Title of Invention

HETARYL-SUBSTITUTED HOMOTETRAMIC AND HOMOTETRONIC ACIDS

Abstract 1. Hetarylsubstituted homotetramic or homotetronic acids of the formula (I) in which Het represents a nitrogen-containing 5-membered heterocyclic ring which is substituted by halogen, alkyl, alkoxy, alkenyloxy, halogenoalkyl, halogenoalkoxy, halogenoalkenyloxy, cyano, nitro, alkylthio, alkylsulphinyl, alkylsulphonyl, optionally substituted phenyl or optionally substituted phenoxy, W represents oxygen or N-D, A represents hydrogen, in each case optionally halogen-substituted alkyl, alkenyl, alkoxyalkyl, polyalkoxyalkyl, alkylthioalkyl, saturated or unsaturated, optionally substituted cycloalkyl in which at least one ring atom is optionally replaced by a hetero atom, or represents aryl, arylalkyl or hetaryl, each of which is optionally substituted by halogen, alkyl, halogenoalkyl, alkoxy, halogenoalkoxy, cyano or nitro, B represents hydrogen or alkyl, or A and B together with the carbon atom to which they are bonded represent a saturated or unsaturated, unsubstituted or substituted cycle which optionally contains at least one hetero atom; D represents hydrogen or an optionally substituted radical from the series comprising alkyl, alkenyl, alkinyl, alkoxyalkyl, polyalkoxyalkyl, alkylthioalkyl, saturated or unsaturated cycloalkyl in which one or more ring members are optionally replaced by hetero atoms, or arylalkyl, aryl, hetarylalkyl or hetaryl, or A and Q1 together represent alkanediyl which is optionally substituted by in each case optionally substituted alkyl or alkoxy and in which two carbon atoms which are not directly adjacent optionally form a further optionally substituted cycle, or D and Q1 together with the atoms to which they are bonded represent a saturated or unsaturated cycle which optionally contains at least one hetero atom and which is unsubstituted or substituted in the D, Q1 moiety, Q1 represents hydrogen, alkyl, alkoxyalkyl, optionally substituted cycloalkyl (in which one methylene group is optionally replaced by oxygen or sulphur) or optionally substituted phenyl, Q2 represents hydrogen or alkyl, or Q1 and Q2 together with the carbon atom to which they are bonded represent an unsubstituted or substituted cycle which optionally contains one hetero atom, G represents hydrogen (a) or one of the groups in which E represents a metal ion or an ammonium ion, L represents oxygen or sulphur, M represents oxygen or sulphur, R1 represents in each case optionally halogen-substituted alkyl, alkenyl, alkoxyalkyl, alkylthioalkyl, polyalkoxyalkyl or represents cycloalkyl which is optionally substituted by halogen, alkyl or alkoxy and which can be interrupted by at least one hetero atom, in each case optionally substituted phenyl, phenylalkyl, hetaryl, phenoxyalkyl or hetaryloxyalkyl, R2 represents in each case optionally halogen-substituted alkyl, alkenyl, alkoxyalkyl, polyalkoxyalkyl or in each case optionally substituted cycloalkyl, phenyl or benzyl, R3 represents optionally alkyl, halogenoalkyl or optionally substituted phenyl or ben2yl, R4 and R5 independently of one another represent in each case optionally halogen-substituted alkyl, alkoxy, alkylamino, dialkylamino, alkylthio, alkenylthio, cycloalkylthio and in each case optionally substituted phenyl, benzyl, phenoxy or phenylthio, R6 and R7 independently of one another represent hydrogen, in each case optionally halogen-substituted alkyl, cycloalkyl, alkenyl, alkoxy,
Full Text FORM 2
THE PATENTS ACT 1970
[39 OF 1970]
COMPLETE SPECIFICATION
[See Section 10]
"HETARYL-SUBSTITUTED HOMOTETRAMIC AND HOMOTETRONIC ACIDS"
BAYER AKTIENGESELLSCHAFT, A German company of D-51368 Leverkusen, Germany
The following specification particularly describes and ascertain the nature of the invention and the manner in which it is to be performed :-


ORIGINAL
1195/MUM/2001

GRANTED
31-1-2007

Le A 34 883-Foreign Countries Gam/AB/NT

Hetarvl-substituted homotetramic and homotetronic acids
The present invention relates to new hetaryl-substituted homotetramic and
5 homotetronic acids, to a plurality of processes for their preaparation, and to their use
as pesticides, microbicides and herbicides.
It is known that certain tetrahydropyridones have herbicidal properties:
JP-A-0 832 530. Moreover, there are known specific 4-hydroxytetrahydropyridones
10 which have acaricidal, insecticidal and herbicidal properties: JP-A-11 152 273.
However, the activity and range of action of these compounds is not always entirely satisfactory, in particular when low application rates and concentrations are used. Furthermore, these compounds are not always sufficiently well tolerated by plants.
15
20
It is furthermore known that certain 5,6-dihydropyrone derivatives, as protease inhibitors, have antiviral properties: WO 95/14012. Furthermore, 4-phenyl-6-(2-phenethyl)-5,6-dihydropyrone is known from the synthesis of kawalactone derivatives: Kappe et al.; Arch. Pharm. 309, 558-64, (1976). Moreover, 5,6-dihydropyrone derivatives are known as intermediates: White, J.D., Brenner, J.B., Deinsdale, M.J., J. Amer. Chem. Soc. 93, 281-2 (1971). Applications in crop protection have not been described as yet.
There have now been found new compounds of the formula (I)
25


Het represents a nitrogen-containing 5-membered heterocyclic ring which is
substituted by halogen, alkyl, alkoxy, alkenyloxy, halogenoalkyl,
halogenoalkoxy, halogenoalkenyloxy, cyano, nitro, alkylthio, alkylsulphinyl,
5 alkylsulphonyl, optionally substituted phenyl or optionally substituted
phenoxy,
W represents oxygen or N-D,
10 A represents hydrogen, in each case optionally halogen-substituted alkyl,
alkenyl, alkoxyalkyl, polyalkoxyalkyl, alkylthioalkyl, saturated or unsaturated, optionally substituted cycloalkyl in which at least one ring atom is optionally replaced by a hetero atom, or represents aryl, arylalkyl or hetaryl, each of which is optionally substituted by halogen, alkyl, halogenoalkyl, alkoxy,
15 halogenoalkoxy, cyano or nitro,
B represents hydrogen or alkyl, or
A and B together with the carbon atom to which they are bonded represent a
20 saturated or unsaturated, unsubstituted or substituted cycle which optionally
contains at least one hetero atom;
D represents hydrogen or an optionally substituted radical from the series
comprising alkyl, alkenyl, alkinyl, alkoxyalkyl, polyalkoxyalkyl,
25 alkylthioalkyl, saturated or unsaturated cycloalkyl in which one or more ring
members are optionally replaced by hetero atoms, or arylalkyl, aryl,
hetarylalkyl or hetaryl, or
A and Q1 together represent alkanediyl which is optionally substituted by in each
30 case optionally substituted alkyl or alkoxy and in which two carbon atoms


Le A 34 883-Foreign Countries

which are not directly adjacent optionally form a further optionally substituted cycle, or
D and Q1 together with the atoms to which they are bonded represent a saturated or
5 unsaturated cycle which optionally contains at least one hetero atom and
which is unsubstituted or substituted in the D, Q1 moiety,
Q1 represents hydrogen, alkyl, alkoxyalkyl, optionally substituted cycloalkyl (in
which one methylene group is optionally replaced by oxygen or sulphur) or
10 optionally substituted phenyl,
Q2 represents hydrogen or alkyl, or
Q1 and Q2 together with the carbon atom to which they are bonded represent an
15 unsubstituted or substituted cycle which optionally contains one hetero atom,
G represents hydrogen (a) or one of the groups

20
in which
E represents a metal ion or an ammonium ion,
25 L represents oxygen or sulphur,
M represents oxygen or sulphur,



R1 represents in each case optionally halogen-substituted alkyl, alkenyl,
alkoxyalkyl, alkylthioalkyl, polyalkoxyalkyl or represents cycloalkyl which is
optionally substituted by halogen, alkyl or alkoxy and which can be
5 interrupted by at least one hetero atom, in each case optionally substituted
phenyl, phenylalkyl, helaryl, phenoxyalkyl or hetaryloxyalkyl,
R2 represents in each case optionally halogen-substituted alkyl, alkenyl,
alkoxyalkyl, polyalkoxyalkyl or in each case optionally substituted cycloalkyl,
10 phenyl or benzyl,
R3 represents optionally alkyl, halogenoalkyl or optionally substituted phenyl or benzyl,
15 R4 and R5 independently of one another represent in each case optionally halogen-
substituted alkyl, alkoxy, alkylamino, dialkylamino, alkylthio, alkenylthio, cycloalkylthio and in each case optionally substituted phenyl, benzyl, phenoxy or phenylthio,
20 R6 and R7 independently of one another represent hydrogen, in each case optionally
halogen-substituted alkyl, cycloalkyl, alkenyl, alkoxy, alkoxyalkyl, optionally substituted phenyl, optionally substituted benzyl, or together with the N atom to which they are bonded represent a cycle which is optionally interrupted by oxygen or sulphur. 25
Depending on the nature of the substituents, the compounds of the formula (I) can
exist as geometric and/or optical isomers or isomer mixtures of various
compositions, and, if appropriate, these can be separated in the customary fashion.
Not only the pure isomers, but also the isomer mixtures, their preparation and use
30 and compositions comprising them are subject-matter of the present invention.
However, the following text will, for the sake of simplicity, always mention



compounds of the formula (I), even though this is understood as meaning not only the pure compounds, but also, if appropriate, mixtures with various amounts of isomeric compounds.
5 Depending on the position of the substituent G, the compounds of the formula (I) can
exist in the two isomeric forms of the formulae (I-A) and (I-B),



(I-A)
which is expressed by the broken line in formula (I).

10

15
20

The compounds of the formulae (I-A) and (I-B) can exist not only as mixtures, but also in the form of their pure isomers. If appropriate, mixtures of the compounds of the formulae (I-A) and (I-B) can be separated in a manner known per se by physical methods, for example by chromatographic methods.
The following text will only mention in each case one of the isomers which are possible, for the sake of clarity. This does not exclude that, if appropriate, the compounds may exist in the form of the isomer mixtures or in each case in the other isomeric form.
Taking into consideration the meanings thiazolyl for Het and oxygen and N-D for W, the following main structures (1-1) and (1-2) result



Le A 34 883-Foreien Countries


Taking into consideration the various meanings (a), (b), (c), (d), (e), (f) and (g) of
5 group G, the following main structures (I-l-a) to (M-g) result if W is N-D (1),


Le A 34 883-Foreign Countries
^

in which
5 A, B, D, E, L, M, Q1, Q2, R1, R2, R3, R4, R5, R6 ,ANd R7 have the abovementioned
meanings,
X represents hydrogen, halogen, alkyl, alkoxy, alkenyloxy, nitro, cyano or optionally substituted phenyl and 10
Y represents halogen, alkyl, halogenoalkyl, alkoxy, halogenoalkoxy, or in each case optionally substituted phenyl or phenoxy.
Taking into consideration the various meanings (a), (b), (c), (d), (e), (f) and (g) of
15 group G, the following main structures (I-2-a) to (I-2-g) result if W is oxygen (2),



Le A 34 883-Foreign Countries





Le A 34 883-Foreign Countries
A, B, E, L, M, Q1, Q2, X, Y, Rl, R2, R3, R4, R5, R6 and R7 have the abovementioned meanings.
Furthermore, it has been found that the new compounds of the formula (I) are
5 obtained by one of the processes described hereinbelow:
(A) Substituted tetrahydropyridine-2,4-diones or their enols of the formula (M-a)

in which
10
A, B, D, Q1, Q2 and Het have the abovementioned meanings
are obtained when
15 N-acylamino acid esters of the formula (II)


in which
20 A, B, D, Q1, Q2 and Het have the abovementioned meanings
and


5


represents alkyl (preferably C1-C6-alkyl)
are subjected to an intramolecular condensation reaction in the presence of a diluent and in the presence of a base.
Furthermore, it has been found
(B) that substituted 5,6-dihydropyrones of the formula (I-2-a)


10

in which
A, B, Q1, Q2 and Het have the abovementioned meanings
15 are obtained when
O-acylhydroxycarboxylic esters of the formula (HI)

20 in which
A, B, Q1, Q2 and Het have the abovementioned meanings,



and
R8 represents alkyl (preferably C1-C6-alkyl)
5 are subjected to an intramolecular condensation reaction in the presence of a
diluent and in the presence of a base.
Furthermore, it has been found,
10 (C) that the compounds of the formulae (I-l-b) to (I-2-b) shown above in which
A, B, Q1, Q2, R1, W and Het have the abovementioned meanings are obtained when compounds of the formulae (I-l-a) to (I-2-a) shown above in which A, B, Q1, Q2, W and Het have the abovementioned meanings are reacted in each case
15
(a) with acid halides of the formula (IV)


in which

20
Rl has the abovementioned meaning and
Hal represents halogen (in particular chlorine or bromine)
25 or

(B) with carboxylic anhydrides of the formula (V)


Le A 34 883-Foreign Countries

in which
Rl has the abovementioned meaning, 5
if appropriate in the presence of a diluent and if appropriate in the presence of an acid binder;
(D) that the compounds of the formulae (I-l-c) to (I-2-c) shown above in which
10 A, B, Q1, Q2, R2, M, W and Het have the abovementioned meanings and L
represents oxygen are obtained when compounds of the formulae (I-l-a) to (I-
2-a) shown above in which A, B, Q1, Q2, W and Het have the
abovementioned meanings are reacted in each case
15 with chloroformic esters or chloroformic thioesters of the formula (VI)

R2-M-CO-Cl (VI)
in which
20 R2 and M have the abovementioned meaning,
if appropriate in the presence of a diluent and if appropriate in the presence of an acid binder;
25 (E) that the compounds of the formulae (I-l-c) to (I-2-c) shown above in which
A, B, QJ, Q2, R2, M, W and Het have the abovementioned meanings and L represents sulphur are obtained when compounds of the formulae (I-l-a) to (I-2-a) shown above in which A, B, Q1, Q2, W and Het have the abovementioned meanings are reacted in each case
30


Le A 34 883-Foreign Countries
with chloromonothioformic esters or chlorodithioformic esters of the formula (VII)
in which 5
M and R2 have the abovementioned meanings,
if appropriate in the presence of a diluent and if appropriate in the presence of an acid binder, 10
and
(F) that compounds of the formulae (I-l-d) to (I-2-d) shown above in which A, B,
Q1, Q2, R3, W and Het have the abovementioned meanings are obtained
15 when compounds of the formulae (M-a) and (I-2-a) shown above in which A,
B, Q1, Q2, W and Het have the abovementioned meanings are reacted in each
case
with sulphonyl chlorides of the formula (VIII) 20
in which
R3 has the abovementioned meaning, 25
if appropriate in the presence of a diluent and if appropriate in the presence of an acid binder,




(G) that compounds of the formulae (I-l-e) to (I-2-e) shown above in which A, B, L. Q1. Q2, R4, R5. W and Het have the abovementioned meanings are obtained when compounds of the formulae (I-l-a) to (I-2-a) shown above in which A, B, Q1, Q2, W and Het have the abovementioned meanings are reacted in each case
with phosphorus compounds of the formula (IX)
(IX)
in which
10
L, R4 and R5 have the abovementioned meanings and
Hal represents halogen (in particular chlorine or bromine),
15 if appropriate in the presence of a diluent and if appropriate in the presence of
an acid binder,
(H) that compounds of the formulae (I-l-f) to (1-2-f) shown above in which A, B,
E, Q1. Q2. W and Het have the abovementioned meanings are obtained when
20 compounds of the formulae (I-l-a) to (I-2-a) in which A, B, Q1, Q2, W and
Het have the abovementioned meanings are reacted in each case
with metal compounds or amines of the formula (X) or (XI)


in which



Le A 34 883-Foreign Countries
Me represents a monovalent or divalent metal (preferably an alkali metal or alkaline earth metal such as lithium, sodium, potassium, magnesium or calcium),
5 t represents the number 1 or 2 and
Rll, R12, R13 independently of one another represent hydrogen or alkyl (preferably C1-C8-alkyl)
10 are reacted, if appropriate in the presence of a diluent,
(I) that compounds of the formulae (I-l-g) to (I-2-g) shown above in which A, B,
L. Q1, Q2, R6, R7, W and Het have the abovementioned meanings are
obtained when compounds of the formulae (I-l-a) to (I-2-a) shown above in
15 which A, B, Q1, Q2, W and Het have the abovementioned meanings are
reacted in each case
(a) with isocyanates or isothiocyanates of the formula (XII)
20 R6-N=C=L (XII)
in which
R6 and L have the abovementioned meanings,
25 if appropriate in the presence of a diluent and if appropriate in the presence of
a catalyst, or
(6) with carbamoyl chlorides or thiocarbamoyl chlorides of the formula (XIII)



Le A 34 883-Foreign Countries

in which

10

L, R.6 and R7 have the abovementioned meanings,
if appropriate in the presence of a diluent and if appropriate in the presence of acid binder.
Furthermore, it has been found that the new compounds of the formula (I) have very good activity as pesticides, preferably as insecticides, acaricides and also herbicides.
Formula (I) provides a general definition of the compounds according to the invention. Preferred substituents or ranges of the radicals stated in the formulae mentioned hereinabove and hereinbelow are illustrated in the following text:


X preferably represents hydrogen, halogen, C1-C6-alkyl, C1-C6-alkoxy, C3-C6-
alkenyloxy, nitro, cyano, or represents phenyl which is optionally substituted
20 by halogen, C1-C6-alkyl, C1-C6-alkoxy, C1-C4halogenoalkyl, C1-C4-
halogenoalkoxy, nitro or cyano,
Y preferably represents halogen, C1-C6-alkyl, C1-C6-halogenoalkyl, C1-C6-alkoxy, C1-C6-halogenoalkoxy or the groups

25


Le A 34 883-Foreign Countries
V1 preferably represents hydrogen, halogen, C1-C12-alkyl, C1-C6-alkoxy, C1-C6-
alkylthio, C1-C6-alkylsulphinyl, C1-C6-alkylsulphonyl, C1-C4-halogenoalkyl,
C1-C4-halogenoaIkoxy, nitro, cyano, or represents phenyl, phenoxy, phenoxy-
5 C1-C4-alkyl, phenyl-C1-C4-alkoxy, phenylthio-C1-C4-alkyl or phenyl-C1-C4-
alkylthio, each of which is optionally monosubstituted or polysubstituted by halogen, C1-C6-alkyl, C1-C6-alkoxy, C1-C4-halogenoalkyl, C1-C4-halogenoalkoxy, nitro or cyano,
10 V2 and V3 preferably independently of one another represent hydrogen, halogen, C1-
C6-alkyl, C1-C6-alkoxy, C1-C4-halogenoalkyl or C1-C4-halogenoalkoxy,
V1 and V2 together with the carbon atoms to which they are bonded preferably
represent a 5- or 6-membered cycle which is optionally substituted by C1-C4-
15 alkyl or halogen and in which one to three carbon atoms can optionally be
replaced by oxygen, sulphur or nitrogen,
A preferably represents hydrogen, or represents C1-C12-alky], C3-C8-alkenyl, C1-C6-alkoxy-C1-C4alkyl, each of which is optionally substituted by
20 halogen, or represents optionally halogen-, C1-C4-alkyl- or C1-C4-alkoxy-
substituted C3-C8-cycloalkyl or C3-C6-cycloalkyl-C1-C4-alkyl in which one or two ring members which are not directly adjacent are optionally replaced by oxygen and/or sulphur, or represents phenyl, benzyl, hetaryl having 5 to 6 ring atoms (for example furanyl, pyridyl, imidazolyl, triazolyl, pyrazolyl,
25 pyrimidyl, thiazolyl or thienyl) or hetaryl-C1-C4-alkyl having 5 to 6 ring
atoms (for example pyridyl, pyrimidyl or thiazolyl), each of these cycles optionally being substituted by halogen, C1-C6-alkyl, C1-C6-halogenoalkyl, C1-C8-alkoxy, C1-C6-halogenoalkoxy, cyano or nitro,
30 B preferably represents hydrogen or C1-C6-alkyl,


Le A 34 883-Foreiegn Countries
A, B and the carbon atom to which they are bonded preferably represent saturated
C3-C10-cycloalkyl or unsaturated C5-C10-cycloalkyl in which one ring
member is optionally replaced by oxygen or sulphur and which are optionally
monosubstituted or disubstituted by C1-C6-alkyI, C3-C8-cycIoalkyl, C1-C6
5 halogenoalkyl, C1-C6-alkoxy, C1-C6-alkylthio, halogen or phenyl,
D preferably represents hydrogen, in each case optionally halogen-substituted
C1-C6-alkyl, C3-Cg-alkenyl, C3-C8-alkinyl, C1-C6-alkoxyC2-C6-alkyl, or
represents optionally halogen-, C1-C4-alkyl-, C3-C6alkoxy- or C1-C4-halo-
10 genoalkyl-substituted C3-C8-cycloalkyl or C3-C6-cycloalkyl-C1-C4-alkyl in
which one ring member is optionally replaced by oxygen or sulphur,
A and Q1 jointly preferably represent C3-C6-alkanediyl which is optionally substituted by C1-C4-alkyl orC1-C4-alkoxy, 15
D and Q1 together preferably represent C3-C6-alkanediyl which is optionally monosubstituted or disubstituted by identical or different substituents from the series consisting of C1-C4alkyl and C1-C4alkoxy, or
20 Q1 preferably represents hydrogen, C1-C6-alkyl, C1-C6-alkoxy-C1-C2-alkyl, or
represents C3-C8-cycloalkyl in which one methylene group is optionally replaced by oxygen or sulphur and which is optionally substituted by fluorine, chlorine, C3-C8-alkyl, C1-C2-halogenoalkyl or C1-C4-alkoxy, or represents phenyl which is optionally substituted by halogen, C1-C4-alkyl, C1-C4-
25 alkoxy, C1-C2-halogenoalkyl, C1-C2-halogenoalkoxy, cyano or nitro, or
Q2 preferably represents hydrogen or C1-C4-alkyl,
Q1 and Q2 preferably together with the carbon atom to which they are bonded
30 represent C3-C7-cycloalkyl in which one ring member is optionally replaced


Le A 34 883-Foreign Countries
by oxygen or sulphur and which is optionally substituted by C1-C6-alkyl, C1-C6-alkoxy or C1-C2-halogenoalkyl,
G preferably represents hydrogen (a) or one of the groups
5


10

E represents a metal ion or an ammonium ion, L represents oxygen or sulphur and M represents oxygen or sulphur,

15 R1 preferably represents C1-C20-alkyl, C2-C20-alkenyl, C1-C8-alkoxy-C1-C8-
alkyl, C1-C8-alkylthio-C1-C8-alkyl, poly-C1-C8-alkoxy-C1-C8-alkyl, each of which is optionally substituted by halogen, or represents C3-C8-cycloalkyl in which one or more (preferably one or two) ring members which are not directly adjacent are optionally replaced by oxygen and/or sulphur and which
20 is optionally substituted by halogen, C1-C6-alkyl or C1-C6alkoxy,
or represents phenyl which is optionally substituted by halogen, cyano, nitro, C1-C6-alkyl, C1-C6-alkoxy, C1-C6-halogenoalkyl, C1-C8-halogenoalkoxy, C1-C6-alkylthio or C1-C6-alkylsulphonyl,
25


Le A 34 883-Foreign Countries

or represents phenyl-C1-C6-alkyl which is optionally substituted by halogen, nitro, cyano, C1-C6-alkyl, C1-C6-alkoxy, C1-C6-halogenoalkyl or C1-C6-halogenoalkoxy,
5 or represents 5- or 6-membered hetaryl (for example pyrazolyl, thiazolyl,
pyridyl, pyrimidyl, furanyl or thienyl) which is optionally substituted by halogen, C1-C6-alkyl or trifluoromethyl,
or represents phenoxy-C1-C6-alkyl which is optionally substituted by halogen
10 orC1-C6-alkyl,
or represents 5- or 6-membered hetaryloxy-C1-C6-alkyl (for example pyridyloxy-C1-C6-alkyl, pyrimidyloxy-C1-C6-alkyl or thiazolyloxy-C1-C6-alkyl), which is optionally substituted by halogen, amino or C1-C8-alkyl, 15
R2 preferably represents C1-C20-alkyl, C2-C20-alkenyl, C1-C6-alkoxy-C2-C6-alkyl, poly-C1-C6-alkoxy-C2-C8-alkyl, each of which is optionally substituted by halogen,
20 or represents C3-Cg-cycloalkyl which is optionally substituted by halogen,
C1-C6-alkyl or C1-C6-alkoxy,
or represents phenyl or benzyl, each of which is optionally substituted by
halogen, cyano, nitro, C1-C6-alkyl, C1-C6-alkoxy, C1-C6-halogenoalkyl or
25 C1-C6-halogenalkoxy,
R3 preferably represents C1-C8-alkyl which is optionally substituted by halogen
or represents phenyl or benzyl, each of which is optionally substituted by
halogen, C1-C6-alkyl, C1-C6-alkoxy, C1-C4-halogenoalkyl, C1-C4-
30 halogenoalkoxy, cyano or nitro,


Le A 34 883-Foreiegn Countries

R4 and R5 preferably independently of one another represent C1-C8-alkyl, C1-C8-
alkoxy, C1-C8-alkylamino, di-(C1-C8-alkyl)amino, C1-C8-alkylthio, C2-C8-
alkenylthio, C3-C7-cycloalkylthio, each of which is optionally substituted by
halogen, or represent phenyl, benzyl, phenoxy or phenylthio, each of which is
5 optionally substituted by halogen, nitro, cyano, C1-C4-alkoxy, C1-C4-
halogenoalkoxy, C1-C4-alkylthio, C1-C4-halogenoalkylthio, C1-C4-alkyl or C 1-C4-halogenoalkyl,
R6 and R7 independently of one another preferably represent hydrogen, or represent
10 Ci-Cg-alkyl, C3-Cg-cycloalkyl, C1-C8-alkoxy, C3-C8-alkenyl, C1-C8-
alkoxy-C1-C8-alkyl, each of which is optionally substituted by halogen, or
represent phenyl which is optionally substituted by halogen, C1-C8-
halogenoalkyl, C1-C8-alkyl or C1-C8alkoxy, or represent benzyl which is
optionally substituted by halogen, C1-C8-alkyl, C1-C8-halogenoalkyl or C1--
15 C8-alkoxy, or together with the N atom to which they are bonded represent a
C3-C6-alkylene radical in which one carbon atom is optionally replaced by oxygen or sulphur and which is optionally substituted by C1-C4alkyl.
In the definitions of radicals mentioned as being preferred, halogen, also as a
20 substituent such as, for example, in halogenoalkyl, represents fluorine, chlorine,
bromine-and iodine, in particular fluorine or chlorine.

