Title of Invention

PYRAZOLECARBOXANILIDE COMPOUNDS, COMPOSITION COMPRISING THEM FOR CONTROLLING HARMFUL FUNGI AND INTERMEDIATE IN THEIR PRODUCTION PROCESS

Abstract The present invention relates to a pyrazolecarboxanilide of the formula I in which X and R1 are as defined in the specification, and a composition comprising them. The invention also relates to novel intermediates in the production process of the claimed compounds.
Full Text Description
The present invention relates to pyrazolecarboxanilides of the formula I

in which the variables are as defined below:
n is zero or 2;
m is 2 or 3;
X1 is fluorine or chlorine;
X2 is halogen;
Y is CN, NO2, C1-C4-alkyl, C1-C4-haloalkyl, methoxy or methylthio;
p is zero or 1;
R1 is fluorine, chlorine, bromine, C1-C4-alkyl or C1-C4-haloalkyl;
R2 is hydrogen or halogen;
R3 is hydrogen, methyl or ethyl;
W is O or S;
with the proviso that, if
a) W = O, R1 = methyl and R3 is hydrogen, R2 is not F, or
b) W = O, n = 0, m = 2, p = 0, R2 and R3 are hydrogen, R1 is not trifluoromethyl or
difluoromethyl.
Here, in the case of multiple substitution, the substituents X1 and X2 may independently
of one another have different meanings.
Moreover, the invention relates to processes for preparing these compounds, to com-
positions comprising them and to methods for their use for controlling harmful fungi, in
particular Botrytis.
Pyrazolecarboxanilides having fungicidal action are known from the literature. Thus, for
example, EP-A 545 099 and EP-A 589 301 describe biphenylanilides of this type which

are monosubstituted at the biphenyi group.
WO 00/14071 describes specific 1,3-dimethyl-5-fluoropyrazolecarboxanilides and their
fungicidal action.
Pyrazolecarboxanilides having a specific triple substitution at the biphenyi group are
known from WO 03/070705 and JP-A 2001/302605.
WO 2004/103975 provides inter alia iodopyrazolecarboxanilides which differ from the
present compounds I in particular in that they have an iodine substituent instead of R1.
It was an object of the present invention to provide pyrazolecarboxanilides whose fun-
gicidal action is better than that of the compounds of the prior art.
We have found that this object is achieved by the compounds I defined at the outset.
Moreover, we have found processes for preparing these compounds, compositions
comprising them and methods for their use for controlling harmful fungi.
Compared to the known compounds, the compounds of the formula I are more effec-
tive against harmful fungi.
The compounds of the formula I can be present in different crystal modifications whose
biological activity may differ. They also form part of the subject matter of the present
invention.
In the formula I, halogen is fluorine, chlorine, bromine or iodine, preferably fluorine or
chlorine;
C1-C4-alkyl is methyl, ethyl, n-propyl, 1-methylethyl, n-butyl, 1-methylpropyl, 2-
methylpropyl or 1,1-dimethylethyl, preferably methyl or ethyl;
C1-C4-haloalkyl is a partially or fully halogenated C1-C4-alkyl radical, where the halogen
atom(s) is/are in particular fluorine and/or chlorine, i.e., for example, chloromethyl,
bromomethyl, dichloromethyl, trichloromethyl, fluoromethyl, difluoromethyl, trifluoro-
methyl, chlorofluoromethyl, dichlorofluoromethyl, chlorodifluoromethyl, 1-chloroethyl, 1-
bromoethyl, 1-fluoroethyl, 2-fluoroethyl, 2,2-difluoroethyl, 2-chloro-2-fluoroethyl, 2,2,2-
trifluoroethyl, 2-chloro-1,1,2-trifluoroethyl, 2-chloro-2,2-difluoroethyl, 2-bromo-2,2-
difluoroethyl, 2,2-dichloro-2-fluoroethyl, 2,2,2-trichloroethyl, 1,1,2,2-tetrafluoroethyl,
1,1,2,2-tetrachloroethyl, pentafluoroethyl, 2,2,3,3-tetrafluoro-1-propyl, 1,1,2,3,3,3-
hexafluoro-1-propyl, 1,1,1,3,3,3-hexafluoro-2-propyi, heptafluoro-1-propyl, heptafluoro-
2-propyl, 2,2,3,3,4,4,4-heptafluoro-1-butyl or nonafluoro-1-butyl, in particular ha-
lomethyl, with particular preference CH2-CI, CH(CI)2, CH2-F, CH(F)2, CF3, CHFCI,
CF2CI or CF(CI)2.

The compounds I are generally obtained by reacting a carbonyl halide of the formula II
in a manner known per se (for example J. March, Advanced Organic Chemistry, 2nd
Ed., 382 f, McGraw-Hill, 1977) in the presence of a base with an aniline of the for-
mula III:

In the formula II, the radical Hal denotes a halogen atom, such as fluorine, chlorine,
bromine and iodine, in particular fluorine, chlorine or bromine. This reaction is usually
carried out at temperatures of from -20°C to 100°C, preferably from 0°C to 50°C.
Suitable solvents are aliphatic hydrocarbons, such as pentane, hexane, cyclohexane
and petroleum ether, aromatic hydrocarbons, such as toluene, o-, m- and p-xylene,
halogenated hydrocarbons, such as methylene chloride, chloroform and chloro-
benzene, ethers, such as diethyl ether, diisopropyl ether, tert-butyl methyl ether, diox-
ane, anisole and tetrahydrofuran, nitriles, such as acetonitrile and propionitrile, ke-
tones, such as acetone, methyl ethyl ketone, diethyl ketone and tert-butyl methyl ke-
tone, alcohols, such as methanol, ethanol, n-propanol, isopropanol, n-butanol and tert-
butanol, and also methylene chloride, dimethyl sulfoxide and dimethylformamide, par-
ticularly preferably toluene, methylene chloride and tetrahydrofuran.
It is also possible to use mixtures of the solvents mentioned.
Suitable bases are, in general, inorganic compounds, such as alkali metal and alkaline
earth metal hydroxides, such as lithium hydroxide, sodium hydroxide, potassium hy-
droxide and calcium hydroxide, alkali metal and alkaline earth metal oxides, such as
lithium oxide, sodium oxide, calcium oxide and magnesium oxide, alkali metal and alka-
line earth metal hydrides, such as lithium hydride, sodium hydride, potassium hydride
and calcium hydride, alkali metal amides, such as lithium amide, sodium amide and
potassium amide, alkali metal and alkaline earth metal carbonates, such as lithium car-
bonate and calcium carbonate, and also alkali metal bicarbonates, such as sodium
bicarbonate, and organometallic compounds, in particular alkali metal alkyls, such as
methyllithium, butyllithium and phenyllithium, alkylmagnesium halides, such as me-
thylmagnesium chloride, and also alkali metal and alkaline earth metal alkoxides, such

as sodium methoxide, sodium ethoxide, potassium ethoxide, potassium tert-butoxide
and dimethoxymagensium, moreover organic bases, for example tertiary amines, such
as trimethylamine, triethylamine, diisopropylethylamine and N-methylpiperidine, pyri-
dine, substituted pyridines, such as collidine, lutidine and 4-dimethylaminopyridine, and
also bicyclic amines.
Particular preference is given to using triethylamine and pyridine.
The bases are generally employed in equimolar amounts, based on the compound II.
However, they can also be used in an excess of from 5 mol% to 30 mol%, preferably
from 5 mol% to 10 mol%, or - if tertiary amines are used - if appropriate, as solvents.
The starting materials are generally reacted with one another in equimolar amounts. In
terms of yield, it may be advantageous to employ II in an excess of from 1 mol% to
20 mol%, preferably from 1 mol% to 10 mol%, based on III.
The starting materials of the formulae II and III required for preparing the compounds I
are known or can be synthesized analogously to known compounds (Helv. Chim. Acta,
60, 978 (1977); Zh. Org. Khim., 26, 1527 (1990); Heterocycles 26, 1885 (1987); Izv.
Akad. Nauk. SSSR Ser. Khim., 2160 (1982); THL 28, 593 (1987); THL 29, 5463
(1988)).
Furthermore, it has been found that compounds of the formula I are obtained by react-
ing, in a known manner, carboxylic acids of the formula IV with an aniline of the formula
III in the presence of dehydrating agents and, if appropriate, an organic base.

