Title of Invention

"BIPHENYL THIAZOLE CARBOXAMIDES OF FORMULA (I) AND METHOD FOR PREPARING THE SAME"

Abstract Biphenyl thiazole carboxamides of Formula (I) where R1, R2, R3, R4, R5, R6, R7, R8, R9, R10 and R11 are herein as described as in the specification and claims.
Full Text The present invention relates to novel biphenyl thiazole carboxamides, several methods for their manufacture and their use for combating undesired microorganisms.
It is already known that numerous carboxamides possess fungicidal properties (see e.g. WO 03/070705, WO 97/08148 and JP-A 2001-302605). Therefore, a multitude of biphenyl carboxamides have already been identified that can be substituted in the biphenyl portion, such as e.g. N-(3',4'-dichloro-3-fluoro-1,1'-biphenyl-2-yl)-l-methyl-3-(trifluoromethyl)-lH-pyrazole-4-carboxamide from WO 03/070705, N-(5-fluoro-4'-methylbiphenyl-2-yl)-2-methyl-4-(trifluoromethyl)-1,3-thiazole-5-carboxamide from WO 97/08148 and N-(4'-methoxy-6-methylbiphenyl-2-yl)-2-methyl-4-(trifluoromethyl)-l,3-thiazole-5-carb-oxamide from JP 2001-302605. The efficacy of these substances is good, however in most cases, e.g. with low application rates, it leaves something to be desired.
Novel biphenyl thiazole carboxamides of Formula (I)
(Formula Removed)
were found, where
R1 stands for hydrogen, halogen, amino, C1-C4-alkylamino, di-(C1-C4-alkyl)amino, cyano, C1-C4-
alkyl or C1-C4-halogenalkyl with 1 to 5 halogen atoms,
R2 stands for halogen, C1-C4-alkyl or C1-C4-halogenalkyl with 1 to 5 halogen atoms,
R3 stands for hydrogen, C1-C8-alkyl, C1-C6-alkylsulphinyl, C1-C6-alkylsulphonyl, C1-C4-alkpxy-C1-C4-alkyl, C3-C8-cycloalkyl; C1-C6-halogenalkyl, C1-C4-halogenalkylthio, C1-C4-halogenal-kylsulphinyl, C1-C4-halogenalkylsulphonyl, halogen-C1-C4-alkoxy-C1-C4-alkyl, C3-C8-halo-gencycloalkyl, each with 1 to 9 fluorine, chlorine and/or bromine atoms; formyl, formyl-C1-C3-alkyl, (C1-C3-alkyl)carbonyl-C1-C3-alkyl, (C1-C3-alkoxy)carbonyl-C1-C3-alkyl; halogen-(C1-C3-alkyl)carbonyl-C1-C3-alkyl, halogen-(C1-C3-alkoxy)carbonyl-C1-C3-alkyl, each with 1 to 13 fluorine, chlorine and/or bromine atoms;
(C1-C8-alkyl)carbonyl, (C1-C8-alkoxy)carbonyl, (C1-C4-alkoxy-C1-C4-alkyl)carbonyl, (C3-C8-cycloa!kyl)carbonyl; (C1-C6-halogenalkyl)carbonyl, (C1-C6-halogenalkoxy)carbonyl, (ha-logen-C1-C4-alkoxy-C1-C4-alkyl)carbonyl, (C3-C8-halogen cycloalkyl)carbonyl, each with 1 to 9 fluorine, chlorine and/or bromine atoms; or -C(=O)C(=O)R6, -CONR7R8 or -CH2NR9R10,
R4 stands for halogen, CrC4-alkyl, C,-C4-alkoxy, -C4-alkylthio or Ci-C4-halogenalkyl with 1
to 9 fluorine, chlorine and/or bromine atoms,
R5 stands for halogen, cyano, nitro, amino, hydroxy, formyl, carboxy, carbamoyl, thiocarbamoyl,
CrC8-alkyl, C2-C6-alkenyl, CrC8-alkoxy, C2-C6-alkenyloxy, CrC8-alkylthio, C,-C8-alkyl
sulphinyl, C-Cg-alkylsulphonyl, C,-C8-hydroxyalkyl, CrC8-oxoalkyl, C]-C8-alkoxyalkyl, Cr
C8-alkylthioalkyl, Ci-C8-dialkoxyalkyl, C|-C6-alkylamino, di(Ci-C6-alkyl)amino, (Ci-Cealkyl)
carbonyl, (C-C6-alkyl)carbonyloxy, (C|-C6-alkoxy)carbonyl, (Ci-C6-alkyl)amino
carbonyl, di(Ci-C6-alkyl)amino carbonyl, (Ci-C6-alkyl)carbonyl amino, (
carbonyl(Ci-C6-alkyl)amino, (C2-C6-alkenyl)carbonyl, (C2-C6-alkinyl)carbonyl,
alkyl, C3-C6-cycloalkyloxy, or for CrC6-halogenalkyl, Ci-C6-halogenalkoxy, Ci-C6-halogen
alkylthio, Ci-C6-halogenalkylsulphinyl or Q-Ce-halogenalkylsulphonyl, each with 1 to 13 halogen
atoms, C2-C6-halogenalkenyl, C2-C6-halogenalkenyloxy, each with 1 to 11 of the same
or different halogen atoms,
R5 further stands for C2-C5-alkenylene possibly substituted once or twice by halogen, -C4-
alkyl or C]-C4-halogenalkyl with 1 to 5 halogen atoms, if two R5 moieties are in ortho
position to each other,
n stands for 2, 3,4 or 5, whereby the R5 moieties can be the same or different,
R6 stands for hydrogen, Cj-C8-alkyl, CrC8-alkoxy, CrC4-alkoxy-C|-C4-alkyl, C3-C8-cycIoalkyl;
C-C6-halogenalkyl, Ci-C6-halogenalkoxy, halogen-Ci-C4-alkoxy-Ci-C4-alkyl, C3-C8-halogen
cycloalkyl, each with 1 to 9 fluorine, chlorine and/or bromine atoms,
R7 and R8, independently of one another, each stand for hydrogen, CpCg-alkyl, C,-C4-alkoxy-C|-C4-
alkyl, C3-C8-cycloalkyl; Ci-Cg-halogenalkyl, halogen-CrC4-alkoxy-C|-C4-alkyl, C3-C8-
halogencycloalkyl, each with 1 to 9 fluorine, chlorine and/or bromine atoms,
R7 and R8, together with the nitrogen atom to which they are bonded, further form a saturated
heterocycle with 5 to 8 ring atoms, possibly substituted once or twice, identically or
variously, by halogen or CrC4-alkyl, in which the heterocycle can contain 1 or 2 additional,
non-adjacent heteroatoms from the group of hydrogen, sulphur or NR11,
R9 and R10, independently of one another, stand for hydrogen, Ci-C8-alkyl, C3-C8-cycloalkyl; Q-C8-halogenalkyl,
C3-C8-halogencycloalkyl, each with 1 to 9 fluorine, chlorine and/or bromine atoms,
R9 and R10, together with the nitrogen atom to which they are bonded, further form a saturated
heterocycle with 5 to 8 ring atoms, possibly substituted once or twice, identically or
variously, by halogen or C]-C4-alkyI, in which the heterocycle can contain 1 or 2 additional,
non-adjacent heteroatoms from the group of hydrogen, sulphur orNR11,
R11 stands for hydrogen or CpCe-alkyl.
Furthermore, it was found that one can obtain biphenyl thiazole carboxamides of Formula (I), by
(a) reacting carboxylic acid derivatives of Formula (IT)
where
R1 and R2 have the meanings specified above and
X1 stands for halogen or hydroxy,
with biphenyl amines of Formula (III)
where R3, R4, R5 and n have the meanings specified above,
in the presence of a catalyst if applicable, in the presence of a condensation agent if
applicable, in the presence of an acid binding agent if applicable and in the presence of a
diluent if applicable, or
(b) by reacting halogen carboxamides of Formula (IV)
where
R1, R2, R3 and R4 have the meanings specified above,
X2 stands for bromine, iodine or trifiuoromethylsulphonate,
with boronic acid derivatives of Formula (V)
where
R5 and n have the meanings specified above and
G1 and G2 each stand for hydrogen or jointly stand for tetramethylethylene,
in the presence of a catalyst, in the presence of an acid binding agent if applicable and in the
presence of a diluent if applicable, or
(c) by reacting boronic acid derivatives of Formula (VI)
(VI),
where
R1, R2, R3 and R4 have the meanings specified above,
G3 and G4 each stand for hydrogen or jointly stand for tetramethylethylene,
with phenyl derivatives of Formula (VII)
R5 and n have the meanings specified above and
X3 stands for chlorine, bromine, iodine or trifluoromethylsulphonate,
in the presence of a catalyst, in the presence of an acid binding agent if applicable and in the
presence of a diluent if applicable, or
(d) by reacting halogen carboxamides of Formula (IV)
(IV),
where
R1, R2, R3 and R4 have the meanings specified above,
X2 stands for bromine, iodine or trifluoromethylsulphonate,
with phenyl derivatives of Formula (VII)
(VII),
where
- 5 -
R5 and n have the meanings specified above and
X3 stands for chlorine, bromine, iodine or trifluoromethylsulphonate,
in the presence of a palladium or nickel catalyst and in the presence of 4,4,4',4',5,5,5',5'-
octamethyl-2,2'-bis-l,3,2-dioxaborolane, in the presence of an acid binding agent if
applicable and in the presence of a diluent if applicable, or
(e) by reacting biphenyl thiazole carboxamides of Formula (I-a)
(I-a),
where
R1, R2, R4, R5 and n have the meanings specified above,
with halogenides of formula (VIII)
R3A—X4 (Vffl),
R3A stands for C,-C8-alkyl, CrC6-alkylsulphinyl, C,-C6-alkylsulphonyl, C,-C4-alkoxy-C|-
C4-alkyl, Ca-Cg-cycloalkyI; Ci-C6-halogenalkyl, Ci-C4-halogenalkylthio, CrC4-halogenalkylsulphinyl,
Ci-C4-halogenalkylsulphonyl, halogen-Ci-C4-alkoxy-CrC4-alkyl,
C3-C8-halogencycloalkyl, each with 1 to 9 fluorine, chlorine and/or bromine atoms;
formyl, formyl-Ci-C3-alkyl, (C|-C3-alkyl)carbonyl-Ci-C3-alkyl, (CrC3-alkoxy)carbony
1-C i -C3-alky 1; halogen-(C i -C3-alkyl)carbony 1-C i -C3-alkyl, halogen-(C i -C3-
alkoxy)carbonyl-C]-C3-alkyl, each with 1 to 13 fluorine, chlorine and/or bromine
atoms;
(C]-C8-alkyl)carbonyl, (CrC8-alkoxy)carbonyl, (C|-C4-alkoxy-C|-C4-alkyl)carbonyl,
(C3-C8-cycloalkyl)carbonyl; (CrC6-halogenalkyl)carbonyl, (CrC6-halogenalkoxy)-
carbonyl, (halogen-Ci-C4-alkoxy-Ci-C4-alkyl)carbonyl, (C3-C8-halogencycloalkyl)
carbonyl, each with 1 to 9 fluorine, chlorine and/or bromine atoms; or
-C(=O)C(=0)R6, -CONRV or -CH2NR9R10,
R6, R7, R8, R9 and R10 have the meanings specified above,
X4 stands for chlorine, bromine or iodine,
in the presence of a base and in the presence of a diluent.
Finally, it was found that the novel biphenyl thiazole carboxamides of formula (I) possess very good
microbicidal properties and can be employed for combating undesired microorganisms as well as in
the areas of plant protection and material protection.
The compounds according to the invention can possibly occur as mixtures of various possible isomer
forms, particularly of stereoisomers, such as e.g. E-isomers and Z-isomers, threo isomers and erythro
isomers, as well as optical isomers; however they can possibly occur as tautomers as well. The claims
of this patent cover the E-isomers and the Z-isomers, as well as the threo isomers and erythro isomers,
and the optical isomers, any mixtures of these isomers, and the possible tautomer forms.
The biphenyl thiazole carboxamides according to the invention are generally defined by Formula (I).
Preferred moiety definitions of the preceding and following formulas are specified in the following
section. These definitions are equally valid for the final products of Formula (I) as well as for all
intermediate products.
R1 preferably stands for hydrogen, fluorine, chlorine, bromine, amino, C|-C4-alkylamino, di(Cr
C4-alkyl)amino, cyano, methyl, ethyl or Ci-Ca-halogenalkyl with 1 to 5 fluorine, chlorine
and/or bromine atoms.
R1 particularly preferably stands for hydrogen, fluorine, chlorine, bromine, amino, methylamino,
dimethylamino, cyano, methyl, ethyl, trifluoromethyl, difluoromethyl, difluorochloromethyl
or trichloromethyl.
R1 quite particularly preferably stands for hydrogen, fluorine, chlorine, bromine, amino,
methylamino, dimethylamino, methyl, trifluoromethyl, difluoromethyl or trichloromethyl.
R1 e^psdally_pjsferably stands for amino, chlorine, methylamino, dimethylamino, methyl or
trifluoromethyl.
R2 preferably stands for fluorine, chlorine, bromine, methyl, ethyl or Ci-C2-halogenalkyl with 1
to 5 fluorine, chlorine and/or bromine atoms.
R2 particularly preferably stands for fluorine, chlorine, bromine, methyl, ethyl, 1-fluoroethyl,
trifluoromethyl, difluoromethyl, difluorochloromethyl or trichloromethyl.
R2 quite particularly preferably stands for fluorine, chlorine, bromine, methyl, trifluoromethyl,
difluoromethyl or trichloromethyl.
R2 especially preferably stands for methyl, trifluoromethyl or difluoromethyl.
R3 preferably stands for hydrogen, C]-C6-alkyl, C]-C4-alkylsulphinyl, CrC4-alkylsulphonyl, CrC3-
alkoxy-CrCralkyl, C3-C6-cycloalkyl; Ci-C4-halogenalkyl, CrC4-halogenalkyIthio, C,-C4-
halogenalkylsulphinyl, Ci-C4-halogenalkylsulphonyl, halogen-Ci-C3-alkoxy-CrC3-alkyl, C3-C8-
-7-
halogencycloalkyl, each with 1 to 9 fluorine, chlorine and/or bromine atoms; formyl, formyl-C
C3-alkyl, (C,-C3-alkyl)carbonyl-CrC3-alkyl, (C,-C3-aIkoxy)carbonyI-Ci-C3-alkyl; halogen-(Cr
C3-alkyl)carbonyl-CrC3-alkyl, halogen-(C]-C3-alkoxy)carbonyl-C-C3-alkyl, each with 1 to 13
fluorine, chlorine and/or bromine atoms;
(C1-C6-alkyl)carbonyl, (C,-C4-alkoxy)carbonyl, (C]-C3-alkoxy-CrC3-alkyl)carbonyl, (C3-C6-
cycloalkyl)carbonyl; (CrC4-halogenalkyl)carbonyl, (Ci-C4-halogenalkoxy)carbonyl, (halogen-
Ci-C3-alkoxy-Ci-C3-alkyl)carbonyl, (C3-C6-halogencycloalkyl)carbonyl, each with 1 to 9
fluorine, chlorine and/or bromine atoms; or -C(=O)C(=O)R6, -CONR7R8 or -CH2NR9R10.
R3 particularly preferably stands for hydrogen, methyl, ethyl, n- or iso-propyl, n-, iso-, sec- or tertbutyl,
pentyl or hexyl, methylsulphinyl, ethylsulphinyl, n- or iso-propylsulphinyl, n-, iso-, sec- or
tert-butylsulphinyl, methylsulphonyl, ethylsulphonyl, n- or iso-propylsulphonyl, n-, iso-, sec- or
tert-butylsulphonyl, methoxymethyl, methoxyethyl, ethoxymethyl, ethoxyethyl, cyclopropyl,
cyclopentyl, cyclohexyl, trifluoromethyl, trichloromethyl, trifluoroethyl, difluoromethylthio, difluorochloromethylthio,
trifluoromethylthio, trifluoromethylsulphinyl, trifluoromethylsulphonyl,
trifluoromethoxymethyl; formyl, -CH2-CHO, -(CH2)2-CHO, -CH2-CO-CH3,
-CH2-CO-CH2CH3, -CH2-CO-CH(CH3)2, -(CH2)2-CO-CH3( -(CH2)2-CO-CH2CH3,
-(CH2)2-CO-CH(CH3)2, -CH2-C02CH3, -CH2-CO2CH2CH3, -CH2-CO2CH(CH3)2,
-(CH2)2-CO2CH3, -(CH2)2-CO2CH2CH3, -(CH2)2-CO2CH(CH3)2, -CH2-CO-CF3, -CH2-CO-CCI3,
-CH2-CO-CH2CF3, -CH2-CO-CH2CC13, -(CH2)2-CO-CH2CF3, -(CH2)2-CO-CH2CCI3,
-CH2-CO2CH2CF3, -CH2-CO2CF2CF3, -CH2-CO2CH2CC13, -CH2-CO2CC12CC13,
-(CH2)2-C02CH2CF3, -(CH2)2-C02CF2CF3, -(CH2)2-CO2CH2CC13) -(CH2)2-CO2CC12CC13;
methyl carbonyl, ethyl carbonyl, n-propylcarbonyl, iso-propylcarbonyl, tert-butylcarbonyl,
methoxycarbonyl, ethoxycarbonyl, tert-butoxycarbonyl, cyclopropylcarbonyl; trifluoromethylcarbonyl,
trifluoromethoxycarbonyl, or -C(=O)C(=O)R6, -CONR7R8 or -CH2NR9R10.
R3 quite particularly preferably stands for hydrogen, methyl, methoxymethyl, formyl, -CH2-CHO,
-(CH2)rCHO, -CH2-CO-CH3, -CH2-CO-CH2CH3, -CH2-CO-CH(CH3)2, -C(=O)CHO,
-C(=O)C(=O)CH3, -C(=O)C(=0)CH2OCH3, -C(=O)CO2CH3, -C(=O)CO2CH2CH3.
R4 preferably stands for fluorine, where fluorine is particularly preferably in the 3-position or
the 5-position, quite particularly preferably in the 5-position of the respective compound [see
e.g. Formula (I)].
R4 particularly preferably stands for chlorine, where chlorine is particularly preferably in the 4-
position or 5-position, quite particularly preferably in the 4-position, as well as quite
particularly preferably in the 5-position of the respective compound.
R4 further preferably stands for trifluoromethyl, where trifluoromethyl is particularly preferably
in the 4-position or 5-position of the respective compound.
R4 further preferably stands for methoxy or methylthio, where methoxy or methylthio is
particularly preferably in the 3-position or the 5-position, quite particularly preferably in the
5-position of the respective compound.
R4 further preferably stands for methyl, where methyl is particularly preferably in the 4-position
or 5-position, quite particularly preferably in the 4-position of the respective compound.
R4 further preferably stands for iso-propyl, where iso-propyl is particularly preferably in the 4-
position or 5-position, quite particularly preferably in the 5-position of the respective
compound.
R5 preferably stands for fluorine, chlorine, bromine, cyano, nitro, amino, hydroxy, formyl,
methyl, ethyl, n- or iso-propyl, n-, iso-, sec- or tert-butyl, vinyl, allyl, methoxy, ethoxy, n- or
iso-propoxy, vinyloxy, allyloxy, methylthio, ethylthio, n- or iso-propylthio, methylsulphinyl,
ethylsulphinyl, n- or iso-propylsulphinyl, methylsulphonyl, ethylsulphonyl, n- or iso-propylsulphonyl,
methoxymethyl, methoxyethyl, ethoxymethyl, ethoxyethyl, methylthiomethyl,
methylthioethyl, ethylthiomethyl, ethylthioethyl, methylamino, ethyl amino, iso-propylamino,
dimethylamino, diethylamino, dipropylamino, diisopropylamino, methyl carbonyl, ethyl
carbonyl, methylaminocarbonyl, dimethylaminocarbonyl, methylcarbonylamino,
methylcarbonylmethlyamino, cyclopropyl, cyclopropyloxy, trifluoromethyl, trichloromethyl,
trifluoroethyl, difluoromethoxy, trifluoromethoxy, difluorochloromethoxy, trifluoroethoxy,
difluoromethylthio, difluorochloromethylthio or trifluoromethylthio.
R5 further preferably stands for C2-C4-alkenylene possibly substituted one or twice by fluorine,
chlorine, bromine, methyl, ethyl, n- or iso-propyl, n-, iso-, sec- or tert-butyl or trifluoromethyl,
if two R5 moieties are in ortho position to each other.
R5 particularly preferably stands for fluorine, chlorine, bromine, methyl, ethyl, n- or iso-propyl,
n-, iso-, sec- or tert-butyl, methoxy, ethoxy, n- or iso-propoxy, methylthio, ethylthio, n- or isopropylthio,
methylsulphonyl, ethylsulphonyl, n- or iso-propylsulphonyl, methoxymethyl,
methylthiomethyl, methylamino, ethyl amino, iso-propylamino, dimethylamino, diethylamino,
diisopropylamino, methyl carbonyl, methylaminocarbonyl, dimethylaminocarbonyl,
methylcarbonylamino, cyclopropyl, trifluoromethyl, trifluoroethyl, difluoromethoxy,
trifluoromethoxy, difluoromethyltriio or trifluoromethylthio.
R5 further particularly preferably stands for -CH=CH-CH=CH- possibly substituted once or
twice by fluorine, chlorine, bromine, methyl, ethyl, n- or iso-propyl, n-, iso-, sec- or tert-butyl
or trifluoromethyl, if two R5 moieties are in ortho position to each other.