X
Het especially preferably represents
W especially preferably represents oxygen or N-D, 25
X especially preferably represents hydrogen, chlorine, bromine, C1-C4-alkyl, or represents phenyl which is optionally monosubstituted to disubstituted by fluorine, chlorine, bromine, C1-C4-alkyl, C1-C2-halogenoalkoxy, nitro or cyano,



Le A 34 883-Foreign Countries
Y especially preferably represents chlorine, bromine, C1-C4alkyl, C1-C4-halogenoalkyl, C1-C4-alkoxy, C1-C4-halogenoalkoxy or the groups
V1 especially preferably represents hydrogen, fluorine, chlorine, bromine, C1-C6-
alkyl, C1-C4-alkoxy, C1-C2-halogenoalkyl, C1-C2-halogenalkoxy, nitro,
cyano, or represents phenyl, phenoxy, phenoxy-C1-C2-alkyl, phenyl-C1-C2
10 alkoxy, phenylthio-C1-C4-alkyl or phenyl-Cj-C2-alkylthio, each of which is
optionally monosubstituted or disubstituted by fluorine, chlorine, bromine, C1-C4-alkyl, C1-C4-alkoxy, C1-C2-halogenoalkyl, C1-C2-halogenoalkoxy, nitro or cyano
15 V2 especially preferably represents hydrogen, fluorine, chlorine, bromine, C1-C4-
alkyl, C1-C4-alkoxy, C1-C2-halogenoalkyl or C1-C2-halogenoalkoxy,
V1 and V2 jointly together with the carbon atoms to which they are bonded especially
preferably represent a 5- or 6-membered cycle in which one or two carbon
20 atoms can optionally be replaced by oxygen and which is optionally
substituted by fluorine or methyl,
A especially preferably represents hydrogen, or represents C1-C8-alkyI or C1
C4-alkoxy-C1-C2-alkyl, each of which is optionally substituted by fluorine, or
25 represents C5-C6-cycloalkyl or C3-C6-cycloalkyl-C1-C2-alkyl in which one
ring member is optionally replaced by oxygen or sulphur and which is optionally substituted by fluorine, chlorine, methyl, ethyl or methoxy, or represents phenyl or benzyl, each of which is optionally substituted by


Le A 34 883-Foreign Countries
fluorine, chlorine, bromine, C1-C4-alkyl, C1-C2-halogenoalkyl, C1-C4-alkoxy or C1-C2-halogenoalkoxy,
B especially preferably represents hydrogen or C1-C4alkyl,
A, B and the carbon atom to which they are bonded especially preferably represent saturated C5-C7-cycloalkyl in which one ring member is optionally replaced by oxygen and which is optionally monosubstituted by C1-C4-alkyl, trifluoromethyl or C1-C4-alkoxy,
10
D especially preferably represents hydrogen, or represents C1-C6-alkyl, C3-C6 alkenyl or C1-C4-alkoxy-C2-C3-alkyl, each of which is optionally substituted by fluorine, or represents C3-C7-cycloalkyl or C3-C6-cycloalkyl-C1-C2-alkyl in which one methylene group is optionally replaced by oxygen and which is optionally substituted by C1-C2-aIkyl, fluorine or chlorine,
A and Q1 jointly especially preferably represent C3-C4-alkanediyl,
D and Q1 jointly especially preferably represent C3-C4-alkanediyl,
20
Q1 especially preferably represents hydrogen, C1-C4-alkyl, C1-C4-alkoxy-C1-C2-alkyl, or represents C3-C6-cycloalkyl in which one methylene group is optionally replaced by oxygen and which is optionally substituted by methyl or methoxy,
25
Q2 especially preferably represents hydrogen, methyl or ethyl,
Q1 and Q2 especially preferably jointly with the carbon atom to which they are
bonded represent saturated C5-C6-cycloalkyl in which one ring member is
30 optionally replaced by oxygen and which is optionally substituted by C1-C4-
alkyl or C1-C4-alkoxy,

Le A 34 883-Foreign Countries



(g), in particular (a), (b), (c) or (g),
in which 5
E represents a metal ion or an ammonium ion, .
L represents oxygen or sulphur and
10 M represents oxygen or sulphur,
Rl especially preferably represents C1-C16-alkyl, C2-C16-alkenyl, C1-C4-
alkoxy-C1-C2-alkyl, C1-C4-alkylthio-C1-C2-alkyl, each of which is
optionally substituted by fluorine or chlorine, or represents C3-C7-cycloalkyl
15 in which one or two ring members which are not directly adjacent are
optionally replaced by oxygen and/or sulphur and which is optionally substituted by fluorine, chlorine, C1-C5-alkyl or C1-C5-alkoxy,
or represents phenyl which is optionally substituted by fluorine, chlorine,
20 bromine, cyano, nitro, C1-C4-alkyl, C1-C4-alkoxy, trifluoromethyl or
trifluoromethoxy;
or represents pyridyl or thienyl, each of which is optionally substituted by fluorine, chlorine, bromine, methyl, ethyl or trifluoromethyl,

25

R2 especially preferably represents C1-C16-alkyl, C2-C16-alkenyl or C1-C4-alkoxy-C2-C4~aIkyl, each of which is optionally substituted by fluorine,


Le A 34 883-Foreiegn Countries
or represents C3-C7-cycloalkyl which is optionally substituted by methyl, ethyl or methoxy,
5 or represents phenyl or benzyl, each of which is optionally substituted by
fluorine, chlorine, bromine, cyano, nitro, C1-C4alkyl, C1-C3-a]koxy, trifluoromethyl or trifluoromethoxy,
R3 especially preferably represents C1-C6-alkyl which is optionally substituted
10 by fluorine, or represents phenyl which is substituted by fluorine, chlorine,
bromine, C1-C4alky], C1-C4alkoxy, trifluoromethyl, trifluoromethoxy, cyano or nitro,
R4 especially preferably represents C1-C6-alkyl, C1-C6-alkoxy, C1-C6-
15 alkylamino, di-(C1-C6-alkyl)amino, C1-C6-alkylthio, or represents phenyl,
benzyl, phenoxy or phenylthio, each of which is optionally substituted by
fluorine, chlorine, bromine, nitro, cyano, C1-C3-alkoxy, trifluoromethoxy,
C]-C3-alkyl or trifluoromethyl,
20 R5 especially preferably represents C1-C4alkyl, C1-C4alkoxy or C1-C4-
alkylthio,
R6 especially preferably represents hydrogen, C1-C6-alkyl, C3-C6~cycloalkyl,
C1-C6-alkoxy, C3-C6-alkenyl, C2-C6-alkoxy-C1-C6-alkyl, or represents
25 phenyl which is optionally substituted by fluorine, chlorine, bromine,
trifluoromethyl, C1-C4-alkyl or C1-C4-alkoxy, or represents benzyl which is optionally substituted by fluorine, chlorine, bromine, methyl, ethyl, trifluoromethyl or methoxy,
30 R7 especially preferably represents hydrogen, C1-C6-alkyl or C3-C6-alkenyl,


I
Le A 34 883-Foreign Countries

R6 and R7 especially preferably together with the N atom to which they are bonded represent a C4-C6-alkylene radical in which one methylene group is optionally replaced by oxygen or sulphur and which is optionally substituted by methyl or ethyl.
In the definitions of radicals which have been mentioned as being especially preferred, halogen, also as substituent such as, for example, in halogenoalkyl, represents fluorine, chlorine, bromine and iodine, especially fluorine and chlorine, very especially fluorine.
10


Het very especially preferably represents
W very especially preferably represents oxygen or N-D,
X very especially preferably represents chlorine, bromine, methyl, ethyl,
15 n-propyl, isopropyl, n-butyl or isobutyl,
Y very especially preferably represents methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl or the group

20

25

V1 very especially preferably represents hydrogen, fluorine, chlorine, bromine, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, methoxy, ethoxy, n-propoxy, isopropoxy, trifluoromethyl, trifluoromethoxy,


Le A 34 883-Foreiegn Countries
V2
very especially preferably represents hydrogen, fluorine, chlorine, methyl, ethyl, n-propyl, isopropyl, methoxy, ethoxy, trifluoromethyl or trifluoromethoxy,
5 A
very especially preferably represents hydrogen, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, methoxymethyl, ethoxymethyl,
B
very especially preferably represents hydrogen, methyl or ethyl,
10 A,B
15
and the carbon atom to which they are bonded ve.ry especially preferably represent saturated C5-C6-cycloalkyl in which one ring member is optionally replaced by oxygen and which is optionally monosubstituted by methyl, ethyl, n-propyl, isopropyl, butyl, trifluoromethyl, methoxy, ethoxy, n-propoxy or n-butoxy,
D
very especially preferably represents hydrogen, methyl, ethyl, propyl, isopropyl, allyl, 2-butenyl, methoxyethyl, ethoxyethyl, cyclopropyl, cyclopentyl or cyclohexyl,
20 A and Q1 jointly very especially preferably represent C3-C4-alkanediyl.
D and Q1 jointly very especially preferably represent C3-C4-alkanediyl,
Q1 very especially preferably represents hydrogen, methyl, ethyl, propyl,
25 isopropyl, cyclopropyl, cyclopentyl or cyclohexyl,
Q2 very especially preferably represents hydrogen, methyl or ethyl,
Q1 and Q2 very especially preferably jointly with the carbon to which they are
30 bonded represent saturated C5-C6-cycloalkyl in which one ring member is

Le A 34 883-Foreign Countries
optionally replaced by oxygen and which is optionally substituted by methyl, ethyl, propyl, isopropyl, methoxy, ethoxy, propoxy or butoxy,
G very especially preferably represents hydrogen (a) or one of the groups
5
E represents a metal ion or an ammonium ion,
10 L represents oxygen or sulphur and
M represents oxygen or sulphur,
very especially preferably represents C1-C14-alkyl, C2-C14-alkenyl, C1-C4-
15 alkoxy-C1-C2-alkyl, C1-C4-alkylthio-C1-C2-alkyl, each of which is
optionally substituted by fluorine or chlorine, or represents C3-C5-cycloalkyl in which one or two ring members which are not directly adjacent are optionally replaced by oxygen and/or sulphur and which is optionally substituted by fluorine, chlorine, methyl, ethyl or methoxy, 20
or represents phenyl which is optionally substituted by fluorine, chlorine, bromine, cyano, nitro, methyl, ethyl, isopropyl, tert-butyl, methoxy, trifluoromethyl or trifluoromethoxy,
25 or represents thienyl or pyridyl, each of which is optionally substituted by
fluorine, chlorine, bromine or methyl,


Le A 34 883-Foreign Countries


10

R2 very especially preferably represents C1-C14-alkyl, C2-C14-alkenyl or C1-C4-alkoxy-C2-C3-alkyl, each of which is optionally substituted by fluorine,
or represents C3-C6-cycloalkyl which is optionally substituted by methyl, ethyl or methoxy,
or represents phenyl or benzyl, each of which is optionally substituted by fluorine, chlorine, cyano, nitro, methyl, ethyl, isopropyl, tert-butyl, methoxy, trifluoromethyl or trifluoromethoxy,
R3 very especially preferably represents methyl, ethyl, n-propyl, isopropyl, each of which is optionally substituted by fluorine, or represents phenyl which is optionally substituted by fluorine, chlorine, bromine, methyl, tert-butyl, methoxy, trifluoromethyl, trifluoromethoxy, cyano or nitro,

15
R4 very especially preferably represents C1-C4-alkyl, C1-C4-alkoxy, C1-C4-
alkylamino, di-(C1-C4-alkyl)amino, C1-C4-alkylthio or represents phenyl,
phenoxy or phenylthio, each of which is optionally substituted by fluorine,
chlorine, bromine, nitro, cyano, C1-C2-alkoxy, trifluoromethoxy or C1-C3-
20 alkyl,
R5 very especially preferably represents methyl, ethyl, methoxy, ethoxy, methylthio or ethylthio,
25 R6 and R7 independently of one another very especially preferably represent
hydrogen, C1-C4alkyl, C3-C6-cycloalkyl, C1-C4-alkoxy, C3-C4-alkenyl, C1-C4-alkoxy-C2-C4-alkyl,
R7 very especially preferably represents hydrogen, C1-C4-alkyl or C3-C4-alkenyl,
30


Le A 34 883-Foreiegn Countries

R6 and R7 very especially preferably together with the N atom to which they are bonded represent a C5-C6-alkylene radical in which one methylene group is optionally replaced by oxygen or sulphur.


Het most especially preferably represents 5

W most especially preferably represents oxygen or N -D,
X most especially preferably represents chlorine, methyl, ethyl, n-propyl or
10 i-propyl,
Y most especially preferably represents

15
A most especially preferably represents hydrogen or methyl,
B most especially preferably represents hydrogen or methyl, 20
A, B and the carbon atom to which they are bonded most especially preferably
represent saturated C6-cycloalkyl in which one ring member is optionally
replaced by oxygen,
25 D most especially preferably represents hydrogen or cyclopropyl,


Le A 34 883-Foreign Countries

5

D and Q1 most especially preferably jointly represent C3-C4-alkanediyl, Q1 most especially preferably represents methyl or hydrogen, Q2 most especially preferably represents methyl or hydrogen,

Q1 and Q2 most especially preferably jointly with the carbon to which they are
bonded represent saturated C6-cycloalkyl in which one ring member is
10 optionally replaced by oxygen,
G most especially preferably represents hydrogen (a) or one of the groups

15
where M represents oxygen or sulphur,
R1 most especially preferably represents C1-C4alkyl, C1-C4alkoxy-C1-C2--alkyl,
OF represents phenyl or pyridyl, each of which is optionally substituted by
20 chlorine,
R2 most especially preferably represents C1-C4alkyl, phenyl or benzyl,
R6 and R7 most especially preferably together with the N atom to which they are
25 bonded represent a C5-C6-alkylene radical in which one methylene group is
optionally replaced by oxygen.
The definitions or explanations stated above in general or in preferred ranges can be combined with each other as desired, that is to say combinations between the


Le A 34 883-Foreign Countries
respective ranges and preferred ranges are also possible. They apply to the end products and, analogously, to the precursors and intermediates.
Preferred in accordance with the invention are the compounds of the formula (I) with
5 a combination of the meanings stated above as being preferred (given preference to).
Especially preferred in accordance with the invention are the compounds of the formula (I) with a combination of the meanings stated above as especially preferred.
10 Very especially preferred in accordance with the invention are the compounds of the
formula (I) with a combination of the meanings stated above as very especially preferred.
Most especially preferred in accordance with the invention are the compounds of the
15 formula (I) with a combination of the meanings stated above as most preferred.
Particularly preferred are compounds of the formula (I) in which G is hydrogen.
Further compounds of the formula (I) which are particularly preferred are those in
20 which D represents hydrogen, methyl, ethyl, propyl, isopropyl, cyclopropyl,
cyclopentyl or cyclohexyl.
Saturated or unsaturated hydrocarbon radicals such as alkyl or alkenyl, also in
connection with hetero atoms such as, for example, in alkoxy, can be in each case
25 straight-chain or branched as far as this is possible.
Unless otherwise defined, optionally substituted radicals can be monosubstituted or polysubstituted, it being possible for the substituents to be identical or different in the case of polysubstitutions. 30


Le A 34 883-Foreign Countries

If, in accordance with process (A), ethyl N-[4-(5-methyl)-2-(4-chlorophenyl)-thiazolylacetyl]-l-aminomethyl-cyclohexane-carboxylate is used as starting material, the course of the process according to the invention can be represented by the following equation:




10

If, in accordance with process (B), ethyl 0-[4-(5-methyl)-2-(4-chlorophenyl)-thiazolylacetyl]-l-hydroxyrnethyl-cyclohexane-carboxylate is used as starting material, the course of the process according to the invention can be represented by the following equation:






15

If, in accordance with process (Da), 3-[4-(5-methyl-2-(3-chlorophenyl)-thiazolyl]-4-hydroxy-6,6-dimethyldihydropyridin-2-one and pivaloyl chloride are used as starting materials, the course of the process according to the invention can be represented by the following equation:



Le A 34 883-Foreign Countries


If, in accordance with process (D6), 3-[4-(5-ethyl-2-(4-methoxyphenyl))-thiazolyl]-4-hydroxy-6,6-dimethyldihydropyrone and acetic anhydride are used as starting materials, the course of the process according to the invention can be represented by the following equation:


10

If, in accordance with process (E), 3-[4-(5-methyl-2-phenyl)-thiazolyl]-6,6-dimethyldihydropyridine-2,4-dione and ethoxyethyl chloroformate are used as starting compounds, the course of the process according to the invention can be represented by the following equation:




Le A 34 883-Foreign Countries

If, in accordance with process (F), 3-[4-(5-methyl-2-(4-fluorophenyl))-thiazolyl]-5,5,6,6-tetramethyldihydropyrone and methyl chloromonothioformate are used as starting materials, the course of the reaction can be represented as follows:
S

If, in accordance with process (G), 3-[4-(5-methyl-3-(4-methylphenyl)-thiazolyl]-6,6-dimethyldihydropyridine-2,4-dione and methanesulphonyl chloride are used as starting materials, the course of the reaction can be represented by the following equation:
10


15

If, in accordance with process (H), 3-[4-(5-methyl-2-phenyI)-thiazoIyl]-4-hydroxy-5,5,6,6-tetramethyldihydropyrone and methanethio-phosphonyl chloride 2,2,2-trifluoroethyl ester are used as starting materials, the course of the reaction can be represented by the following equation:



Le A 34 883-Foreign Countries


If, in accordance with process (I,) 3-[4-(5-methyl-2-(4-trifluoromethylphenyI))-thiazoIyl]-6,6-dimethyl-dihydropyridine-2,4-dione and NaOH are used as reactants, the course of the process according to the invention can be represented by the following equation:

If, in accordance with process (Jα), 3-[4-(5-methyl-2-(3-trifluoromethylphenyl))-
10 thiazolyl]-4-hydroxy-5,5,6,6-tetramethyldihydropyrone and ethyl isocyanate are used
as starting materials, the course of the reaction can be represented by the following equation:


Le A 34 883-Foreign Countries


If, in accordance with process (JB), 3-[4-(5-methyl-2-phenyl)-thiazolyl]-6,6-dimethyl-dihydropyridine-2,4-dione and dimethylcarbamoyl chloride are used as starting materials, the course of the reaction can be represented by the following scheme:

10 in which
A, B, D, Q1, Q2, Het and R8have the abovementioned meanings


Le A 34 883-Foreign Countries

and which are required as starting materials in process (A) according to the invention are new.
The acylamino acid esters of the formula (II) are obtained, for example, from amino
5 acid derivatives of the formula (XIV)



10 A, B, Q1,Q2, R8 and D have the abovementioned meanings
are acylated with substituted hetaryl acetic acid derivatives of the formula (XV)


o
15 in which.
Het has the abovementioned meaning and
U represents a leaving group introduced by reagents for the activation of
20 carboxylic acids, such as carbonyldiimidazole, carbonyldiimide (such as, for
example, dicyclohexylcarbodiimide), phosphorylating agents (such as, for
example, POCl3, BOP-C1), halogenating agents, for example thionyl chloride,
oxalyl chloride, phosgene or chloroformic ester
25 (Chem. Reviews 52, 237-416 (1953); Bhattacharya, Indian J. Chem. 6, 341-5,1968)


Le A 34 883-Foreien Countries
or when acylamino acids of the formula (XVI)



5 in which
A, B, D, Q1, Q2 and Het have the abovementioned meanings
are esterified (Chem. Ind. (London) 1568 (1968)). 10
The compounds of the formula (XVI)

in which
15
A, B, D, Q1, Q2 and Het have the abovementioned meanings
are new.
20 The compounds of the formula (XVI) are obtained when B-amino acids of the
formula (XVII)


Le A 34 883-Foreiegn Countries





5
10
15
20

A, B, Q1, Q2 and D have the abovementioned meanings
are acylated with substituted hetaryl acetic acid derivatives of the formula (XV)

in which
Het and U have the abovementioned meanings,
for example following the method of Schotten-Baumann (Organikum [Organic Chemistry], VEB Deutscher Verlag der Wissenschaften, Berlin 1977, p. 505).
Some of the compounds of the formula (XV) are new. They can be synthesized by methods known in principle (see, for example, H. Henecka, Houben-Weyl, Methoden der Organischen Chemie [Methods in Organic Chemistry], Vol. 8, pp. 467-469 (1952)) or they are prepared in situ with the abovementioned reagents.
The compounds of the formula (XV) are obtained, for example, by reacting substituted hetaryl acetic acids of the formula (XVIII)




IE A 34 883-Foreiegn Countries

in which
Het has the abovementioned meaning
with halogenating agents (for example thionyl chloride, thionyl bromide, oxalyl chloride, phosgene, phosphorus trichloride, phosphorus tribromide or phosphorus pentachloride), if appropriate in the presence of a diluent (for example optionally chlorinated aliphatic or aromatic hydrocarbons such as toluene or methylene chloride) at temperatures of from -20°C to 150°C, preferably from -10°C to 100°C.
10
Some of the hetaryl acetic acids of the formula (XVITJ) are commercially available,
some of them are known or can be prepared by processes known in principle (C.S.
Rooney et al. J. Med. Chem. 26, 700-714 (1983); EP-A-368 592; M.S. Malamas et
al. J. Med. Chem. 39, 237-246 (1996); J. L. Collins et al. J. Med. Chem. 41, 5037-
15 5054 (1998); NL-A-66 14 130).
Some of the compounds of the formulae (XIV) and (XVII) are known and/or can be synthesized by known methods (see, for example, T. Suzuki et al., Synthetic Commun. 28,701 (1998), R. Graf, Justus Liebigs Ann. Chem. 661, 111 (1963)).
20
Furthermore, the starting materials of the formula (II)

in which
25
A, B, D, Q1, Q2, Het and R8 have the abovementioned meanings and which are used in the above process (A)


Le A 34 883-Foreiegn Countries
can be prepared when aminonitriles of the formula (XIX)

10
15


in which
A, B, Q1, Q2 and D have the abovementioned meanings
are reacted with substituted hetaryl acetic acid derivatives of the formula (XV)
in which
Het and U have the abovementioned meanings
to give compounds of the formula (XX)




20

in which
A, B, D, Q1, Q2 and Het have the abovementioned meanings


Le A 34 883-Foreign Countries

and subsequently subjecting the latter to acid alcoholysis.
The compounds of the formula (XX) are also new.
5 Some of the aminonitriles of the formula (XIX) are new and/or can be prepared by
known processes (T. Suzuki et al., Chem. Pharm. Bull. 46, 1116 (1998)).
The compounds of the formula (HI)


10

in which
A, B, Q1, Q2, Het and R8 have the abovementioned meanings
15 and which are required as starting materials in process (B) according to the invention
are new.
The acylhydroxycarboxylic esters of the formula (HI) are obtained, for example, when hydroxycarboxylic esters of the formula (XXI)


20

in which



Le A 34 883-Foreign Countries
A, B, Q1, Q2 and R8 have the abovementioned meanings are acylated with substituted hetaryl acetic acid derivatives of the formula (XV) 5
in which
Het and U have the abovementioned meaning 10
(see preparation example of compounds of the formula (HI)).
Some of the compounds of the formula (XXI) are known, commercially available or
can be prepared by processes known in principle, for example by Reformatskij
15 Synthesis (Organikum, VEB Deutscher Verlag der Wissenschaften, Berlin 1990, 18th
Ed., p. 501 et seq.)
The acid halides of the formula (IV), carboxylic anhydrides of the formula (V), chloroformic esters or chloroformic thioesters of the formula (VI),
20 chloromonothioformic esters or chlorodithioforrnic esters of the formula (VII),
sulphonyl chlorides of the formula (VIE), phosphorus compounds of the formula (IX) and metal hydroxides, metal alkoxides or amines of the formulae (X) and (XI) and isocyanates of the formula (XII) and carbamoyl chlorides of the formula (XIII), all of which are furthermore required as starting materials for carrying out processes (C),
25 (D), (E), (F), (G), (H) and (I) according to the invention, are generally known
compounds of organic or inorganic chemistry.
Some of the compounds of the formulae (XIV), (XVII), (XVIII), (XIX) and (XXI) are
commercially available, some of them are known and/or can be prepared by methods
30 known in principle.