Suitable solvents are aliphatic hydrocarbons, such as pentane, hexane, cyclohexane
and petroleum ether, aromatic hydrocarbons, such as toluene, o-, m- and p-xylene,
halogenated hydrocarbons, such as methylene chloride, chloroform and chloro-

benzene, ethers, such as diethyl ether, diisopropyl ether, tert-butyl methyl ether, diox-
ane, anisole and tetrahydrofuran, nitriles, such as acetonitrile and propionitrile, ke-
tones, such as acetone, methyl ethyl ketone, diethyl ketone and tert-butyl methyl ke-
tone, and also dimethyl sulfoxide and dimethylformamide, particularly preferably me-
thylene chloride, toluene and tetrahydrofuran.
It is also possible to use mixtures of the solvents mentioned.
Suitable dehydrating agents are 1,1'-carbonyldiimidazole, bis(2-oxo-3-oxazolidinyl)-
phosphoryl chloride, carbodiimides, such as N,N'-dicyclohexylcarbodiimide, N-(3-
dimethylaminopropyl)-N'-ethylcarbodiimide, phosphonium salts, such as (benzotriazol-
1 -yloxy)tris(dimethylamino)phosphonium hexafluorophosphate, bromotripyrrolidino-
phosphonium hexafluorophosphate, bromotris(dimethylamino)phosphonium
hexafluorophosphate, chlorotripyrrolidinophosphonium hexafluorophosphate, uranium
and thiuronium salts, such as P-(benzotriazo!-1-yl)-N,N,N',N'-tetramethyluronium
hexafluorophosphate, O-(7-azabenzotriazol-1-yl)-N,N,N',N'-tetramethyluronium
hexafluorophosphate, S-(1 -oxido-2-pyridyl)-N,N,N',N'-etramethylthiuronium tetra-
fluoroborate, O-(2-oxo-1(2H)pyridyl)-N,N,N',N'-tetramethyluronium tetrafluoroborate, O-
[(ethoxycarbonyl)cyanomethylenamino]-N,N,N',N'-tetramethyluronium tetrafluoroborate,
carbenium salts, such as (benzotriazol-l-yloxy)dipyrrolidinocarbenium hexafluoro-
phosphate, (benzotriazol-1 -yloxy)dipiperidinocarbenium hexafluorophosphate,
O-(3,4-dihydro-4-oxo-1,2,3-benzotriazin-3-yl)-N,N,N',N'-tetramethyluronium tetra-
fluoroborate, chloro-N',N'-bis(tetramethylene)formamidinium tetrafluoroborate, chloro-
dipyrrolidinocarbenium hexafluorophosphate, chloro-N,N,N',N,-bis(pentamethylene)-
formamidinium tetrafluoroborate, imidazolium salts, such as 2-chloro-1,3-dimethyl-
imidazolidinium tetrafluoroborate, preferably 1,1'-carbonyldiimidazole, bis(2-oxo-
3-oxazolidinyl)phosphoryl chloride, N,N'-dicyclohexylcarbodiimide and N-(3-dimethyl-
aminopropyl)-N'-ethylcarbodiimide.
Suitable organic bases are tertiary amines, such as trimethylamine, triethylamine,
diisopropylethylamine and N-methylpiperidine, pyridine, substituted pyridines, such as
collidine, lutidine and 4-dimethylaminopyridine, and also bicyclic amines. Particular
preference is given to using triethylamine and pyridine. The bases are generally em-
ployed in an excess of from 10 mol% to 200 mol%, preferably from 50 mol% to
150 mol%, based on the compound IV.
The starting materials are generally reacted with one another in equimolar amounts. In
terms of yield, it may be advantageous to use an excess of from 1 mol% to 20 mol%,
preferably from 1 mol% to 10 mol%, of one of the compounds. The dehydrating agents
are generally employed in an excess of from 5 mol% to 100 mol%, preferably from
5 mol% to 60 mol%.

The starting materials of the formulae III and IV required for preparing the compounds I
are known or can be synthesized analogously to the known compounds.
Compounds of the formula I where R3 = methyl or ethyl can be obtained by reacting
compounds of the formula I where R3 = H in a manner known per se in the presence of
a base with an alkylating agent:

Suitable solvents are aliphatic hydrocarbons, such as pentane, hexane, cyclohexane
and petroleum ether, aromatic hydrocarbons, such as toluene, o-, m- and p-xylene,
halogenated hydrocarbons, such as methylene chloride, chloroform and chloro-
benzene, ethers, such as diethyl ether, diisopropyl ether, tert-butyl methyl ether, diox-
ane, anisole and tetrahydrofuran, and also dimethyl sulfoxide and dimethylformamide,
particularly preferably diethyl ether, tert-butyl methyl ether, tetrahydrofuran and di-
methylformamide.
It is also possible to use mixtures of the solvents mentioned.
Suitable alkylating agents (XCH3 orXC2H5) are alkyl halides, such as methyl iodide,
ethyl iodide, methyl bromide, ethyl bromide, methyl chloride, ethyl chloride, alkyl per-
fluoroalkylsulfonates, such as methyl trifluoromethylsulfonate and ethyl trifluoromethyl-
sulfonate, alkyl alkylsulfonates, such as methyl methylsulfonate and ethyl methylsul-
fonate, alkyl arylsulfonates, such as methyl p-tolylsulfonate and ethyl p-tolylsulfonate,
oxonium salts, such as trimethyloxonium tetrafluoroborate and triethyloxonium tetra-
fluoroborate.
Particular preference is given to methyl iodide, ethyl iodide, methyl bromide, ethyl bro-
mide, methyl chloride and ethyl chloride.
Suitable bases are, in general, inorganic compounds, such as alkali metal and alkaline
earth metal hydroxides, such as lithium hydroxide, sodium hydroxide, potassium hy-
droxide and calcium hydroxide, alkali metal and alkaline earth metal oxides, such as
lithium oxide, sodium oxide, calcium oxide and magnesium oxide, alkali metal and alka-