R5 quite particularly preferably stands for fluorine, chlorine, bromine, methyl, iso-propyl, tertbutyl,
methoxy, iso-propoxy, methylthio, iso-propylthio, methoxymethyl, methylthiomethyl,
methylamino, dimethylamino, methylaminocarbonyl, methylcarbonylamino, cyclopropyl,
trifluoromethyl, trifluoroethyl, difluoromethoxy, trifluoromethoxy, difluoromethylthio or
trifluoromethylthio.
R5 gspeciaUy.preferably stands for fluorine, chlorine, bromine, methyl, trifluoromethyl, difluoromethoxy
or trifluoromethoxy.
n preferably stands for 2, 3 or 4, whereby the R5 moieties can be the same or different,
n particularly preferably stands for 2 or 3, whereby the R5 moieties can be the same or
different,
n quite particularly preferably stands for 2, particularly in the 3',4'-position, 2',4'-position, 3',5'-
position, 2',3'-position or 2',5'-position, whereby the R5 moieties can each be the same or
different,
n further quite particularly preferably stands for 3, particularly in the 2',4',6'-position or 3',4',5'-
position, whereby the R5 moieties can be the same or different.
R6 preferably stands for hydrogen, CrC6-alkyl, CrC4-alkoxy, Ci-C3-alkoxy-CrC3-alkyl, C3-C6-
cycloalkyl; C]-C4-halogenaIkyl, CrC4-halogenalkoxy, halogen-CrC3-alkoxy-Ci-C3-alkyl, C3-
Ce-halogencycloalkyl, each with 1 to 9 fluorine, chlorine and/or bromine atoms.
R6 particularly preferably stands for hydrogen, methyl, ethyl, n- or iso-propyl, tert-butyl,
methoxy, ethoxy, n- or iso-propoxy, tert-butoxy, methoxymethyl, cyclopropyl; trifluoromethyl,
trifluoromethoxy.
R7 and R8, independently of one another, preferably stand for hydrogen, CrC6-alkyl, C,-C3-alkoxy-
CrC3-alkyl, C3-C6-cycloalkyl; CrC4-halogenalkyl, halogen-C,-C3-alkoxy-C,-C3-alkyl, C3-C6-
halogencycloalkyl, each with 1 to 9 fluorine, chlorine and/or bromine atoms.
R7 and R8 further preferably form, together with the nitrogen atom to which they are bonded, a
saturated heterocycle with 5 or 6 ring atoms possibly substituted one to four times identically
or variously by halogen or Ci-C4-alkyl, in which the heterocycle can contain 1 or 2
additional, non-adjacent heteroatoms from the group of oxygen, sulphur or NR11.
R7 and R8, independently of one another, particularly preferably stand for hydrogen, methyl, ethyl, nor
iso-propyl, n-, iso-, sec- or tert-butyl, methoxymethyl, methoxyethyl, ethoxymethyl,
ethoxyethyl, cyclopropyl, cyclopentyl, cyclohexyl; trifluoromethyl, trichloromethyl, trifluoroethyl,
trifluoromethoxymethyK
R7 and R8 further particularly preferably form, together with the nitrogen atom to which they are
bonded, a saturated heterocycle from the group of morpholine, thiomorpholine or piperazine
possibly substituted one to four times, identically or variously, by fluorine, chlorine, bromine
or methyl, in which the piperazine can be substituted by R" on the second nitrogen atom.
R9 and R10, independently of one another, preferably stand for hydrogen, Q-Ce-alkyl, C3-C6-cycloalkyl;
C]-C4-halogenalkyl, Cs-Ce-halogencycloalkyl, each with 1 to 9 fluorine, chlorine and/or
bromine atoms.
R9 and R10 further preferably form, together with the nitrogen atom to which they are bonded, a
saturated heterocycle with 5 or 6 ring atoms possibly substituted one to four times, identically
or variously, by halogen or Ci-C4-alkyl, in which the heterocycle can contain 1 or 2
additional, non-adjacent heteroatoms from the group of oxygen, sulphur or NR11.
R9 and R10, independently of one another, particularly preferably stand for hydrogen, methyl, ethyl, nor
iso-propyl, n-, iso-, sec- or tert-butyl, methoxymethyl, methoxyethyl, ethoxymethyl,
ethoxyethyl, cyclopropyl, cyclopentyl, cyclohexyl; trifluoromethyl, trichloromethyl, trifluoroethyl,
trifluoromethoxymethyl.
R9 and R10 further particularly preferably form, together with the nitrogen atom to which they are
bonded, a saturated heterocycle from the group of morpholine, thiomorpholine or piperazine
possibly substituted one to four times, identically or variously, by fluorine, chlorine, bromine
or methyl, in which the piperazine can be substituted by R11 on the second nitrogen atom.
R1' preferably stands for hydrogen or CrC4-alkyl.
R" particularly preferably stands for hydrogen, methyl, ethyl, n- or iso-propyl, n-, iso-, sec- or
tert-butyl.
Those compounds of Formula (I) are preferred, in which all moieties respectively have the
abovementioned preferred definitions.
Those compounds of Formula (I) are particularly preferred, in which all moieties respectively have
the abovementioned particularly preferred definitions.
Those compounds of Formula (I) are quite particularly preferred, in which all moieties respectively
have the abovementioned quite particularly preferred definitions.
The following groups of novel carboxamides are preferred and are to be understood as respective
subsets of the abovementioned compounds of Formula (I):
Group 1: Biphenyl thiazole carboxamides of Formula (I-a)
(I-a),
where R1, R2, R4, R5 and n have the meanings specified above.
Group 2: Biphenyl thiazole carboxamides of Formula (I-b)
(I-b),
where R1, R2, R3A, R4, R5 and n have the meanings specified above.
R3A preferably stands for d-C6-alkyI, CrC4-alkylsulphinyl, Ci-C4-alkylsulphonyl, CrC3-alkoxy-
Ci-C3-alkyl, CrCe-cycloalkyl; CrQ-halogenalkyl, Q-C^halogenalkylthio, C]-C4-halogenalkylsulphinyl,
CrC4-halogenalkylsulphonyl, halogen-Ci-C3-alkoxy-C]-C3-alkyl, C3-C8-halogencycloalkyl,
each with 1 to 9 fluorine, chlorine and/or bromine atoms; formyl, formyl-Cr
C3-alkyl, (Ci-Cralkyl)carbonyI-C,-C3-alkyl, (CrC3-alkoxy)carbonyl-C,-C3-alkyl; halogen-
(CrC3-alkyl)carbonyl-Ci-C3-alkyl, halogen-(Ci-C3-alkoxy)carbonyl-Ci-C3-alkyl, each with 1
to 13 fluorine, chlorine and/or bromine atoms;
(C,-C6-alkyl)carbonyl, (CrC4-alkoxy)carbonyl, (CrC3-alkoxy-CrC3-allcyl)carbonyl, (C3-C6-
cycloalkyl)carbonyl; (Ci-C4-halogenalkyl)carbonyl, (Ci-C4-halogenalkoxy)carbonyl, (halogen-
C|-C3-alkoxy-Ci-C3-alkyl)carbonyl, (C3-C6-halogencycloalkyl)carbonyl, each with 1 to 9
fluorine, chlorine and/or bromine atoms; or -C(=O)C(=O)R6, -CONR7R8 or -CH2NR9R10.
R3A particularly preferably stands for methyl, ethyl, n- or iso-propyl, n-, iso-, sec- or tert-butyl,
pentyl or hexyl, methylsulphinyl, ethylsulphinyl, n- or iso-propylsulphinyl, n-, iso-, sec- or
tert-butylsulphinyl, methylsulphonyl, ethylsulphonyl, n- or iso-propylsulphonyl, n-, iso-, secor
tert-butylsulphonyl, methoxymethyl, methoxyethyl, ethoxymethyl, ethoxyethyl, cyclopropyl,
cyclopentyl, cyclohexyl, trifluoromethyl, trichloromethyl, trifluoroethyl, difluoromethylthio,
difluorochloromethylthio, trifluoromethylthio, trifluoromethylsulphinyl, trifluoromethylsulphonyl,
trifluoromethoxymethyl; formyl, -CH2-CHO, -(CH2)2-CHO, -CH2-CO-CH3,
-CH2-CO-CH2CH3, -CH2-CO-CH(CH3)2, -(CH2)2-CO-CH3, -(CH2)2-CO-CH2CH35
-(CH2)2-CO-CH(CH3)2, -CH2-C02CH3, -CH2-CO2CH2CH3, -CH2-CO2CH(CH3)2,
-(CH2)2-C02CH3, -(CH2)2-C02CH2CH3, -(CH2)2-CO2CH(CH3)2, -CH2-CO-CF3, -CH2-CO-CC13,
-CH2-CO-CH2CF3, -CH2-CO-CH2CC13, -(CH2)2-CO-CH2CF3, -(CH2)2-CO-CH2CC13,
-CH2-CO2CH2CF3, -CH2-C02CF2CF3, -CH2-CO2CH2CC13, -CH2-CO2CC12CC13,
-(CH2)2-C02CH2CF3, -(CH2)2-C02CF2CF3, -(CH2)2-CO2CH2CC13, -(CH2)2-CO2CC12CC13;
methyl carbonyl, ethyl carbonyl, n-propylcarbonyl, iso-propylcarbonyl, tert-burylcarbonyl,
methoxycarbonyl, ethoxycarbonyl, tert-butoxycarbonyl, cyclopropylcarbonyl; trifluoromethylcarbonyl,
trifluoromethoxycarbonyl, or -C(=O)C(=O)R6, -CONR7R8 or -CH2NR9R10.
R3A quite particularly preferably stands for methyl, methoxymethyl, formyl, -CH2-CHO,
-(CH2)2-CHO, -CH2-CO-CH3, -CH2-CO-CH2CH3) -CH2-CO-CH(CH3)2, -C(=O)CHO,
-C(=O)C(=O)CH3, -C(=O)C(=O)CH2OCH3, -C(=O)CO2CH3, -C(=O)CO2CH2CH3.
Group 3: Biphenyl thiazole carboxamides of Formula (I-c)
where R1, R2, R3 and R4 have the meanings specified above and R5A and R5B have the
meanings of R5 independently of one another.
Group 4: Biphenyl thiazole carboxamides of Formula (I-d)
where R1, R2, R3 and R4 have the meanings specified above and R5A and R5B have the
meanings of R5 independently of one another.
Group 5: Biphenyl thiazole carboxamides of Formula (I-e)
(I-e),
where R1, R2, R3 and R4 have the meanings specified above and R5A and R5B have the
meanings of R5 independently of one another.
-13-
Group 6: Biphenyl thiazole carboxamides of Formula (I-f)
Rwhere R1, R2, R3 and R4 have the meanings specified above and R5A and R5B and R5C
have the meanings of R5 independently of one another.
Group 7: Biphenyl thiazole carboxamides of Formula (I-g)
(I-g),
where R , R , R , R , R and n have the meanings specified above.
Group 8: Biphenyl thiazole carboxamides of Formula (I-h)
d-h),
where R1, R2, R3, R4, R5 and n have the meanings specified above.
Group 9: Biphenyl thiazole carboxamides of Formula (I-i)
(I-i),
where R , R , R , R , R and n have the meanings specified above.
Group 10: Biphenyl thiazole carboxamides of Formula (I-j)
(l-j),
where R , R , R, R and n have the meanings specified above.
Group 11: Biphenyl thiazole carboxamides of Formula (I-k)
where R , R , R , R and n have the meanings specified above.
Group 12: Biphenyl thiazole carboxamides of Formula (1-1)
(1-0,
where R , R , R , R and n have the meanings specified above.
Group 13: Biphenyl thiazole carboxamides of Formula (I-m)
where R , R , R , R and n have the meanings specified above.
-15-
Group 14: Biphenyl thiazole carboxamides of Formula (I-n)
Group 15:
Group 16:
(I-n),
where R1, R2, R3 and R4 have the meanings specified above and R5A and R5B have the
meanings of R5 independently of one another.
Biphenyl thiazole carboxamides of Formula (I-o)
where R , R , R and R have the meanings specified above and R and R have the
meanings of R5 independently of one another.
Biphenyl thiazole carboxamides of Formula (I-p)
R , R , R and R have the meanings specified above and R and R have the
meanings of R5 independently of one another.
Group 17: Biphenyl thiazole carboxamides of Formula (I-q)
where R1, R2, R3 and R4 have the meanings specified above and R5A and R5B have the
meanings of R5 independently of one another.
Group 18: Biphenyl thiazole carboxamides of Formula (I-r)
where R1, R2, R3 and R4 have the meanings specified above and R5A and R5B have the
meanings of R5 independently of one another.
Group 19: Biphenyl thiazole carboxamides of Formula (I-s)
(I-s),
where R1, R2, R3 and R4 have the meanings specified above and R5A and R5B have the
meanings of R5 independently of one another.
Compounds of Formula (I) are emphasised (as are Groups 1 to 19), in which R1 stands for methyl.
Compounds of Formula (I) are emphasised (as are Groups 1 to 19), in which R2 stands for
difluoromethyl ortrifluoromethyl.
Compounds of Formula (I) are emphasised (as are Groups 1 to 9), in which R4 stands for chlorine,
bromine, Ci-Cralkyl, Ci-C^alkoxy, Q-Cralkylthio or Ci-Chalogenalkyl with 1 to 9 fluorine,
chlorine and/or bromine atoms.
Compounds of Formula (I) are emphasised (as are Groups 1 to 9), in which R4 stands for chlorine,
methyl, trifluoromethyl, methoxy or methylthio, and especially for chlorine.
Compounds of Formula (I) are emphasised (as are Groups 1 to 19), in which R3 stands for formyl.
Furthermore, compounds of Formula (I) are emphasised (as are Groups 1 to 19), in which R3 stands
for -C(=O)C(=O)R6, where R6 has the meanings specified above.
Examples for the compounds of Formulae (I-j) to (I-s) are given in Table 1 below:
(Table Removed) Saturated or unsaturated hydrocarbon moieties such as alkyl or alkenyl can be straight-chained or
branched, respectively, including in combination with heteroatoms such as e.g. in alkoxy, if possible.
Possibly substituted moieties can be substituted once or several times, and if substituted several
times, the substituents can be the same or different. Thus, the definition for dialkylamino also
includes an amino group asymmetrically substituted by alkyl such as, for example, methylethylamino.
Moieties substituted with halogen such as e.g. halogenalkyl can be halogenated once or several times.
If halogenated several times, the halogen atoms can be the same or different. In this case, halogen
stands for fluorine, chlorine, bromine and iodine, particularly for fluorine, chlorine and bromine.
The general definitions and the preferred moiety definitions and explanations indicated above can be
combined in any manner among the respective groups and preferred groups. They are valid for the
final products, preliminary products and intermediate products. In particular, the compounds named
in Groups 1 to 6 can be combined with the general, preferred, particularly preferred, etc. definitions,
whereby all respective combinations among the preferred definitions are possible as well.
Description of the Methods According to the Invention for the Preparation of the Biphenyl
Thiazole Carboxamides of Formula (D as well as the Intermediate Products
Method (a)
If 2-methyl-4-(trifluoromethyl)-l,3-thiazole-5-carbonylchloride and 4'-chloro-3',5-difluorobiphenyl-2-
amine are used as initial substances, Method (a) according to the invention can be illustrated by the
following reaction diagram:
Base
arboxylic acid derivatives, which are necessary as initial substances for carrying out Method (a)
according to the invention, are generally defined by Formula (II). In Formula (II), R1 and R2
preferably, particularly preferably and quite particularly preferably stand for those meanings that
were already indicated for these moieties as preferred, particularly preferred and quite particularly
preferred in reference to the description of the compounds of Formula (I) according to the invention.
X1 preferably stands for chlorine, bromine or hydroxy.
The carboxylic acid derivatives of Formula (II) are known and/or can be manufactured according to
known methods (see WO 03/066609, WO 03/066610, EP-A 0545099, EP-A 0589301, EP-A
0589 313 and US 3,547,917).
The biphenyl amines, which are further necessary as initial substances for carrying out Method (a)
according to the invention, are generally defined by Formula (III). In Formula (III), R3, R4, R5 and erably, particularly preferably and quite particularly preferably have those meanings that were
already indicated for these moieties or this index as preferred, particularly preferred and quite
particularly preferred in reference to the description of compounds of Formula (I) according to the
invention.
The biphenyl amines of Formula (HI) are partially known or can be obtained according to known
methods (see e.g. WO 03/070705, WO 97/08148, and JP 2001-302605).
It is also possible, to first manufacture biphenyl amines of Formula (III-a)
(in-a),
where R3A, R4, R5 and n have the meanings specified above, and then to react these with halogenides
of Formula (VIII)
R3A—X4 (VID),
where R3A and X4 have the meanings specified above, in the presence of a base and in the presence of
a diluent. [The reaction conditions of (e) according to the invention apply accordingly.]
Method (b)
If A-(2-bromo-4-fluorophenyl)-2-methyl-4-(trifluoromethyl)-l,3-thiazole-5-carboxamide and (4-
chloro-3-fluorophenyl)boronic acid are used as initial substances and a catalyst is employed as well,
the progression of Method (b) according to the invention can be illustrated by the following reaction
diagram:
The halogen carboxamides, which are necessary as initial substances for carrying out Method (b)
according to the invention, are generally defined by Formula (IV). In Formula (IV), R1, R2, R3 and R4
preferably, particularly preferably and quite particularly preferably have those meanings that were
already indicated for these moieties as preferred, particularly preferred and quite particularly
preferred in reference to the description of compounds of Formula (I) according to the invention.
stands for bromine or iodine.
The halogen carboxamides of Formula (EV) are not yet known. As novel chemical compounds, they
are a further subject of the present patent application. They are obtained by reacting
(f) carboxylic acid derivatives of Formula (II)
where R1, Hal an dJ vXl1 have the meanings specified above,
with halogen anilines of Formula (EX)
(IX),
where R3, R4 and X2 have the meanings specified above,
in the presence of a catalyst if applicable, in the presence of a condensation agent if
applicable, in the presence of an acid binding agent if applicable and in the presence of a
diluent if applicable.
The carboxylic acid derivatives of Formula (II), which are necessary as initial substances for carrying
out Method (f) according to the invention, were already described in reference to Method (a)
according to the invention.
The halogen anilines, which are further necessary as initial substances for carrying out Method (f)
according to the invention, are generally defined by Formula (EX). In Formula (EX), R3, R4 and X2
preferably, particularly preferably and quite particularly preferably have those meanings that were