Le A 34 883-Foreiegn Countries
Process (A) is characterized in that compounds of the formula (II) in which A, B, D, Q1, Q2, Het and R8 have the abovementioned meanings are subjected to an intramolecular condensation reaction in the presence of a base. 5
Diluents which can be employed in process (A) according to the invention are all
inert organic solvents. The following can preferably be used: hydrocarbons such as
toluene and xylene, furthermore ethers such as dibutyl ether, tetrahydrofuran,
dioxane, glycol dimethyl ether and diglycol dimethyl ether, moreover polar solvents,
10 such as dimethyl sulphoxide, sulpholane, dimethylformamide, dimethylacetamide
and N-methyl-pyrrolidone, and also alcohols such as methanol, ethanol, propanol, isopropanol, butanol, isobutanol and tert-butanol.
Bases (deprotonating agents) which can be employed when carrying out process (A)
15 according to the invention are all customary proton acceptors. The following can
preferably be used: the oxides, hydroxides and carbonates of alkali metals and
alkaline earth metals, such as sodium hydroxide, potassium hydroxide, magnesium
oxide, calcium oxide, sodium carbonate, potassium carbonate and calcium carbonate,
all of which can also be employed in the presence of phase-transfer catalysts such as,
20 for example, triethylbenzylammonium chloride, tetrabutylammonium bromide,
Adogen-464 (=methy]trialkyl(C8-C10)ammonium chloride) or TDA1 (=tris-
(methoxyethoxyethyl)-amine). Alkali metals such as sodium or potassium can
furthermore be used. Amides and hydrides of alkali metals and alkaline earth metals,
such as sodium amide, sodium hydride and calcium hydride are further possible
25 materials which can be used, as are, moreover, alkali metal alkoxides such as sodium
methoxide, sodium ethoxide and potassium tert-butoxide.
When carrying out process (A) according to the invention, the reaction temperatures
can be varied within a substantial range. In general, the process is carried out at
30 temperatures of between -80°C and 180°C, preferably between -50°C and 120°C.


Le A 34 883-Foreign Countries
Process (A) according to the invention is generally carried out under atmospheric pressure.
When carrying out process (A) according to the invention, the reactants of the
5 formula (II) and the deprotonating bases are generally employed in approximately
twice the equimolar amounts. However, it is possible to use one or the other reactants in a larger excess (up to 3 mol).
Process (B) is characterized in that compounds of the formula (HI) in which A, B,
10 Q1, Q2, Het and R8have the abovementioned meanings are subjected to an
intramolecular condensation reaction in the presence of a diluent and in the presence of a base.
Diluents which can be employed in process (B) according to the invention are all
15 inert organic solvents. The following can preferably be used: 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-methyl-
pyrrolidone, and also alcohols such as methanol, ethanol, propanol, isopropanol,
20 butanol, isobutanol and tert-butanol.
Bases (deprotonating agents) which can be employed when carrying out process (B) according to the invention are all customary proton acceptors. The following can preferably be used: the oxides, hydroxides and carbonates of alkali metals and
25 alkaline earth metals, such as sodium hydroxide, potassium hydroxide, magnesium
oxide, calcium oxide, sodium carbonate, potassium carbonate and calcium carbonate, all of which can also be employed in the presence of phase-transfer catalysts such as, for example, triethylbenzylammonium chloride, tetrabutylammonium bromide, Adogen 464 (=methyltrialkyl(C8-C10)amrnoniurn chloride) or TDA1 (=tris-
30 (methoxyethoxyethyl)-amine). Alkali metals such as sodium or potassium can
furthermore be used. Amides and hydrides of alkali metals and alkaline earth metals,


Le A 34 883-Foreign Countries
such as sodium amide, sodium hydride and calcium hydride are further possible materials which can be used, as are, moreover, alkali metal alkoxides such as sodium methoxide, sodium ethoxide and potassium tert-butoxide.
5 When carrying out process (B) according to the invention, the reaction temperatures
can be varied within a substantia] range. In general, the process is carried out at temperatures of between -80°C and 180°C, preferably between -50°C and 120°C.
Process (B) according to the invention is generally carried out under atmospheric
10 pressure.
When carrying out process (B) according to the invention, the reactants of the
formula (II) and the deprotonating bases are generally employed in approximately
twice the equimolar amounts. However, it is possible to use one or the other reactants
15 in a larger excess (up to 3 mol).
Process (C-α) is characterized in that compounds of the formulae (I-l-a) to (I-2-a) are in each case reacted with carboxylic acid halides of the formula (IV), if appropriate in the presence of a diluent and if appropriate in the presence of an acid binder.
20
Diluents" which can be employed in process (C-a) according to the invention are all solvents which are inert to the acid halides. The following can preferably be used: hydrocarbons such as benzine, benzene, toluene, xylene and tetralin, furthermore halogenohydrocarbons such as methylene chloride, chloroform, carbon tetrachloride,
25 chlorobenzene and o-dichlorobenzene, moreover ketones such as acetone and methyl
isopropyl ketone, furthermore ethers such as diethyl ether, tetrahydrofuran and dioxane, in addition carboxylic esters such as ethyl acetate, nitriles such as acetonitrile, or else strongly polar solvents such as dimethylformamide, dimethylacetamide, dimethyl sulphoxide and sulpholane. If the acid halide is
30 sufficiently stable to hydrolysis, the reaction may also be carried out in the presence
of water.


Le A 34 883-Foreign Countries
Suitable acid binders when carrying out the reaction in accordance with process (C-
α) according to the invention are all customary acid acceptors. The following can
preferably be used: tertiary amines such as triethylamine, pyridine,
5 diazabicyclooctane (DABCO), diazabicycloundecene (DBU), diazabicyclononene
(DBN), Hunig Base and N,N-dimethyl-anilin, furthermore alkali metal oxides such
as magnesium oxide and calcium oxide, moreover alkali metal carbonates and
alkaline earth metal carbonates such as sodium carbonate, potassium carbonate and
calcium carbonate, and alkali metal hydroxides such as sodium hydroxide and
10 potassium hydroxide.
When carrying out process (C-a) according to the invention, the reaction
temperatures may be varied within a substantial range. In general, the process is
carried out at temperatures of between -20°C and +150°C, preferably between 0°C
15 and 100°C.
When carrying out process (C-a) according to the invention, the starting materials of
the formulae (I-l-a) to (I-2-a) and the carboxylic acid halide of the formula (IV) are
generally in each case used in approximately equivalent amounts. However, it is also
20 possible to employ the carboxylic acid halides in a larger excess (of up to 5 mol).
Work-up is carried out by customary methods.
Process (C-6) is characterized in that compounds of the formulae (I-l-a) to (I-2-a) are
reacted with carboxylic anhydrides of the formula (V), if appropriate in the presence
25 of a diluent and if appropriate in the presence of an acid binder.
Diluents which can be used in process (C-B) according to the invention are preferably those diluents which are also preferably suitable when acid halides are used. Besides, a carboxylic anhydride used in excess may also simultaneously act as the diluent. 30


Le A 34 883-Foreign Countries
Suitable acid binders which are optionally added in process (C-B) are preferably those acid binders which are also preferably suitable when acid halides are used.
When carrying out process (C-6), the reaction temperatures can be varied within a
5 substantial range. In general, the process is carried out at temperatures of between
-20°C and +150°C, preferably between 0°C and 100°C.
When carrying out process (C-8) according to the invention, the starting materials of
the formulae. (I-l-a) to (I-2-a) and the carboxylic anhydride of the formula (V) are
10 generally employed in each case in approximately equivalent amounts. However, it is
also possible to employ the carboxylic anhydride in a larger excess (of up to 5 mol). Work-up is carried out by customary methods.
In general, a procedure is followed in which diluent, excess carboxylic anhydride and
15 the carboxylic acid which forms are removed by distillation or by washing with an
organic solvent or with water.
Process (D) is characterized in that compounds of the formulae (I-l-a) to (I-2-a) are
reacted in each case, with chloroformic esters or chloroformic thioesters of the
20 formula (VII), if appropriate in the presence of a diluent and if appropriate in the
presence Of acid binder.
Suitable acid binders for the reaction in accordance with process (D) according to the
invention are all customary acid acceptors. The following can preferably be used:
25 tertiary amines such as triethylamine, pyridine, DABCO, DBU, DBA, Htinig base
and N,N-dimethyl-anilin, furthermore alkali metal oxides such as magnesium oxide and calcium oxide, moreover alkali metal carbonates 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.
30


Le A 34 883-Foreign Countries
Diluents which can be employed in process (D) according to the invention are all
solvents which are inert to the chloroformic esters or chloroformic thioesters. The
following can preferably be used: hydrocarbons such as benzine, benzene, toluene,
xylene and tetraline, furthermore halogeno-hydrocarbons such as methylene chloride,
5 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, in addition carboxylic esters such as ethyl acetate, nitriles such as acetonitrile and also strongly polar solvents such as dimethylformamide, dimethylacetamide, dimethyl sulphoxide and sulpholane.
10
When carrying out process (D) according to the invention, the reaction temperatures can be varied within a substantial range. If the process is carried out in the presence of a diluent and of an acid binder, the reaction temperatures are generally between -20°C and +100°C, preferably between 0°C and 50°C.
15
Process (D) according to the invention is generally carried out under atmospheric pressure.
When carrying out process (D) according to the invention, the starting materials of
20 the formulae (I-l-a) to (I-2-a) and the corresponding chloroformic ester or
chloroformic thioester of the formula (VI) are generally used in each case in
approximately equivalent amounts. However, it is also possible to employ one or the
other reactant in a larger excess (of up to 2mol). Work-up is carried out by
customary methods. In general, a procedure is followed in which the salts which have
25 precipitated are removed and the reaction mixture which remains is concentrated by
stripping off the diluent.
Process (E) according to the invention is characterized in that compounds of the
formulae (I-l-a) to (I-2-a) are reacted in each case with compounds of the formula
30 (VII) in the presence of a diluent and, if appropriate, in the presence of an acid
binder.


V:

Le A 34 883-Foreign Countries
In preparation process (E), approximately 1 mol of chloromonothioformic ester or chlorodithioformic ester of the formula (VII) is reacted at from 0 to 120°C, preferably at from 20 to 60°C, per mole of starting compound of the formulae (I-l-a) to (I-2-a). 5
Suitable diluents which are optionally added are all inert polar organic solvents such as nitriles, esters, ethers, amides, sulphones, sulphoxides, but also halogenoalkanes.
Substances which are preferably employed are acetonitrile, ethyl acetate, dimethyl
10 sulphoxide, tetrahydrofuran, dimethylformamide or methylene chloride.
If, in a preferred embodiment, the enolate salt of the compounds (I-l-a) to (I-2-a) by
addition of strong deprotonating agents such as, for example, sodium hydride or
potassium tertiary-butyl ate, the further addition of acid binders can be dispensed
15 with.
If acid binders are employed, then customary inorganic or organic bases are suitable, with sodium hydroxide, sodium carbonate, potassium carbonate, pyridine and triethylamine being mentioned by way of example. 20
The reaction can be carried out under atmospheric pressure or under elevated pressure, preferably under atmospheric pressure. Work-up is carried out by customary methods.
25 Process (F) according to the invention is characterized in that compounds of the
formulae (I-l-a) to (I-2-a) are reacted in each case with sulphonyl chloride of the formula (VIII), if appropriate in the presence of a diluent and if appropriate in the presence of an acid binder.


Le A 34 883-Foreiegn Countries
In preparation process (F), approximately 1 mol of sulphonyl chloride of the formula (VIII) is reacted at from -20 to 150°C, preferably at from 20 to 70°C, per mole of starting compound of the formulae (I-l-a) to (I-2-a).
5 Suitable diluents which are optionally added are all inert polar organic solvents such
as nitriles, esters, ethers, amides, nitriles, sulphones, sulphoxides or halogenated hydrocarbons such as methylene chloride.
Substances which are preferably employed are acetonitrile, ethyl acetate, dimethyl
10 sulphoxide, tetrahydrofuran, dimethylformamide, methylene chloride.
If, in a preferred embodiment, the enolate salt of the compounds (I-l-a) to (I-2-a) is
synthesized by addition of strong deprotonating agents (such as, for example, sodium
hydride or potassium tertiary-butoxide), the further addition of acid binders can be
15 dispensed with.
If acid binders are employed, customary inorganic or organic bases are suitable, with sodium hydroxide, sodium carbonate, potassium carbonate, pyridine and triethylamine being mentioned by way of example. 20
The reaction can be carried out under atmospheric pressure or under elevated pressure, preferably under atmospheric pressure. Work-up is carried out by customary methods.
25 Process (G) according to the invention is characterized in that compounds of the
formulae (I-l-a) to (I-2-a) are reacted in each case with phosphorus compounds of the formula (IX), if appropriate in the presence of a diluent and if appropriate in the presence of an acid binder.
30 In preparation process (G), 1 to 2, preferably 1 to 1.3, mole of the phosphorus
compound of the formula (IX) are reacted at temperatures of between -40°C and


Le A 34 883-Foreign Countries
150°C, preferably between -10 and 110°C, per mole of the compounds (I-l-a) to (1-2-a) in order to obtain compounds of the formulae (I-l-e) to (I-2-e).
Suitable diluents which are optionally added are all inert polar organic solvents such
5 as ethers, amides, nitriles, alcohols, sulphides, sulphones, sulphoxides and the like.
Substances which are preferably employed are acetonitrile, dimethyl sulphoxide, tetrahydrofuran, dimethylformamide, methylene chloride.
10 Suitable acid binders which are optionally added are customary inorganic or organic
bases such as hydroxides, carbonates or amines. Examples which may be mentioned are sodium hydroxide, sodium carbonate, potassium carbonate, pyridine, triethylamine.
15 The reaction can be carried out under atmospheric pressure or under elevated
pressure, preferably under atmospheric pressure. Work-up is carried out by customary methods of organic chemistry. The resulting end products are preferably purified by crystallization, chromatography or by what is known as "incipient distillation", that is to say removal of the volatile components in vacuo.
20
Process (H) is characterized in that compounds of the formulae (I-l-a) to (I-2-a) are reacted with metal hydroxides or metal alkoxides of the formula (X) or amines of the formula (XI), if appropriate in the presence of a diluent.
25 Diluents which can be employed in process (I) according to the invention are,
preferably, ethers such as tetrahydrofuran, dioxane, diethyl ether, or else alcohols such as methanol, ethanol, isopropanol, but also water.
Process (H) according to the invention is generally carried out under atmospheric
30 pressure.


Le A 34 883-Foreign Countries

In general, the reaction temperatures are between -20°C and 100°C, preferably between 0°C and 50°C.
Process (I) according to the invention is characterized in that compounds of the
5 formulae (I-l-a) to (I-2-a) are reacted in each case with compounds of the formula
(XII) (I-a), if appropriate in the presence of a diluent and if appropriate in the presence of a catalyst, or (1-β) with compounds of the formula (XIII), if appropriate in the presence of a diluent and if appropriate in the presence of an acid binder.
10 When carrying out preparation process (I-a), approximately 1 mol of isocyanate of
the formula (XII) is reacted at from 0 to 100°C, preferably at from 20 to 50°C, per mole of starting compound of the formulae (I-l-a) to (I-2-a).
Suitable diluents which are optionally added are all inert organic solvents, such as
15 ethers, amides, nitriles, sulphones, sulphoxides.
If appropriate, catalysts may be added to accelerate the reaction. Catalysts which can be employed very advantageously are organotin compounds such as, for example, dibutyltin dilaurate. The process is preferably carried out under atmospheric pressure. 20
When carrying out preparation process (1-β), approximately I mol of carbamoyl chloride of the formula (XIII) is reacted at from -20 to 150°C, preferably at from 0 to 70°C, per mole of starting compound of the formulae (I-l-a) to (I-2-a).
25 Suitable diluents which are optionally added are all inert polar organic solvents such
as nitriles, esters, ethers, amides, sulphones, sulphoxides or halogenated hydrocarbons.
The substances which are preferably employed are acetonitrile, ethyl acetate,
30 dimethyl sulphoxide, tetrahydrofuran, dimethylformamide or methylene chloride.


Le A 34 883-Foreign Countries
If, in a preferred embodiment, the enolate salt of the compound (I-l-a) to (I-2-a) is synthesized by adding strong deprotonating agents (such as, for example, sodium hydride or potassium tertiary-butoxide), the further addition of acid binders can be dispensed with. 5
The active compounds are suitable for controlling animal pests, in particular insects,
arachnids and nematodes found in agriculture, in forests, in the protection of stored
products and materials, and in the hygiene sector, while being well tolerated by plants
and exhibiting a favourable toxicity to warm-blooded species. They can preferably be
10 employed as crop protection agents. They are active against normally sensitive and
resistant species and against all individual developmental stages. The abovementioned pests include:
From the order of the Isopoda, for example, Oniscus asellus, Armadillidium vulgare,
15 Porcellio scaber.
From the order of the Diplopoda, for example, Blaniulus guttulatus.
From the order of the Chilopoda, for example, Geophilus carpophagus, Scutigera
20 spp..
From the order of the Symphyla, for example, Scutigerella immaculata.
From the order of the Thysanura, for example, Lepisma saccharina. 25
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., Schistocerca gregaria. 30


Le A 34 883-Foreign Countries
From the order of the Blattaria, for example, Blatta orientalis, Periplaneta americana, Leucophaea maderae, Blattella germanica.
From the order of the Dermaptera, for example, Forficula auricularia. 5
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.. 10
From the order of the Thysanoptera, for example, Hercinothrips femoralis, Thrips tabaci, Thrips palmi, Frankliniella accidentalis.
From the order of the Heteroptera, for example, Eurygaster spp., Dysdercus
15 intermedius, Piesma quadrata, Cimex lectularius, Rhodnius prolixus, 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,
20 Phylloxera vastatrix, Pemphigus spp., Macrosiphum avenae, Myzus spp., Phorodon
humuli," Rhopalosiphum padi, Empoasca spp., Euscelis bilobatus, Nephotettix cincticeps, Lecanium comi, Saissetia oleae, Laodelphax striatellus, Nilaparvata lugens, Aonidiella aurantii, Aspidiotus hederae, Pseudococcus spp., Psylla spp.
25 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 jnsulana, Heliothis spp., Mamestra brassicae, Panolis flammea, Spodoptera
30 spp., Trichoplusia ni, Carpocapsa pomonella, Pieris spp., Chilo spp., Pyrausta
nubilaiis, Ephestia kuehniella, Galleria mellonella, Tineola bisselliella, Tinea


Le A 34 883-Foreign Countries
pellionella, Hofmannophila pseudospretella, Cacoecia podana, Capua reticulana, Choristoneura fumiferana, Clysia ambiguella, Homona magnanima, Tortrix viridana, Cnaphalocerus spp., Oulema oryzae.
5 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., Sitophilus spp., Otiorrhynchus sulcatus,
10 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, Costelytra zealandica, Lissorhoptrus oryzophilus.
15
From the order of the Hymenoptera, for example, Diprion spp., Hoplocampa spp., Lasius spp., Monomorium pharaonis, Vespa spp.
From the order of the Diptera, for example, Aedes spp., Anopheles spp., Culex spp.,
20 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., Liriomyza spp.. 25
From the order of the Siphonaptera, for example, Xenopsylla cheopis, Ceratophyllus
spp..
From the class of the Arachnida, for example, Scorpio maurus, Latrodectus mactans,
30 Acarus siro, Argas spp., Ornithodoros spp., Dermanyssus gallinae, Eriophyes ribis,
Phyllocoptruta oleivora, Boophilus spp., Rhipicephalus spp., Amblyomma spp.,


Le A 34 883-Foreign Countries
Hyalomma spp., Ixodes spp., Psoroptes spp., Chorioptes spp., Sarcoptes spp., Tarsonemus spp., Bryobia praetiosa, Panonychus spp., Tetranychus spp., Hemitarsonemus spp., Brevipalpus spp..
5 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., Bursaphelenchus spp..
10 If appropriate, the compounds according to the invention, in specific concentrations
or at specific application rates, can also be used as herbicides and microbicides, for example as fungicides, antimycotics and bactericides. If appropriate, they may also be used as intermediates or precursors for the synthesis of further active compounds.
15 All plants and plant parts can be treated in accordance with the invention. Plants are
understood, in the present context, as meaning all plants and plant populations such as desired and undesired wild plants or crop plants (including naturally occurring crop plants). Crop plants may be plants which can be obtained by conventional breeding and optimization methods or else by biotechnological and recombinant
20 methods or combinations of these methods, including the transgenic plants and the
plant varieties which can be protected or which cannot be protected by Plant Breeders' Rights. Plant parts are understood as meaning all aerial and subterraneous parts and organs of the plants, such as shoot, leaf, flower and root, with leaves, needles, stems, stalks, flowers, fruiting bodies, fruits and seeds and also roots, tubers
25 and rhizomes being mentioned by way of example. The plant parts also include
harvested material and vegetative and generative propagation material, for example cuttings, tubers, rhizomes, shoots and seeds.
The treatment according to the invention of the plants and plant parts with the active
30 compounds is affected directly or by acting on their environment or the surroundings
in which they grow or in which they are stored, using customary treatment methods,


Le A 34 883-Foreign Countries
for example by immersion, spraying, atomizing, forging, spreading, brushing on and, in the case of propagation material, in particular seeds, furthermore by coating with one or more coats.
5 The active compounds can be converted into the customary formulations such as
solutions, emulsions, wettable powders, suspensions, powders, dusts, pastes, soluble powders, granules, suspended emulsion concentrates, natural and synthetic materials impregnated with active compounds, and microencapsulations and polymeric substances.
10
These formulations are prepared in the known manner, for example by mixing the active compounds with extenders, that is to say liquid solvents and/or solid carriers, if appropriate using surfactants, that is to say emulsifiers and/or dispersants and/or foam formers.
15
If water is used as extender, it is also possible, for example, to use organic solvents as auxiliary solvents. Suitable liquid solvents are essentially: aromatics such as xylene, toluene, or alkylnaphthalenes, chlorinated aromatics and chlorinated aliphatic hydrocarbons, such as chlorobenzenes, chloroethylenes or methylene chloride,
20 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, and water.
25
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
30 synthetic minerals such as highly disperse silica, alumina and silicates; suitable solid
carriers for granules are: for example, crushed and fractionated natural rocks such as


Le A 34 883-Foreign Countries
calcite, marble, pumice, sepiolite, dolomite, and synthetic granules of inorganic or
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, non-ionic and anionic emulsifiers such as polyoxyethylene fatty acid esters,
5 polyoxyethylene fatty alcohol ethers, for example alkylaryl polyglycol ethers,
alkylsulphonates, alkyl sulphates, arylsulphonates and protein hydrolysates; suitable dispersants are: for example, lignin-sulphite waste liquors and methylcellulose.
Adhesives such as carboxymethylcellulose, natural and synthetic polymers in the
10 form of powders, granules or latices such as gum arabic, polyvinyl alcohol, polyvinyl
acetate, and natural phospholipids such as cephalins and lecithins and synthetic phospholipids may be used in the formulations. Other additives may be mineral and vegetable oils.
15 Colorants such as inorganic pigments, for example iron oxide, titanium oxide,
Prussian Blue, and organic dyestuffs such as alizarin, azo and metal phthalocyanin dyes and micronutrients such as salts of iron, manganese, boron, copper, cobalt, molybdenum and zinc may be used.
20 In general, the formulations 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,
may also be used in a mixture with known fungicides, bactericides, acaridices,
25 nematicides or insecticides, for example to widen the spectrum of action or to
prevent the build-up of resistance. In many cases, synergistic effects result, i.e. the activity of the mixture exceeds the activity of the individual components.
Examples of suitable components in mixtures are the following compounds:


Le A 34 883-Foreign Countries
Fungicides:
aldimorph, ampropylfos, ampropylfos-potassium, andoprim, anilazine, azaconazole,
5 azoxystrobin,
benalaxyl, benodanil, benomyl, benzamacril, benzamacryl-isobutyl, bialaphos, binapacryl, biphenyl, bitertanol, blasticidin-S, bromuconazole, bupirimate, buthiobate,
10 calcium polysulphide, capsimycin, captafol, captan, carbendazim, carboxin, carvone,
quinomethionate, chlobenthiazone, chlorfenazole, chloroneb, chloropicrin, chlorothalonil, chlozolinate, clozylacon, cufraneb, cymoxanil, cyproconazole, cyprodinil, cyprofuram,
15 debacarb, dichlorophen, diclobutrazole, diclofluanid, diclomezin, dicloran,
diethofencarb, difenoconazole, dimethirimol, dimethomorph, diniconazole, diniconazole-M, dinocap, diphenylamin, dipyrithione, ditalimfos, dithianon, dodemorph, dodine, drazoxolon,
20 ediphenphos, epoxiconazole, etaconazole, ethirimol, etridiazole,
famoxadon, fenapanil, fenarimol, fenbuconazole, fenfuram, fenitropan, fenpiclonil,
fenpropidin, fenpropimorph, fentin acetate, fentin hydroxyde, ferbam, ferimzone,
fluazinam, flumetover, fluoromid, fluquinconazole, flurprimidol, flusilazole,
25 flusulfamide, flutolanil, flutriafol, folpet, fosetyl-aluminium, fosetyl-sodium, fthalide,
fuberidazole, furalaxyl, furametpyr, furcarbonil, furconazole, furconazole-cis, furmecyclox,
guazatine, 30
hexachlorobenzene, hexaconazole, hymexazol,


Le A 34 883-Foreign Countries
imazalil, imibenconazole, iminoctadine, iminoctadine albesilate, iminoctadine triacetate, iodocarb, ipconazole, iprobenfos (EBP), iprodione, irumamycin, isoprothiolan, isovaledione, 5
kasugamycin, kresoxim-methyl, copper preparations such as: copper hydroxide, copper naphthenate, copper oxychloride, copper sulphate, copper oxide, oxine-copper and Bordeaux mixture,
10 mancopper, mancozeb, maneb, meferimzone, mepanipyrim, mepronil, metalaxyl,
metconazole, methasulphocarb, methfuroxam, metiram, metomeclam, metsulfovax, mildiomycin, myclobutanil, myclozolin,
nickel dimethyldithiocarbamate, nitrothal-isopropyl, nuarimol, 15
ofurace, oxadixyl, oxamocarb, oxolinic acid, oxycarboxim, oxyfenthiine,
paclobutrazole, pefurazoate, penconazole, pencycuron, phosdiphen, picoxystrobin,
pimaricin, piperalin, polyoxin, polyoxorim, probenazole, prochloraz, procymidone,
20 propamocarb, propanosine-sodium, propiconazole, propineb, pyraclostrobin,
pyrazophos, pyrifenox, pyrimethanil, pyroquilon, pyroxyfur,
quinconazole, quintozene (PCNB),
25 sulphur and sulphur preparations,
tebuconazole, tecloftalam, tecnazene, tetcyclacis, tetraconazole, thiabendazole,
thicyofen, thifluzamide, thiophanate-methyl, thiram, tioxymid, tolclofos-methyl,
tolylfluanid, triadimefon, triadimenol, triazbutil, triazoxide, trichlamide, tricyclazole,
30 tridemorph, trifloxystrobin, triflumizole, triforine, triticonazole,


Le A 34 883-Foreign Countries

uniconazole,
validamycin A, vinclozolin, viniconazole,
5 zarilamid, zineb, ziram and also
Dagger G,
OK-8705, 10
OK-8801,
α -( 1,1 -dimethylethyl-β-(2-phenoxyethyl)- 1H-1,2,4-triazole-1 -ethanol,
α-(2,4-dichlorophenyl)-β-fluoro-6-propyl-lH-l,2,4-triazole-l-ethanoI,
15 α-(2,4-dichlorophenyl)-β-methoxy-a-methyl-lH-l,2,4-triazole-l-ethanol,
α-(5-methyl-l,3-dioxan-5-yl)-β-[[4-(trifluoromethyl)-phenyl]-methylene]-lH-l,2,4-triazole-1-ethanol,
(5RS,6RS)-6-hydroxy-2,2,7,7-tetramethyl-5-(lH-l,2,4-triazol-l-yl)-3-octanone,
20 (E)-α-(methoxyimino)-N-methyl-2-phenoxy-phenylacetamide,
1 -isopropyl {2-methyl-1 -[[[ 1 -(4-methylphenyl)-ethyl]-amino]-carbonyl]-propyl} -
carbonate
25 l-(2,4-dichlorophenyl)-2-(lH-l,2,4-triazol-l-yl)-ethanoneO-(phenylmethyl)-oxime,
1-(2-methyl-1-naphthalenyl)-lH-pyrrole-2,5-dione,
l-(3,5-dichlorophenyl)-3-(2-propenyl)-2,5-pyrrolidinedione,
l-[(diiodomethyl)-sulphonyl]-4-methyl-benzene,
l-[[2-(2,4-dichlorophenyl)-l,3-dioxolan-2-yl]-methyl]-lH-imidazole,
30 l-[[2-(4-chlorophenyl)-3-phenyloxiranyl]-methyl]-lH-l,2,4-triazole,
l-[l-[2-[(2,4-dichlorophenyl)-methoxy]-phenyl]-ethenyl]-lH-imidazole,


Le A 34 883-Foreign Countries
l-methyl-5-nonyl-2-(phenylmethyl)-3-pyrroIidino],
2',6-dibromo-2-methy]-4'-trifluoromethoxy-4-trifluoromethy]-l,3-thiazole-5-
carboxanilide,
2,2-dichloro-N-[ 1 -(4-chlorophenyl)-ethyl]-1 -ethyl-3-methyl-cyclopropanecarboxamide,
5 2,6-dichloro-5-(methyJthio)-4-pyrimidinyl thiocyanate,
2,6-dichloro-N-(4-trifluoromethy]benzy])-benzamide,
2,6-dich]oro-N-[[4-(trifluoromethyl)-phenyl]-methyl]-benzamide,
2-(2,3,3-triiodo-2-propenyl)-2H-tetrazole,
2-[(l-methylethyl)-sulphonyl]-5-(trichloromethy])-l,3,4-thiadiazole,
10 2-([6-deoxy-4-0-(4-0-methyl-β-D-glycopyranosyl)-a-D-glucopyranosyl]-amino]-4-
methoxy-lH-pyrrolo[2,3-d]pyrimidine-5-carbonitrile,
2-aminobutane,
2-bromo-2-(brommethy])-pentanedJnitrile,
2-chloro-N-(2,3-dihydro-l,l,3-trimethyl-lH-inden-4-yl)-3-pyridinecarboxamide,
15 2-chloro-N-(2,6-dimethylphenyl)-N-(isothiocyanatomethyl)-acetamide,
2-phenylphenol(OPP),
3,4-dichloro-1-[4-(difluoromethoxy)-phenyl]-lH-pyrrole-2,5-dione,
3,5-dichIoro-N-[cyano[(l-methyl-2-propynyl)-oxy]-methyl]-benzamide,
3-(l,l-dimethy]propyl-l-oxo-lH-indene-2-carbonitrile,
20 3-[2-(4-chlorophenyl)-5-ethoxy-3-isoxazolidinyl]-pyridine,
4-chloro-2-cyano-N,N-dimethyl-5-(4-methylphenyl)-lH-imidazole-l-sulphonamide,
4-methyl-tetrazolo[ 1,5-a]quinazolin-5(4H)-one,
8-(l,l-dimethylethyl)-N-ethyl-N-propyl-l,4-dioxaspii:o[4.5]decane-2-methanamine)
8-hydroxyquinolin sulphate,
25 9H-xanthene-9-carboxylic acid 2-[(phenylamino)-carbonyl]-hydrazide,
bis-(l-methy]ethyl)-3-methyl-4-[(3-methylbenzoyl)-oxy]-2,5-thiophenedicarboxy]ate,
cis-l-(4-chlorophenyl)-2-(lH-l,2,4-triazol-l-yl)-cycloheptanol,
cis-4-[3-[4-(l,l-dimethylpropyl)-phenyl-2-methylpropyl]-2,6-dimethyl-morpholine
hydrochloride,
30 Ethyl [(4-chlorophenyl)-azo]-cyanoacetate,
potassium hydrogen carbonate,


Le A 34 883-Foreign Countries
sodium methane tetrathiolate,
methyl l-(2,3-dihydro-2,2-dimethyl-lH-inden-l-yl)-lH-imidazole-5-carboxy]ate,
methyl N-(2,6-dimethylphenyl)-N-(5-isoxazolylcarbonyl)-DL-alaninate,
methyl N-(chloroacetyl)-N-(2,6-dimethylphenyl)-DL-alaninate,
5 N-(2,3-dichloro-4-hydroxyphenyl)-l-methyl-cyclohexanecarboxamide,
N-(2,6-dimethylphenyl)-2-methoxy-N-(tetrahydro-2-oxo-3-furanyl)-acetamide,
N-(2,6-dimethylphenyl)-2-methoxy-N-(tetrahydro-2-oxo-3-thienyl)-acetamide,
N-(2-chloro-4-nitrophenyl)-4-methyl-3-nitro-benzenesulphonamide,
N-(4-cyclohexylphenyl)-l,4,5,6-tetrahydro-2-pyrimidinamine,
10 N-(4-hexylphenyl)-l,4,5,6-tetrahydro-2-pyrimidinamine,
N-(5-chloro-2-methylphenyl)-2-methoxy-N-(2-oxo-3-oxazolidinyl)-acetamide,
N-(6-methoxy)-3-pyridinyl)-cyclopropanecarboxamide,
N-[2,2,2-trichloro-l-[(chloroacetyl)-amino]-ethyl]-benzamide,
N-[3-chloro-4,5-bis-(2-propinyloxy)-phenyl]-N-methoxy-methanimidamide,
15 sodium N-formyl-N-hydroxy-DL-alaninate,
0,0-diethyl [2-(dipropylamino)-2 oxoethyl]-ethylphosphoramidothioate,
O-methyl S-phenyl phenylpropylphosphoramidothioate,
S-methyl 1,2,3-benzothiadiazole-7-carbothioate,
spiro[2H]-l-benzopyran-2,l,(3'H)-isobenzofuran]-3'-one,
20 4-[3,4-dimethoxyphenyl)-3-(4-fluorophenyl)-acryloyl]-morpho)ine
Bactericides:
bronopol, dichlorpphen, nitrapyrin, nickel dimethyldithiocarbamate, kasugamycin, oc-
25 thilinone, furancarboxylic acid, oxytetracyclin, probenazole, streptomycin, tecloftalam,
copper sulphate and other copper preparations.


Le A 34 883-Foreign Countries
Insecticides / Acaricides / Nematicides:
abamectin, acephate, acetamiprid, acrinathrin, alanycarb, aldicarb, aldoxycarb, alpha-
cypermethrin, alphamethrin, amitraz, avermectin, AZ 60541, azadirachtin,
5 azamethiphos, azinphos A, azinphos M, azocyclotin,
Bacillus popilliae, Bacillus sphaericus, Bacillus subtilis, Bacillus thuringiensis,
baculoviruses, Beauveria bassiana, Beauveria tenella, bendiocarb, benfuracarb,
bensultap, benzoximate, betacyfluthrin, bifenazate, bifenthrin, bioethanomethrin,
10 biopermethrin, bistrifluron, BPMC, bromophos A, bufencarb, buprofezin,
butathiofos, butocarboxim, butylpyridaben,
cadusafos, carbaryl, carbofuran, carbophenothion, carbosulphan, cartap,
chloethocarb, chlorethoxyfos, chlorfenapyr, chlorfenvinphos, chlorfluazuron,
15 chlormephos, chlorpyrifos, chlorpyrifos M, chlovaporthrin, chromafenozide, cis-
resmethrin, cispermethrin, clocythrin, cloethocarb, clofentezine, clothianidine, cyanophos, cycloprene, cycloprothrin, cyfluthrin, cyhalothrin, cyhexatin, cypermethrin, cyromazine,
20 deltamethrin, demeton M, demeton S, demeton-S-methyl, diafenthiuron, diazinon,
dichlorvos, dicofol, diflubenzuron, dimethoate, dimethylvinphos, diofenolan, disulfoton, docusate-sodium, dofenapyn,
eflusilanate, emamectin, empenthrin, endosulfan, Entomophthora spp., esfenvalerate,
25 ethiofencarb, ethion, ethoprophos, etofenprox, etoxazole, etrimfos,
fenamiphos, fenazaquin, fenbutatin oxide, fenitrothion, fenothiocarb, fenoxacrim,
fenoxycarb, fenpropathrin, fenpyrad, fenpyrithrin, fenpyroximate, fenvalerate,
fipronil, fluazinam, fluazuron, flubrocythrinate, flucycloxuron, flucythrinate,
30 flufenoxuron, flumethrin, flutenzine, fluvalinate, fonophos, fosmethilan, fosthiazate,
fubfenprox, furathiocarb,


Le A 34 883-Foreign Countries
granulosis viruses
halofenozide, HCH, heptenophos, hexaflumuron, hexythiazox, hydroprene, 5
imidacloprid, indoxacarb, isazofos, isofenphos, isoxathion, ivermectin,
nuclear polyhedrosis viruses
10 lambda-cyhalothrin, lufenuron
malathion, mecarbam, metaldehyde, methamidophos, Metharhizium anisopliae,
Metharhizium flavoviride, methidathion, methiocarb, methoprene, methomyl,
methoxyfenozide, metolcarb, metoxadiazone, mevinphos, milbemectin, milbemycin,
15 monocrotophos,
naled, nitenpyram, nithiazine, novaluron
omethoate, oxamyl, oxydemethon M 20
Paecilomyces fumosoroseus, parathion A, parathion M, permethrin, phenthoate,
phorate, phosalone, phosmet, phosphamidon, phoxim, pirimicarb, pirimiphos A,
pirimiphos M, profenofos, promecarb, propargite, propoxur, prothiofos, prothoate,
pymetrozine, pyraclofos, pyresmethrin, pyrethrum, pyridaben, pyridathion,
25 pyrimidifen, pyriproxyfen,
quinalphos,
ribavirin 30
salithion, sebufos, silafluofen, spinosad, spirodiclofen, sulfotep, sulprofos,


Le A 34 883-Foreiegn Countries
tau-fluvalinate, tebufenozide, tebufenpyrad, tebupirimiphos, teflubenzuron,
tefluthrin, temephos, temivinphos, terbufos, tetrachlorvinphos, tetradifon, theta-
cypermethrin, thiacloprid, thiamethoxam, thiapronil, thiatnphos, thiocyclam
5 hydrogen oxalate, thiodicarb, thiofanox, thuringiensin, tralocythrin, tralomethrin,
triarathene, triazamate, triazophos, triazuron, trichlophenidine, trichlorfon, triflumuron, trimethacarb,
vamidothion-, vaniliprole, Verticillium lecanii 10
YI5302
zeta-cypermethrin, zolaprofos
15 (lR-cis)-[5-(phenylmethyl)-3-furanyl]-methyl-3-[(dihydro-2-oxo-3(2H)-
furanylidene)-methyl] 2,2-dimethylcyclopropanecarboxylate
(3-phenoxyphenyl)-methyl 2,2,3,3-tetramethylcyclopropanecarboxylate
20 l-[(2-chloro-5-thiazolyl)methyl]tetrahydro-3,5-dimethyl-N-nitro-l,3,5-triazin-2(lH)-
imine
2-(2-chloro-6-fluorophenyl)-4-[4-(l, 1 -dimethylethyl)phenyl]-4,5-dihydro-oxazole
2-(acetyloxy)-3-dodecyl-l,4-naphthalenedione
25 2-chloro-N-[[[4-(l-phenylethoxy)-phenyl]-amino]-carbonyl]-benzamide
2-chloro-N-[[[4-(2,2-dichloro-l,l-difluorethoxy)-phenyl]-amino]-carbonyl]-
benzamide
3-methylphenyl propylcarbamate
4-[4-(4-ethoxyphenyl)-4-methylpentyl]-l-fluoro-2-phenoxy-benzene
30 4-chloro-2-(l,l-dimethylethyl)-5-[[2-(2,6-dimethyl-4-phenoxyphenoxy)ethyl]thio]-
3 (2H)-pyri dazinone


Le A 34 883-Foreign Countries
4-chloro-2-(2-chloro-2-methylpropyl)-5-[(6-iodo-3-pyridinyl)methoxy]-3(2H)-
pyridazinone
4-chloro-5-[(6-chloro-3-pyridinyl)methoxy]-2-(3,4-dichlorphenyl)-3(2H)-
pyridazinone
5 Bacillus thuringiensis strain EG-2348
[2-benzoyl-1 -(1,1 -di methylethyl )]-benzohydrazide
2,2-dimethyl-3-(2,4-dichlorophenyl)-2-oxo-l-oxaspiro[4.5]dec-3-en-4-yl-ester
butanoate
[3-[(6-chJoro-3-pyridinyl)methyl]-2-thiazolidinylidene]-cyanamide
10 dihydro-2-(nitromethylene)-2H-l,3-thiazine-3(4H)-carboxaldehyde
ethyl [2-[[l,6-dihydro-6-oxo-l-(phenylmethyl)-4-pyridazinyl]oxy]ethyl]-carbamate
N-(3,4,4-trifluoro-l-oxo-3-butenyl)-glycine
N-(4-chlorophenyl)-3-[4-(difluoromethoxy)phenyl]-4,5-dihydro-4-phenyl-lH-
pyrazole-1-carboxamide
15 N-[(2-chloro-5-thiazolyl)methyl]-N'-methyl-N"-nitro-guanidine
N-methyl-N'-(l-methyl-2-propenyl)-l,2-hydrazinedicarbothioamide
N-methyl-N'-2-propenyl-l ,2-hydrazine dicarbothioamide
0,0-diethyl [2-(dipropylamino)-2-oxoethy]]-ethylphosphoramidothioate
N-cyanomethyl-4-trifluoromethyl-nicotinamide
20 3,5-dich]oro-l-(3(3-dichloro-2-propenyloxy)-4-[3-(5-trifluoromethylpyridin-2-
yloxy)-propoxy]-benzene
A mixture with other known active compounds such as herbicides or with fertilizers and growth regulators is also possible.
25
When employed as insecticides, the active compounds according to the invention, in their commercially available formulations and in the use forms prepared from these formulations, may furthermore be present in a mixture with synergists. Synergists are compounds by which the action of the active compounds is increased without it being
30 necessary for the synergist added to be active itself.


Le A 34 883-Foreign Countries

The active compound content of the use forms prepared from the commerically available formulations can vary within wide ranges. The active compound concentration of the use forms can be from 0.0000001 to 95% by weight of active compound, preferably between 0.0001 and 1% by weight. 5
They are applied in a customary manner adapted to suit the use forms.
When used against hygiene and stored-product pests, the active compound is
distinguished by outstanding residual action on wood and clay and by good stability
10 to alkali on limed substrates.
As already mentioned above, all plants and their parts may be treated in accordance with the invention. In a preferred embodiment, plant species and plant varieties which occur in the wild or which have been obtained by conventional biological
15 breeding methods, such as hybridization or protoplast fusion, and parts of these plant
species and plant varieties are treated. In another preferred embodiment, transgenic plants and plant varieties which have been obtained by genetic engineering methods, if appropriate in combination with conventional methods (genetic modified organisms), and parts of these plants and plant varieties are treated. The term "parts"
20 and "parts of plants" or "plant parts" has been illustrated above.
Plants which are especially preferably treated in accordance with the invention are
those of the plant varieties which are commercially available or in use. Plant varieties
are understood as meaning plants with novel properties ("traits") which have been
25 bred by conventional breeding, by mutagenesis and also be recombinant DNA
techniques. They can take the form of varieties, biotypes and genotypes.
Depending on the plant species or plant varieties, their location and growth
conditions (soils, climate, vegetation period, nutrition), superadditive ("synergistic")
30 effects may also occur as a result of the treatment in accordance with the invention.
Thus, for example, reduced application rates and/or a widened spectrum of action


Le A 34 883-Foreign Countries
and/or an increased action 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 water or soil salinity, increased
flowering performance, facilitated harvesting, accelerated maturation, higher yields,
5 higher quality and/or higher nutritional value of the harvested products, better
storability and/or processability of the harvested products are possible, which exceed the actual effects to be expected.
The preferred transgenic plants or plant varieties (obtained by recombinant methods)
10 to be treated in accordance with the invention include all plants which, owing to
modification by recombinant means, contain genetic material which imparts 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 water or soil salinity, increased flowering performance,
15 facilitated harvesting, accelerated maturation, higher yields, higher quality and/or
higher nutritional value of the harvested products, better storability and/or processability of the harvested products. Other especially emphasized examples of such traits are an increased defence of the plants against animal and microbial pests such as against insects, mites, phytopathogenic fungi, bacteria and/or viruses, and an
20 increased tolerance of the plants to certain herbicidal active compounds. Examples of
transgenic plants which may be mentioned are important crop plants such as cereals (wheat, rice), maize, soya, potato, cotton, oil seed rape and fruit plants (with the fruits apples, pears, citrus fruit and grapes), with particular emphasis being placed on maize, soya, potato, cotton and oil seed rape. Traits which are particularly
25 emphasized are the increased defence of the plants against insects by toxins formed
in the plants, in particular those which are generated by the genetic material from Bacillus thuringiensis (for example, by the genes CrylA(a), CryLA(b), CryLA(c), CryIIA, CryIIIA, CryIIIB2, Cry9c Cry2Ab, Cry3Bb and CryIF and their combinations) in the plants (hereinbelow "Bt plants"). Other traits which are
30 particularly emphasized are the increased defence of plants against fungi, bacteria
and viruses by systemic acquired resistance (SAR), systemin, phytoalexins, elicitors


Le A 34 883-Foreign Countries

and resistance genes and correspondingly expressed proteins and toxins. Other traits
which are furthermore particularly emphasized are the increased tolerance of the
plants to certain herbicidal active compounds, for example imidazolinones, sulphonyl
ureas, glyphosate or phosphinothricin (for example "PAT" gene). The genes which
5 impart each of the desired traits may also occur in combination with each other in the
transgenic plants. Examples of "Bt plants" which may be mentioned are varieties of maize, cotton, soya and potato which are commercially available under the trade names YIELD GARD® (for example, maize, cotton, soya), KnockOut® (for example maize), StarLink® (for example maize), Bollgard® (cotton), Nucotn®
10 (cotton) and NewLeaf® (potato). Examples of herbicide-tolerant plants which may
be mentioned are varieties of maize, cotton and soya which are commercially available under the trade names Roundup Ready® (tolerance to glyphosate, for example maize, cotton, soya), Liberty Link® (tolerance to phosphinothricin, for example oil seed rape), IMI® (tolerance to imidazolinones) and STS® (tolerance to
15 sulphonyl ureas, for example maize). Herbicide-resistant plants (bred conventionally
for herbicide tolerance) which may also be mentioned are the varieties which are commercially available under the name Clearfield® (for example maize). Naturally, these statements also apply to plant varieties which will be developed in the future or which will be marketed in the future and which have these genetic traits, or genetic
20 traits to be developed in the future.
The plants stated can be treated particularly advantageously in accordance with the
invention with the compounds of the general formula I or the active compound
mixtures according to the invention. The preferred ranges stated above for the active
25 compounds or mixtures also apply to the treatment of these plants. The treatment of
plants with the compounds or mixtures specifically stated in the present text may be particularly emphasized.
The active compounds according to the invention not only act against plant, hygiene
30 and stored-product pests, but also, in the veterinary medicine sector, against animal
parasites (ectoparasites) such as hard ticks, soft ticks, scab mites, harvest mites, flies


Le A 34 883-Foreign Countries
(stinging and licking), parasitic fly larvae, lice, hair lice, bird lice and fleas. These parasites include:
From the order of the Anoplurida, for example, Haematopinus spp., Linognathus
5 spp., Pediculus spp., Phtirus spp., Solenopotes spp..
From the order of the Mallophagida and the suborders Amblycerina and
Ischnocerina, for example, Trimenopon spp., Menopon spp., Trinoton spp., Bovicola
spp., Werneckiella spp., Lepikentron spp., Damalina spp., Trichodectes spp., Felicola
10 spp..
From the order Diptera and the suborders Nematocenna and Brachycerina, for
example, Aedes spp., Anopheles spp., Culex spp., Simulium spp., Eusimulium spp.,
Phlebotomus spp., Lutzomyia spp., Culicoides spp., Chrysops spp., Hybomitra spp.,
15 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., Melophagus spp.. 20
From the order of the Siphonapterida, for example, Pulex spp., Ctenocephalides spp.,
Xenopsylla spp., Ceratophyllus spp..
From the order of the Heteropterida, for example, Cimex spp., Triatoma spp.,
Rhodnius spp., Panstrongylus spp.. 25
From the order of the Blattarida, for example, Blatta orientalis, Periplaneta
americana, Blattella germanica, Supella spp..
From the subclass of the Acaria (Acarida) and the orders of the Metastigmata and
30 Mesostigmata, for example, Argas spp., Ornithodorus spp., Otobius spp., Ixodes spp.,
Amblyomma spp., Boophilus spp., Dermacentor spp., Haemophysalis spp.,


Le A 34 883-Foreign Countries
Hyalomma spp., Rhipicephalus spp., Dermanyssus spp., Raillietia spp., Pneumonyssus spp., Sternostoma spp., Varroa spp..
From the order of the Actinedida (Prostigmata) and Acaridida (Astigmata), for
5 example, Acarapis spp., Cheyletiella spp., Omithocheyletia 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., Laminosioptes spp..
10
The active compounds of the formula (I) according to the invention are also suitable for controlling arthropodes which attack agricultural livestock such as, for example, cattle, sheep, goats, horses, pigs, donkeys, camels, buffalo, rabbits, chickens, turkeys, ducks, geese, honeybees, other domestic animals such as, for example, dogs, cats,
15 cage birds, aquarium fish and what are known as experimental animals such as, for
example, hamsters, guineapigs, rats and mice. By controlling these arthropodes, it is intended to reduce deaths and reduced performance (in meat, milk, wool, hides, eggs, honey and the like) so that more economic and simpler animal keeping is possible by employing the active compounds according to the invention.
20
The active compounds according to the invention are applied in the veterinary sector in a known manner by enteral administration in the form of, for example, tablets, capsules, drinks, drenches, granules, pastes, bolisis, the feed-through method, suppositories, by parenteral administration such as, for example, by injections
25 (intramuscular, subcutaneous, intravenous, intraperitoneal and the like), implants, by
nasal application, by dermal application in the form of, for example, immersing or bathing (dipping), spraying, pouring-on and spotting-on, washing, dusting and with the aid of shaped articles comprising active compound, such as collars, ear marks, tail marks, limb bands, halters, marking devices and the like.
30


Le A 34 883-Foreign Countries

When used for livestock, poultry, domestic animals and the like, the active
compounds of the formula (I) can be used as formulations (for example powders,
emulsions, flowables) comprising the active compounds in an amount of from 1 to
80% by weight, either directly or after 100 to 10 000-fold dilution, or they may be
5 used as a chemical bath.
Moreover, it has been found that the compound according to the invention has a potent insecticidal action against insects which destroy industrial materials.
10 The following insects may be mentioned by way of example and by preference, but
without limitation:
Beetles such as
Hylotrupes bajulus, Chlorophorus pilosis, Anobium punctatum, Xestobium
15 rufovillosum, Ptilinus pecticornis, Dendrobium pertinex, Emobius 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.
20 Hymenoptera 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
25 darwiniensis, Zootermopsis nevadensis, Coptotermes formosanus.
Bristle tails such as Lepisma saccharina.
Industrial materials in the present context are understood as meaning non-live
materials such as, preferably, polymers, adhesives, glues, paper and board, leather,
30 wood, tin products and paints.