line earth metal hydrides, such as lithium hydride, sodium hydride, potassium hydride
and calcium hydride, alkali metal amides, such as lithium amide, sodium amide and
potassium amide, alkali metal and alkaline earth metal carbonates, such as lithium car-
bonate, sodium carbonate, potassium carbonate and calcium carbonate, and also alkali
metal bicarbonates, such as sodium bicarbonate, or organometallic compounds, in
particular alkali metal alkyls, such as methyllithium, butyllithium and phenyllithium, al-
kylmagnesium halides, such as methylmagnesium chloride, and also alkali metal and
alkaline earth metal alkoxides, such as sodium methoxide, sodium ethoxide, potassium
ethoxide and potassium tert-butoxide.
Particular preference is given to sodium carbonate, potassium carbonate, sodium hy-
dride, potassium hydride, butyllithium and potassium tert-butoxide.
The bases are generally employed in equimolar amounts, based on the compound I.
However, they can also be used in an excess of from 5 mol% to 30 mol%, preferably
from 5 mol% to 10 mol%.
The starting materials are generally reacted with one another in approximately equimo-
lar amounts. In terms of yield, but it may be advantageous to employ the alkylating
agent in an excess of from 1 mo!% to 20 mol%, preferably from 1 mol% to 10 mol%.
With a view to the biological activity of the compounds I, preference is given to the fol-
lowing meanings of the variables, in each case either on their own or in combination:
n is zero;
m is 3;
X1 is chlorine;
X2 is fluorine or chlorine, preferably fluorine;
Y is C1-C4-alkyl, C1-C4-haloalkyl or methoxy, in particular
methyl, difluoromethyl, trifluoromethyl or methoxy;
particularly preferably methyl or trifluoromethyl;
p is zero;
R1 is fluorine, chlorine, C1-C4-alkyl or C1-C4-haloalkyl, in particular F, CI, methyl,
fluoromethyl, difluoromethyl, chlorofluoromethyl, chlorodifluoromethyl, dichloro-
fluoromethyl or trifluoromethyl;
particularly preferably methyl, fluoromethyl, difluoromethyl, chlorofluoromethyl or
trifluoromethyl, in particular difluoromethyl or trifluoromethyl;
very particularly preferably difluoromethyl;
R2 is hydrogen, fluorine or chlorine, in particular hydrogen or chlorine, particularly
preferably hydrogen;
R3 is hydrogen or methyl, in particular hydrogen;
W is oxygen.

In the case of m = 3, the radicals X2 are preferably located in the 2,4,5- or 3,4,5-
position, in particular in the 3,4,5-position.
Particular preference is given to compounds I having the following substituent combina-
tions in which the substituents are as defined below:
X2 is fluorine or chlorine;
Y is methyl, difluoromethyl, trifluoromethyl or methoxy;
R1 is F, chlorine, methyl, fluoromethyl, difluoromethyl, chlorofluoromethyl, chlorodi-
fluoromethy!, dichlorofluoromethyl, trifluoromethyl;
R2 is hydrogen, fluorine or chlorine;
R3 is hydrogen or methyl;
W is oxygen.
Preference is furthermore also given to the following combinations of substituents hav-
ing the following meanings:
X2 is fluorine or chlorine;
n is zero;
p is zero;
R1 is F, chlorine, methyl, fluoromethyl, difluoromethyl, chlorofluoromethyl,
chlorodifluoromethyl, dichlorofluoromethyl or trifluoromethyl, in particular fluorine,
chlorine, fluoromethyl, difluoromethyl, chlorofluoromethyl, chlorodifluoromethyl,
dichlorofluoromethyl or trifluoromethyl;
R2 is hydrogen, fluorine or chlorine;
R3 is hydrogen;
W is oxygen.
Preference is also given to compounds I where m = 2, in particular to those in which
R1 is methyl, fluoromethyl, chlorofluoromethyl or chlorodifluoromethyl and/or R2 is hy-
drogen or chlorine, in particular hydrogen. Here, the radicals X are preferably located in
the 2,4- or 3,4-position, in particular in the 3,4-position.
In particular with a view to their use as fungicides, preference is given to the com-
pounds of the general formulae I-A and l-B:

























Compounds of the general formula l-A in which R2 is CI, R3 is hydrogen and R1 and B
for each individual compound correspond in each case to one row of Table A.
Table 3:
Compounds of the general formula l-A in which R2 is F, R3 is hydrogen and R1 and B
for each individual compound correspond in each case to one row of Table A except for
rows 397 to 462.
Table 4:
Compounds of the general formula l-A in which R2 is hydrogen, R3 is methyl and R1
and B for each individual compound correspond in each case to one row of Table A.
Table 5:
Compounds of the general formula l-A in which R2 is hydrogen, R3 is ethyl and R1 and
B for each individual compound correspond in each case to one row of Table A.
Table 6:
Compounds of the general formula l-B in which R2 is hydrogen and R1 and B for each
individual compound correspond in each case to one row of Table A.
Preference is furthermore also given to the compounds of the general formulae l-C and
l-D.








Table 8:
Compounds of the general formula l-D in which B for each individual compound corre-
spond in each case to one row of Table B.
The compounds I are suitable for use as fungicides. They are distinguished by excel-
lent activity against a broad spectrum of phytopathogenic fungi in particular from the
classes of the Ascomycetes, Deuteromycetes, Peronasporomycetes (syn. Oomycetes)
and Basidiomycetes. Some of them are systemically active and can be used in crop
protection as foliar fungicides, as soil fungicides and as fungicides for seed dressing.
They are particularly important in the control of a large number of fungi on various crop
plants, such as wheat, rye, barley, oats, rice, corn, grass, bananas, cotton, soybeans,
coffee, sugar cane, grapevines, fruit and ornamental plants and vegetables, such as
cucumbers, beans, tomatoes, potatoes and cucurbits, and also the seeds of these
plants.
They are especially suitable for controlling the following plant diseases:
Alternaria species on vegetables, rapeseed, sugar beet and fruit and rice (for
example A. solani or A. alternata on potato and other plants),
Aphanomyces species on sugar beet and vegetables,
Bipolaris and Drechslera species on corn, cereals, rice and lawns (for example D.
teres on barley, D. tritci-repentis on wheat),
Blumeria graminis (powdery mildew) on cereals,
Botrytis cinerea (gray mold) on strawberries, vegetables, flowers and grapevines,
Bremia lactucae on lettuce,
Cercospora species on com, soybeans, rice and sugar beet (for example C.
beticula on sugar beet),
Cochliobolus species on corn, cereals, rice (for example Cochliobolus sativus on
cereals, Cochliobolus miyabeanus on rice),
Colletotricum species on soybeans, cotton and other plants (for example C. acu-
tatum on various plants),
Exserohilum speciea on corn,
Erysiphe cichoracearum and Sphaerotheca fuliginea on cucurbits,
Fusarium and Verticillium species (for example V. dahliae) on various plants (for
example F. graminearum on wheat),
Gaeumanomyces graminis on cereals,
Gibberella species on cereals and rice (for example Gibberella fujikuroi on rice),
Grainstaining complex on rice,
Helminthosporium species (for example H. graminicola) on corn and rice,
Michrodochium nivale on cereals,