already indicated for these moieties as preferred, particularly preferred and quite particularly
preferred in conjunction with the description of compounds of Formula (I) according to the invention
and the description of the preliminary products of Formula (IV) according to the invention.
The halogen anilines of Formula (IX) are commercially available synthesis chemicals or can be
obtained according to known methods.
It is also possible to first manufacture halogen anilines of Formula (EX-a)
(LX-a),
where R4 and X2 have the meanings specified above, and subsequently react them with halogenides of
Formula (VIET)
where R3A and X4 have the meanings specified above, in the presence of a base and in the presence of
a diluent. [The reaction conditions of (i) according to the invention apply accordingly.]
The boronic acid derivatives, which are further necessary as initial substances for carrying out Method
(b) according to the invention, are generally defined by Formula (V). In Formula (V), R5 and n
preferably, particularly preferably and quite particularly preferably have those meanings that were
already indicated for this moiety and index as preferred, particularly preferred and quite particularly
preferred in conjunction with the description of compounds of Formula (I) according to the invention.
G1 and G2 each stand for hydrogen or together stand for tetramethylethylene.
The boronic acid derivatives of Formula (V) are known and/or can be manufactured according to
known methods (see e.g. WO 01/90084, JP-A 2001-302605 and US 5,633,218).
Method (c)
If [5-fluoro-2-({[2-methyl-4-(trifluoromethyl)-l,3-thiazole-5-yl]carbonyl}amino)phenyl]boronic acid
and 4-bromo-l,2-dichlorobenzene are used as initial substances and a catalyst is employed as well,
the progression of Method (c) according to the invention can be illustrated by the following reaction
hich are necessary as initial substances for carrying out Method (c)
according to the invention, are generally defined by Formula (VI). In Formula (VI), R1, R2, R3 and R4
preferably, particularly preferably and quite particularly preferably have those meanings that were
already indicated for these moieties as preferred, particularly preferred and quite particularly
preferred in conjunction with the description of compounds of Formula (I) according to the invention.
G3 and G4 each stand for hydrogen or jointly stand for tetramethylethylene.
The boronic acid derivatives of Formula (VI) are not yet known. As novel chemical compounds, they
are a further subject of the present patent application. They are obtained by reacting
(g) a carboxylic acid derivative of Formula (II)
where R1, R2 and X1 have the meanings specified above,
with an aniline boronic acid derivative of Formula (X)
where R3, R4, G3 and G4 have the meanings specified above,
in the presence of a catalyst if applicable, in the presence of a condensation agent if
applicable, in the presence of an acid binding agent if applicable and in the presence of a
diluent if applicable.
The carboxylic acid derivatives of Formula (II), which are necessary as initial substances for carrying
out Method (g) according to the invention, were already described in reference to Method (a)
according to the invention.
The aniline boronic acid derivatives, which are additionally necessary as initial substances for carrying
out Method (g) according to the invention, are generally described by Formula (X). In Formula (X), R3
and R4 preferably, particularly preferably and quite particularly preferably have those meanings that
were already indicated for these moieties as preferred, particularly preferred and quite particularly
preferred in conjunction with the description of compounds of Formula (I) according to the invention.
G3 and G4 each stand for hydrogen or jointly stand for tetramethylethylene.
The aniline boronic acid derivatives of Formula (X) are known synthesis chemicals or can be
obtained according to known methods.
It is also possible to first manufacture aniline boronic acid derivatives of Formula (X-a)
where R4, G3 and G4 have the meanings specified above, and to subsequently react them with
halogenides of Formula (VIII),
where R3A and X4 have the meanings specified above, in the presence of a base and in the presence of
a diluent. [The reaction conditions of (i) according to the invention apply accordingly.]
The phenyl derivatives, which are further necessary as initial substances for carrying out Method (c)
according to the invention, are generally defined by Formula (VII). In Formula (VII), R5 and n
preferably, particularly preferably and quite particularly preferably have those meanings that were
already indicated for this moiety and index as preferred, particularly preferred and quite particularly
preferred in conjunction with the description of compounds of Formula (I) according to the invention.
X3 stands for chlorine, bromine, iodine or trifluoromethylsulphonate.
The phenyl derivatives of Formula (VII) are known synthesis chemicals.
Method (d)
If A/-(2-bromo-4-fluorophenyl)-2-methyl-4-(trifluoromethyl)-l,3-thiazole-5-carboxamide and 4-
bromo-l,2-dichlorobenzene are used as initial substances, and a catalyst and 4,4,4',4',5,5,5',5'-octamethyl-
2,2'-bis-l,3,2-dioxaborolane are employed as well, the progression of Method (d) according to
the invention can be illustrated by the following reaction diagram:
[Key: Katalysator = Catalyst]
The halogen carboxamides of Formula (FV), which are necessary as initial substances for carrying out
Method (d) according to the invention, as well as the phenyl derivatives of Formula (VII), were
already described in conjunction with Methods (b) and (c) according to the invention.
The 4,4,4',4',5,5,5',5'-octamethyl-2,2'-bis-l,3,2-dioxaborolane, which is further necessary for carrying
out Method (d) according to the invention, is a commercially available synthesis chemical.
Method (e)
If 7V-(3',4'-dichloro-5-fluorobiphenyl-2-yl)-2-methyl-4-(trifluoromethyl)-l,3-thiazole-5-carboxamide
and acetyl chloride are used as initial substances, the progression of Method (e) according to the
invention can be illustrated by the following reaction diagram:
The biphenyl thiazole carboxamides, which are necessary as initial substances for carrying out
Method (e) according to the invention, are generally defined by Formula (I-a). In Formula (I-a), R1,
R2, R4, R5 and n preferably, particularly preferably and quite particularly preferably have those
meanings that were already indicated for these moieties and index as preferred, particularly preferred
and quite particularly preferred in conjunction with the description of compounds of Formula (I)
according to the invention.
The compounds of Formula (I-a) are invention-related compounds and can be prepared according to
Methods (a) to (d).
The halogenides, which are further necessary for carrying out Method (e) according to the invention
are generally defined by Formula (VIII). In Formula (VIII), R3A preferably, particularly preferably
and quite particularly preferably stand for those meanings that were already indicated above for this
moiety as preferred, particularly preferred and quite particularly preferred for the compounds of
Formula (I-b). X4 stands for chlorine, bromine or iodine.
Halogenides of Formula (VIII) are known.
Reaction Conditions
All inert organic solvents come into consideration as diluents for carrying out Methods (a), (f) and (g)
according to the invention. Preferred examples are: aliphatic, alicyclic or aromatic hydrocarbons,
such as e.g. petroleum ether, hexane, heptane, cyclohexane, methylcyclohexane, benzene, toluene,
xylene or decalin; halogenated hydrocarbons, such as e.g. chlorobenzene, dichlorobenzene, dichloro-
methane, chloroform, tetrachloromethane, dichloroethane or trichloroethane; ethers, such as diethylether,
diisopropylether, methyl-t-butylether, methyl-t-amylether, dioxane, tetrahydrofuran, 1,2-
dimethoxyethane, 1,2-diethoxyethane or anisole; ketones, such as acetone, butanone, methyl-isobutylketone
or cyclohexanone; nitriles, such as acetonitrile, propionitrile, n- or i-butyronitrile or benzonitrile;
amides, such as N,N-dimethylformamide, N,N-dimethylacetamide, N-methylformanilide, Nmethylpyrrolidone
or hexamethylphosphoric acid triamide; mixtures of these with water or pure
water.
Methods (a), (f) and (g) according to the invention are carried out in the presence of a suitable acid
acceptor, if necessary. All customary inorganic or organic bases come into consideration as such.
Preferred examples are: alkaline earth metallic or alkali metallic hydrides, hydroxides, amides,
alcoholates, acetates, carbonates or hydrogen carbonates, such as e.g. sodium hydride, sodium amide,
lithiumdiisopropylamide, sodium-methylate, sodium-ethylate, potassium-tert.-butylate, sodium
hydroxide, potassium hydroxide, sodium acetate, sodium carbonate, potassium carbonate, potassium
hydrogen carbonate, sodium hydrogen carbonate or ammonium carbonate, as well as tertiary amines,
such as trimethylamine, triethylamine, tributylamine, N,N-dimethylaniline, N,N-dimethyl-benzylamine,
pyridine, N-methylpiperidine, N-methylmorpholine, N,N-dimethylaminopyridine, diazabicyclooctane
(DABCO), diazabicyclononene (DBN) or diazabicycloundecene (DBU).
Methods (a), (f) and (g) according to the invention are carried out in the presence of a condensation
agent, if necessary. All customarily applicable condensation agents come into consideration as such.
Examples are: acid halide forming agents such as phosgene, phosphorous tribromide, phosphorous
trichloride, phosphorous pentachloride, phosphorous oxychloride or thionyl chloride; anhydride
forming agents such as chloroformic acid ethyl ester, chloroformic acid methyl ester, chloroformic
acid propyl ester, chloroformic acid butyl ester or methanesulphonylchloride; carbodiimides, such as
N,N'-dicyclohexylcarbodiimide (DCC) or other customary condensation agents, such as phosphorous
pentoxide, polyphosphoric acid, N,N'-carbonyldiimidazole, 2-ethoxy-N-ethoxycarbonyl-l,2-dihydroquinoline
(EEDQ), triphenylphosphine/tetrachlorocarbon or bromo-tripyrrolidinophosphoniumhexafluoroph
osphate.
Methods (a), (f) and (g) according to the invention are carried out in the presence of a catalyst, if
necessary. Examples are: 4-dimethylaminopyridine, 1-hydroxy-benzotriazole or dimethylformamide.
The reaction temperatures can be varied within a wide range when carrying out Methods (a), (f) and
(g) according to the invention. In general, the work is performed at temperatures of 0°C to 150°C,
preferably at temperatures of 0°C to 80°C.
In order to perform Method (a) according to the invention for preparing the compounds of Formula
(I), generally 0.8 to 15 Mol, preferably 0.8 to 8 Mol of the aniline derivative of Formula (HI) is used
per Mol of the carboxylic acid derivative of Formula (II).
In order to perform Method (f) according to the invention for preparing the compounds of Formula
(FV), generally 0.8 to 15 Mol, preferably 0.8 to 8 Mol of halogen anilines of Formula (IX) are used
per Mol of the carboxylic acid derivative of Formula (II).
In order to perform Method (g) according to the invention for preparing the compounds of Formula
(VI), generally 0.8 to 15 Mol, preferably 0.8 to 8 Mol of the aniline boronic acid derivative of
Formula (X) is used per Mol of the carboxylic acid derivative of Formula (II).
All inert organic solvents come into consideration as diluents for carrying out Methods (b), (c) and (d).
Preferred examples are: aliphatic, alicyclic or aromatic hydrocarbons, such as e.g. petroleum ether,
hexane, heptane, cyclohexane, methylcyclohexane, benzene, toluene, xylene or decalin; ethers, such as
diethyl ether, diisopropyl ether, methyl-t-butyl ether, methyl-t-amyl ether, dioxane, tetrahydrofuran, 1,2-
dimethoxyethane, 1,2-diethoxyethane or anisole; nitriles, such as acetonitrile, propionitrile, n- or i-buryronitrile
or benzonitrile; amides, such as N,N-dimethylformamide, N,N-dimethylacetamide, N-methylformanilide,
N-methylpyrrolidone or hexamethylphosphoric acid triamide; esters such as acetic acid
methyl ester or acetic acid ethyl ester; sulphoxides, such as dimethylsulphoxide; sulphones, such as
sulpholane; alcohols, such as methanol, ethanol, n- or i-propanol, n-, i-, sec- or tert-butanol, ethanediol,
propane-1,2-diol, ethoxyethanol, methoxyethanol, diethyleneglycol monomethyl ether, diethylene glycol
monoethyl ether, mixtures of these with water or pure water.
When performing Methods (b), (c) and (d) according to the invention , the reaction temperatures can
be varied within a wide range. In general, the work is performed at temperatures of 0°C to 180°C,
preferably at temperatures of 20°C to 150°C.
Methods (b), (c) and (d) according to the invention are carried out in the presence of a suitable acid
acceptor, if necessary. All customary inorganic or organic bases come into consideration as such.
Preferred examples are: alkaline earth metallic or alkali metallic hydrides, hydroxides, amides,
alcoholates, acetates, fluorides, phosphates, carbonates or hydrogen carbonates, such as e.g. sodium
hydride, sodium amide, lithiumdiisopropylamide, sodium-methylate, sodium-ethylate, potassiumtert.-
butylate, sodium hydroxide, potassium hydroxide, sodium acetate, sodium phosphate, potassium
phosphate, potassium fluoride, caesium fluoride, sodium carbonate, potassium carbonate, potassium
hydrogen carbonate, sodium hydrogen carbonate or caesium carbonate, as well as tertiary amines,
such as trimethylamine, triethylamine, tributylamine, N,N-dimethylaniline, N,N-dimethyl-benzylamine,
pyridine, N-methylpiperidine, N-methylmorpholine, N,N-dimethylaminopyridine, diazabicyclooctane
(DABCO), diazabicyclononene (DBN) or diazabicycloundecene (DBU).
Methods (b), (c) and (d) according to the invention are carried out in the presence of a catalyst, if
necessary, such as e.g. a palladium salt or palladium complex. Preferred examples are: palladium
chloride, palladium acetate, tetrakis-(triphenylphosphine)palladium, bis(triphenylphosphine)-
palladium dichloride or (l,l'-bis(diphenylphosphino)ferrocene palladium (II) chloride).
A palladium complex can also be created in the reaction mixture, if a palladium salt and a complex
ligand, such as e.g. triethylphosphane, tri-tert-butylphosphane, tricyclohexylphosphane, 2-(dicyclohexylphosphane)-
biphenyl, 2-(di-tert-butylphosphane)-biphenyl, 2-(dicyclohexylphosphane)-2'-(N,Ndimethylamino)-
biphenyl, triphenylphosphane, tris-(o-tolyl)-phosphane, sodium-3-(diphenylphosphino)
benzene sulphonate, tris-2-(methoxyphenyl)-phosphane, 2,2'-bis-(diphenylphosphane)-1,1 '-
binaphthyl, l,4-bis-(diphenylphosphane)-butane, l,2-bis-(diphenylphosphane)-ethane, 1,4-bis-
(dicyclohexylphosphane)-butane, 1,2-bis-(dicycIohexylphosphane)-ethane, 2-(dicyclohexylphosphane)-
2'-(N,N-dimethylamino)-biphenyl, bis-(diphenylphosphino)ferrocene or tris-(2,4-tert-butylphenyl)-
phosphite, are separately added to the reaction.
In order to perform Method (b) according to the invention for preparing the compounds of Formula
(I), generally 1 to 15 Mol, preferably 2 to 8 Mol of boronic acid derivatives of Formula (V) are used
per Mol of the halogen carboxamide of Formula (IV).
In order to perform Method (c) according to the invention for preparing the compounds of Formula
(I), generally 0.8 to 15 Mol, preferably 0.8 to 8 Mol of phenyl derivatives of Formula (VII) are used
per Mol of the boronic acid derivative of Formula (VI).
; !
In order to perform Method (d) according to the invention for preparing the compounds of Formula
(I), generally 0.8 to 15 Mol, preferably 0.8 to 8 Mol of the phenyl derivative of Formula (VII) and 0.8
to 15 Mol, preferably 0.8 to 8 Mol of 4,4,4',4',5,5,5',5'-octamethyl-2,2'-bis-l,3,2-dioxaborolane are
used per Mol of the halogen carboxamide of Formula (IV).
All inert organic solvents come into consideration as diluents for performing Method (e) according to
the invention. Preferred examples are: aliphatic, alicyclic or aromatic hydrocarbons, such as e.g.
petroleum ether, hexane, heptane, cyclohexane, methylcyclohexane, benzene, toluene, xylene or
decalin; halogenated hydrocarbons, such as e.g. chlorobenzene, dichlorobenzene, dichloromethane,
chloroform, tetrachloromethane, dichloroethane or trichloroethane; ethers, such as diethyl ether,
diisopropyl ether, methyl-tert-butyl ether, methyl-tert-amyl ether, dioxane, tetrahydrofuran, 1,2- dimethoxyethane,
1,2-diethoxyethane or anisole or amides, such as N,N-dimethylformamide, N,Ndimethylacetamide,
N-methylformanilide, N-methylpyrrolidone or hexamethylphosphoric acid
triamide.
Method (e) according to the invention is carried out in the presence of a base. All customary