Le A 34 883-Foreign Countries
The material to be protected from insect attack is very especially preferably wood and timber products.
Wood and timber products which can be protected by the agent according to the
5 invention or mixtures comprising it are to be understood as meaning, for example:
Construction timber, wooden beams, railway sleepers, bridge components, jetties,
vehicles made of wood, boxes, pallets, containers, telephone poles, wood lagging,
windows and doors made of wood, plywood, chipboard, joinery, or timber products
10 which quite generally are used in house construction or building joinery.
The active compounds can be used as such, in the form of concentrates or generally customary formulations such as powders, granules, solutions, suspensions, emulsions or pastes.
15
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 desired desiccants and UV stabilizers, and if desired colorants and pigments and other processing aids.
20
The insecticidal compositions or concentrates used for the protection of wood and timber products comprise the active compound according to the invention in a concentration of from 0.0001 to 95% by weight, in particular from 0.001 to 60% by weight.
25
The amount of the compositions or concentrates employed depends on the species and the abundance of the insects and of the medium. The optimal quantity to be employed can be determined in each case upon application by test series. In general, however, it will suffice to employ from 0.0001 to 20% by weight, preferably from
30 0.001 to 10% by weight, of the active compound, based on the material to be
protected.

Le A 34 883-Foreign Countries
A suitable solvent and/or diluent 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
5 appropriate, an emulsifier and/or wetter.
Organochemical solvents which are preferably employed are oil or oil-type solvents
with an evaporation number of above 35 and a flash point of above 30°C, preferably
above 45°C Such oily and oil-type solvents which are insoluble in water and of low
10 volatility and which are used are suitable mineral oils or their aromatic fractions or
mineral-oil-containing solvent mixtures, preferably white spirit, petroleum and/or alkyl benzene.
Mineral oils which are advantageously used are those with a boiling range of from
15 170 to 220°C, white spirit with a boiling range of from 170 to 220°C, spindle oil with
a boiling range of from 250 to 350°C, petroleum and aromatics with a boiling range of from 160 to 280°C, oil of turpentine, and the like.
In a preferred embodiment, liquid aliphatic hydrocarbons with a boiling range of
20 from 180 to 210°C or high-boiling mixtures of aromatic and aliphatic hydrocarbons
with a boiling range of from 180 to 220°C and/or spindle oil and/or monochloronaphthalene, preferably α-monochloronaphthalene, are used.
The organic oily or oil-type solvents of low volatility and with an evaporation
25 number of above 35 and a flash point of above 30°C, preferably above 45°C, can be
replaced in part 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 flash point of above 30°C, preferably above 45°C, and that the insecticide/fungicide mixture is soluble or emulsifiable in this solvent mixture. 30


Le A 34 883-Foreign Countries
In a preferred embodiment, some of the organochemical solvent or solvent mixture is replaced by an aliphatic polar organochemical solvent or solvent mixture. Aliphatic organochemical solvents which contain hydroxyl and/or ester and/or ether groups are preferably used, such as, for example, glycol ethers, esters or the like. 5
Organochemical binders used for the purposes of the present invention are the synthetic resins and/or binding drying oils which are known per se and which can be diluted in water and/or dissolved or dispersed or emulsified in the organochemical solvents employed, in particular binders composed of, or comprising, an acrylate
10 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/coumarone resin, silicone resin, drying vegetable and/or drying oils and/or physically drying binders based on a natural and/or synthetic resin.
15
The synthetic resin employed as binder can be employed in the form of an emulsion, dispersion or solution. Bitumen or bitumenous substances may also be used as binders, in amounts of up to 10% by weight. In addition, colorants, pigments, water repellents, odour-masking agents, and inhibitors or anticorrosive agents and the like,
20 all of which are known per se, can be employed.
In accordance with the invention, the composition or the concentrate preferably
comprises, as organochemical binder, at least one alkyd resin or modified alkyd resin
and/or a drying vegetable oil. Alkyd resins which are preferably used in accordance
25 with the invention are those with an oil content of over 45% by weight, preferably 50
to 68% by weight.
Some or all of the abovementioned binder can be replaced by a fixative (mixture) or
a plasticizer (mixture). These additives are intended to prevent volatilization of the
30 active compounds, and also crystallization or precipitation. They preferably replace
from 0.01 to 30% of the binder (based on 100% of the binder employed).


Le A 34 883-Foreign Countries
The plasticizers are from the chemical classes of the phthalic esters, such as dibutyl
phthalate, dioctyl phthalate or benzyl butyl phthalate, phosphoric esters such as
tributyl phosphate, adipic esters such as di-(2-ethylhexyl)-adipate, stearates such as
5 butyl stearate or amyl stearate, oleates such as butyl oleate, glycerol ethers or higher-
molecular-weight glycol ethers, glycerol esters and p-toluenesulphonic esters.
Fixatives are based chemically on polyvinyl alkyl ethers such as, for example,
polyvinyl methyl ether, or ketones such as benzophenone and ethylene
10 benzophenone.
Other suitable solvents or diluents are, in particular, also water, if appropriate in a mixture with one or more of the abovementioned organochemical solvents or diluents, emulsifiers and dispersants. 15
Particularly effective timber protection is achieved by industrial-scale impregnating processes, for example the vacuum, double-vacuum or pressure processes.
If appropriate, the compositions which are ready for use can additionally comprise
20 further insecticides and, if appropriate, additionally one or more fungicides.
Additional components in mixtures which are suitable are, preferably, the insecticides and fungicides stated in WO 94/29 268. The compounds stated in this document are expressly part of the present application. 25
Very especially preferred components in mixtures which can be used are insecticides such as chlorpyriphos, phoxim, silafluofin, alphamethrin, cyfluthrin, cypermethrin, deltamethrin, permethrin, imidacloprid, NI-25, flufenoxuron, hexaflumuron, transfluthrin, thiacloprid, methoxyphenoxide and triflumuron,


Le A 34 883-Foreign Countries
and fungicides such as epoxyconazole, hexaconazole, azaconazole, propiconazole, tebuconazole, cyproconazole, metconazole, imazalil, dichlorfluanid, tolylfluanid, 3-iod-2-propinyl butylcarbamate, N-octyl-isothiazolin-3-one and 4,5-dichloro-N-octylisothiazolin-3-one. 5
The compounds according to the invention can simultaneously also be employed for protecting objects which come into contact with salt water and brackish water, such as hulls, screens, nets, buildings, moorings and signalling systems, from fouling.
10 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
15 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.
20
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
25 active compounds, the use of heavy metals such as, for example, in bis(trialkyltin)
sulphides, tri-n-butyltin laurate, tri-n-butyltin chloride, copper(I) oxide, triethyltin chloride, tri-n-butyl(2-phenyl-4-chlorophenoxy)tin, tributyltin oxide, molybdenum disulphide, antimony oxide, polymeric butyl titanate, phenyl-(bispyridine)-bismuth chloride, tri-n-butyltin fluoride, manganese ethylenebisthiocarbamate, zinc
30 dimethyldithiocarbamate, zinc ethylenebisthiocarbamate, zinc salts and copper salts
of pyridine-2-thiol l-oxide, bisdimethyldithiocarbamoylzinc


Le A 34 883-Foreign Countries
ethylenebisthiocarbamate, zinc oxide, copper(I) ethylene-bisthiocarbamate, copper thiocyanate, copper naphthenate and tributyltin halides can be dispensed with, or the concentration of these compounds can be substantially reduced.
5 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
) 10 according to the invention are:
Algicides such as
2-tert-butylamino-4-cyclopropylamino-6-methylthio-l,3,5-triazine, dichlorophen,
15 diuron, endothal, fentin acetate, isoproturon, methabenzthiazuron, oxyfluorfen,
quinoclamine and terbutryn;
Fungicides such as
20 benzo[b]thiophenecarboxylic acid cyclohexylamide S,S-dioxide, dichlofluanid,
fluorfolpet, 3-iodo-2-propiny] butylcarbamate, tolylfluanid and azoles such as
azaconazole, cyproconazole, epoxyconazole, hexaconazole, metconazole, propi-conazole and tebuconazole;
Molluscicides such as
fentin acetate, metaldehyde, methiocarb, niclosamid, thiodicarb and trimethacarb; or traditional antifouling active compounds such as 30
4,5-dichloro-2-octyl-4-isothiazolin-3-one, diiodomethylparatryl sulphone, 2-(N,N-di-

Le A 34 883-Foreign Countries
methylthiocarbamoylthio)-5-nitrothiazyl, potassium salts, copper salts, sodium salts
and zinc salts of pyridine-2-thiol 1-oxide, pyridine-triphenylborane,
tetrabutyldistannoxane, 2,3,5,6-tetrachloro-4-(methyIsulphonyl)-pyridine, 2,4,5,6-
tetrachloroisophthalonitrile, tetramethylthiuram disulphide and 2,4,6-
5 trichlorophenylmaleinimide.
The antifouling compositions used comprise the active compound according to the
invention of the compounds according to the invention in a concentration of from
0.001 to 50% by weight, in particular 0.01 to 20% by weight. 10
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. 15
Besides the algicidal, fungicidal, molluscicidal active compounds and the insecticidal
active compounds according to the invention, antifouling paints comprise, in
particular, binders.
20 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/styrene/acrylonitrile rubbers, drying oils such as linseed oil, resin esters or
25 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
30 colorants which are preferably soluble in salt water. Paints may furthermore comprise
materials such as kolophonium to allow controlled release of the active compounds.


Le A 34 883-Foreign Countries
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. 5
The active compounds 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, either alone or
10 in combination with other active compounds and auxiliaries. They are effective
against sensitive and resistant species and against all developmental stages. These pests include:
From the order of the Scorpionidea, for example, Buthus occitanus.
15
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.
20
From the order of the Araneae, for example, Aviculariidae, Araneidae.
From the order of the Opiliones, for example, Pseudoscorpiones chelifer, Pseudoscorpiones cheiridium, Opiliones phalangium. 25
From the order of the Isopoda, for example, Oniscus asellus, Porcellio scaber.
From the order of the Diplopoda, for example, Blaniulus guttulatus, Polydesmus spp.. 30
From the order of the Chilopoda, for example, Geophilus spp..


Le A 34 883-Foreign Countries
From the order of the Zygentoma, for example, Ctenolepisma spp., Lepisma saccharina, Lepismodes inquilinus.
5 From the order of the Blattaria, for example, Blatta orientalies, Blattella germanica,
BJatJeJla asahinal, Leucophaea maderae, Panchlora spp., Parcoblatta spp., Periplaneta australasiae, Periplaneta americana, Periplaneta brunnea, Periplaneta fuliginosa, Supella longipalpa.
10 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. 15
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,
20 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
25 canicularis, Musca domestica, Phlebotomus spp., Sarcophaga carnaria, 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. 30


Le A 34 883-Foreign Countries
From the order of the Siphonaptera, for example, Ctenocephalides canis, Ctenocephalides felis, Pulex irritans, Tunga penetrans, Xenopsylla cheopis.
From the order of the Hymenoptera, for example, Camponotus herculeanus, Lasius
5 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. 10
From the order of the Heteroptera, for example, Cimex hemipterus, Cimex lectularius, Rhodinus prolixus, Triatoma infestans.
Application in the field of domestic insecticides is affected alone or in combination
15 with other suitable active compounds such as phosphoric esters, carbamates,
pyrethroides, growth regulators or active compounds from other known classes of insecticides.
They are used as aerosols, pressure-free spray products, for example pump and
20 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. 25
The active compounds according to the invention can also be used as defoliants,
desiccants, haulm killers and, especially, as weedkillers. By weeds, in the broadest
sense, are to be understood all plants which grow in locations where they are
undesired. Whether the substances according to the invention act as total or selective
30 herbicides depends essentially on the amount used.


Le A 34 883-Foreign Countries
The active compounds according to the invention can be used, for example, in connection with the following plants:
Dicotyledonous weeds of the genera: Abutilon, Amaranthus, Ambrosia, Anoda,
5 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, PJantago, Polygonum, Portulaca, Ranunculus, Raphanus, Rorippa, Rotala,
10 Rumex, Salsola, Senecio, Sesbania, Sida, Sinapis, Solanum, 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,
15 Nicotiana, Phaseolus, Pisum, Solanum, Vicia.
Monocotyledonous weeds of the genera: Aegilops, Agropyron, Agrostis, Alopecurus,
Apera, Avena, Brachiaria, Bromus, Cenchrus, Comrnelina, Cynodon, Cyperus,
Dactyloctenium, Digitaria, Echinochloa, Eleocharis, Eleusine, Eragrostis, Eriochloa,
20 Festuca, Fimbristylis, Heteranthera, Imperata, Ischaemum, Leptochloa, Lolium,
Monochbria, Panicum, Paspalum, Phalaris, Phleum, Poa, Rottboellia, Sagittaria, Scirpus, Setaria, Sorghum.
Monocotyledonous crops of the genera: Allium, Ananas, Asparagus, Avena,
25 Hordeum, Oryza, Panicum, Saccharum, Secale, Sorghum, Triticale, Triticum, Zea.
However, the use of the active compounds according to the invention is in no way restricted to these genera, but also extends in the same manner to other plants.
30 Depending on the concentration, the compounds are suitable for total weed control,
for example on industrial terrain and rail tracks, and on paths and areas with or


Le A 34 883-Foreign Countries
without tree stands. Equally, the compounds 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
5 plantings and hop fields, in lawns, turf and pastures, and for selective weed control in
annual crops.
The compounds of the formula (I) according to the invention show a potent
herbicidal activity and a broad spectrum of action when used on the soil and on aerial
10 plant parts. To a certain extent, they are also suitable for the selective control of
monocotyledonous and dicotyledonous weeds in monocotyledonous and dicotyledonous crops, both pre- and post-emergence.
At certain concentrations or application rates, the active compounds according to the
15 invention can also be used for controlling animal pests and fungal or bacterial plant
diseases. If appropriate, they can also be used as intermediates or precursors for the synthesis of further active compounds.
The active compounds can be converted into the customary formulations, such as
20 solutions, emulsions, wettable powders, suspensions, powders, dusts, pastes, soluble
powders, granules, suspoemulsion concentrates, natural and synthetic materials impregnated with active compound, and microencapsulations in polymeric substances.
25 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.
30 If water is used as an extender, organic solvents can, for example, also be used as
cosolvents. Liquid solvents which are mainly suitable are: aromatics such as xylene,


Le A 34 883-Foreign Countries

toluene or alkylnaphthalenes, chlorinated aromatics and chlorinated aliphatic
hydrocarbons such as chlorobenzenes, chloroethylenes or methylene chloride,
aliphatic hydrocarbons such as cyclohexane or paraffins, for example petroleum
fractions, mineral and vegetable oils, alcohols such as butanol or glycol as well as
5 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, and water.
Suitable solid carriers are: for example, ammonium salts and ground natural minerals
10 such as kaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite or
diatomaceous earth, and ground synthetic minerals 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
15 material such as sawdust, coconut shells, maize cobs and tobacco stalks; suitable
emulsifiers and/or foam formers are: for example, non-ionic and anionic emulsifiers,
such as polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers, for
example alkylaryl polyglycol ethers, alkylsulphonates, alkyl sulphates,
arylsulphonates and protein hydrolysates; suitable dispersants are: for example,
20 lignin-sulphite waste liquors and methylcellulose.
Adhesives 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
25 synthetic phospholipids can be used in the formulations. Further 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 dyestuffs such as alizarin dyestuffs,
30 azo dyestuffs and metal phthalocyanine dyestuffs, and trace nutrients such as salts of
iron, manganese, boron, copper, cobalt, molybdenum and zinc.


Le A 34 883-Foreign Countries
The formulations generally comprise between 0.1 and 95 per cent by weight of active compound, preferably between 0.5 and 90%.
5 For controlling weeds, the active compounds according to the invention, as such or in
the form of their formulations, can also be used as mixtures with known herbicides and/or with substances which improve the crop plant tolerance ("safeners"), ready mixes or tank mixes being possible. Thus, mixtures with weed killers comprising one or more known herbicides and a safener are also possible. 10
Suitable herbicides for the mixtures are known herbicides, for example
acetochlor, acifluorfen ( sodium), aclonifen, alachlor, alloxydim (-sodium), ametryne, amicarbazone, amidochlor, amidosulfuron, anilofos, asulam, atrazine,
15 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,
20 chloridazon, chlorimuron (-ethyl), chlomitrofen, 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, di-allate, dicamba, dichlorprop (-P), diclofop
25 (-methyl), diclosulam, diethatyl (-ethyl), difenzoquat, diflufenican, diflufenzopyr,
dimefuron, dimepiperate, dimethachlor, dimethametryn, dimethenamid, dimexyflam, dinitramine, diphenamid, diquat, dithiopyr, diuron, dymron, epropodan, EPTC, esprocarb, ethalfluralin, ethametsulfuron (-methyl), ethofumesate, ethoxyfen, ethoxysulfuron, etobenzanid, fenoxaprop (-P-ethyl), fentrazamide, flamprop
30 (-isopropyl, -isopropyl-L, -methyl), flazasulfuron, florasulam, fluazifop (-P-butyl),
fluazolate, flucarbazone (-sodium), flufenacet, flumetsulam, flumiclorac (-pentyl),


Le A 34 883-Foreign Countries
flumioxazin, flumipropyn, flumetsulam, fluometuron, fluorochloridone,
fluoroglycofen (-ethyl), flupoxam, flupropacil, flurpyrsulfuron (-methyl, -sodium),
flurenol (-butyl), fluridone, fluroxypyr (-butoxypropyl, -meptyl), flurprimidol,
flurtamone, fluthiacet (-methyl), fluthiamide, fomesafen, foramsulfuron, glufosinate
5 (-ammonium), glyphosate (-isopropylammonium), halosafen, haloxyfop
( ethoxyethyl, -P-methyl), 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,
10 mecoprop, mefenacet, mesotrione, metamitron, metazachlor, methabenzthiazuron,
metobenzuron, metobromuron, (alpha-) metolachlor, metosulam, metoxuron, metribuzin, metsulfuron (-methyl), molinate, monolinuron, naproanilide, naprop-amide, neburon, nicosulfuron, norflurazon, orbencarb, oryzalin, oxadiargyl, oxa-diazon, oxasulfuron, oxaziclomefone, oxyfluorfen, paraquat, pelargonic acid, pendi-
15 methalin, pendralin, pentoxazone, phenmedipham, picolinafen, 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, pyriftalid,
20 pyriminobac (-methyl), pyrithiobac (-sodium), quinchlorac, quinmerac,
quinoclamine, quizalofop (-P-ethyl, -P-tefuryl), rimsulfuron, sethoxydim, simazine, simetryn, sulcotrione, sulfentrazone, sulfometuron (-methyl), sulfosate, sulfosulfuron, tebutam, tebuthiuron, tepraloxydim, terbuthylazine, terbutryn, thenylchlor, thiafluamide, thiazopyr, thidiazimin, thifensulfuron (-methyl), thiobencarb,
25 tiocarbazil, tralkoxydim, tri-allate, triasulfuron, tribenuron (-methyl), triclopyr,
tridiphane, trifluralin, trifloxysulfuron, triflusulfuron (-methyl), tritosulfuron.
Furthermore, safeners which are suitable for the mixtures are known safeners, for
example:
30 AD-67, BAS-145138, benoxacor, cloquintocet (-mexyl), cyometrinil, 2,4-D, DKA-
24, dichlormid, dymron, fenclorim, fenchlorazol (-ethyl), flurazole, fluxofenim,


Le A 34 883-Foreign Countries
furilazole, isoxadifen (-ethyl), MCPA, mecoprop (-P), mefenpyr (-diethyl), MG-191, oxabetrinil, PPG-1292, R-29148.
Mixtures with other known active compounds such as fungicides, insecticides,
5 acaricides, nematicides, bird repellants, plant nutrients and soil conditioners are also
possible.
The active compounds can be used as such, in the form of their formulations or in the
use forms prepared therefrom by further dilution, such as ready-to-use solutions,
10 suspensions, emulsions, powders, pastes and granules. They are used in the
customary manner, for example by watering, spraying, atomizing or spreading.
The active compounds according to the invention can be applied either before or after emergence of the plants. They can also be incorporated into the soil before sowing.
15
The amount of active compound used can vary within a substantial range. It depends essentially on the nature of the desired effect. In general, the amounts used are between 1 g and 10 kg of active compound per hectare of soil surface, preferably between 5 g and 5 kg per ha.
20
The substances according to the invention exhibit a potent microbicidal action and can be employed for controlling undesired microorganisms, such as fungi and bacteria, in crop protection and in the protection of materials.
25 Fungicidal agents are employed in crop protection for controlling
Plasmodiophoromycetes, Oomycetes, Chytridiomycetes, Zygomycetes, Ascomycetes, Basidiomycetes and Deuteromycetes.
Bactericidal agents are employed in crop protection for controlling
30 Pseudomonadaceae, Rhizobiaceae, Enterobacteriaceae, Corynebacteriaceae and
Streptomycetaceae.