Mycosphaerella species on cereals, bananas and peanuts (M. graminicola on
wheat, M. fijiesis on bananas,),
Phakopsara pachyrhizi and Phakopsara meibomiae on soybeans,
Phomopsis species on soybeans, sunflowers and grapevines (P. viticola on
grapevines, P. helianthii on sunflowers,),
Phytophthora infestans on potatoes and tomatoes,
Plasmopara viticola on grapevines,
Podosphaera leucotricha on apples,
Pseudocercosporella herpotrichoides on cereals,
Pseudoperonospora species on hops and cucurbits (for example P. cubenis on
cucumbers),
Puccinia species on cereals, corn and asparagus (P. triticina and P. striformis on
wheat, P. asparagi on asparagus),
Pyrenophora species on cereals,
Pyricularia oryzae, Corticium sasakii, Sarocladium oryzae, S.attenuatum, En-
tyloma oryzae on rice,
Pyricularia grisea on lawns and cereals,
Pythium spp. on lawns, rice, corn, cotton, rapeseed, sunflowers, sugar beet,
vegetables and other plants,
Rhizoctonia-spedes (for example R. solani) on cotton, rice, potatoes, lawns,
corn, rapeseed, potatoes, sugar beet, vegetables and other plants,
Sclerotinia species (for example S. sclerotiorum) on rapeseed, sunflowers and
other plants,
Septoria tritici and Stagonospora nodorum on wheat,
Erysiphe (syn. Uncinula necator) on grapevines,
Setospaeria species on corn and lawns,
Sphacelotheca reilinia on corn,
Thievaliopsis species on soybeans and cotton,
Tilletia species on cereals,
Ustilago species on cereals, corn and sugar beet and
Venturia species (scab) on apples and pears (for example V. inaequalis on ap-
ples).
The compounds I are furthermore suitable for controlling harmful fungi in the protection
of materials (for example wood, paper, paint dispersions, fibers or fabrics) and in the
protection of stored products. In the protection of wood, particular attention is paid to
the following harmful fungi: Ascomycetes, such as Ophiostoma spp., Ceratocystis spp.,
Aureobasidium pullulans, Sclerophoma spp., Chaetomium spp., Humicola spp.,
Petriella spp., Trichurus spp.; Basidiomycetes, such as Coniophora spp., Coriolus spp.,
Gloeophyllum spp., Lentinus spp., Pleurotus spp., Poria spp., Serpula spp. and Tyro-
myces spp., Deuteromycetes, such as Aspergillus spp., Cladosporium spp., Penicillium
spp., Trichoderma spp., Alternaria spp., Paecilomyces spp. and Zygomycetes, such as

Mucor spp., additionally in the protection of materials the following yeasts: Candida
spp. and Saccharomyces cerevisae.
The compounds I are employed by treating the fungi or the plants, seeds, materials or
soil to be protected from fungal attack with a fungicidally effective amount of the active
compounds. The application can be carried out both before and after the infection of
the materials, plants or seeds by the fungi.
The fungicidal compositions generally comprise between 0.1 and 95%, preferably be-
tween 0.5 and 90%, by weight of active compound.
When employed in plant protection, the amounts applied are, depending on the kind of
effect desired, between 0.01 and 2.0 kg of active compound per ha.
In seed treatment, for example by dusting, coating or drenching seed, amounts of ac-
tive compound of from 1 to 1000 g/100 kg, preferably from 5 to 100 g/100 kg, of seed
are generally necessary.
When used in the protection of materials or stored products, the amount of active com-
pound applied depends on the kind of application area and on the desired effect.
Amounts customarily applied in the protection of materials are, for example, 0.001 g to
2 kg, preferably 0.005 g to 1 kg, of active compound per cubic meter of treated mate-
rial.
The compounds I can be converted into the customary formulations, for example solu-
tions, emulsions, suspensions, dusts, powders, pastes and granules. The use form
depends on the particular intended purpose; in each case, it should ensure a fine and
even distribution of the compound according to the invention.
The formulations are prepared in a known manner, for example by extending the active
compound with solvents and/or carriers, if desired using emulsifiers and dispersants.
Solvents/auxiliaries suitable for this purpose are essentially:
- water, aromatic solvents (for example Solvesso products, xylene), paraffins (for ex-
ample mineral oil fractions), alcohols (for example methanol, butanol, pentanol, ben-
zyl alcohol), ketones (for example cyclohexanone, gamma-butyrolactone), pyrrolido-
nes (NMP, NOP), acetates (glycol diacetate), glycols, fatty acid dimethylamides,
fatty acids and fatty acid esters. In principle, solvent mixtures may also be used,
- carriers such as ground natural minerals (for example kaolins, clays, talc, chalk) and
ground synthetic minerals (for example highly disperse silica, silicates); emulsifiers
such as nonionogenic and anionic emulsifiers (for example polyoxyethylene fatty al-
cohol ethers, alkylsulfonates and arylsulfonates) and dispersants such as lignosul-
fite waste liquors and methylcellulose.

Suitable surfactants used are alkali metal, alkaline earth metal and ammonium salts of
lignosulfonic acid, naphthalenesulfonic acid, phenolsulfonic acid,
dibutylnaphthalenesulfonic acid, alkylarylsulfonates, alkyl sulfates, alkylsulfonates, fatty
alcohol sulfates, fatty acids and sulfated fatty alcohol glycol ethers, furthermore
condensates of sulfonated naphthalene and naphthalene derivatives with
formaldehyde, condensates of naphthalene or of naphthalenesulfonic acid with phenol
and formaldehyde, polyoxyethylene octylphenyl ether, ethoxylated isooctylphenol,
octylphenol, nonylphenol, alkylphenyl polyglycol ethers, tributylphenyl polyglycol ether,
thstearylphenyl polyglycol ether, alkylaryl polyether alcohols, alcohol and fatty alcohol
ethylene oxide condensates, ethoxylated castor oil, polyoxyethylene alkyl ethers,
ethoxylated polyoxypropylene, lauryl alcohol polyglycol ether acetal, sorbitol esters,
lignosulfite waste liquors and methylcellulose.
Substances which are suitable for the preparation of directly sprayable solutions,
emulsions, pastes or oil dispersions are mineral oil fractions of medium to high boiling
point, such as kerosene or diesel oil, furthermore coal tar oils and oils of vegetable or
animal origin, aliphatic, cyclic and aromatic hydrocarbons, for example toluene, xylene,
paraffin, tetrahydronaphthalene, alkylated naphthalenes or their derivatives, methanol,
ethanol, propanol, butanol, cyclohexanol, cyclohexanone, isophorone, highly polar
solvents, for example dimethyl sulfoxide, N-methylpyrrolidone and water.
Powders, materials for spreading and dustable products can be prepared by mixing or
concomitantly grinding the active substances with a solid carrier.
Granules, for example coated granules, impregnated granules and homogeneous
granules, can be prepared by binding the active compounds to solid carriers. Examples
of solid carriers are mineral earths such as silica gels, silicates, talc, kaolin, attaclay,
limestone, lime, chalk, bole, loess, clay, dolomite, diatomaceous earth, calcium sulfate,
magnesium sulfate, magnesium oxide, ground synthetic materials, fertilizers, such as,
for example, ammonium sulfate, ammonium phosphate, ammonium nitrate, ureas, and
products of vegetable origin, such as cereal meal, tree bark meal, wood meal and
nutshell meal, cellulose powders and other solid carriers.
Formulations for the treatment of seed may additionally comprise binders and/or gelling
agents and, if appropriate, colorants.
Binders may be added to increase the adhesion of the active compounds on the seed
after the treatment. Suitable binders are, for example, EO/PO block copolymer surfac-
tants, but also polyvinyl alcohols, polyvinylpyrrolidones, polyacrylates, polymethacry-
lates, polybutenes, polyisobutylenes, polystyrenes, polyethylenamines, poly-
ethylenamides, polyethylenimines (Lupasol®, Polymin®), polyethers, polyurethanes,