inorganic or organic bases come into consideration as such. Preferred examples are: alkaline earth
metallic or alkali metallic hydrides, hydroxides, amides, alcoholates, acetates, carbonates or hydrogen
carbonates, such as e.g. sodium hydride, sodium amide, sodium-methylate, sodium-ethylate,
potassium-tert.-butylate, sodium hydroxide, potassium hydroxide, ammonium hydroxide, sodium
acetate, potassium acetate, calcium acetate, ammonium acetate, sodium carbonate, potassium
carbonate, potassium hydrogen carbonate, sodium hydrogen carbonate or caesium carbonate, as well
as tertiary amines, such as trimethylamine, triethylamine, tributylamine, N,N-dimethylaniline, N,Ndimethyl-
benzylamine, pyridine, N-methylpiperidine, N-methylmorpholine, N,N-dimethylaminopyridine,
diazabicyclooctane (DABCO), diazabicyclononene (DBN) or diazabicycloundecene
(DBU).
When performing Method (e) according to the invention, the reaction temperatures can be varied
within a wide range. In general, the work is performed at temperatures of 0°C to 150°C, preferably at
temperatures of 20°C to 110°C.
In order to perform Method (e) according to the invention for preparing the compounds of Formula
(I), generally 0.2 to 5 Mol, preferably 0.5 to 2 Mol of the halogenide of Formula (VIII) is used per
Mol of the biphenyl thiazole carboxamide of Formula (I-a).
If nothing else is indicated, all methods according to the invention are generally performed at normal
pressure. However, it is possible to perform the work at increased or decreased pressures - generally
between 0.1 bar and 10 bar.
The invention-related substances exhibit a strong microbicidal effect and can be used for combating
undesired microorganisms, such as fungi and bacteria, in the areas of plant protection and material
protection.
Fungicides can be used in the area of plant protection for combating Plasmodiophoromycetes,
Oomycetes, Chytridiomycetes, Zygomycetes, Ascomycetes, Basidiomycetes and Deuteromycetes.
Bactericides can be used in the area of plant protection for combating Pseudomonadaceae, Rhizobiaceae,
Enterobacteriaceae, Corynebacteriaceae and Streptomycetaceae.
The following pathogens of fungal and bacterial diseases that fall under the abovementioned genera
are mentioned as examples, however they should not be considered all-inclusive:
Xanthomonas species, such as e.g. Xanthomonas campestris pv. oryzae;
Pseudomonas species, such as e.g. Pseudomonas syringae pv. lachrymans;
Erwinia species, such as e.g. Erwinia amylovora;
Pythium species, such as e.g. Pythium ultimum;
Phytophthora species, such as e.g. Phytophthora infestans;
Pseudoperonospora species, such as e.g. Pseudoperonospora humuli or
Pseudoperonospora cubensis;
Plasmopara species, such as e.g. Plasmopara viticola;
Bremia species, such as e.g. Bremia lactucae;
Peronospora species, such as e.g. Peronospora pisi or P. brassicae;
Erysiphe species, such as e.g. Erysiphe graminis;
Sphaerotheca species, such as e.g. Sphaerotheca fuliginea;
Podosphaera species, such as e.g. Podosphaera leucotricha;
Venturia species, such as e.g. Venturia inaequalis;
Pyrenophora species, such as e.g. Pyrenophora teres or P. graminea
(conidial form: Drechslera, syn: Helminthosporium);
Cochliobolus species, such as e.g. Cochliobolus sativus
(conidial form: Drechslera, syn: Helminthosporium);
Uromyces species, such as e.g. Uromyces appendiculatus;
Puccinia species, such as e.g. Puccinia recondita;
Sclerotinia species, such as e.g. Sclerotinia sclerotiorum;
Tilletia species, such as e.g. Tilletia caries;
Ustilago species, such as e.g. Ustilago nuda or Ustilago avenae;
Pellicularia species, such as e.g. Pellicularia sasakii;
Pyricularia species, such as e.g. Pyricularia oryzae;
Fusarium species, such as e.g. Fusarium culmorum;
Botrytis species, such as e.g. Botrytis cinerea;
Septoria species, such as e.g. Septoria nodorum;
Leptosphaeria species, such as e.g. Leptosphaeria nodorum;
Cercospora species, such as e.g. Cercospora canescens;
Alternaria species, such as e.g. Alternaria brassicae;
Pseudocercosporella species, such as e.g. Pseudocercosporella herpotrichoides;
Rhizoctonia species, such as e.g. Rhizoctonia solani.
The invention-related substances exhibit a strong fortifying effect in plants. Therefore, they are
suitable for mobilising the plants' own defences against contamination by undesired microorganisms.
In the present context, plant-fortifying (resistance-inducing) substances are to be understood as those
substances that are capable of stimulating the defence system in plants in such a way that the treated
plants develop considerable resistance to these microorganisms following subsequent inoculation.
In the present context, undesired microorganisms are to be understood to be phytopathogenic fungi,
bacteria, and viruses. The invention-related substances can also be used to protect plants against
contamination by the named pathogens for a certain time period following treatment. The time
period, for which this protection is provided, generally ranges from 1 to 10 days, preferably 1 to 7
days following treatment of the plants with the active compounds.
The good plant tolerance of the active compounds according to the invention at the concentrations
required for controlling plant diseases allows treatment of above-ground parts of plants, of
propagation stock and seeds, and of the soil.
The active compounds according to the invention can be employed particularly successfully for
controlling cereal diseases, such as, for example, against Puccinia species, diseases in viticulture and
fruit and vegetable production such as, for example, against Botrytis, Venturia or Alternaria species.
The active compounds according to the invention are also suitable for increasing the harvest yield.
Moreover, they exhibit low toxicity and are well tolerated by plants.
The active compounds according to the invention can also be used in certain concentrations and at
certain application rates as herbicides, for influencing plant growth rates, and for combating animal
pests, if applicable. They can also be used as intermediate products and preliminary products for the
synthesis of additional active compounds, if applicable.
All plants and plant parts can be treated with the substances according to the invention. Plants in this
context are taken to mean all plants and plant populations, such as desired and undesired wild plants
or crop plants (including naturally occurring crop plants). Crop plants can be plants which can be
obtained by conventional breeding and optimisation methods, or by biotechnological and genetic
engineering methods, or by combinations of these methods, including the transgenic plants and
including the plant varieties which are capable, or incapable, of being protected by Plant Breeders'
Rights. Plant parts are to be taken to mean all above-ground and below-ground parts and organs of the
plants, such as the shoot, leaf, flower and root; examples mentioned being leaves, needles, stalks,
stems, flowers, fruit bodies, fruits and seeds, and also roots, tubers and rhizomes. The plant parts also
include harvested material and vegetative and generative propagation material, for example cuttings,
tubers, rhizomes, offshoots and seeds.
The invention-related treatment of the plants and plant parts with the active compounds occurs
directly or by affecting the environment, habitat or storage area according to customary treatment
methods, e.g. by dipping, spraying, vaporising, atomising, scattering, brushing on, and in the case of
propagation material, particularly in the case of seeds, by further encasing it with one or more layers.
In the area of material protection, the compounds according to the invention can be employed for
protecting industrial materials against infection with, and destruction by, undesirable
microorganisms.
Industrial materials in the present context are understood to mean non-living materials, which have
been prepared for use in industry. For example, industrial materials which are intended to be
protected by active compounds according to the invention from microbial change or destruction can
be glues, pastes, paper and cardboard, 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
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,
pastes, paper and cardboard, leather, wood, paints, cooling lubricants and heat-transfer liquids,
particularly preferably wood.
The following are mentioned as examples of microorganisms that can cause a decomposition or
change in industrial materials: bacteria, fungi, yeasts, algae and slime organisms. The active
compounds according to the invention preferably have an effect on fungi, particularly moulds, wooddiscolouring
and wood-destroying fungi (Basidiomycetes) as well as on slime organisms and algae.
Microorganisms of the following genera may be mentioned by way of example:
Alternaria, such as Alternaria tenuis,
Aspergillus, such as Aspergillus niger,
Chaetomium, such as Chaetomium globosum,
Coniophora, such as Coniophora puetana,
Lentinus, such as Lentinus tigrinus,
Penicillium, such as Penicillium glaucum,
Polyporus, such as Polyporus versicolor,
Aureobasidium, such as Aureobasidium pullulans,
Sclerophoma, such as Sclerophoma pityophila,
Trichoderma, such as Trichoderma viride,
Escherichia, such as Escherichia coli,
Pseudomonas, such as Pseudomonas aeruginosa,
Staphylococcus, such as Staphylococcus aureus.
Depending on their respective physical and/or chemical characteristics, the active compounds can be
converted into the customary formulations, such as solutions, emulsions, suspensions, powders,
foams, pastes, granules, aerosols, fine encapsulations in polymer substances and in coatings for seeds,
as well as ULV cold and warm fog formulations.
These formulations are produced in a known manner, e.g. by mixing the active compounds with
extenders, or liquid solvents, liquefied gases under pressure and/or solid carrier substances, while
using surface active agents if applicable, or emulsifiers and/or dispersants and/or foam-producing
agents. If water is used as an extender, organic solvents can also be used as auxiliary solvents, for
example. The following fundamentally come into consideration as liquid solvents: aromates, such
xylene, toluene or alkylnaphthalines, chlorated aromates or chlorated aliphatic hydrocarbons, such as
chlorobenzenes, chloroethylenes or methylenechloride, aliphatic hydrocarbons, such as cyclohexane
or paraffins, e.g. petroleum fractions, alcohols, such as butanol or glycol as well as their ethers and
esters, ketones, such as acetone, methylethylketone, methylisobutylketone or cyclohexanone, strongly
polar solvents, such as dimethylformamide and dimethylsulphoxide, as well as water. With liquefied
gaseous extenders or carrier substances, those liquids are meant, which are gaseous at normal
temperatures and normal pressure, e.g. aerosol propellants, such as halogen hydrocarbons as well as
butane, propane, nitrogen and carbon dioxide. Suitable solid carriers are: for example, ground natural
minerals such as kaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous
earth, and ground synthetic minerals such as highly dispersed silicic acid, aluminium oxide and
silicates. Suitable solid carriers for granules are: for example crushed and fractionated natural rocks
such as calcite, marble, pumice, sepiolite and dolomite, or else synthetic granules of inorganic and
organic meals, and granules of organic material such as sawdust, coconut shells, maize cobs and
tobacco stalks. Suitable emulsifiers and/or foam-producing agents 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, or else
protein hydrolysates. Suitable dispersants are: for example, lignin sulphite waste liquors and
methylcellulose.
Adhesives such as carboxymethylcellulose, and natural and synthetic polymers in the form of
powders, granules or latex, such as gum arabic, polyvinyl alcohol and polyvinyl acetate, or else
natural phospholipids such as cephalins and lecithins and synthetic phospholipids can be used in the
formulations. Other 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, azo dyestuffs and metal
phthalocyanine dyestuffs, and trace nutrients such as salts of iron, manganese, boron, copper, cobalt,
molybdenum and zinc.
The formulations generally comprise between 0.1 and 95 percent by weight of active compound,
preferably between 0.5 and 90%.
The active compounds according to the invention, as such or in their formulations, can also be used in
a mixture with known fungicides, bactericides, acaricides, nematicides or insecticides, for example to
widen the spectrum of action or to prevent the development of resistance. In many cases, synergistic
effects are obtained, that is the activity of the mixture is greater than the activity of the individual
components.
Examples of suitable components in mixtures are the following:
Fungicides:
2-phenylphenol; 8-hydroxyquinoline sulphate; acibenzolar-S-methyl; aldimorph; amidoflumet; ampropylfos;
ampropylfos-potassium; andoprim; anilazin; azaconazole; azoxystrobin; benalaxyl; benalaxyl-M;
benodanil; benomyl; benthiavalicarb-isopropyl; benzamacril; benzamacril-isobutyl; bilanafos; binapacryl;
biphenyl; bitertanol; blasticidin-S; boscalid; bromuconazole; bupirimate; buthiobate; butylamine;
calcium polysulphide; capsimycin; captafol; captan; carbendazim; carboxin; carpropamid; carvone;
quinomethionate; chlobenthiazone; chlorfenazole; chloroneb; chlorothalonil; chlozolinate; clozylacon;
cyazofamid; cyflufenamid; cymoxanil; cyproconazole; cyprodinil; cyprofuram; Dagger G; debacarb;
dichlofluanid; dichlone; dichlorophen; diclocymet; diclomezine; dicloran; diethofencarb;
difenoconazole; diflumetorim; dimethirimol; dimethomorph; dimoxystrobin; diniconazole; dinicon-
azole-M; dinocap; diphenylamine; dipyrithione; ditalimfos; dithianon; dodine; drazoxolon; edifenphos;
epoxiconazole; ethaboxam; ethirimol; etridiazole; famoxadon; fenamidone; fenapanil; fenarimol;
fenbuconazole; fenfuram; fenhexamid; fenitropan; fenoxanil; fenpiclonil; fenpropidin; fenpropimorph;
ferbam; fluazinam; flubenzimine; fludioxonil; flumetover; flumorph; fluoromide; fluoxastrobin;
fluquinconazole; flurprimidol; flusilazole; flusulphamide; flutolanil; flutriafol; folpet; fosetyl-Al;
fosetyl-sodium; fuberidazole; furalaxyl; furametpyr; furcarbanil; furmecyclox; guazatine;
hexachlorobenzene; hexaconazole; hymexazole; imazalil; imibenconazole; iminoctadine triacetate;
iminoctadine tris(albesilate); iodocarb; ipconazole; iprobenfos; iprodione; iprovalicarb; irumamycin;
isoprothiolane; isovaledione; kasugamycin; kresoxim-methyl; mancozeb; maneb; meferimzone;
mepanipyrim; mepronil; metalaxyl; metalaxyl-M; metconazole; methasulphocarb; methfuroxam;
metiram; metominostrobin; metsulphovax; mildiomycin; myclobutanil; myclozolin; natamycin; nicobifen;
nitrothal-isopropyl; noviflumuron; nuarimol; ofurace; orysastrobin; oxadixyl; oxolinic acid;
oxpoconazole; oxycarboxin; oxyfenthiin; paclobutrazol; pefurazoate; penconazole; pencycuron;
phosdiphen; phthalide; picoxystrobin; piperalin; polyoxins; polyoxorim; probenazole; prochloraz; procymidone;
propamocarb; propanosine-sodium; propiconazole; propineb; proquinazid; prothioconazole;
pyraclostrobin; pyrazophos; pyrifenox; pyrimethanil; pyroquilon; pyroxyfur; pyrrolnitrine;
quinconazole; quinoxyfen; quintozene; simeconazole; spiroxamine; sulphur; tebuconazole; tecloftalam;
tecnazene; tetcyclacis; tetraconazole; thiabendazole; thicyofen; thifluzamide; thiophanate-methyl;
thiram; tioxymid; tolclofos-methyl; tolylfluanid; triadimefon; triadimenol; triazbutil; triazoxide; tricyclamide;
tricyclazole; tridemorph; trifloxystrobin; triflumizole; triforine; triticonazole; uniconazole;
validamycin A; vinclozolin; zineb; ziram; zoxamide; (2S)-N-[2-[4-[[3-(4-chlorophenyl)-2-propynyl]
oxy]-3-methoxyphenyl]ethyl]-3-methyl-2-[(methylsulphonyl)amino]-butanamide; 1 -(1 -naphthalinyl)-
lH-pyrrol-2,5-dione; 2,3,5,6-tetrachloro-4-(methylsulphonyl)-pyridine; 2-amino-4-methyl-Nphenyl-
5-thiazolecarboxamide; 2-chloro-N-(2,3-dihydro-l,l,3-trimethyl-lH-indene-4-yl)-3-pyridinecarboxamide;
3,4,5-trichloro-2,6-pyridinedicarbohitrile; actinovate;cis-l-(4-chlorophenyl)-2-(lH-l,2,4-
triazole-1 -yl)-cycloheptanol; methyl 1 -(2,3-dihydro-2,2-dimethyl-1 H-indene-1 -yl)-1 H-imidazole-
carboxylate; monopotassiumcarbonate; N-(6-methoxy-3-pyridinyl)-cyclopropanecarboxamide; N-butyl-
8-( 1,1 -dimethylethyl)-!-oxaspiro[4.5]decane-3-amine; sodiumtetracarbonate;
as well as copper salts and preparation, such as Bordeaux mixture; copper hydroxide; copper
naphthenate; copper oxychloride; copper sulphate; cufraneb; cuprous oxide; mancopper; oxinecopper.
Bactericides:
Bronopol, dichlorophen, nirrapyrin, nickel-dimethyldithiocarbamate, kasugamycin, octhilinone,
