830-del-2006-form-5.pdf

830-DEL-2006-GPA-(25-10-2010).pdf

830-del-2006-gpa.pdf

830-DEL-2006-Petition-137-(25-10-2010).pdf


Patent Number 244369
Indian Patent Application Number 830/DEL/2006
PG Journal Number 50/2010
Publication Date 10-Dec-2010
Grant Date 03-Dec-2010
Date of Filing 27-Mar-2006
Name of Patentee BAYER CROPSCIENCE AG
Applicant Address ALFRED-NOBEL-STR, 50, 40789 MONHEIM, GERMANY
Inventors:
# Inventor's Name Inventor's Address
1 REINER FISCHER NELLY-SACHS-STR.,23, 40789 MONHEIM, GERMANY
2 ASTRID ULLMANN MEROWINGERSTR, 31, 50677 KOLN, GERMANY
3 THOMAS BRETSCHNEIDER TALSTR. 29B, 53797 LOHMAR, GERMANY
4 STEFAN LEHR FRANKFURTER ALLEE 8A, 65835 LEIDEERBACH, GERMANY
5 KALUS KUNZ VAUTIERSTRASSE 87, 40235 DUSSELDORF, GERMANY
6 JORG KONZE MAGAZINSTR. 61, 51147 KOLN, GERMANY
7 OLGA MALSM BERGHOVENER STR. 67, 53227 BONN, GERMANY
8 WAHED AHMED MORADI GERSTENKAMP 12, 51061 KOLN, GERMANY
9 GUIDO BOJACK HOFACKERSTR. 23, 65207 WIESBADEN-NAUROD, GERMANY
10 THOMAS AULER BONNER STR. 15, 65812 BAD SODEN, GERMANY
11 MARTIN JEFFREY HILLS AM ITZELGRUND 5 B, 65510 IDSTEIN, GERMANY
12 HEINZ KEHNE ILTILSEG 7A, 65719, HOFHEIM, GERMANY
13 MARK WILHELM DREWES 38, 40764 LANGENFELD, GERMANY
14 DIETER FEUCHT HOLDERLIN STR. 9, 65779 KELKHEIM, GERMANY
15 ULRIKE WACHENDORFF-NEUMANN OBERER MARKENWEG 85, 56566 NEUWEID, GERMANY
16 KARL-HEINZ KUCK PASTOR-LOH-STR. 30, 40764 LANGENFELD, GERMANY
PCT International Classification Number C07D
PCT International Application Number N/A
PCT International Filing date
PCT Conventions:
# PCT Application Number Date of Convention Priority Country
1 NA