polyvinyl acetates, tylose and copolymers of these polymers. A suitable gelling agent
is, for example, carrageen (Satiagel®).
In general, the formulations comprise from 0.01 to 95% by weight, preferably from 0.1
to 90% by weight, of the active compound. The active compounds are employed in a
purity of from 90% to 100%, preferably 95% to 100% (according to NMR spectrum).
The concentrations of active compound in the ready-for-use preparations can be varied
within relatively wide ranges. In general, they are between 0.0001 and 10%, preferably
between 0.01 and 1%.
The active compounds can also be used with great success in the ultra-low volume
(ULV) process, it being possible to apply formulations with more than 95% by weight of
active compound or even to apply the active compound without additives.
For the treatment of seed, the formulations in question give, after two- to ten-fold
dilution, active compound concentrations of from 0.01 to 60% by weight, preferably
from 0.1 to 40% by weight, in the ready-to-use preparations.
The following are examples of formulations: 1. Products for dilution with water
A) Water-soluble concentrates (SL)
10 parts by weight of a compound I according to the invention are dissolved in 90 parts
by weight of water or in a water-soluble solvent. As an alternative, wetting agents or
other auxiliaries are added. The active compound dissolves upon dilution with water. In
this way, a formulation having a content of 10% by weight of active compound is
obtained.
B) Dispersible concentrates (DC)
20 parts by weight of a compound I according to the invention are dissolved in 70 parts
by weight of cyclohexanone with addition of 10 parts by weight of a dispersant, for
example polyvinylpyrrolidone. Dilution with water gives a dispersion. The active
compound content is 20% by weight.
C) Emulsifiable concentrates (EC)
15 parts by weight of a compound I according to the invention are dissolved in 75 parts
by weight of xylene with addition of calcium dodecylbenzenesulfonate and castor oil
ethoxylate (in each case 5 parts by weight). Dilution with water gives an emulsion. The
formulation has an active compound content of 15% by weight.
D) Emulsions (EW, EO)

25 parts by weight of a compound I according to the invention are dissolved in 35 parts
by weight of xylene with addition of calcium dodecylbenzenesulfonate and castor oil
ethoxylate (in each case 5 parts by weight). This mixture is introduced into 30 parts by
weight of water by means of an emulsifying machine (for example Ultraturrax) and
made into a homogeneous emulsion. Dilution with water gives an emulsion. The
formulation has an active compound content of 25% by weight.
E) Suspensions (SC, OD)
In an agitated ball mill, 20 parts by weight of a compound I according to the invention
are comminuted with addition of 10 parts by weight of dispersants and wetting agents
and 70 parts by weight of water or an organic solvent to give a fine active compound
suspension. Dilution with water gives a stable suspension of the active compound. The
active compound content in the formulation is 20% by weight.
F) Water-dispersible granules and water-soluble granules (WG, SG)
50 parts by weight of a compound I according to the invention are ground finely with
addition of 50 parts by weight of dispersants and wetting agents and prepared as
water-dispersible or water-soluble granules by means of technical appliances (for
example extrusion, spray tower, fluidized bed). Dilution with water gives a stable
dispersion or solution of the active compound. The formulation has an active
compound content of 50% by weight.
G) Water-dispersible powders and water-soluble powders (WP, SP)
75 parts by weight of a compound I according to the invention are ground in a rotor-
stator mill with addition of 25 parts by weight of dispersants, wetting agents and silica
gel. Dilution with water gives a stable dispersion or solution of the active compound.
The active compound content of the formulation is 75% by weight.
2. Products to be applied undiluted
H) Dustable powders (DP)
5 parts by weight of a compound I according to the invention are ground finely and
mixed intimately with 95 parts by weight of finely divided kaolin. This gives a dustable
product having an active compound content of 5% by weight.
J) Granules (GR, FG, GG, MG)
0.5 part by weight of a compound I according to the invention is ground finely and
associated with 99.5 parts by weight of carriers. Current methods are extrusion, spray-
drying or the fluidized bed. This gives granules to be applied undiluted having an active
compound content of 0.5% by weight.
K) ULV solutions (UL)

10 parts by weight of a compound I according to the invention are dissolved in 90 parts
by weight of an organic solvent, for example xylene. This gives a product to be applied
undiluted having an active compound content of 10% by weight.
The active compounds can be used as such, in the form of their formulations or the use
forms prepared therefrom, for example in the form of directly sprayable solutions,
powders, suspensions or dispersions, emulsions, oil dispersions, pastes, dustable
products, materials for spreading, or granules, by means of spraying, atomizing,
dusting, spreading or pouring. The use forms depend entirely on the intended
purposes; they are intended to ensure in each case the finest possible distribution of
the active compounds according to the invention.
Aqueous use forms can be prepared from emulsion concentrates, pastes or wettable
powders (wettable powders, oil dispersions) by adding water. To prepare emulsions,
pastes or oil dispersions, the substances, as such or dissolved in an oil or solvent, can
be homogenized in water by means of a wetting agent, tackifier, dispersant or
emulsifier. However, it is also possible to prepare concentrates composed of active
substance, wetting agent, tackifier, dispersant or emulsifier and, if appropriate, solvent
or oil, and such concentrates are suitable for dilution with water.
The active compound concentrations in the ready-to-use preparations can be varied
within relatively wide ranges. In general, they are from 0.0001 to 10%, preferably from
0.01 to1%.
The active compounds may also be used successfully in the ultra-low-volume process
(ULV), by which it is possible to apply formulations comprising over 95% by weight of
active compound, or even to apply the active compound without additives.
Various types of oils, wetters, adjuvants, herbicides, fungicides, other pesticides, or
bactericides may be added to the active compounds, if appropriate not until
immediately prior to use (tank mix). These agents can be admixed with the agents
according to the invention in a weight ratio of 1:100 to 100:1, preferably 1:10 to 10:1.
Suitable adjuvants in this sense are in particular: organically modified polysiloxanes, for
example Break Thru S 240®; alcohol alkoxylates, for example Atplus 245®, Atplus MBA
1303®, Plurafac LF 300® and Lutensol ON 30®; EO/PO block polymers, for example
Pluronic RPE 2035® and Genapol B®; alcohol ethoxylates, for example Lutensol
XP 80®; and sodium dioctylsulfosuccinate, for example Leophen RA®.
The compositions according to the invention can, in the use form as fungicides, also be
present together with other active compounds, for example with herbicides, insecti-
cides, growth regulators, such as prohexadione-Ca, fungicides or else with fertilizers.
By mixing the compounds I or the compositions comprising them with one or more fur-