furancarboxylic acid, oxytetracycline, probenazole, streptomycin, tecloftalam, copper sulphate and
other copper preparations.
Insecticides / Acaricides / Nematicides:
1. Acetylcholine esterase (AChE) inhibitors
1.1 Carbamates (e.g. alanycarb, aldicarb, aldoxycarb, allyxycarb, aminocarb, azamethiphos,
bendiocarb, benfuracarb, bufencarb, butacarb, butocarboxim, butoxycarboxim, carbaryl, carbofuran,
carbosulphan, chloethocarb, coumaphos, cyanofenphos, cyanophos, dimetilan, ethiofencarb,
fenobucarb, fenothiocarb, formetanate, furathiocarb, isoprocarb, metam-sodium, methiocarb,
methomyl, metolcarb, oxamyl, pirimicarb, promecarb, propoxur, thiodicarb, thiofanox, triazamate,
trimethacarb, XMC, xylylcarb)
1.2 Organophosphates (e.g. acephate, azamethiphos, azinphos (-methyl, -ethyl), bromophos-ethyl,
bromfenvinfos (-methyl), butathiofos, cadusafos, carbophenothion, chlorethoxyfos, chlorfenvinphos,
chlormephos, chlorpyrifos (-methyl/-ethyl), coumaphos, cyanofenphos, cyanophos, chlorfenvinphos,
demeton-S-methyl, demeton-S-methylsulphon, dialifos, diazinon, dichlofenthion, dichlorvos/DDVP,
dicrotophos, dimethoate, dimethylvinphos, dioxabenzofos, disulphoton, EPN, ethion, ethoprophos,
etrimfos, famphur, fenamiphos, fenitrothion, fensulphothion, fenthion, flupyrazofos, fonofos, formothion,
fosmethilan, fosthiazate, heptenophos, iodofenphos, iprobenfos, isazofos, isofenphos, isopropyl
O-salicylate, isoxathion, malathion, mecarbam, methacrifos, methamidophos, methidathion,
mevinphos, monocrotophos, naled, omethoate, oxydemeton-methyl, parathion (-methyl/-ethyl),
phenthoate, phorate, phosalone, phosmet, phosphamidon, phosphocarb, phoxim, pirimiphos (-
methylAethyl), profenofos, propaphos, propetamphos, prothiofos, prothoate, pyraclofos,
pyridaphenthion, pyridathion, quinalphos, sebufos, sulfotep, sulprofos, tebupirimfos, temephos,
terbufos, tetrachlorvinphos, thiometon, triazophos, triclorfon, vamidothion)
2. Sodium channel modulators / Voltage-dependent sodium channel blockers
2.1 Pyrethroids (e.g. acrinathrin, allethrin (d-cis-trans, d-trans), beta-cyfluthrin, bifenthrin, bioallethrin,
bioallethrin-S-cyclopentyl-isomer, bioethanomethrin, biopermethrin, bioresmethrin, chlovaporthrin,
cis-cypermethrin, cis-resmethrin, cis-permethrin, clocythrin, cycloprothrin, cyfluthrin,
cyhalothrin, cypermethrin (alpha-, beta-, theta-, zeta-), cyphenothrin, DDT, deltamethrin, empenthrin
(IR-isomer), esfenvalerate, etofenprox, fenfluthrin, fenpropathrin, fenpyrithrin, fenvalerate,
flubrocythrinate, flucythrinate, flufenprox, flumethrin, fluvalinate, fubfenprox, gamma-cyhalothrin,
imiprothrin, kadethrin, lambda-cyhalothrin, metofluthrin, permethrin (cis-, trans-), phenothrin (1Rtrans
isomer), prallethrin, profluthrin, protrifenbute, pyresmethrin, resmethrin, RU 15525, silafluofen,
tau-fluvalinate, tefluthrin, terallethrin, tetramethrin (IR-isomer), tralomethrin, transfluthrin, ZXI
8901, pyrethrins (pyrethrum))
2.2 Oxadiazines (e.g. indoxacarb)
3. Acetylcholine receptor agonists /Acetylcholine receptor antagonists
-39-
3.1 Chloronicotinyls/neonicotinoids (e.g. acetamiprid, clothianidin, dinotefuran, imidacloprid, nitenpyram,
nithiazine, thiacloprid, thiamethoxam)
3.2 Nicotine, bensultap, cartap
4. Acetylcholine receptor modulators
4.1 Spinosyns (e.g. spinosad)
5. GABA-gated chloride channel antagonists
5.1 Cyclodiene organochlorines (e.g. camphechlor, chlordane, endosulphan, gamma-HCH, HCH,
heptachlor, lindane, methoxychlor
5.2 Fiproles (e.g. acetoprole, ethiprole, fipronil, vaniliprole)
6. Chloride channel activators
6.1 Mectins (e.g. abamectin, avermectin, emamectin, emamectin-benzoate, ivermectin, milbemectin,
milbemycin)
7. Juvenile hormone mimics
(e.g. diofenolan, epofenonane, fenoxycarb, hydroprene, kinoprene, methoprene, pyriproxifen,
triprene)
8. Ecdysone agonists /disruptors
8.1 Diacylhydrazines (e.g. chromafenozide, halofenozide, methoxyfenozide, tebufenozide)
9. Chitin biosynthesis inhibitors
9.1 Benzoyl urea compounds (e.g. bistrifluron, chlofluazuron, diflubenzuron, fluazuron,
flucycloxuron, flufenoxuron, hexaflumuron, lufenuron, novaluron, noviflumuron, penfluron,
teflubenzuron, triflumuron)
9.2 Buprofezin
9.3 Cyromazine
10. Oxidative phosphorylation inhibitors, ATP-disruptors
10.1 Diafenthiuron
10.2 Organotines (e.g. azocyclotin, cyhexatin, fenbutatin-oxide)
11. Oxidative phosphorylation decouplers through interruption of the H-proton gradient
11.1 Pyrroles (e.g. chlorfenapyr)
11.2 Dinitrophenols (e.g. binapacyrl, dinobuton, dinocap, DNOC)
12. Site I electron transport inhibitors
12.1 METI's (e.g. fenazaquin, fenpyroximate, pyrimidifen, pyridaben, tebufenpyrad, tolfenpyrad)
12.2 Hydramethylnone
12.3Dicofol
13. Site II electron transport inhibitors
13.1 Rotenone
14. Site III electron transport inhibitors
14.1 Acequinocyl, Fluacrypyrim
75. Microbial disrupters of the insect midgut membrane
Bacillus thuringiensis strains
16. Lipid synthesis inhibitors
16.1 Tetronic acids (e.g. spirodiclofen, spiromesifen)
16.2 Tetramic acids [e.g. 3-(2,5-dimethylphenyl)-8-methoxy-2-oxo-l-azaspiro[4.5]dec-3-ene-4-yl
ethyl carbonate (alias: carbonic acid, 3-(2,5-dimethylphenyl)-8-methoxy-2-oxo-l-azaspiro[4.5]dec-3-
ene-4-yl ethyl ester, CAS-Reg.-No.: 382608-10-8) and carbonic acid, cis-3-(2,5-dimethylphenyl)-8-
methoxy-2-oxo-l-azaspiro[4.5]dec-3-ene-4-yl ethyl ester (CAS-Reg.-No.: 203313-25-1)]
17. Carboxamides
(e.g. flonicamide)
18. Octopaminergic agonists
(e.g. amitraz)
19. Magnesium-stimulatedATPase inhibitors
(e.g. propargite)
20. Phthalamides
(e.g. N2-[l,l-dimethyl-2-(methylsulphonyl)ethyl]-3-iodo-N'-[2-methyl-4-[l,2,2,2-tetrafluoro-l-
(trifluoromethyl)ethyl]phenyl]-l,2-benzenedicarboxamide (CAS-Reg.-No.: 272451-65-7),
flubendiamide)
21. Nereistoxin analogues
(e.g. thiocyclam hydrogen oxalate, thiosultap-sodium)
22. Biologies, hormones orpheromones
(e.g. azadirachtin, Bacillus spec., Beauveria spec., codlemone, Metarrhizium spec., Paecilomyces
spec., thuringiensin, Verticillium spec.)
23. Active compounds with unknown or non-specific mode of action
23.1 Fumigants (e.g. aluminium phosphide, methyl bromide, sulphuryl fluoride)
23.2 Selective feeding blockers (e.g. cryolite, flonicamide, pymetrozine)
23.3 Mite growth inhibitors (e.g. clofentezine, etoxazole, hexythiazox)
23.4 Amidoflumet, benclothiaz, benzoximate, bifenazate, bromopropylate, buprofezin, quinomethionate,
chlordimeform, chlorobenzilate, chloropicrin, clothiazoben, cycloprene, cyflumetofen, dicyclanil,
fenoxacrim, fentrifanil, flubenzimine, flufenerim, flutenzin, gossyplure, hydramethylnone,
japonilure, metoxadiazone, petroleum, piperonyl butoxide, potassium oleate, pyrafluprole, pyridalyl,
pyriprole, sulphluramide, tetradifon, tetrasul, triarathene, verbutin,
as well as the compound 3-methyl-phenyl-propylcarbamate (tsumacide Z), the compound 3-(5-chloro-3-
pyridinyl)-8-(2,2,2-trifluoroethyl)-8-azabicyclo[3.2.1]octane-3-carbonitrile(CAS-Reg.-Nr. 185982-80-3)
and the corresponding 3-endo-isomers (CAS-Reg.-Nr. 185984-60-5) (see WO 96/37494, WO
98/25923), as well as preparations, which contain insecticidal plant extracts, nematodes, fungi or
viruses.
A mixture with other known active compounds such as herbicides, or with fertilisers and growth
regulators, safeners or semiochemicals is also possible.
In addition, the compounds of Formula (I) according to the invention also have very good antimycotic
activity. They have a very broad antimycotic activity spectrum in particular against dermatophytes
and yeasts, moulds and diphasic fungi (for example against Candida species, such as Candida
albicans, Candida glabrata), and Epidermophyton floccosum, Aspergillus species, such as Aspergillus
niger and Aspergillus fumigatus, Trichophyton species, such as Trichophyton mentagrophytes,
Microsporon species such as Microsporon canis and audouinii. The list of these fungi by no means
limits the mycotic spectrum covered, but is only for illustration.
The active compounds can be used as such, in the form of their formulations or the usage forms
prepared from them, such as ready-to-use solutions, suspensions, soluble powders, pastes, soluble
powders, dusts and granules. Application is carried out in a customary manner, for example by
watering, spraying, atomising, scattering, dusting, foaming, spreading, etc. 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. It is also possible to treat the seeds of the
plants.
When using the active compounds according to the invention as fungicides, the application rates can
be varied within a relatively wide range, depending on the kind of application. For the treatment of
parts of plants, the active compound application rates are generally between 0.1 and 10,000 g/ha,
preferably between 10 and 1,000 g/ha. For seed dressing, the active compound application rates are
generally between 0.001 and 50 g per kilogram of seed, preferably between 0.01 and 10 g per
kilogram of seed. For treatment of the soil, the active compound application rates are generally
between 0.1 and 10,000 g/ha, preferably between 1 and 5,000 g/ha.
As already mentioned above, it is possible to treat all plants and their parts according to the invention.
In a preferred embodiment, wild plant species and plant cultivars, or those obtained by conventional
biological breeding, such as crossing or protoplast fusion, and parts thereof, are treated. In a further
preferred embodiment, transgenic plants and plant cultivars obtained by genetic engineering, if
appropriate in combination with conventional methods (Genetically Modified Organisms), and parts
thereof are treated. The term "parts" or "parts of plants" or "plant parts" has been explained above.
Particularly preferably, plants of the plant cultivars, which are in each case commercially available or
in use, are treated according to the invention. Plant cultivars are understood to mean plants with novel
characteristics ("traits"), which are grown by conventional cultivation, by mutagenesis or by
recombinant DNA techniques. These may be pure species, cultivars, biotypes or genotypes.
Depending on the plant species or plant cultivars, their location and growth conditions (soils, climate,
vegetation period, nutrition), the treatment according to the invention may also result in superadditive
("synergistic") effects. Thus, for example, reduced application rates and/or a widening of the activity
spectrum and/or an increase in the activity of the substances and compositions to be used according to
the invention, better plant growth, increased tolerance to high or low temperatures, increased
tolerance to drought or to water or soil salt content, increased flowering performance, easier
harvesting, accelerated maturation, higher harvest yields, better quality and/or a higher nutritional
value of the harvested products, better storage stability and/or processability of the harvested products
are possible, which exceed the effects that were actually expected.
The transgenic plants or plant cultivars (i.e. those obtained by genetic engineering), which are
preferably to be treated according to the invention include all plants which, in the genetic
modification, received genetic material, which imparted particularly advantageous useful properties
("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 salt content, increased
flowering performance, easier harvesting, accelerated maturation, higher harvest yields, better quality
and/or a higher nutritional value of the harvested products, better storage stability and/or
processability of the harvested products. Further and particularly emphasized examples of such
properties are a better defence of the plants against animal and microbial pests, such as against
insects, mites, phytopathogenic fungi, bacteria and/or viruses, and also increased tolerance of the
plants to certain herbicidally active compounds. Examples of transgenic plants which may be
mentioned are the important crop plants, such as cereals (wheat, rice), maize, Soya beans, potatoes,
cotton, tobacco, oilseed rape and also fruit plants (with the fruits apples, pears, citrus fruits and
grapes), and particular emphasis is given to maize, Soya beans, potatoes, cotton, tobacco and oilseed
rape. Traits that are emphasized are in particular increased defence of the plants against insects,
arachnids, nematodes and snails by toxins formed in the plants, in particular those formed in the
plants by the genetic material from Bacillus thuringiensis (for example by the genes CrylA(a),
CrylA(b), CrylA(c), CryllA, CrylllA, CryIIIB2, Cry9c Cry2Ab, Cry3Bb and CrylF and also
combinations thereof) (hereinafter referred to as "Bt plants"). Traits, which are also particularly
emphasised, are the increased resistance of plants to fungi, bacteria and viruses by systemic acquired
resistance (SAR), systemin, phytoalexins, elicitors and resistance genes and the correspondingly
expressed proteins and toxins. Traits that are furthermore particularly emphasized are the increased
tolerance of the plants to certain herbicidally active compounds, for example imidazolinones,
sulphonylureas, glyphosate or phosphinotricin (for example the "PAT" gene). The genes, which
impart the desired traits in question, can also be present in combination with one another in the
transgenic plants. Examples of "Bt plants" which may be mentioned are maize varieties, cotton
varieties, Soya bean varieties and potato varieties which are sold under the trade names YIELD
GARD® (for example maize, cotton, Soya beans), KnockOut® (for example maize), StarLink® (for
example maize), Bollgard® (cotton), Nucotn® (cotton) and NewLeaf® (potato). Examples of
herbicide-tolerant plants which may be mentioned are maize varieties, cotton varieties and Soya bean
varieties which are sold under the trade names Roundup Ready® (tolerance to glyphosate, for
example maize, cotton, Soya bean), Liberty Link® (tolerance to phosphinotricin, for example oilseed
rape), IMI® (tolerance to imidazolinones) and STS® (tolerance to sulphonylureas, for example
maize). Herbicide-resistant plants (plants bred in a conventional manner for herbicide tolerance),
which may be mentioned, include the varieties sold under the name Clearfield® (for example maize).
Of course, these statements also apply to plant cultivate having these genetic traits or genetic traits
still to be developed, which will be developed and/or marketed in the future.
The plants listed can be treated according to the invention in a particularly advantageous manner with
the compounds of Formula (I) or the active compound mixtures according to the invention. The
preferred ranges stated above for the active compounds or mixtures also apply to the treatment of
these plants. Particular emphasis is given to the treatment of plants with the compounds or mixtures
specifically mentioned in the present text.
The preparation and the use of the active compounds according to the invention are illustrated by the
following examples.
Preparation Examples
Example 1 (Compound 2.18)
0.10 ml (1.1 mmol) oxalylchloride and 0.1 ml dimethylformamide are added to a solution consisting
of 211.2mg (1.0 mmol) 2-methyl-4-trifluoromethyl-thiazole-5-carboxylic acid in 9ml
dichloromethane. After stirring for 2 hours at room temperature, this solution is added to a solution
consisting of 240.0 mg (1.0 mmol) 4'-chloro-5,3'-difluoro-biphenyl-2-yl-amine and 0.18ml
(1.3 mmol) triethylamine in 9ml dichloromethane. The reaction mixture is stirred for 16 hours at
room temperature and subsequently mixed with 7 ml 2 N hydrochloric acid. The organic phase is
dried over magnesium sulphate and concentrated in vacuum.
The reaction yields 316.5 mg (73 % of the theoretical yield) of N-(4'-chloro-3',5-difluorobiphenyl-2-
yl)-2-methyl-4-(trifluoromethyl)-l,3-thiazole-5-carboxamide [log P (pH 2.3) = 3.67].
Preparation of Initial Substances of Formula (III)
Example (01-1)
,F
30.0 g (0.172 mol) 4-chloro-3-fluoro-phenylboronic acid and 29.7 g (0.156 mol) 2-bromo-4-
fluoroaniline, in an oxygen-free atmosphere, are suspended in a mixture of 170 ml toluene, 17 ml
ethanol and 160 ml of saturated sodium carbonate solution in an argon atmosphere. 3.6g
tetrakis(triphenylphosphine) palladium (0) is added to the reaction mixture, and it is stirred for 12
hours at 80°C. The organic phase is separated and the aqueous phase is extracted with acetic acid
ethyl ester. The combined organic phases are concentrated, and the residue is chromatographed with
cyclohexane / acetic acid ethyl ester (3:1) on silica gel.
The reaction yields 26.1 g (69.7% of the theoretical yield) of 4'-chloro-3',5-difluorobiphenyl-2-amine
[log P(pH 2.3) = 3.18].
Analogously to the above example and in accordance with the general preparation procedures, the
compounds listed in Table 2 below can be obtained. (Table Removed)