Le A 34 883-Foreign Countries
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:
5 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;
15 Pseudoperonospora species, such as, for example, Pseudoperonospora humuli or
Pseudoperonospora cubensis;
Plasmopara species, such as, for example, Plasmopara viticola;
20 Bremia species, such as, for example, Bremia lactucae
Peronospora species, such as, for example, Peronospora pisi or P. brassicae;
Erysiphe species,, such as, for example, Erysiphe graminis; 25
Sphaerotheca species, such as, for example, Sphaerotheca fuliginea;
Podosphaera species, such as, for example, Podosphaera leucotricha;
30 Venturia species, such as, for example, Venturia inaequalis;


Le A 34 883-Foreign Countries
Pyrenophora species, such as, for example, Pyrenophora teres or P. graminea
(conidial form: Drechslera, syn: Helminthosporium);
5 Cochliobolus species, such as, for example, Cochliobolus sativus
(conidial form: Drechslera, syn: Helminthosporium);
Uromyces species, such as, for example, Uromyces appendiculatus;
10 Puccinia species, such as, for example, Puccinia recondita;
Sclerotinia species, such as, for example, Sclerotinia sclerotiorum
Tilletia species, such as, for example, Tilletia caries; 15
Ustilago species, such as, for example, Ustilago nuda or Ustilago avenae;
Pellicularia species, such as, for example, Pellicularia sasakii;
20 Pyricularia species, such as, for example, Pyricularia oryzae;
Fusarium species, such as, for example, Fusarium culmorum;
Botrytis species, such as, for example, Botrytis cinerea; 25
Septoria species, such as, for example, Septoria nodorum;
Leptosphaeria species, such as, for example, Leptosphaeria nodorum;
30 Cercospora species, such as, for example, Cercospora canescens;


Le A 34 883-Foreien Countries

Alternaria species, such as, for example, Altemaria brassicae and
Pseudocercosporella species, such as, for example, Pseudocercosporella herpotrichoides. 5
The active compounds according to the invention also exhibit a potent strengthening effect in plants. They are therefore suitable for mobilizing the plants' intrinsic defences against attack by undesired microorganisms.
10 Plant-strengthening (resistance-inducing) substances are to be understood as meaning,
in the present context, those substances which are capable of stimulating the defence system of plants in such a way that the treated plants, when subsequently inoculated with undesired microorganisms, develop a high degree of resistance to these microorganisms.
15
Undesired microorganisms are understood as meaning, in the present case, phytopathogenic fungi, bacteria and viruses. The substances according to the invention can thus be employed to protect plants against infection by the abovementioned pathogens within a specific period post-treatment. The period within which protection
20 is brought about generally extends from 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 aerial plant parts, of
25 propagation stock and seeds, and of the soil.
The active compounds according to the invention are also suitable for increasing the yield. Moreover, they have a low degree of toxicity and are well tolerated by plants.
30 If appropriate, the active compounds according to the invention can also be employed
in specific concentrations and application rates as herbicides, for influencing plant


Le A 34 883-Foreign Countries

growth, and for controlling animal pests. If appropriate, they may also be employed as intermediates and precursors for the synthesis of further active compounds.
In the protection of materials, the substances according to the invention can be
5 employed for protecting industrial materials against infection with, and destruction by,
undesired microorganisms.
Industrial materials in the present context are understood as meaning non-live materials which have been prepared for use in industry. For example, industrial materials which
10 are intended to be protected by active compounds according to the invention from
microbial change or destruction can be glues, sizers, paper and board, textiles, leather, wood, paints and synthetic 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 multiplication of
15 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 glues, sizers, paper and board, leather, wood, paints, cooling lubricants and heat-transfer liquids, especially preferably wood.
20 Microorganisms which may bring about degradation of, or change in, the industrial
materials, and 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.
25
Microorganisms of the following genera may be mentioned by way of example:
Altemaria, such as Altemaria tenuis,
30 Aspergillus, such as Aspergillus niger,


Le A 34 883-Foreign Countries
Chaetomium, such as Chaetomium globosum,
Coniophora, such as Coniophora puetana,
5 Lentinus, such as Lentinus tigrinus,
Penicillium, such as Penicillium glaucum,
Polyporus, such as Polyporus versicolor, 10
Aureobasidium, such as Aureobasidium pullulans,
Sclerophoma, such as Sclerophoma pityophila,
15 Trichoderma, such as Trichoderma viride,
Escherichia, such as Escherichia coli,
Pseudomonas, such as Pseudomonas aeruginosa, 20
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,
25 emulsions, suspensions, powders, foams, pastes, granules, aerosols,
microencapsulations in polymeric substances and in coating compositions for seed, and also ULV cold- and warm-fogging products.
These formulations are produced in a known manner, for example by mixing the
30 active compounds with extenders, that is liquid solvents, pressurized liquified gases
and/or solid carriers, optionally with the use of surfactants, that is emulsifiers and/or


Le A 34 883-Foreign Countries
dispersants and/or foam-formers. If water is used as an extender, organic solvents
can, for example, also be used as cosolvents. Liquid solvents which are mainly
suitable are: aromatics such as xylene, toluene or alkylnaphthalenes, chlorinated
aromatics and chlorinated aliphatic hydrocarbons such as chlorobenzenes,
5 chloroethylenes or methylene chloride, aliphatic hydrocarbons such as cyclohexane
or paraffins, for example petroleum fractions, mineral and vegetable oils, alcohols such as butanol or glycol as well as 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, and water. Liquified
10 gaseous extenders or carriers are those liquids which are gaseous at normal
temperature and under atmospheric pressure, for example aerosol propellents such as halogenohydrocarbons and also butane, propane, nitrogen and carbon dioxide. Solid carriers which are suitable are: for example, ground natural minerals such as kaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth, and
15 ground synthetic minerals 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, and 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
20 formers are: for example, non-ionic and anionic emulsifiers, such as polyoxyethylene
fatty acid esters, polyoxyethylene fatty alcohol ethers, for example alkylaryl polyglycol ethers, alkylsulphonates, alkyl sulphates, arylsulphonates and protein hydrolysates. Suitable dispersants are: for example, lignin-sulphite waste liquors and methylcellulose.
25
Adhesives 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 natural phospholipids such as cephalins and lecithins, and synthetic phospholipids can be used in the formulations. Further additives can be
30 mineral and vegetable oils.


Le A 34 883-Foreign Countries
It is possible to use colourants 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. 5
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 may be present, as such or in their
10 formulations, in a mixture with known fungicides, .bactericides, acaridices,
nematicides, or insecticides, for example to widen the spectrum of action or to prevent the build-up of resistance. In many cases, synergistic effects result, i.e. the activity of the mixture exceeds the activity of the individual components.
15 Examples of suitable components in mixtures are the following compounds:
Fungicides:
aldimorph, ampropylfos, ampropylfos-potassium, andoprim, anilazine, azaconazole,
20 azoxystrobin,
benalaxyl, benodanil, benomyl, benzamacril, benzamacryl-isobutyl, bialaphos, binapacryl, biphenyl, bitertanol, blasticidin-S, bromuconazole, bupirimate, buthiobate,
25 calcium polysulphide, capsimycin, captafol, captan, carbendazim, carboxin, carvone,
quinomethionate, chlobenthiazone, chlorfenazole, chloroneb, chloropicrin, chlorothalonil, chlozolinate, clozylacon, cufraneb, cymoxanil, cyproconazole, cyprodinil, cyprofuram,
30 debacarb, dichlorophen, diclobutrazole, diclofluanid, diclomezin, dicloran,
diethofencarb, difenoconazole, dimethirimol, dimethomorph, diniconazole,


Le A 34 883-Foreign Countries
diniconazole-M, dinocap, diphenylamin, dipyrithione, ditalimfos, dithianon, dodemorph, dodine, drazoxolon,
ediphenphos, epoxiconazole, etaconazole, ethirimol, etridiazole, 5
famoxadon, fenapanil, fenarimol, fenbuconazole, fenfuram, fenitropan, fenpiclonil,
fenpropidin, fenpropimorph, fentin acetate, fentin hydroxyde, ferbam, ferimzone,
fluazinam, flumetover, fluoromid, fluquinconazole, flurprimidol, flusilazole,
flusulfamide, flutolanil, flutriafol, folpet, fosetyl-aluminium, fosetyl-sodium, fthalide,
10 fuberidazole, furalaxyl, furametpyr, furcarbonil, furconazole, furconazole-cis,
furmecyclox,
guazatine,
15 hexachlorobenzene, hexaconazole, hymexazol,
imazalil, imibenconazole, iminoctadine, iminoctadine albesilate, iminoctadine triacetate, iodocarb, ipconazole, iprobenfos (IBP), iprodione, irumamycin, isoprothiolan, isovaledione, 20
kasugamycin, kresoxim-methyl, copper preparations such as: copper hydroxide, copper naphthenate, copper oxychloride, copper sulphate, copper oxide, oxine-copper and Bordeaux mixture,
25 mancopper, mancozeb, maneb, meferimzone, mepanipyrim, mepronil, metalaxyl,
metconazole, methasulfocarb, methfuroxam, metiram, metomeclam, metsulfovax, mildiomycin, myclobutanil, myclozolin,
nickel dimethyldithiocarbamate, nitrothal-isopropyl, nuarimol, 30
ofurace, oxadixyl, oxamocarb, oxolinic acid, oxycarboxim, oxyfenthiine,


Le A 34 883-Foreign Countries
paclobutrazole, pefurazoate, penconazole, pencycuron, phosdiphen, picoxystrobin,
pimaricin, piperalin, polyoxin, polyoxorim, probenazole, prochloraz, procymidone,
propamocarb, propanosine-sodium, propiconazole, propineb, pyraclostrobin,
5 pyrazophos, pyrifenox, pyrimethanil, pyroquilon, pyroxyfur,
quinconazole, quintozene (PCNB),
sulphur and sulphur preparations,
10
tebuconazole, tecloftalam, tecnazene, tetcyclacis, tetraconazole, thiabendazole, thicyofen, thifluzamide, thiophanate-methyl, thiram, tioxymid, tolclofos-methyl, tolylfluanid, triadimefon, triadimenol, triazbutil, triazoxide, trichlamide, tricyclazole, tridemorph, trifloxystrobin, triflumizole, triforine, triticonazole,
15
uniconazole,
validamycin A, vinclozolin, vjniconazole,
20 zarilamid, zineb, ziram and also
Dagger G,
OK-8705, 25
OK-8801,
α-( 1,1 -dimethylethyl)-β-(2-phenoxyethyl)-1H-1,2,4-triazole-1 -ethanol,
α-(2,4-dichlorophenyl)-β-fluoro-b-propyl-lH-l,2,4-triazo]e-l-ethanol,
30 α-(2,4-dichlorophenyl)-β-methoxy-a-methyl-lH-l,2,4-triazole-l-ethanol,


Le A 34 883-Foreign Countries
α-(5-methyl-l,3-dioxan-5-yl)-8-[[4-(trifluoromethyl)-phenyl]-methylene]-lH-l,2,4-triazole-1-ethanol,
(5RS,6RS)-6-hydroxy-2,2,7,7-tetramethy]-5-(lH-l,2,4-triazoM-y])-3-octanone,
5 (E)-a-(methoxyimino)-N-methyl-2-phenoxy-phenylacetamide,
1-isopropyl {2-methyl-l-[[[l-(4-methylphenyl)-ethyl]-amino]-carbonyl]-propyl}-
carbonate
10 l-(2,4-dichlorophenyl)-2-(lH-l ,2,4-triazol-l-yl)-ethanone 0-(phenylmethyl)-oxime,
l-(2-methyl-l-naphthalenyl)-lH-pyrrole-2,5-dione,
l-(3,5-dichlorophenyl)-3-(2-propenyl)-2,5-pyrrolidinedione,
l-[(diiodomethyl)-sulphonyl]-4-methyl-benzene,
l-[[2-(2,4-dichlorophenyl)-l,3-dioxo]an-2-y]]-methyI]-lH-imidazo]e,
15 l-[[2-(4-chlorophenyl)-3-phenyloxiranyl]-methyl]-lH-l,2,4-triazole,
l-[l-[2-[(2,4-dichlorophenyl)-methoxy]-phenyl]-ethenyl]-lH-imidazole,
l-methyl-5-nony]-2-(phenylmethy])-3-pyrrolidinol,
2,,6'-dibrorno-2-rnethy]4,-trif]uoromethoxy-4'-trif]uoroniethy]-l,3-thiazole-5-
20 carboxanilide,
2,2-dichloro-N-[l-(4-chlorophenyl)-ethyl]-l-ethyl-3-methyl-cyclopropanecarboxamide,
2,6-dichIoro-5-(methylthio)-4-pyrimidinyl thiocyanate,
2,6-dichloro-N-(4-trifluoromethylbenzyl)-benzamide,
2,6-dichloro-N-[[4-(trifluoromethyl)'phenyl]-methyl]-benzamide,
25 2-(2,3,3-triiodo-2-propenyl)-2H-tetrazole,
2-[(l-methylethy])-su]phonyl]-5-(trichloromethyl)-l,3,4-thiadiazo]e,
2-[[6-deoxy-4-0-(4-0-methy]-B-D-glycopyranosyl)-a-D-glucopyranosyl]-amino]-4-
methoxy-lH-pyrrolo[2,3-d]pyrimidine-5-carbonitri]e,
2-aminobutane,
30 2-bromo-2-(brommethyl)-pentanedinitrile,
2-chloro-N-(2,3-dihydro-1,1,3-trimethyl- lH-inden-4-yl)-3-pyridinecarboxamide,


a

Le A 34 883-Foreign Countries
2-chloro-N-(2,6-dimethy]phenyl)-N-(isothiocyanatomethy])-acetamide, 2-phenylphenol(OPP),
3,4-dich]oro-l-[4-(difluoromethoxy)-pheny]]-lH-pyrrole-2,5-dione,
5 3,5-dichloro-N-[cyano[(l-methyl-2-propynyl)-oxy]-methyl]-benzamide,
3-( 1,1 -dimethylpropyl-1 -oxo- lH-indene-2-carbonitrile, 3-[2-(4-chlorophenyl)-5-ethoxy-3-isoxazolidinyl]-pyridine,
4-chloro-2-cyano-N,N-dimethyI-5-(4-rnethy]phenyl)-lH-imidazole-l-sulphonamide,
10 4-methyl-tetrazolo[l,5-a]quinazolin-5(4H)-one,
8-(l,l-dimethylethyl)-N-ethy]-N-propyl-l,4-dioxaspiro[4.5]decane-2-methanamine, 8-hydroxyquinolin sulphate,
9H-xanthene-9-carboxylic acid 2-[(phenylarnino)-carbonyl]-hydrazide,
15
bis(l-methylethyl)-3-methyl-4-[(3-methylbenzoyl)-oxy]-2,5-thiophenedicarboxylate, cis-1 -(4-chlorophenyl)-2-( 1H-1,2,4-triazol-1 -yl)-cycloheptanol, cis-4-[3-[4-(l,l-dimethy]propyl)-phenyl-2-methylpropyl]-2,6-dimethyJ-morpho]ine hydrochloride,
20
Ethyl [(4-chlorophenyl)-azo]-cyanoacetate,
potassium hydrogen carbonate,
25 Sodium methane tetrathiolate,
methyl l-(2,3-dihydro-2,2-dimethyl-lH-inden-l-yl)-lH-imidazole-5-carboxylate, methyl N-(2,6-dimethylphenyl)-N-(5-isoxazolylcarbonyl)-DL-alaninate, methyl N-(chloroacetyI)-N-(2,6-dimethylphenyl)-DL-alaninate, N-(2,3-dichloro-4-hydroxyphenyl)-1 -methyl-cyclohexanecarboxamide,
30 N-(2,6-dimethylphenyl)-2-methoxy'N-(tetrahydro-2-oxo-3-furanyl)-acetamide,
N-(2,6-dimethylphenyl)-2-methoxy-N-(tetrahydro-2-oxo-3-thienyl)-acetamide,


Le A 34 883-Foreign Countries
N-(2-chloro-4-nitrophenyJ)-4-methyJ-3-nitro-benzenesulphonamide,
N-(4-cyc]ohexylphenyl)-l,4,5,6-tetrahydro-2-pyrimidinamine,
N-(4-hexylphenyl)-l,4,5,6-tetrahydro-2-pyrimidinamine,
N-(5-chloro-2-methy]phenyl)-2-methoxy-N-(2-oxo-3-oxazolidiny])-acetamide,
5 N-(6-methoxy)-3-pyridinyl)-cyclopropanecarboxamide,
N-[2,2,2-trich]oro-l-[(chloroacetyl)-amino]'ethyl]-benzamide, N-[3-chloro-4,5-bis-(2-propinyloxy)-phenyl]-N'-rnethoxy-rnethanimidamide, sodium N-formyl-N-hydroxy-DL-alaninate,
0,0-diethyl [2-(dipropy]amino)-2-oxoethyl]-ethylphosphoramidothioate,
10 O-methyl S-phenyl phenylpropylphosphoramidothioate,
S-methy] J,2,3-benzothiadiazole-7-carbothioate, spiro[2H]-1 -benzopyran-2,1 '(3 H)-isobenzofuran]-3 -one, 4-[3,4-dimethoxypheny])-3-(4-fluorophenyl)-acryloyl]-moipholine 15
Bactericides:
bronopol, dichlorophen, nitrapyrin, nickel dimethyldithiocarbamate, kasugamycin, oc-
thilinone, furancarboxylic acid, oxytetracyclin, probenazole, streptomycin, tecloftalam,
20 copper sulphate and other copper preparations.
Insecticides / Acaricides / Nematicides:
abamectin, acephate, acetamiprid, acrinathrin, alanycarb, aldicarb, aldoxycarb, alpha-
25 cypermethrin, alphamethrin, amitraz, avermectin, AZ 60541, azadirachtin,
azamethiphos, azinphos A, azinphos M, azocyclotin,
Bacillus popilliae, Bacillus sphaericus, Bacillus subtilis, Bacillus thuringiensis,
Baculoviruses, Beauveria bassiana, Beauveria tenella, bendiocarb, benfuracarb,
30 bensultap, benzoximate, betacyfluthrin, bifenazate, bifenthrin, bioethanomethnn,


Le A 34 883-Foreign Countries

biopermethrin, bistrifluron, BPMC, bromophos A, bufencarb, buprofezin, butathiofos, butocarboxim, butylpyridaben,
cadusafos, carbaryl, carbofuran, carbophenothion, carbosulfan, cartap, chloethocarb,
5 chlorethoxyfos, chlorfenapyr, chlorfenvinphos, chlorfluazuron, chlormephos,
chlorpyrifos, chlorpyrifos M, chlovaporthrin, chromafenozide, cis-resmethrin, cispermethrin, clocythrin, cloethocarb, clofentezine, clothianidine, cyanophos, cycloprene, cycloprothrin, cyfluthrin, cyhalothrin, cyhexatin, cypermethrin, cyromazine, 10
deltamethrin, demeton M, demeton S, demeton-S-methyl, diafenthiuron, diazinon, dichJorvos, dicofol, diflubenzuron, dimethoate, dimethylvinphos, diofenoJan, disulfoton, docusate-sodium, dofenapyn,
15 eflusilanate, emamectin, empenthrin, endosulfan, Entomophthora spp., esfenvalerate,
ethiofencarb, ethion, ethoprophos, etofenprox, etoxazole, etrimfos,
fenamiphos, fenazaquin, fenbutatin oxide, fenitrothion, fenothiocarb, fenoxacrim,
fenoxycarb, fenpropathrin, fenpyrad, fenpyrithrin, fenpyroximate, fenvalerate,
20 fipronil, fluazinam, fluazuron, flubrocythrinate, flucycloxuron, flucythrinate,
flufenoxDron, flumethrin, flutenzine, fluvalinate, fonophos, fosmethilan, fosthiazate, fubfenprox, furathiocarb,
granulosis viruses 25
halofenozide, HCH, heptenophos, hexaflumuron, hexythiazox, hydroprene,
imidacloprid, indoxacarb, isazofos, isofenphos, isoxathion, ivermectin,
30 nuclear polyhedrosis viruses


Le A 34 883-Foreign Countries
lambda-cyhalothrin, lufenuron
malathion, mecarbam, metaldehyde, methamidophos, Metharhizium anisopliae,
Metharhizium flavoviride, methidathion, methiocarb, methoprene, methomyl,
5 methoxyfenozide, metolcarb, metoxadiazone, mevinphos, milbemectin, milbemycin,
monocrotophos,
naled, nitenpyram, nithiazine, novaluron
10 omethoate, oxamyl, oxydemethon M
Paecilomyces fumosoroseus, parathion A, parathion M, permethrin, phenthoate,
phorate, phosalone, phosmet, phosphamidon, phoxim, pirimicarb, pirimiphos A,
pirimiphos M, profenofos, promecarb, propargite, propoxur, prothiofos, prothoate,
15 pymetrozine, pyraclofos, pyresmethrin, pyrethrum, pyridaben, pyridathion,
pyrimidifen, pyriproxyfen,
quinalphos,
20 ribavirin
salithion, sebufos, silafluofen, spinosad, spirodiclofen, sulfotep, sulprofos,
tau-fluvalinate, tebufenozide, tebufenpyrad, tebupirimiphos, teflubenzuron,
25 tefluthrin, temephos, temivinphos, terbufos, tetrachlorvinphos, tetradifon, theta-
cypermethrin, thiacloprid, thiamethoxam, thiapronil, thiatriphos, thiocyclam hydrogen oxalate, thiodicarb, thiofanox, thuringiensin, tralocythrin, tralomethrin, triarathene, triazamate, triazophos, triazuron, trichlophenidine, trichlorfon, triflumuron, trimethacarb, 30
vamidothion, vaniliprole, Verticillium lecanii

Le A 34 883-Foreign Countries
YI5302
zeta-cypermethrin, zolaprofos 5
(lR-cis)-[5-(phenylmethyl)-3-furanyl]-methyl-3-[(dihydro-2-oxo-3(2H)-furanylidene)-methyl] 2,2-dimethylcyclopropanecarboxylate
(3-phenoxypheny])-methyl 2,2,3,3-tetramethylcyclopropanecarboxylate 10
l-[(2-chloro-5-thiazolyl)methyl]tetrahydro-3,5-dimethyl-N-nitro-l,3,5-triazin-2(lH)-imine
2-(2-chloro-6-fluorophenyl)-4-[4-(l,l-dimethylethyl)phenyl]-4,5-dihydro-oxazole
15 2-(acetlyoxy)-3-dodecyI-l,4-naphthalenedione
2-chloro-N-[[[4-(l-phenylethoxy)-phenyl]-amino]-carbonyl]-benzamide
2-ch]oro-N-[[[4-(2,2-dichloro-l,l-difluorethoxy)-phenyl]-amino]-carbonyl]-
benzamide
3-methylphenyl propylcarbamate
20 4-[4-(4-ethoxyphenyl)-4-methylpentyl]-l-fluoro-2-phenoxy-benzene
4-chloror2-(l,l-dimethylethyl)-5-[[2-(2,6-dimethyl-4-phenoxyphenoxy)ethyl]thio]-
3(2H)-pyridazinone
4-chloro-2-(2-chloro-2-methylpropyl)-5-[(6-iodo-3-pyridinyl)methoxy]-3(2H)-
pyridazinone
25 4-chloro-5-[(6-chloro-3-pyridinyl)methoxy]-2-(3,4-dichloiphenyl)-3(2H)-
pyridazinone
Bacillus thuringiensis strain EG-2348
[2-benzoyI-l-(l,l-dimethylethyl)]-benzohydrazide
2,2-dimethyl-3-(2,4-dichlorophenyl)-2-oxo-l-oxaspiro[4.5]dec-3-en-4-yl-ester
30 butanoate
[3-[(6-chloro-3-pyridinyl)methyl]-2-thiazolidinylidene]-cyanamide


Le A 34 883-Foreign Countries
dihydro-2-(nitromethylene)-2H-l,3-thiazine-3(4H)-carboxaldehyde ethyl [2-[[l,6-dihydro-6-oxo-l-(phenylmethyl)-4-pyridazinyl]oxy]ethyl]-carbamate N-(3,4,4-trifluoro-l-oxo-3-butenyl)-glycine
N-(4-chlorophenyl)-3-[4-(difluoromethoxy)phenyl]-4,5-dihydro-4-phenyl-lH-
5 pyrazol e-1 -c arbox ami de
N-[(2-chloro-5-thiazolyl)methyl]-N'-methyl-N"-nitro-guanidine
N-methyl-N'-(l-methyl-2-propenyl)-l,2-hydrazine dicarbothioamide
N-methyl-N-2-propenyl-l ,2-hydrazine dicarbothioamide
0,0-diethyl [2-(dipropylamino)-2-oxoethyl]-ethylphosphoramidothioate
10 N-cyanomethyl-4-trifluoromethyl-nicotinamide
3,5-dichloro-l-(3,3-dichloro-2-propenyloxy)-4-[3-(5-trifluoromethylpyridin-2-yloxy)-propoxy]-benzene
A mixture with other known active compounds such as herbicides or with fertilizers
15 and growth regulators is also possible.
In addition, the compounds of the formula (I) according to the invention also exhibit
very good antimycotic actions. They have a very broad antimycotic spectrum of
action, in particular against dermatophytes and yeasts, moulds and diphasic fungi (for
20 example against Candida species such as Candida albicans, Candida glabrata) and
also Eprdermophyton floccosum, Aspergillus species such as Aspergillus niger and Aspergillus fumigatus, Trichophyton species such as Trichophyton mentagrophytes,
Microsporon species such as Microsporon canis and audouinii. The elimination of
25 these fungi constitutes in no way a limitation of the mycotic spectrum which can be
controlled, but has merely illustrative character.
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
30 powders, pastes, soluble powders, dusts and granules. They are applied in the
customary fashion, for example by pouring, spraying, atomizing, spreading, dusting,


Le A 34 883-Foreign Countries
foaming, brushing on and the like. It is furthermore possible to apply the active compounds by the ultra-low-volume method or to inject the active compound preparation, or the active compound itself, into the soil. The seed of the plants may also be treated. 5
When employing the active compounds according to the invention as fungicides, the
application rates can be varied within a substantial range, depending on the type of
application. When treating plant parts, the application rates of active compounds are
generally between 0.1 and l0 000g/ha, preferably between 10 and 1000 g/ha. In the
10 treatment of seed, the application rates of active compound are generally between 0.001
and 50 g per kilogram of seed, preferably between 0.01 and 10 g per kilogram of seed. In the treatment of the soil, the application rates of active compound are generally between 0.1 and 10 000 g/ha, preferably between 1 and 5 000 g/ha.
15 The preparation and the use of the active compounds according to the invention can
be seen from the examples which follow.


Le A 34 883-Foreign Countries

Preparation Examples
Example I-l-a-1




10

13.8 g of the compound of Example (II-l) in 28 ml of absolute DMF are added dropwise at 0 - 10°C to 8.95 g (0.075 mol) of potassium tert-butoxide in 23 ml of absolute dimethylformamide (DMF).
The mixture is stired at 20°C until the reaction has ended (check by thin-layer chromatography (TLC)).

250 ml of ice-water are added, the mixture is acidified at 0 - 10°C with concentrated
15 hydrochloric acid to pH 2 and filtered with suction. This is followed by washing with
ice-water, drying and boiling up in methyl tert-butyl ether (MTBE)/n-hexane.