ther active compounds, in particular fungicides, it is in many cases possible to broaden
the activity spectrum or to prevent the development of resistance. In many cases, syn-
ergistic effects are obtained.
The following list of fungicides, with which the compounds according to the invention
can be used in conjunction, is intended to illustrate the possible combinations but does
not limit them:
strobilurins
azoxystrobin, dimoxystrobin, enestrostrobin, fluoxastrobin, kresoxim-methyl, metomino-
strobin, picoxystrobin, pyraclostrobin, trifloxystrobin, orysastrobin, methyl (2-chloro-5-
[1-(3-methylbenzyloxyimino)ethyl]benzyl)carbamate, methyl (2-chloro-5-[1-(6-
methylpyridin-2-ylmethoxyimino)-ethyl]benzyl)carbamate, methyl 2-(ortho-(2,5-
dimethylphenyloxymethylene)phenyl)-3-methoxyacrylate.
carboxamides
- carboxanilides: benalaxyl, benodanil, boscalid, carboxin, mepronil, fenfuram, fen-
hexamid, flutolanil, furametpyr, metalaxyl, ofurace, oxadixyl, oxycarboxin, pen-
thiopyrad, thifluzamide, tiadinil, N-(4'-bromobiphenyl-2-yl)-4-difluoromethyl-2-
methylthiazole-5-carboxamide, N-(4'-trifluoromethylbiphenyl-2-yl)-4-difluoromethyl-
2-methylthiazole-5-carboxamide, N-(4'-chloro-3'-fluorobiphenyl-2-yl)-4-
difluoromethyl-2-methylthiazole-5-carboxamide, N-(3',4'-dichloro-4-fluorobiphenyl-2-
yl)-3-difluoromethyl-1-methylpyrazole-4-carboxamide, N-(2-cyanophenyl)-3,4-
dichloroisothiazole-5-carboxamide;
- carboxylic acid morpholides: dimethomorph, flumorph;
- benzamides: flumetover, fiuopicolide (picobenzamid), zoxamide;
- other carboxamides: carpropamid, diclocymet, mandipropamid, N-(2-(4-[3-(4-chloro-
phenyl)prop-2-ynyloxy]-3-methoxyphenyl)ethyl)-2-methanesulfonylamino-3-methyl-
butyramide, N-(2-(4-[3-(4-chlorophenyl)prop-2-ynyloxy]-3-methoxyphenyl)ethyl)-2-
ethanesulfonylamino-3-methylbutyramide;
azoles
- triazoles: bitertanol, bromuconazole, cyproconazole, difenoconazole, diniconazole,
enilconazole, epoxiconazole, fenbuconazole, flusilazole, fluquinconazole, flutriafol,
hexaconazole, imibenconazole, ipconazole, metconazole, myclobutanil, pencona-
zole, propiconazole, prothioconazole, simeconazole, tebuconazole, tetraconazole,
triadimenol, thadimefon, triticonazole;
- imidazoles: cyazofamid, imazalil, pefurazoate, prochloraz, triflumizole;
- benzimidazoles: benomyl, carbendazim, fuberidazole, thiabendazole;
- others: ethaboxam, etridiazole, hymexazole;

nitrogenous heterocyclyl compounds

- pyridines: fluazinam, pyrifenox, 3-[5-(4-chlorophenyl)-2,3-dimethylisoxazolidin-3-yl]-
pyridine;
- pyrimidines: bupirimate, cyprodinil, ferimzone, fenarimol, mepanipyrim, nuarimoi,
pyrimethanil;
- piperazines: triforine;
- pyrroles: fludioxonil, fenpiclonil;
- morpholines: aldimorph, dodemorph, fenpropimorph, tridemorph;
- dicarboximides: iprodione, procymidone, vinclozolin;
- others: acibenzo!ar-S-methyl, anilazine, captan, captafol, dazomet, diclomezine,
fenoxanil, folpet, fenpropidin, famoxadone, fenamidone, octhilinone, probenazole,
proquinazid, pyroquilon, quinoxyfen, tricyclazole, 5-chloro-7-(4-methylpiperidin-1-yl)-
6-(2,4,6-trifluorophenyl)-[1,2,4]triazolo[1,5-a]pyrimidine, 2-butoxy-6-iodo-3-propyl-
chromen-4-one, N,N-dimethyl-3-(3-bromo-6-fluoro-2-methylindole-1-sulfonyl)-
[1,2,4]triazole-1 -sulfonamide;
carbamates and dithiocarbamates
- dithiocarbamates: ferbam, mancozeb, maneb, metiram, metam, propineb, thiram,
zineb, ziram;
- carbamates: diethofencarb, flubenthiavalicarb, iprovalicarb, propamocarb, methyl 3-
(4-chlorophenyl)-3-(2-isopropoxycarbonylamino-3-methylbutyrylamino)propionate, 4-
fluorophenyl N-(1-(1-(4-cyanophenyl)ethanesulfonyl)but-2-yl)carbamate;
other fungicides
- guanidines: dodine, iminoctadine, guazatine;
- antibiotics: kasugamycin, polyoxins, streptomycin, validamycin A;
- organometallic compounds: fentin salts;
- sulfur-containing heterocyclyl compounds: isoprothiolane, dithianon;
- organophosphorus compounds: edifenphos, fosetyl, fosetyl-aluminum, iprobenfos,
pyrazophos, tolclofos-methyl, phosphorous acid and its salts;
- organochlorine compounds: thiophanate-methyl, chlorothalonil, dichlofluanid,
tolylfluanid, flusulfamide, phthalide, hexachlorobenzene, pencycuron, quintozene;
- nitrophenyl derivatives: binapacryl, dinocap, dinobuton;
- inorganic active compounds: Bordeaux mixture, copper acetate, copper hydroxide,
copper oxychloride, basic copper sulfate, sulfur;
- others: spiroxamine, cyflufenamid, cymoxanil, metrafenone.
Synthesis examples
Example 1:
N-(3'-chloro-4'-fluorobiphenyl-2-yl)-1,3-dimethyl-1H-pyrazole-4-carboxamide
At room temperature, 0.47 g of 3'-chloro-4'-fluoro-2-aminobiphenyl and 0.82 g of

bis(2-oxo-3-oxazolidinyl)phosphoryl chloride were added to a solution of 0.30 g of 1,3-
dimethyl-1H-pyrazole-4-carboxylic acid and 0.43 g of triethylamine in 30 ml of di-
chloromethane. The mixture was stirred at room temperature for 12 hours. The mixture
was then washed successively twice with dilute hydrochloric acid, twice with aqueous
sodium bicarbonate solution and once with water. The organic phase was dried and
concentrated. The crude product was purified by silica gel column chromatography
using cyclohexane/methyl tert-butyl ether 1:2. This gave 0.56 g of the desired product
as white crystals of m.p. 177-180°C.
Example 2:
N-(3'-chloro-4'-fluorobiphenyl-2-yl)-3-fluoromethyl-1-methyl-1H-pyrazole-4-carboxamide
At room temperature, 0.27 g of 3-fluoromethyl-1 -methyl-1 H-pyrazoie-4-carbonyl chlo-
ride was added dropwise to a solution of 0.33 g of 3'-chloro-4'-fluoro-2-aminobiphenyl
and 0.18 g of pyridine in 10 mi of toluene, and the mixture was stirred at room tempera-
ture for 16 hours. 10 ml of tetrahydrofuran and 30 ml of methyl tert-butyl ether were
added, and the organic phase was washed successively with 2% strength hydrochloric
acid, twice with 2% strength aqueous sodium hydroxide solution and then with dilute
aqueous sodium chloride solution. The organic phase was dried and concentrated un-
der reduced pressure. The crude product was triturated with 10 ml of diisopropyl ether
and the solid that remained was filtered off with suction and dried. This gave 0.46 g of
the desired product as a white powder of m.p. 133-134°C.
Example 3:
N-(3',4'-dichlorobiphenyl-2-yl)methyl-1-methyl-3-trifluoromethyl-1H-pyrazole-4-
carboxamide
With ice cooling, 0.25 g of N-(3',4'-dichlorobiphenyl-2-yl)-1-methyl-3-trifluoromethyl-1H-
pyrazole-4-carboxamide and 0.09 g of methyl iodide were added to a solution of 0.02 g
of sodium hydride in 5 ml of N,N-dimethylformamide. The mixture was stirred at room
temperature for 12 hours, and 1% strength hydrochloric acid and methyl tert-butyl ether
were then added. The organic phase was washed successively with water and satu-
rated aqueous sodium chloride solution, and the solution was concentrated under re-
duced pressure. The crude product was purified by silica gel column chromatography
using cyclohexane/ethyl acetate 1:1. This gave 0.15 g of the desired product as a milk-
like oil.
Example 4:
N-(3',4'-dichlorobiphenyl-2-yl)-3-(dichlorofluoromethyl)-1-methyl-1/-/-pyrazole-4-
carboxamide