We Claim:
1. Biphenyl thiazole carboxamides of Formula (I)
(Formula Removed)
where R1 stands for hydrogen, halogen, amino, C1-C4-alkylamino, di-(C1-C4-alkyl)amino,
cyano, C1-C4-alkyl or C1-C4-halogenalkyl with 1 to 5 halogen atoms,
R2 stands for halogen, C1-C4-alkyl or C1-C4-halogenalkyl with 1 to 5 halogen atoms,
R3 stands for hydrogen, C1-C8-alkyl, C1-C6-alky!sulphinyl, C1-C6-alkylsulphonyl, C1-C4-
alkoxy-C1-C4-alkyl, C3-C8-cycloalkyl; C1-C6-halogenalkyl, C1-C4-halogenaIkylthio,
C1-C4-halogenalkylsulphinyl, C1-C4-halogenalkylsulphonyl, halogen-C1-C4-alkoxy-
C1-C4-alkyl, C3-C8-halogencycloalkyl, each with 1 to 9 fluorine, chlorine and/or
bromine atoms; formyl, fornryl-C1-C3-alkyl, (C1-C3-alkyl)carbonyl-C1-C3-alkyl, (C1-
C3-alkoxy)carbonyl-C1-C3-alkyl; halogen-{C1-C3-alkyl)carbonyl-C1-C3-aIkyl,
halogen-(C1-C3-alkoxy)carbonyl-C1-C3-alkyl, each with 1 to 13 fluorine, chlorine and/or bromine atoms; (C1-C8-alkyl)carbonyl, (C1-C8-alkoxy)carbonyl, (C1-C4-alkoxy-C1-C4-alkyl)carbonyl, (C3-C8-cycloalkyi)carbonyl; (C1-C6-halogenalkyl)car-bonyl, (C1-C6-halogenalkoxy)carbonyl, (halogen-C1-C4-alkoxy-C1-C4-alkyl)carbonyi, (C3-C8-halogencycloalkyl)carbonyl, each with 1 to 9 fluorine, chlorine and/or bromine atoms; or -C(=O)C(=O)R6, -CONR7R8 or -CH2NR9R10, R4 stands for halogen, C1-C4-alkyl, C1-C4-alkoxy, C1-C4-alkylthio or C1-C4-halogenalkyl
with 1 to 9 fluorine, chlorine and/or bromine atoms, R5 stands for halogen, cyano, nitro, amino, hydroxy, formyl, carboxy, carbamoyl, thio-carbamoyl, C1-C8-alkyl, C2-C6-alkenyl, C1-C8-alkoxy, C2-C6-alkenyloxy, C1-C8-alkylthio, C1-C8-alkylsulphinyl, C1-C8-alkylsulphonyl, C1-C8-hydroxyalkyl, C1-C8 oxoalkyl, C1-C8-alkoxyalkyl, C1-C8-alkyltliioalkyl, C1-C8-dialkoxyalkyl, C1-C6-alkyl-amino, di(C1-C6-alkyl)amino, (C1-C6-alkyl)carbonyl, (C1-C6-alkyl)carbonyloxy, (C1-C6-alkoxy)carbonyl, (C1-C6-alkyi)aminocarbonyl, di(C1-C6-alkyl)aminocarbonyl, (C1-C6-alkyl)carbonylamino, (C1-C6-alkyl)carbonyl(C1-C6-alkyl)amino, (C2-C6-alkenyl-)carbonyl, (C2-C6-alkinyl)carbonyl, C3-C6-cycbalkyl, C3-C6-cycloalkyloxy, or for C1-C6-halogenalkyl, C1-C6-halogenalkoxy, C1-C6-halogenalkylthio, C1-C6-halogen-alkylsulphinyl or C1-C6-halogenalkylsulphonyl, each with 1 to 13 halogen atoms, C2-
C6-halogenalkenyl, C2-C6-halogenalkenyloxy, each with 1 to 11 of the same or different halogen atoms,
R5 further stands for C2-C5-alkenylene possibly substituted once or twice by halogen, C1-C4-alkyl or C1-C4-halogenalkyl with 1 to 5 halogen atoms, if two R5 moieties are in ortho position to each other,
n can stand for 2,3, 4 or 5, whereby the R5 moieties can be the same or different,
R6 stands for hydrogen, C1-C8-alkyl C1-C8-alkoxy, C1-C4-alkoxy-C1-C4-alkyl, C3-C8-cyclo-alkyl; C1-C6-halogenalkyl, C1-C6-halogenalkoxy, halogen-C1-C4-alkoxy-C1-C4-alkyl, C3-C8-halogencycloalkyl, each with 1 to 9 fluorine, chlorine and/or bromine atoms,
R7 and R8, independently of one another, each stand for hydrogen, C1-C8-alkyl, C1-C4-alkoxy-C1-C4-alkyl, C3-C8-cycloalkyl; C1-C8-halogenalkyl, halogen-C1-C4-alkoxy-C1-C4-alkyl, C3-C8-halogencycloalkyl, each with 1 to 9 fluorine, chlorine and/or bromine atoms,
R7 and R8, together with the nitrogen atom to which they are bonded, further form a saturated heterocycle with 5 to 8 ring atoms, possibly substituted once or several times, identically or variously, by halogen or C1-C4-alkyl, in which the heterocycle can contain 1 or 2 additional, non-adjacent heteroatoms from the group of oxygen, sulphur or NR11,
R9 and R10, independently of one another, stand for hydrogen, C1-C8-alkyl, C3-C8-cycloalkyl; C1-C8-halogenalkyl, C3-C8-halogencycloalkyl, each with 1 to 9 fluorine, chlorine and/or bromine atoms,
R9 and R10, together with the nitrogen atom to which they are bonded, further form a saturated heterocycle with 5 to 8 ring atoms, possibly substituted once or several times, identically or variously, by halogen or C1-C4-alkyl, in which the heterocycle can contain 1 or 2 additional, non-adjacent heteroatoms from the group of oxygen, sulphur or NR11, R1' stands for hydrogen or C1-C6-alkyl.
2. Biphenyl thiazole carboxamides Formula (I) as claimed in claim 1, where R1 stands for hydrogen, fluorine, chlorine, bromine, amino, C1-C4-alkylamino, di(C1-C4-
alkyl)amino, cyano, methyl, ethyl or C1-C2-halogenalkyl with 1 to 5 fluorine,
chlorine and/or bromine atoms, R2 stands for fluorine, chlorine, bromine, methyl, ethyl or C1-C2-halogenalkyl with 1 to
5 fluorine, chlorine and/or bromine atoms, R3 stands for hydrogen, C1-C6-alkyl, C1-C4-alkylsulphinyl, C1-C4-alkylsulphonyl, C1-C3-
alkoxy-C1-C3-alkyl, C3-C6-cycloalkyl; C1-C4-halogenalkyl, C1-C4-halogenalkylthio, C1-
C4-halogenalkylsulphinyl, C1-C4-halogenalkylsulphonyl, halogen-C1-C3-alkoxy-C1-C3-
alkyl, C1-C8-halogencycloalkyl, each with 1 to 9 fluorine, chlorine and/or bromine atoms; formyl, fbrmyl-C1-C3-alkyl, (C1-C3-alkyl)carbonyl-C1-C3-alkyl, (C1-C3-alkoxy)-carbonyl-C1-C3-alkyl; halogen-(C1-C3-alkyl)carbonyl-C1-C3-alkyl, halogen-(C1-C3-alk-oxy)carbonyl-C1-C3-alkyl, each with 1 to 13 fluorine, chlorine and/or bromine atoms; (C1-C6-alkyI)carbonyl, (C1-C4-alkoxy)carbonyl, (C1-C3-alkoxy-C1-C3-alkyl)carbonyl, (C3-C6-cycloalkyl)carbony!; (C1-C4-halpgenalkyl)carbonyl, (C1-C4-halogen-alkoxy)carbonyl, {halogen-C1-C3-alkoxy-C1-C3-alkyl)carbonyl, (C3-C6-halogen-cycloalkyl)carbonyl, each with 1 to 9 fluorine, chlorine and/or bromine atoms; or -C(=O)C(=O)R6, -CONR7R8 or -CH2NR9R10,
R4 stands for fluorine, chlorine, methyl, iso-propyl, methoxy, methylthio or trifluorome-thyl,
R5 stands for fluorine, chlorine, bromine, cyarto, nitro, amino, hydroxy, formyl, methyl, ethyl, n- or iso-propyl, n-, iso-, sec- or tert-butyl, vinyl, allyl, methoxy, ethoxy, n- or iso-propoxy, vinyloxy, allyloxy, methylthio, ethylthio, n- or iso-propylthio, methyl-sulphinyl, ethylsulphinyl, n- or iso-propylsulphinyl, methylsulphonyl, ethyl-sulphonyl, n- or iso-prbpylsulphonyl, methoxymethyl, methoxyethyl, ethoxymethyl, ethoxyethyl, methylthiomethyi, methylthioethyl, ethylthiomethyl, ethylrhioethyl, methylamino, ethylamino, iso-propylamino, dimethylamino, diethylamino, dipropyl-amino, diisopropylamino, methylcarbonyl, ethylcarbonyl, methylaminocarbonyl. di-mcthylaminocarbonyl, methylcarbonylamino, methylcarbonylmethlyamino, cyclo-propyl, cyclopropyloxy, trifluoromethyl, trichloromethyl, trifluoroethyl, difluoro-methoxy, trifluoromethoxy, difluorochloromethoxy, trifluoroethoxy, difluoromethyl-thio, difluorochloromethylthio or trifluoromethylthio,
R5 further stands for C2-C4-alkenylene possibly substituted once or twice by fluorine, chlorine, bromine, methyl, ethyl, n- or iso-propyl, n-, iso-. sec- or tert-butyJ or trifiuoromethyl., if two R5 moieties are in or tho position to each odter,
n can stand for 2, 3 or 4, whereby the R5 moieties can be the same or different,
R6 stands for hydrogen, C1-C6-alkyl, C1-C4-alkoxy, C1-C3-alkoxy-C1-C3-alkyl, C3-C6-cycloalkyl; C1-C4-halogenalkyl, C1-C4-halogenalkoxy, halogen-C1-C3-alkoxy-C1-C3-alkyl, C3-C6-halogencycloalkyl, each with 1 to 9 fluorine, chlorine and/or bromine atoms,
R7 and Rs, independently of one another, each stand for hydrogen, C1-C6-alkyl, C1-C3-alkoxy-C1-C3-alkyl, C3-C6-cyeloalkyl; C1-C4-halogenalkyl, halogen-C1-C3-alkoxy-C1-C3-alkyl, C3-C6-halogencycloalkyl, each with 1 to 9 fluorine, chlorine and/or bromine atoms,
R7 and R8, together with the nitrogen atom to which they are bonded, further form a saturated heterocycle with 5 or 6 ring atoms, possibly substituted one to four times, identically