20

This is followed by purification by column chromatography on silica gel (dichloromethane/acetone, 5:1). Yield: 10.58 g (86% of theory)



Le A 34 883-Foreign Countries
The following compounds of the formula (I-l-a) are obtained analogously to Example (I-l-a-1) and following the general preparation instructions:
IK




Le A 34 883-Foreign Countries
Example I-l-b-1

5 1.05 g of the compound of Ex. I-l-a-1 are introduced into 30 ml of anhydrous ethyl
acetate and treated with 0.46 ml (3.3 mmol) of triethylamine. 0.34 ml (0.0033 mol) of
isobutyrol chloride in 5 ml of anhydrous ethyl acetate is added dropwise under reflux,
and stirring is continued under reflux until the reaction has ended (check by thin-
layer chromatography). The solvent is distilled off in vacuo and the residue is taken
10 up in dichloromethane. This is washed 2 x with 20 ml of 0.5 N NaOH solution and
dried, and the solvent is evaporated.
This is followed by purification by column chromatography over silica gel (dichloromethane/ethyl acetate 3:1) Yield: 0.57 g (45% of theory), M.p.: 189°C.
15
The following compounds of the formula I-l-b are obtained analogously to Example I-I-b-1 and following the general preparation instructions:


Le A 34 883-Foreign Countries



(I-l-b)


Example I-l-c-1

0.1 ml (1 mmol) of ethyl chloroformate in 1 ml of absolute dichloromethane are
10 added at 10 - 20°C to 0.35 g of the compound of Example (I-l-a-1) in 11 ml of
absolute dichloromethane and 0.1 ml (1 mmol) of triethylamine.
The mixture is stirred at room temperature until the reaction has ended (TLC check)


Le A 34 883-Foreign Countries

and the solvent is evaporated on a rotary evaporator. The precipitate is taken up in dichloromethane and the mixture is washed twice with 5 ml of 0.5 N sodium hydroxide solution, dried and concentrated.
5 This is followed by purification by column chromatography on silica gel
(dichloromethane/ethyl acetate 5:1). Yield: 0.17 g (40% of theory)



The following compounds of the formula (I-l-c) are obtained analogously to
10 Example (I-l-c-1) and following the general preparation instructions

Le A 34 883-Foreign Countries
Ex. No. I-l-g-1




10

1.05 g of the compound of Example I-l-a-1 are introduced into 10 ml of anhydrous ethyl acetate, and 0.42 ml (3 mmol) of triethylamine were added. 0.4 ml (0.0033 mol) of morpholinocarbamoyl chloride in 2 ml of anhydrous ethyl acetate are added dropwise under reflux, and stirring is continued under reflux until the reaction has ended (check by thin-layer chromatography). The solvent is distilled off and the residue is taken up in dichloromethane. The mixture is washed 2 x with 20 ml of 0.5 N NaOH solution and dried, and the solvent is evaporated.



15

This is followed by purification by column chromatography over silica gel (dichloromethane/ethyl acetate, 5:1) Yield: 0.22 g (15% of theory), M.p.: 217°C.


Le A 34 883-Foreign Countries

Example II-1




10
15

18 g of 5-methyl-2-(4-chloro-phenyl)-thiazolylacetic acid are added to 10 g of ethyl 3-amino-3-methyl-butyrate in 250 ml of absolute tetrahydrofuran and 12 ml of triethylamine, and the mixture is stirred for 15 minutes at room temperature. 13.2 ml of triethylamine are subsequently added, and 3.4 ml of phosphorus oxychloride are immediately added dropwise in such a way that the solution boils moderately.
The mixture is stirred for a further 30 minutes under reflux. Then, the reaction solution is stirred into 800 ml of ice-water and extracted with dichloromethane, and the dichloromethane phase is dried and evaporated. This is followed by purification by column chromatography on silica gel (n-hexane/ethyl acetate, 2:1) Yield: 13.81 g (52% of theory), M.p. 101°C



Le A 34 883-Foreign Countries

The following compounds of the formula (II) are obtained analogously to Example (II-l) and following the general preparation instructions:


(II)





Le A 34 883-Foreign Countries
Example I-2-a-l

5 1.5 g of the" compound of Example III-1 in 5 ml of absolute acetonitrile are added at
room temperature to 0.68 g (6 mmol) of potassium tert-butoxide in 10 ml of absolute acetonitrile.
The mixture is stirred for 3 hours at room temperature. The solution is poured into
10 ice-water, acidified with 1 N hydrochloric acid, filtered off with suction and dried.
This is followed by purification by column chromatography on silica gel (n-hexane/ethyl acetate 5:1). Yield: 0.23 g (16% of theory) M.p. 138-140°C
15 The following compounds of the formula (I-2-a) are obtained analogously to

Example (I-2-a-l) and following the general preparation instructions:


Le A 34 883-Foreign Countries







190 mg of the compound of Example I-2-a-l in 5 ml of anhydrous dichloromethane are treated with 0.105 ml of triethylamine. 115 mg of 6-chloronicotinoyl chloride are added with ice-cooling, and the mixture is stirred at room temperature.
10 The reaction solution is washed 1 x with 10% citric acid solution, the aqueous phase
is extracted with dichloromethane, the organic phase is washed 1 x with 1 N NaOH, and the aqueous phase is extracted with dichloromethane. This is followed by drying and evaporation of the solvent on a rotary evaporator.
15 Yield: 0.17 g (65% of theory)

20

H NMR (DMSO, 400 MHz): 8= 1.30, 1.56 (2 s, in each case 6H, 4 CH3) 2.29 (s, 3H, thiazolyl-CH3), 7.41, 7.59 (2d, in each case 2H, Ar-H) 7.57 (d, 1H, pyridyl-H), 8.25 (d, 1H, pyridyl-H), 8.83 (s, 1H, pyridyl-H) ppm.
The following compounds of the formula (I-2-b) are obtained analogously to



Le A 34 883-Foreign Countries


Example (I-2-b-l) and following the general preparation instructions


Le A 34 883-Foreign Countries
Example-No. I-2-c-l




10
15

300 mg (0.8mmol) of the compound of Example I-2-a-l in 10 ml of anhydrous dichloromethane are treated with 0.17 ml (1.2mmol) of triethylamine. 0.1ml (1.04 mmol) of ethyl chloroformate is subsequently added at 0°C
The mixture is stirred at room temperature.
The reaction solution is washed 1 x with 10% citric acid solution, the aqueous phase is extracted with dichloromethane, the organic phase is washed 1 x with 1 N NaOH, and the aqueous phase is extracted with dichloromethane. This is followed by drying and evaporation of the solvent on a rotary evaporator.
Yield: 0.3 g (83% of theory).

1H NMR (400 MHz, CDC13): 8 = 0.94 (t, 3H, CH3-CH2O), 1.22 (s, 6H, 2CH3), 1.48
(s, 6H, 2CH3), 1.27 (s, 3H, CH3), 3.95 (q, CH3-CH2-0), 7.56 (d, 2H, arom. CH),
20 7.83 (d, 2H, arom. CH) ppm.
The following compound of the formula (I-2-c) is obtained analogously to Example (I-2-c-l) and following the general preparation instructions


Le A 34 883-Foreign Countries



(I-2-c)



Example III-l




10
15

1.6 ml of triethylamine are added to 1.12 g (6.4 mmol) of ethyl 3-hydroxy-2,2,3-trimethyl-butyrate in 20 ml of absolute tetrahydrofuran. The mixture is stirred for 5 minutes, and 1.07 g (4 mmol) of 5-methyl-2-(4-chlorophenyl)-thiazolylacetic acid are added. After a further 15 minutes, 0.9 ml of triethylamine is added, and 0.2 ml of phosphorus oxychloride is immediately added in such a way that the solution boils moderately. The mixture is stirred for 1 hour under reflux.
The mixture is concentrated and the product is purified by column chromatography on silica gel (dichloromethane -» dichloromethane : ethyl acetate, 3:1) Yield: 1.5 g (88% of theory)



Le A 34 883-Foreign Countries
1H NMR (400 MHz, DMSO):
8 = 1.11, 1.12 (2 s, in each case 6H, 4-CH3), 1.17 (t, 3H, CH3-CH2-0),
2.41 (s, CH3-thiazolyI), 7.52, 7.82 (2 d, in each case 2H, aryl-H) ppm.
5 The following compounds of the formula (HI) are obtained analogously to Example
(III-1) and following the general preparation instructions:




Spectroscopic data, Ex.III-4: 1H NMR (400 MHz, PMSO):
δ = 1.04, 1.10,1.11,1.50 (4 s, in each case 3 H, 4-CH3), 1.20 (m, 3H, CH3-CH2-0),
15 4.02 (m, -2 H, CH3-CH2-0) ppm.
* The oils were converted into the corresponding compounds of the formula I-2-a without being characterized further.


Le A 34 883-Foreign Countries

Use Examples
Example A Meloidogyne test
5
Solvent: 30 parts by weight of dimethylformamide
Emulsifier: 1 part by weight of alkylaryl polyglycol ether
To prepare a suitable active compound preparation, 1 part by weight of active
10 compound is mixed with the stated amounts of solvent.and emulsifier and the
concentrate is diluted to the desired concentration with water.
Containers are filled with sand, active compound solution, Meloidogyne incognita
egg/larval suspension and lettuce seeds. The lettuce seeds germinate and the plantlets
15 develop. The galls develop on the roots.
After the desired time, the nematicidal efficacy is determined in % with reference to gall formation. 100% means that no galls were found; 0% means that the number of galls on the treated plants corresponds to that of the untreated control.
20
In this test, a destruction rate of 100% is shown, for example, by the compounds of Preparation Examples I-l-c-1 and I-2-a-l at an active compound concentration of 20 ppm, and a destruction rate of 98% after 14 days by the compound of Preparation Example I-2-a-3 at an active compound concentration of 20 ppm.
25


Le A 34 883-Foreign Countries
Example B Myzus test
Solvent: 30 parts by weight of dimethylformamide
5 Emulsifier: 1 part by weight of alkylaryl polyglycol ether
To prepare a suitable active compound preparation, 1 part by weight of active compound is mixed with the stated amounts of solvent and emulsifier and the concentrate is diluted to the desired concentration with emulsifier-containing water. 10
Cabbage leaves (Brassica oleracea) which are severely infested by the green peach aphid (Myzus persicae) are treated by immersing into the active compound preparation of the desired concentration.
15 After the desired time, the destruction rate is determined in %. 100% means that all
of the aphids have been destroyed; 0% means that none of the aphids have been destroyed.
In this test, a destruction rate of 90% was caused, after 6 days, by the compound of
20 Preparation Example I-2-a-l at an active compound concentration of 500 ppm.


Le A 34 883-Foreign Countries
Example C Phaedon Larvae test
Solvent: 30 parts by weight of dimethylformamide
5 Emulsifier: 1 part by weight of alkylaryl polyglycol ether
To prepare a suitable active compound preparation, 1 part by weight of active compound is mixed with the stated amounts of solvent and emulsifier and the concentrate JS diluted to the desired concentration with emulsifier-containing water. 10
Cabbage leaves (Brassica oleracea) are treated by immersing in the active compound preparation of the desired concentration and populated with larvae of the mustard beetle (Phaedon cochleariae) while the leaves are still moist.
15 After the desired time, the destruction rate is determined in %. 100% means that all
the beetle larvae have been destroyed; 0% means that none of the beetle larvae have been destroyed.
In this test, a destruction rate of 100% is shown, after 7 days, for example by the
20 compounds of Preparation Examples I-l-a-1 and I-2-a-2 at an active compound
concentration of 1000 ppm, and a destruction rate of 100% after 7 days by the compound of Preparation Example I-2-a-l at an active compound concentration of 500 ppm.

Le A 34 883-Foreign Countries
Example D
Plutella test/Synthetic feed
Solvent: 100 parts by weight of acetone
5 Emulsifier: 1900 parts by weight of methanol
To prepare a suitable active compound preparation, 1 part by weight of active compound is mixed with the stated amounts of solvent and emulsifier and the concentrate is diluted to the desired concentration with methanol.
10
A stated amount of active compound preparation of the desired concentration is pipetted onto a standardized amount of synthetic feed. After the methanol has evaporated, a film can lid populated with approx. 100 Plutella eggs is placed into each cavity. The freshly hatched larvae migrate onto the treated synthetic feed.
15
After the desired time, the destruction rate is determined in %. 100% means that all of the animals have been destroyed; 0% means that none of the animals have been destroyed.
20 In this test, a destruction rate of 100% is shown, after 7 days, for example by the
compound of Preparation Example I-2-a-4 at an active compound concentration of 1000 ppm.





Le A 34 883-Foreign Countries
Example E
Spodoptera frugiperda test
Solvent: 30 parts by weight of dimethylformamide
5 Emulsifier: 1 part by weight of alkylaryl polyglycol ether
To prepare a suitable active compound preparation, 1 part by weight of active compound is mixed with the stated amounts of solvent and emulsifier and the concentrate is diluted to the desired concentration with emulsifier-containing water.
Cabbage leaves (Brassica oleracea) are treated by immersing in the active compound preparation of the desired concentration and populated with larvae of the fall armyworm caterpillars (Spodoptera frugiperda) while the leaves are still moist.
15 After the desired time, the destruction rate is determined in %. 100% means that all
the caterpillars have been destroyed; 0% means that none of the caterpillars have been destroyed.
In this test, a destruction rate of 100% is shown, after 7 days, for example by the
20 compounds of Preparation Examples I-2-a-2 at an active compound concentration of
1000 ppm and I-2-a-l at an active compound concentration of 500 ppm.


Le A 34 883-Foreign Countries
Example F
Tetranychus test (OP resistant/immersion treatment)
Solvent: 30 parts by weight of dimethylformamide
5 Emulsifier: 1 part by weight of alkylaryl polyglycol ether
To prepare a suitable active compound preparation, 1 part by weight of active compound is mixed with the stated amounts of solvent and emulsifier and the concentrate is diluted to the desired concentration with emulsifier-containing water. 10
Bean plants (Phaseolus vulgaris) which are severely infested by all stages of the two-spotted spider mite (Tetranychus urticae) are immersed into an active compound preparation of the desired concentration.
15 After the desired time, the efficacy is determined in %, 100% means that all of the
spider mites have been destroyed; 0% means that none of the spider mites have been destroyed.
In this test, destruction rates of 100% (Example I-2-a-l), 99% (Example I-2-a-2),
20 98% (Example I-l-a-1) and 90% (Examples I-2-a-3 and I-2-a-4), respectively, are
shown by the compounds of Preparation Examples I-l-a-1, I-2-a-2, I-2-a-3, I-2-a-l and I-2-a-4 at an active compound composition of 100 ppm.


Le A 34 883-Foreign Countries
Example G Post-emergence test
Solvent: 5 parts by weight of acetone
5 Emulsifier: 1 part by weight of alkylaryl polyglycol ether
To prepare a suitable active compound preparation, 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
10 concentration.
Test plants which have a height of 5 to 15 cm are sprayed with the active compound
preparation in such a way that the active compound quantities desired in each case
are applied per unit area. The concentration of the spray mixture is chosen such that
15 the active compound quantities desired in each case are applied in 1000 1 of water/ha.
After three weeks, the degree of damage to the plants is scored in % damage in comparison with the development of the untreated control.
20 The figures denote:
0% = no effect (like untreated control) 100% - total destruction

Le A 34 883-Foreign Countries
Example H Pre-emergence test
Solvent: 5 parts by weight of acetone
5 Emulsifier: 1 part by weight of alkylaryl polyglycol ether
To prepare a suitable active compound preparation, 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
10 concentration.
Seeds of the test plants are sown in normal soil. After approximately 24 hours, the
soil is sprayed with the active compound preparation in such a way that the active
compound quantities desired in each case are applied per unit area. The concentration
15 of the spray mixture is chosen such that the active compound quantities desired in
each case are applied in 1000 1 of water/ha.
After three weeks, the degree of damage to the plants is scored in % damage in comparison with the development of the untreated control. 20
The figures denote:
0% = no effect (like untreated control) 100% = total destruction
25




Le A 34 883-Foreign Countries



Le A 34 883-Foreign Countries
Example I
Limit concentration test / soil-dwelling insects - treatment of transgenic plants
5 Test insect: Diabrotica balteata larvae in the soil
Solvent: 7 parts by weight of acetone
Emulsifier: 1 part by weight of alkylaryl polyglycol ether
10 To prepare a suitable active compound preparation, 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.
15 The active compound preparation is poured onto the soil. The concentration of the
active compound in the preparation is of virtually no importance, only the weight of active substance per unit volume of soil, which is indicated in ppm (mg/1), being decisive. The soil is filled into 0.25 1 pots, and these are left to stand at 20°C.
20 Immediately after the test is set up, 5 pregerminated maize kernels cv. YIELD
GUARD (trademark of Monsanto Comp., USA) are placed into each pot. The appropriate test insects are put in to the heated soil after 2 days. After a further 7 days, the efficacy of the active compound is determined by counting the maize plants which have emerged (1 plant = 20% action).


Le A 34 883-Foreign Countries
Example J
Heliothis virescens test - Treatment of transgenic plants
5 Solvent: 7 parts by weight of acetone
Emulsifier. 1 part by weight of alkylaryl polyglycol ether
To prepare a suitable active compound preparation, 1 part by weight of active
compound is mixed with the stated amount of solvent, the stated amount of
10 emulsifier is added, and the concentrate is diluted with water to the desired
concentration.
Sojabean shoots (Glycine max) cv. Roundup Ready (trademark of Monsanto Comp.
USA) are treated by immersing into the active compound preparation of the desired
15 concentration and populated with the tobacco budworm Heliothis virescens while the
leaves are still moist.
The destruction of the insects is determined after the desired time.


WE CLAIM:
1. Hetarylsubstituted homotetramic or homotetronic acids of the formula (I)
in which
Het represents a nitrogen-containing 5-membered heterocyclic ring which is substituted by halogen, alkyl, alkoxy, alkenyloxy, halogenoalkyl, halogenoalkoxy, halogenoalkenyloxy, cyano, nitro, alkylthio, alkylsulphinyl, alkylsulphonyl, optionally substituted phenyl or optionally substituted phenoxy,
W represents oxygen or N-D,
A represents hydrogen, in each case optionally halogen-substituted alkyl, alkenyl, alkoxyalkyl, polyalkoxyalkyl, alkylthioalkyl, saturated or unsaturated, optionally substituted cycloalkyl in which at least one ring atom is optionally replaced by a hetero atom, or represents aryl, arylalkyl or hetaryl, each of which is optionally substituted by halogen, alkyl, halogenoalkyl, alkoxy, halogenoalkoxy, cyano or nitro,
B represents hydrogen or alkyl, or
A and B together with the carbon atom to which they are bonded represent a saturated or unsaturated, unsubstituted or substituted cycle which optionally contains at least one hetero atom;


D represents hydrogen or an optionally substituted radical from the series comprising alkyl, alkenyl, alkinyl, alkoxyalkyl, polyalkoxyalkyl, alkylthioalkyl, saturated or unsaturated cycloalkyl in which one or more ring members are optionally replaced by hetero atoms, or arylalkyl, aryl, hetarylalkyl or hetaryl, or
A and Q1 together represent alkanediyl which is optionally substituted by in each case optionally substituted alkyl or alkoxy and in which two carbon atoms which are not directly adjacent optionally form a further optionally substituted cycle, or
D and Q1 together with the atoms to which they are bonded represent a saturated or unsaturated cycle which optionally contains at least one hetero atom and which is unsubstituted or substituted in the D, Q1 moiety,
Q1 represents hydrogen, alkyl, alkoxyalkyl, optionally substituted cycloalkyl (in which one methylene group is optionally replaced by oxygen or sulphur) or optionally substituted phenyl,
Q2 represents hydrogen or alkyl, or
Q1 and Q2 together with the carbon atom to which they are bonded represent an unsubstituted or substituted cycle which optionally contains one hetero atom,
G represents hydrogen (a) or one of the groups



in which
E represents a metal ion or an ammonium ion,
L represents oxygen or sulphur,
M represents oxygen or sulphur,
R1 represents in each case optionally halogen-substituted alkyl, alkenyl, alkoxyalkyl, alkylthioalkyl, polyalkoxyalkyl or represents cycloalkyl which is optionally substituted by halogen, alkyl or alkoxy and which can be interrupted by at least one hetero atom, in each case optionally substituted phenyl, phenylalkyl, hetaryl, phenoxyalkyl or hetaryloxyalkyl,
R2 represents in each case optionally halogen-substituted alkyl, alkenyl, alkoxyalkyl, polyalkoxyalkyl or in each case optionally substituted cycloalkyl, phenyl or benzyl,
R3 represents optionally alkyl, halogenoalkyl or optionally substituted phenyl or ben2yl,
R4 and R5 independently of one another represent in each case optionally halogen-substituted alkyl, alkoxy, alkylamino, dialkylamino, alkylthio, alkenylthio, cycloalkylthio and in each case optionally substituted phenyl, benzyl, phenoxy or phenylthio,


R6 and R7 independently of one another represent hydrogen, in each case optionally halogen-substituted alkyl, cycloalkyl, alkenyl, alkoxy, alkoxyalkyl, optionally substituted phenyl, optionally substituted benzyl, or together with the N atom to which they are bonded represent a cycle which is optionally interrupted by oxygen or sulphur.
2. Compounds of the formula (I) as claimed in claim 1 in which
Het represents
W represents oxygen or N-D,
X represents hydrogen, halogen, C1-C6-alkyl, C1-C6-alkoxy, C3-C6-alkenyloxy, nitro, cyano, or represents phenyl which is optionally substituted by halogen, C1-C6-alkyl, C1-C6-alkoxy, C1-C4- halogenoalkyl, C1-C4-halogenoalkoxy, nitro or cyano,
Y represents halogen, C1-C6-alkyl, C1-C6-halogenoalkyl, C1-C6-alkoxy, C1-C6-halogenoalkoxy or the groups

V1 represents hydrogen, halogen, C1-C12-alkyl, C1-C6-alkoxy, C1-C6-alkylthio, C1-C6-alkylsulphinyl, C1-C6-alkylsulphonyl, C1-C4-halogenoalkyl, C1-C4-halogenoalkoxy, nitro, cyano, or represents phenyl, phenoxy, phenoxy-C1-C4-alkyl, phenyl-C1C4-alkoxy,


phenylthio-C1-C4-alkyl or phenyl-C1-C4-alkylthio, each of which is optionally monosubstituted or polysubstituted by halogen, C1-C6- alkyl, C1-C6-alkoxy, C1-C4-halogenoalkyl, C1-C4-halogenoalkoxy, nitro or cyano,
V2 and V3 independently of one another represent hydrogen, halogen, C1-C6-alkyl, C1-C6-alkoxy, C1-C4-halogenoalkyl or C1-C4-halogenoalkoxy,
V1 and V2 together with the carbon atoms to which they are bonded represent a 5- or 6-membered cycle which is optionally substituted by C1-C4-alkyl or halogen and in which one to three carbon atoms can optionally be replaced by oxygen, sulphur or nitrogen,
A represents hydrogen, or represents C1-C12-alkyl, C3-C8-alkenyl, C1-C12-alkoxy-C1-C4-alkyl, each of which is optionally substituted by halogen, or represents optionally halogen-, C1-C4-alkyl- or C1-C4- alkoxy-substituted C3-C8-cycloalkyl or C3-C6-cycloalkyl-C1-C4-alkyl in which one or two ring members which are not directly adjacent are optionally replaced by oxygen and/or sulphur, or represents phenyl, benzyl, hetaryl having 5 to 6 ring atoms or hetaryl-C1-C4-alkyl having 5 to 6 ring atoms each of which is optionally substituted by halogen, C1-C6-alkyl, C1-C6-halogenoalkyl, C1-C6-alkoxy, C1-C6-halogenoalkoxy, cyano or nitro,
B represents hydrogen or C1-C6-alkyl,
A, B and the carbon atom to which they are bonded represent saturated C3-C10-cycloalkyl or unsaturated C5-C1o-cycloalkyl in which one ring member is optionally replaced by oxygen or sulphur and which are optionally monosubstituted or


disubstituted by C1-C6-alkyl, C3-C8-cycloalkyl, C1-C6-halogenoalkyl, C1-C6-alkoxy, C1-C6-alkylthio, halogen or phenyl,
D represents hydrogen, in each case optionally halogen-substituted C1-C6-alkyl, C3-C8-alkenyl, C3-C8-alkinyl, C1-C6-alkoxy-C2-C6-alkyl, or represents optionally halogen-, C1-C4-alkyl-, C1-C4-alkoxy-or C1-C4-halogenoalkyl-substituted C3-C8-cycloalkyl or C3-C6- cycloalkyl-C1-C4-alkyl in which one ring member is optionally replaced by oxygen or sulphur,
A and Q1 jointly represent C3-C6-alkanediyl which is optionally substituted by C1-C4-alkyl or Cl-C4-alkoxy,
D and Q1 together represent C3-C6-alkanediyl which is optionally monosubstituted or disubstituted by identical or different substituents from the series consisting of C1-C4-alkyl and C1-C4-alkoxy, or
Q1 represents hydrogen, C1-C6-alkyl, C1-C6-alkoxy-C1-C2-alkyl, or represents C3-C8-cycloalkyl in which one methylene group is optionally replaced by oxygen or sulphur and which is optionally substituted by fluorine, chlorine, C1-C4-alkyl, C1-C2-halogenoalkyl or C1-C4-alkoxy, or represents phenyl which is optionally substituted by halogen, C1-C4-alkyl, C1-C4-alkoxy, C1-C2-halogenoalkyl, C1-C2- alogenoalkoxy, cyano or nitro, or
Q2 represents hydrogen or C1-C4-alkyl,
Q1 and Q2 together with the carbon atom to which they are bonded represent C3-C7-cycloalkyl in which one ring member is optionally replaced by oxygen or sulphur and which is optionally substituted by Ci-Ce-alkyl, C1-C6-alkoxy or C1-C2-halogenoalkyl,