a) N-(3',4-Dichlorobiphenyl-2-yl)-3-(dichlorofluoromethyl)-1 -methyl-1 H-pyrazoie-

4-carboxamide
0.37 g of the oil from 4b was added dropwise to a solution of 0.36 g of 3',4'-dichloro-2-
aminobiphenyl and 0.18 g of pyridine in 10 ml of toluene, and the reaction mixture was
stirred at room temperature for 16 hours. 10 ml of tetrahydrofuran and 30 ml of methyl
tert-butyl ether were then added. The organic phase was washed successively with 2%
strength hydrochloric acid, twice with aqueous sodium bicarbonate solution and with
dilute aqueous sodium chloride solution. The organic phase was dried and concen-
trated under reduced pressure. The crude product was triturated with 10 ml of diisopro-
pyl ether, and the solid that remained was filtered off with suction and dried. This gave
0.48 g of the desired product as a white powder of m.p. 145-146°C.
b) 3-Dichlorofluoromethyl-1-methyl-4-pyrazolecarbonyl chloride
A mixture of 5.3 g of 3-dichlorofluoromethyl-1-methyl-4-pyrazolecarboxylic acid and
27.8 g of thionyl chloride was heated at reflux for 2 hours. The reaction mixture was
then concentrated using a rotary evaporator and twice codistilled with 50 ml of toluene.
The isolated oil was directly reacted further, without further purification.
c) 3-Dichlorofluoromethyl-1-methyl-4-pyrazolecarboxyIic acid
At room temperature, a solution of 10.20 g of ethyl 3-dich!orofluoromethyl-1-methyl-
4-carboxylate in 20 ml of tetrahydrofuran was added dropwise to a mixture of 5.13 g of
potassium trimethylsilanolate and 100 ml of tetrahydrofuran, and the mixture was
stirred at room temperature for 12 hours. The precipitate was filtered off with suction,
washed with tetrahydrofuran and dried under reduced pressure. The resulting solid was
dissolved in 200 ml of ice-water, and the solution was adjusted to pH 2 using 10%
strength hydrochloric acid. The precipitate was extracted twice with methyl tert-butyl
ether, and the combined organic phases were washed with saturated aqueous sodium
chloride solution. After drying and evaporation of the solvent under reduced pressure,
5.50 g of the above acid were isolated as a white powder of m.p. 167-169°C.
The compounds of the general formula I where W = O listed in Table 9 below were
prepared using the procedures given here.









Use examples
The fungicidal action of the compounds I according to the invention was demonstrated
by the following tests:
The active compounds were prepared as a stock solution comprising 25 mg of active
compound which was made up to 10 ml using a mixture of acetone and/or dimethyl
sulfoxide and the emulsifier Uniperol® EL (wetting agent having an emulsifying and
dispersing action based on ethoxylated alkylphenols) in a volume ratio of sol-
vent/emulsifier of 99:1. The mixture was then made up to 100 ml with water. This stock
solution was diluted with the solvent/emulsifier/water mixture described to give the de-
sired concentration of active compounds.

Activity against gray mold on bell pepper leaves caused by Botrytis cinerea, pro-
tective application
Bell pepper seedlings of the cultivar "Neusiedler Ideal Elite" were, after 2-3 leaves were
well developed, sprayed to runoff point with an aqueous suspension having the concen-
tration of active compounds stated below. The next day, the treated plants were inocu-
lated with a spore suspension of Botrytis cinerea which comprised 1.7 x 106 spores/ml in
a 2% strength aqueous biomalt solution. The test plants were then placed into a dark cli-
matized chamber at 22-24°C and high atmospheric humidity. After 5 days, the extent of
the fungal infection on the leaves could be determined visually in %.
In this test, the plants which had been treated with 250 mg/l of compounds 9.1, 9.3,
9.12, 9.13, 9.14, 9.17, 9.18, 9.19, 9.20, 9.30, 9.32, 9.33, 9.35, 9.36, 9.37, 9.38, 9.39,
9.40, 9.42, 9.43, 9.44 and 9.45 from Table 9 showed an infection of at most 20%,
whereas the untreated plants were 90% infected.
Activity against leaf blotch on wheat caused by Leptosphaeria nodorum
Pots of wheat plants of the cultivar "Kanzler" were sprayed to runoff point with an
aqueous suspension having the concentration of active compounds stated below. The
next day, the pots were inoculated with an aqueous spore suspension of Leptosphaeria
nodorum (syn.Stagonosporoa nodorum, Septoroia nodorum). The plants were then
placed into a chamber at 20°C and maximum atmospheric humidity. After 8 days, the
leaf blotch on the untreated but infected control plants had developed to such an extent
that the infection could be determined visually in %.
In this test, the plants which had been treated with 250 mg/l of compounds 9.1, 9.2,
9.13 and 9.27 from Table 9 showed an infection of at most 20%, whereas the untreated
plants were 60% infected.
Curative activity against brown rust on wheat caused by Puccinia recondita
Leaves of potted wheat seedlings of the cultivar "Kanzler" were inoculated with a spore
suspension of brown rust (Puccinia recondita). The pots were then placed into a chamber
with high atmospheric humidity (90 to 95%) at 20-22°C for 24 hours. During this time, the
spores germinated and the germ tubes penetrated into the leaf tissue. The next day, the
infected plants were sprayed to runoff point with an aqueous suspension having the con-
centration of active compounds stated below. The suspension or emulsion was prepared
as described above. After the spray coating had dried on, the test plants were cultivated in
a greenhouse at temperatures between 20 and 22°C and at 65 to 70% relative atmos-
pheric humidity for 7 days. The extent of the rust fungus development on the leaves was
then determined.