or variously, by halogen or C1-C4-alkyl, in which the heterocycle can contain 1 or 2 additional, non-adjacent heteroatoms from the group of oxygen, sulphur or NR11,
R9 and R10, independently of one another, stand for hydrogen, C1-C6-alkyl, C3-C6-cycloalkyl; C1-C4-halogenalkyl, C3-C6-halogencycloalkyl, each with 1 to 9 fluorine, chlorine and/or bromine atoms,
R9 and R10, together with the nitrogen atom to which they are bonded, further form a saturated heterocycle with 5 or 6 ring atoms, possibly substituted one to four times, identically or variously, by halogen or C1-C4-alkyI, in which the heterocycle can contain 1 or 2 additional, non-adjacent heteroatoms from the group of oxygen, sulphur or NR11,
R11 stands for hydrogen or C1-C4-alkyl.
3. Method for preparation of the biphenyl thiazole carboxamides of Formula (I) as claimed in
claim 1, wherein
(a) carboxylic acid derivatives of Formula (II)
(Formula Removed)
where
R1 and R2 have the meanings specified in Claim I and
X1 stands for halogen or hydroxy,
are reacted with biphenyl amines of Formula (III)
(Formula Removed)
wherein R3, R4, R5 and n have the meanings specified in claim 1, in the presence of a catalyst as an optional component, in the presence of a condensation agent as an optional component, in the presence of binding agent as an optional component and in the presence of diluents as an optional component.
4. Biphenyl thiazole carboxamide of Formula (I) as claimed in main claim as and when used as an agent for combating undesired microorganisms in addition to extenders and/or surface-active substances.