G represents hydrogen (a) or one of the groups

in which
E represents a metal ion or an ammonium ion,
L represents oxygen or sulphur and
M represents oxygen or sulphur,
R1 represents C1-C20-alkyl, C2-C20-alkenyl, C1-C8-alkoxy-C1-C8-alkyl, C1-C8-alkylthio-C1-C8-alkyl, poly-C1-C8-alkoxy-C1-C8 alkyl, each of which is optionally substituted by halogen, or represents C3-C8-cycloalkyl in which one or more ring members which are not directly adjacent are optionally replaced by oxygen and/or sulphur and which is optionally substituted by halogen, C1-C6-alkyl or C1-C6-alkoxy,
or represents phenyl which is optionally substituted by halogen, cyano, nitro, C1-C6-alkyl, C1-C6-alkoxy, C1-C6-halogenoalkyl, C1-C6-halogenoalkoxy, C1-C6-alkylthio or C1-C6-alkylsulphonyl,
or represents phenyl-C1-C6-alkyl which is optionally substituted by


halogen, nitro, cyano, C1-C6-alkyl, C1-C6-alkoxy, C1-C6-halogenoalkyl or C1-C6-halogenoalkoxy,
or represents 5- or 6-membered hetaryl which is optionally substituted by halogen, C1-C6-alkyl or trifluoromethyl,
or represents phenoxy-C1-C6-alkyl which is optionally substituted by halogen or C1-C6-alkyl,
or represents 5- or 6-membered hetaryloxy-C1-C6-alkyl, which is optionally substituted by halogen, amino or C1-C6-alkyl,
R2 represents C1-C20-alkyl, C2-C2o-alkenyl, C1-C8-alkoxy-C2-C8-alkyl, poly-C1-C8-alkoxy-C2-C8-alkyl, each of which is optionally substituted by halogen,
or represents C3-C8-cycloalkyl which is optionally substituted by halogen, C1-C6-alkyl or C1-C6-alkoxy,
or represents phenyl or benzyl, each of which is optionally substituted by halogen, cyano, nitro, C1-C6-alkyl, C1-C6-alkoxy, C1-C6- halogenoalkyl or C1-C6-halogenalkoxy,
R3 represents C1-8-alkyl which is optionally substituted by halogen or represents phenyl or benzyl, each of which is optionally substituted by halogen, C1-C6-alkyl, C1-C6-alkoxy, C1-C4-halogenoalkyl, C1-C4- halogenoalkoxy, cyano or nitro,
R4 and R5 independently of one another represent C1-C8-alkyl, C1-C8-alkoxy, C1-C8-alkylamino, di-(C1-C8-alkyl)amino, C1-C8-alkylthio, C1-C8-alkenylthio, C3-C7-cycloalkylthio, each of which is optionally substituted by halogen, or represent phenyl, benzyl, phenoxy or phenylthio, each of which is optionally substituted by halogen, nitro, cyano, C1-C4-alkoxy, C1-C4-


halogenoalkoxy, C1-C4-alkylthio, C1-C4-halogenoalkylthio, C1-C4-alkyl or C1-C4-halogenoalkyl,
R6 and R7 independently of one another represent hydrogen, or represent C1-C8-alkyl, C3-C8-cycloalkyl, C1-C8-alkoxy, C3-C8-alkenyl, C1-C-8lkoxy-C1-C8-alkyl, each of which is optionally substituted by halogen, or represent phenyl which is optionally substituted by halogen, C1-C8-halogenoalkyl, Ci-Cs-alkyl or C1-C8-alkoxy, or represent benzyl which is optionally substituted by halogen, C1-C8- alkyl, Ci-Cs-halogenoalkyl or Ci-Cs-alkoxy, or together with the N atom to which they are bonded represent a C3-C6-alkylene radical in which one carbon atom is optionally replaced by oxygen or sulphur and which is optionally substituted by C1-C4-alkyl.
3. Compounds of the formula (I) as claimed in claim 1 in which
Het represents
W represents oxygen or N-D,
X represents hydrogen, chlorine, bromine, C1-C4-alkyl, or represents phenyl which is optionally monosubstituted to disubstituted by fluorine, chlorine, bromine, C1-C4-alkyl, C1-C2-halogenoalkoxy, nitro or cyano,
Y represents chlorine, bromine, C1-C4-alkyl, C1-C4-halogenoalkyl, C1-C4-alkoxy, C1-C4-halogenoalkoxy or the groups



V1 represents hydrogen, fluorine, chlorine, bromine, C1-C6-alkyl, C1-C4-alkoxy, C1-C2-halogenoalkyl, C1-C2-halogenalkoxy, nitro, cyano, or represents phenyl, phenoxy, phenoxy-C1-C2-alkyl, phenyl-C1-C2- alkoxy, phenylthio-C1-C2-alkyl or phenyl-C1-C2~ alkylthio, each of which is optionally monosubstituted or disubstituted by fluorine, chlorine, bromine, C1-C4-alkyl, C1-C4-alkoxy, C1-C2-halogenoalkyl, C1-C2-halogenoalkoxy, nitro or cyano
V2 represents hydrogen, fluorine, chlorine, bromine, C1-C4-alkyl, C1-C4-alkoxy, C1-C2-halogenoalkyl or C1-C2-halogenoalkoxy,
V1 and V2 jointly together with the carbon atoms to which they are bonded represent a 5- or 6-membered cycle in which one or two carbon atoms can optionally be replaced by oxygen and which is optionally substituted by fluorine or methyl,
A represents hydrogen, or represents C1-C8-alkyl or C1-C4-alkoxy-C1-C2-alkyl, each of which is optionally substituted by fluorine, or represents C5-C6-cycloalkyl or C3-C6-cycloalkyl-C1-C2-alkyl in which one ring member is optionally replaced by oxygen or sulphur and which is optionally substituted by fluorine, chlorine, methyl, ethyl or methoxy, or represents phenyl or benzyl, each of which is optionally substituted by fluorine, chlorine, bromine, C1-C4-alkyl, C1-C2-halogenoalkyl, C1-C4-alkoxy or C1-C2-halogenoalkoxy,
B represents hydrogen or C1-C4-alkyl,
A, B and the carbon atom to which they are bonded represent


saturated C5-C7-cycloalkyl in which one ring member is optionally replaced by oxygen and which is optionally monosubstituted by C1-C4-alkyl, trifluoromethyl or C1-C4-alkoxy,
D represents hydrogen, or represents C1-C6-alkyl, C3-C6-alkenyl or C1-C4-alkoxy-C2-C3-alkyl, each of which is optionally substituted by fluorine, or represents C3-C7-cycloalkyl or C3-C6-cycloalkyl-C1-C2-alkyl in which one methylene group is optionally replaced by oxygen and which is optionally substituted by C1-C2-alkyl, fluorine or chlorine,
A and Q1 jointly represent C3-C4-alkanediyl,
D and Q1 jointly represent C3-C4-alkanediyl,
Q1 represents hydrogen, C1-C4-alkyl, C1-C4-alkoxy-C1-C2-alkyl, or represents C3-C6-cycloalkyl in which one methylene group is optionally replaced by oxygen and which is optionally substituted by methyl or methoxy,
Q2 represents hydrogen, methyl or ethyl,
Q1 and Q2 jointly with the carbon atom to which they are bonded represent saturated C5-C6-cycloalkyl in which one ring member is optionally replaced by oxygen and which is optionally substituted by C1-C4-alkyl or C1-C4-alkoxy,
G represents hydrogen (a) or one of the groups



E (f) or L (g), in particular (a), (b), (c) or (g),
in which
E represents a metal ion or an ammonium ion,
L represents oxygen or sulphur and
M represents oxygen or sulphur,
R1 represents C1-C16-alkyl, C2-C16-alkenyl, C1-C4-alkoxy-C1-C2-alkyl, C1-C4-alkylthio-C1-C2-alkyl, each of which is optionally substituted by fluorine or chlorine, or represents C3-C7-cycloalkyl in which one or two ring members which are not directly adjacent are optionally replaced by oxygen and/or sulphur and which is optionally substituted by fluorine, chlorine, C1-C5-alkyl or C1-C5-alkoxy,
or represents phenyl which is optionally substituted by fluorine, chlorine, bromine, cyano, nitro, C1-C4-alkyl, C1-C4-alkoxy, trifluoromethyl or trifluoromethoxy;
or represents pyridyl or thienyl, each of which is optionally substituted by fluorine, chlorine, bromine, methyl, ethyl or trifluoromethyl,
R2 represents C1-C16-alkyl, C2-C16-alkenyl or C1-C4-alkoxy-C2-C4-alkyl, each of which is optionally substituted by fluorine,
or represents C3-C7-cycloalkyl which is optionally substituted by methyl, ethyl or methoxy,


or represents phenyl or benzyl, each of which is optionally substituted by fluorine, chlorine, bromine, cyano, nitro, C1-C4-alkyl, C1-C3-alkoxy, trifluoromethyl or trifluoromethoxy,
R3 represents C1-C6-alkyl which is optionally substituted by fluorine, or represents phenyl which is substituted by fluorine, chlorine, bromine, C1-C4-alkyl, C1-C4-alkoxy, trifluoromethyl, trifluoromethoxy, cyano or nitro,
R4 represents C1-C6-alkyl, C1-C6-alkoxy, Ci-Ce-alkyl amino, di-(C1-C6-alkyl)amino, C1-C6-alkylthio, or represents phenyl, benzyl, phenoxy or phenylthio, each of which is optionally substituted by fluorine, chlorine, bromine, nitro, cyano, C1-C3-alkoxy, trifluoromethoxy, C1-C3-alkyl or trifluoromethyl,
R5 represents C1-C4-alkyl, C1-C4-alkoxy or C1-C4-alkylthio,
R6 represents hydrogen, Ci-Ce-alkyl, C3-C6-cycloalkyl, C1-C6-alkoxy, C3-C6-alkenyl, C1-C6-alkoxy-C1-C6-alkyl, or represents phenyl which is optionally substituted by fluorine, chlorine, bromine, trifluoromethyl, C1-C4-alkyl or C1-C4-alkoxy, or represents benzyl which is optionally substituted by fluorine, chlorine, bromine, methyl, ethyl, trifluoromethyl or methoxy,
R7 represents hydrogen, C1-C6-alkyl or C3-C6-alkenyl,
R6 and R7 together with the N atom to which they are bonded represent a C4-C6-alkylene radical in which one methylene group is optionally replaced by oxygen or sulphur and which is optionally substituted by methyl or ethyl.
4. Compounds of the formula (1) as claimed in claim 1 in which


Het represents
W represents oxygen or N-D,
X represents chlorine, bromine, methyl, ethyl, n-propyl, isopropy], n-butyl or isobutyl,
Y represents methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl or the group

V1 represents hydrogen, fluorine, chlorine, bromine, methyl, ethyl, n-propyl isopropyl, n-butyl, isobutyl, tert-butyl, methoxy, ethoxy, n propoxy isopropoxy, trifluoromethyl, trifluoromethoxy,
V2 represents hydrogen, fluorine, chlorine, methyl, ethyl, n-propyl, isopropyl, methoxy, ethoxy, trifluoromethyl or trifluoromethoxy,
A represents hydrogen, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, methoxymethyl, ethoxymethyl,
B represents hydrogen, methyl or ethyl,
A, B and the carbon atom to which they are bonded represent saturated C5-C6-cycloalkyl in which one ring member is optionally replaced by oxygen and which is optionally monosubstituted by methyl, ethyl, -n-propyl, isopropyl, butyl, trifluoromethyl, methoxy, ethoxy, n-propoxy or n-butoxy,


D represents hydrogen, methyl, ethyl, propyl, isopropyl, allyl, 2-butenyl, methoxyethyl, ethoxyethyl, cyclopropyl, cyclopentyl or cyclohexyl,
A and Q1 jointly represent C3-C4-alkariediyl
D and Q1 jointly represent C3-C4-alkanediyl,
Q1 represents hydrogen, methyl, ethyl, propyl, isopropyl, cyclopropyl, cyclopentyl or cyclohexyl,
Q2 represents hydrogen, methyl or ethyl,
Q1 and Q2 jointly with the carbon to which they are bonded represent saturated C5-C6-cycioalkyI in which one ring member is optionally replaced by oxygen and which is optionally substituted by methyl, ethyl, propyl, isopropyl, methoxy, ethoxy, propoxy or butoxy,


in which
E represents a metal ion or an ammonium ion,

G represents hydrogen (a) or one of the groups

L represents oxygen or sulphur and
M represents oxygen or sulphur,
R1 represents C1-C14-alkyl, C2-C14-alkenyl, C1-C4-alkoxy-C1-C2-alkyl, C1-C4-alkylthio-C1-C2-alkyl, each of which is optionally substituted by fluorine or chlorine, or represents C3-C6-cycloalkyl in which one or two ring members which are not directly adjacent are optionally replaced by oxygen and/or sulphur and which is optionally substituted by fluorine, chlorine, methyl, ethyl or methoxy,
or represents phenyl which is optionally substituted by fluorine, chlorine, bromine, cyano, nitro, methyl, ethyl, isopropyl, tert-butyl, methoxy, trifluoromethyl or trifluoromethoxy,
or represents thienyl or pyridyl, each of which is optionally substituted by fluorine, chlorine, bromine or methyl,
R2 represents C1-C14-alkyl, C2-C14-alkenyl or C1-C4-alkoxy-C2-C3-alkyl, each of which is optionally substituted by fluorine,
or represents C3-C6-cycloalkyl which is optionally substituted by methyl, ethyl or methoxy,
or represents phenyl or benzyl, each of which is optionally substituted by fluorine, chlorine, cyano, nitro, methyl, ethyl, isopropyl, tert-butyl, methoxy, trifluoromethyl or trifluoromethoxy,
R3 represents methyl, ethyl, n-propyl, isopropyl, each of which is optionally substituted by fluorine, or represents phenyl which is optionally substituted by fluorine, chlorine, bromine, methyl,


tert butyl methoxy, trifluoromethyl, trifluoromethoxy, cyano or nitro,
R4 represents C1-C4-alkyl, C1-C4-alkoxy, C1-C4-alkylamino, di-(C1-C4-alkyl)amino, C1-C4-alkylthio or represents phenyl, phenoxy or phenylthio, each of which is optionally substituted by fluorine, chlorine, bromine, nitro, cyano, C1-C2-alkoxy, trifluoromethoxy or C1-C3-alkyl,
R5 represents methyl, ethyl, methoxy, ethoxy, methylthio or ethylthio,
R6 and R7 independently of one another, represent hydrogen, C1-C4-alkyl, C3-C6-cycloalkyl, C1-C4-alkoxy, C3-C4-alkenyl, C1-C4-alkoxy-C1- C4-alkyl,
R7 represents hydrogen, C1-C4-alkyl or C3-C4-alkenyl,
R6 and R7 together with the N atom to which they are bonded represent a C5-C6-alkylene radical in which one methylene group is optionally replaced by oxygen or sulphur.
5. Compounds of the formula (I) as claimed in claim 1 in which

X
Het represents
W represents oxygen or N-D,
X represents chlorine, methyl, ethyl, n-propyl or i-propyl,
Y represents



A represents hydrogen or methyl,
B represents hydrogen or methyl,
A, B and the carbon atom to which they are bonded represent saturated C6-cycloalkyl in which one ring member is optionally replaced by oxygen,
D represents hydrogen or cyclopropyl,
D and Q1 jointly represent C3-C4-alkanediyl,
Q1 represents hydrogen or methyl,
Q2 represents hydrogen or methyl,
Q1 and Q2 jointly with the carbon to which they are bonded represent saturated C6-cycloalkyl in which one ring member is optionally replaced by oxygen,
G represents hydrogen (a) or one of the groups



where M represents oxygen or sulphur,
R1 represents C1-C4-alkyl, C1-C4-alkoxy-C1-C2-alkyl, or represents phenyl or pyridyl, each of which is optionally substituted by chlorine,
R2 represents C1-C4-alkyl, phenyl or benzyl,
R6 and R7 together with the N atom to which they are bonded represent a C5-C6-alkylene radical in which one methylene group is optionally replaced by oxygen.
6. Process for the preparation of compounds of the formula (I) as claimed in claim 1, wherein, to obtain
(A) substituted tetrahydropyridine-2,4-diones or their enols of the formula (I-l-a)

in which
A, B, D, Q1, Q2 and Het have the abovementioned meanings,
N-acylamino acid esters of the formula (II)



in which
A, B, D, Q1, Q2 and Het have the abovementioned meanings,
and
R8 represents alkyl,
are subjected to an intramolecular condensation reaction in the presence of a diluent and in the presence of a base,
(B) substituted 5,6-dihydropyrones of the formula (I-2-a)

A, B, Q1, Q2 and Het have the abovementioned meanings, O-acylhydroxycarboxylic esters of the formula (III)



in which
A, B, Q1, Q2 and Het have the abovementioned meanings
and
R8 represents alkyl
are subjected to an intramolecular condensation reaction in the presence of a diluent and in the presence of a base,
(C) compounds of the above-shown formulae (I-l-b) to (I-2-b), in which A, B, Q1, Q2, R1, W and Het have the abovementioned meanings, compounds of the above-shown formulae (I-l-a) to (I-2-a), in which
A, B, Q1, Q2, W and Het have the abovementioned meanings are reacted in each case
(a) with acid halides of the formula (IV)


in which

R1 has the abovementioned meaning and
Hal represents halogen
or
(P) with carboxylic anhydrides of the formula (V)
R1-CO-O-CO-R1 (V)
in which
R1 has the abovementioned meaning,
if appropriate in the presence of a diluent and if appropriate in the presence of an acid binder;
(D) compounds of the formulae (I-l-c) to (I-2-c) shown above, in which A, B, Q1, Q2, R2, M, W and Het have the abovementioned meanings and L represents oxygen, compounds of the formulae (I-l-a) to (I-2-a) shown above, in which A, B, Q1, Q2, W and Het have the abovementioned meanings are reacted in each case
with chloroformic esters or chloroformic thioesters of the formula (VI)
R2-M-CO-Cl (VI)
in which
R2 and M have the abovementioned meanings,
if appropriate in the presence of a diluent and if appropriate in the presence of an acid binder;


(E) compounds of the formulae (I-l-c) to (I-2-c) shown above, in
which A, B, Q1, Q2, R2, M, W and Het have the abovementioned
meanings and L represents sulphur, compounds of the formulae (1-1-
a) to (I-2-a) shown above, in which A, B, Q1, Q2, W and Het have the
abovementioned meanings are reacted in each case,
with chloromonothioformic esters or chiorodithioformic esters of the formula (VII)

in which
M and R2 have the abovementioned meanings,
if appropriate in the presence of a diluent and if appropriate in the presence of an acid binder,
(F) compounds of the formulae (I-l-d) to (I-2-d) shown above, in
which A, B, Q1, Q2, R3, W and Het have the abovementioned
meanings, compounds of the formulae (I-l-a) and (I-2-a) shown
above, in which A, B, Q1, Q2, W and Het have the
abovementioned meanings are reacted in each case
with sulphonyl chlorides of the formula (VIII)
in which
R3 has the abovementioned meaning,


if appropriate in the presence of a diluent and if appropriate in the presence of an acid binder,
(G) compounds of the formulae (I-l-e) to (I-2-e) shown above, in which A, B, L, Q1, Q2, R4, R5, W and Het have the abovementioned meanings, compounds of the formulae (I-l-a) to (I-2-a) shown above, in which A, B, Q1, Q2, W and Het have the abovementioned meanings are reacted in each case
with phosphorus compounds of the formula (IX)

in which
L, R4 and R5 have the abovementioned meanings and
Hal represents halogen,
if appropriate in the presence of a diluent and if appropriate in the presence of an acid binder,
(H) compounds of the formulae (I-l-f) to (I-2-f) shown above, in which A, B, E, Q1, Q2, W and Het have the abovementioned meanings, compounds of the formulae (I-l-a) to (I-2-a), in which A, B, Q1, Q2, W and Het have the abovementioned meanings are reacted in each case
with metal compounds or amines of the formulae (X) or (XI)


in which
Me represents a monovalent or divalent metal,
t represents the number 1 or 2 and
R11, R12, R13 independently of one another represent hydrogen or alkyl,
if appropriate in the presence of a diluent,
(I) compounds of the formulae (I-l-g) to (I-2-g) shown above, in which A, B, L, Q1, Q2, R6, R7, w and Het have the abovementioned meanings, compounds of the formulae (I-l-a) to (I-2-a) shown above, in which A, B, Q1, Q2, W and Het have the abovementioned meanings are reacted in each case
(a) with isocyanates or isothiocyanates of the formula (XII)
R6-N=C=L (XII)
in which
R6 and L have the abovementioned meanings,
if appropriate in the presence of a diluent and if appropriate in the presence of a catalyst, or
β ) with carbamoyl chlorides or thiocarbamoyl chlorides of the
formula (XIII)




in which
L, R6 and R7 have the abovementioned meanings,
if appropriate in the presence of a diluent and if appropriate in the presence of an acid binder.
7. Compounds of the formula (II)

in which
A, B, D, Q1, Q2, Het and R8 have the abovementioned meanings,
8. Compounds of the formula (XVI)


in which



A, B, D, Q1, Q2 and Het have the abovementioned meanings.
9. Compounds of the formula (XX)

in which
A, B, D, Q1, Q2 and Het have the abovementioned meanings.
10. Compounds of the formula (III)


in which

A, B, Q1, Q2, Het and R8 have the abovementioned meanings.
11. Pestidices, microbicides and herbicides, wherein it has a content of at least one compound of the formula (I) as claimed in claim 1.
12. Process for the preparation of pesticides, microbicides and herbicides, wherein compounds of the formula (I) as claimed in claim 1 are mixed with extenders and/or surfactants.


13. Compounds of the formula I as defined in claim 1 substantially as herein described with reference to the foregoing examples.
14. Pesticides, microbicides and herbicides substantially as herein described with reference to the foregoing examples.
15. Process for the preparation of pesticides microbicides and herbicides substantially as herein described with reference to the foregoing examples.
Dated this 2.0th day of December, 2001.
[SHUKADEV KHURAIJAM]
OF REMFRY & SAGAR
ATTORNEY FOR THE APPLICANT

Documents:

1195-mum-2001-cancelled pages(31-01-2007).pdf

1195-mum-2001-claims(granted)-(31-01-2007).doc

1195-mum-2001-claims(granted)-(31-01-2007).pdf

1195-mum-2001-correspondence(31-01-2007).pdf

1195-mum-2001-correspondence(ipo)-(19-06-2007).pdf

1195-mum-2001-form 1(20-12-2001).pdf

1195-mum-2001-form 18(20-06-2005).pdf

1195-mum-2001-form 2(granted)-(31-01-2007).doc

1195-mum-2001-form 2(granted)-(31-01-2007).pdf

1195-mum-2001-form 3(27-03-2002).pdf

1195-mum-2001-form 3(31-01-2007).pdf

1195-mum-2001-form 5(20-12-2001).pdf

1195-mum-2001-petition under rule 137(31-01-2007).pdf

1195-mum-2001-petition under rule 138(31-01-2007).pdf

1195-mum-2001-power of authority(20-12-2001).pdf

1195-mum-2001-power of authority(31-01-2007).pdf


Patent Number 209029
Indian Patent Application Number 1195/MUM/2001
PG Journal Number 35/2007
Publication Date 31-Aug-2007
Grant Date 17-Aug-2007
Date of Filing 20-Dec-2001
Name of Patentee BAYER AKTIENGESELLSCHAFT
Applicant Address D-51368 LEVERKUSEN,
Inventors:
# Inventor's Name Inventor's Address
1 REINER FISCHER NELLY-SACHS-STR. 23, 40789 MONHEIM,
2 ASTRID ULLMANN MEROWINGERSTR. 31, 50677 KOLN,
3 AXEL TRAUTWEIN IM AEHLEMAAR 23, 51467 BERGISCH GLADBACH,
4 MARK WILHELM DREWES GOETHESTR. 38, 40764 LANGENFELD,
5 CHRISTOPH ERDELEN UNTERNUSCHERHOF 15, 42799 LEICHLINGEN,
6 PETER DAHMEN ALTEBRUSCHERHOF STR. 61, 41470 NEUSS,
7 DIETER FEUCHT ACKERWEG 9, 40789 MONHEIM,
8 ROLF PONTZEN AM KLOSTER 69, 42799 LEICHLINGEN,
9 PETER LOSEL LOHRSTRASSE 90A, 51371 LEVERKUSEN,
PCT International Classification Number C07D 417/04
PCT International Application Number N/A
PCT International Filing date
PCT Conventions:
# PCT Application Number Date of Convention Priority Country
1 101 00175.4 2001-01-04 Germany