Documents:

1556-delnp-2007-Abstract-(03-12-2010).pdf

1556-DELNP-2007-Abstract-(09-09-2011).pdf

1556-delnp-2007-abstract.pdf

1556-delnp-2007-Claims-(03-12-2010).pdf

1556-DELNP-2007-Claims-(09-09-2011).pdf

1556-delnp-2007-claims.pdf

1556-delnp-2007-Correspondence Others-(03-12-2010).pdf

1556-DELNP-2007-Correspondence Others-(09-09-2011).pdf

1556-delnp-2007-correspondence-others-1.pdf

1556-DELNP-2007-Correspondence-Others.pdf

1556-delnp-2007-Description (Complete)-(03-12-2010).pdf

1556-delnp-2007-description(complete).pdf

1556-delnp-2007-Form-1-(03-12-2010).pdf

1556-delnp-2007-form-1.pdf

1556-delnp-2007-form-18.pdf

1556-delnp-2007-Form-2-(03-12-2010).pdf

1556-delnp-2007-form-2.pdf

1556-DELNP-2007-Form-3-(09-09-2011).pdf

1556-DELNP-2007-Form-3.pdf

1556-delnp-2007-form-5.pdf

1556-delnp-2007-gpa.pdf

1556-delnp-2007-pct-210.pdf

1556-delnp-2007-pct-notification.pdf

1556-DELNP-2007-Petition-137-(09-09-2011).pdf

abstract.jpg


Patent Number 250056
Indian Patent Application Number 1556/DELNP/2007
PG Journal Number 48/2011
Publication Date 02-Dec-2011
Grant Date 01-Dec-2011
Date of Filing 27-Feb-2007
Name of Patentee BAYER CROPSCIENCE AG
Applicant Address ALFRED-NOBEL-STR. 50, 40789 MONHEIM, GERMANY
Inventors:
# Inventor's Name Inventor's Address
1 ULRIKE WACHENDORFF-NEUMANN OBERER MARKENWEG 85, 56566 NEUWIED,GERMANY
2 PETER DAHMEN ALTEBRUCKER STR. 63, 41470 NEUSS,GERMANY
3 KARL HEINZ KUCK PASTOR-LOH-STR. 30A, 40764 LANGENFELD, GERMANY
4 RALF DUNKEL 9/11 RUE PIERRE DUPONT,69001 LYON,FRANCE
5 HANS-LUDWIG ELBE DASNOCKEL 59, 42329 WUPPERTAL,GERMANY
6 JORG NICO GREUL AM SANDBERG 30A,42799 LEICHLINGEN, GERMANY
7 BENOIT HARTMANN 12 CHEMIN DE ANTOINETTE, 69110 SAINTE FOY LES LYON, FRANCE
8 HERBERT GAYER SANDSTR. 66,40789 MONHEIM, GERMANY
9 THOMAS SEITZ RIETHERBACH 10B, 40764 LANGENFELD, GERMANY
PCT International Classification Number C07D277/56; A01N43/78; C07D277/00
PCT International Application Number PCT/EP2005/008837
PCT International Filing date 2005-08-13
PCT Conventions:
# PCT Application Number Date of Convention Priority Country
1 10 2004 041 530.7 2004-08-27 Germany