Irvthis test, the plants which had been treated with 250 mg/l of compounds 9.1, 9.3, 9.4,
9.5, 9.6, 9.7, 9.8, 9.9, 9.10, 9.11, 9.12, 9.13, 9.14, 9.15, 9.17, 9.18, 9.19, 9.20, 9.21,
9.25, 9.26, 9.27, 9.28, 9.29, 9.33, 9.34, 9.35, 9.36, 9.37, 9.38, 9.39, 9.40, 9.42, 9.43,
9.44 and 9.45 from Table 9 showed an infection of at most 20%, whereas the untreated
plants were 90% infected.
Comparative experiment - activity against gray mold on bell pepper leaves
caused by Botrytis cinerea, protective application
Compound No. 47 of Table 1 from EP-A 0 589 301 was compared to compounds 9.17
and 9.20 according to the invention from Table 9.
Bell pepper seedlings of the cultivar "Neusiedler Ideal Elite" were, after 2-3 leaves were
well developed, sprayed to runoff point with an aqueous suspension having the concen-
tration of active compounds stated below. The next day, the treated plants were inocu-
lated with a spore suspension of Botrytis cinerea which comprised 1.7 x 106 spores/ml in
a 2% strength aqueous biomalt solution. The test plants were then placed into a dark cli-
matized chamber at 22-24°C and high atmospheric humidity. After 5 days, the extent of
the fungal infection on the leaves could be determined visually in %.



As can be seen from the biological data of Table 10, the compounds 9.17 and 9.20
according to the invention clearly have improved fungicidal action compared to the
structurally most similar compound of the prior art.

We claim:
1. A pyrazolecarboxanilide of the formula I

in which
X is halogen, where the radicals X may have different meanings, and
R1 is C1-C4-haloalkyl.
2. The pyrazolecarboxanilide of the formula I as claimed in claim 1, selected from
the group consisting of
N-(3',4',5'-trifluorobiphenyl-2-yl)-1-methyl-3-trifluoromethyl-1H-pyrazole-4-
carboxamide,
N-(2',4',5'-trifluorobiphenyl-2-yl)-1-methyl-3-trifIuoromethyl-1H-pyrazole-4-
carboxamide,
N-(2',3',4'-trifluorobiphenyl-2-yl)-1-methyl-3-trifiuoromethyl-1H-pyrazole-4-
carboxamide,
N-(3',4',5'-trifluorobiphenyl-2-yl)-1-methyl-3-difluoromethyl-1H-pyrazole-4-
carboxamide,
N-(2',4',5'-trifluorobiphenyl-2-yl)-1-methy!-3-difluoromethyl-1H-pyrazole-4-
carboxamide,
N-(3',4',5'-trifluorobiphenyl-2-yl)-1-methyl-3-chlorodifluoromethyl-1H-pyrazole-4-
carboxamide,
N-(3',4',5'-trifiuorobiphenyl-2-yl)-1-methyl-3-chlorofluoromethyl-1H-pyrazole-4-
carboxamide,
N-(3',4',5'-trifluorobiphenyl-2-yl)-1-methyl-3-fluoromethyl-1H-pyrazole-4-
carboxamide,
N-(2',3',4,-trifluorobiphenyl-2-yl)-1-methyl-3-fluoromethyl-1H-pyrazole-4-
carboxamide and
N-(2',4',5'-trifluorobiphenyl-2-yl)-1 -methyl-3-fluoromethyl-1 H-pyrazole-4-
carboxamide.
3. A composition for controlling harmful fungi, which composition comprises a fungicidal
amount of a compound of the formula I as claimed in claim 1 or 2 and at least one inert
additive.

4. The composition as claimed in claim 3, additionally comprising a further active
compound.
5. The composition as claimed in claim 3 or 4, wherein said composition is useful for
controlling phytopathogenic harmful fungi.
6. An aniline of the formula III

wherein X has the meaning given in claim 1.


ABSTRACT

PYRAZOLECARBOXANILIDE COMPOUNDS, COMPOSITION COMPRISING THEM FOR
CONTROLLING HARMFUL FUNGI AND INTERMEDIATE IN THEIR PRODUCTION
PROCESS
The present invention relates to a pyrazolecarboxanilide of the formula I

in which X and R1 are as defined in the specification, and a composition comprising them.
The invention also relates to novel intermediates in the production process of the
claimed compounds.

Documents:

03068-kolnp-2007-abstract.pdf

03068-kolnp-2007-claims 1.0.pdf

03068-kolnp-2007-claims 1.1.pdf

03068-kolnp-2007-correspondence others.pdf

03068-kolnp-2007-description complete.pdf

03068-kolnp-2007-form 1.pdf

03068-kolnp-2007-form 3.pdf

03068-kolnp-2007-form 5.pdf

03068-kolnp-2007-international publication.pdf

03068-kolnp-2007-international search report.pdf

03068-kolnp-2007-others.pdf

03068-kolnp-2007-pct request form.pdf

03068-kolnp-2007-priority document.pdf

3068-KOLNP-2007-(29-02-2012)-ABSTRACT.pdf

3068-KOLNP-2007-(29-02-2012)-AMANDED CLAIMS.pdf

3068-KOLNP-2007-(29-02-2012)-ASSIGNMENT.pdf

3068-KOLNP-2007-(29-02-2012)-DESCRIPTION (COMPLETE).pdf

3068-KOLNP-2007-(29-02-2012)-EXAMINATION REPORT REPLY RECEIVED.pdf

3068-KOLNP-2007-(29-02-2012)-FORM-1.pdf

3068-KOLNP-2007-(29-02-2012)-FORM-2.pdf

3068-KOLNP-2007-(29-02-2012)-FORM-3.pdf

3068-KOLNP-2007-(29-02-2012)-OTHERS.pdf

3068-KOLNP-2007-(29-02-2012)-PETITION UNDER RULE 137.pdf

3068-KOLNP-2007-ASSIGNMENT.pdf

3068-KOLNP-2007-CORRESPONDENCE OTHERS 1.1.pdf

3068-KOLNP-2007-CORRESPONDENCE.pdf

3068-KOLNP-2007-EXAMINATION REPORT.pdf

3068-KOLNP-2007-FORM 3 1.2.pdf

3068-KOLNP-2007-FORM 3-1.1.pdf

3068-KOLNP-2007-FORM 5 1.2.pdf

3068-KOLNP-2007-FORM 5-1.1.pdf

3068-KOLNP-2007-GPA 1.1.pdf

3068-KOLNP-2007-GPA.pdf

3068-KOLNP-2007-GRANTED-ABSTRACT.pdf

3068-KOLNP-2007-GRANTED-CLAIMS.pdf

3068-KOLNP-2007-GRANTED-DESCRIPTION (COMPLETE).pdf

3068-KOLNP-2007-GRANTED-FORM 1.pdf

3068-KOLNP-2007-GRANTED-FORM 2.pdf

3068-KOLNP-2007-GRANTED-SPECIFICATION.pdf

3068-KOLNP-2007-INTENATIONAL PUBLICATION.pdf

3068-KOLNP-2007-INTERNATIONAL SEARCH REPORT.pdf

3068-KOLNP-2007-OTHERS.pdf

3068-KOLNP-2007-PCT REQUEST FORM.pdf

3068-KOLNP-2007-REPLY TO EXAMINATION REPORT.pdf

3068-KOLNP-2007-TRANSLATED COPY OF PRIORITY DOCUMENT.pdf

abstract-03068-kolnp-2007.jpg


Patent Number 253216
Indian Patent Application Number 3068/KOLNP/2007
PG Journal Number 27/2012
Publication Date 06-Jul-2012
Grant Date 04-Jul-2012
Date of Filing 21-Aug-2007
Name of Patentee BASF AKTIENGESELLSCHAFT
Applicant Address 67056 LUDWIGSHAFEN
Inventors:
# Inventor's Name Inventor's Address
1 RHEINHEIMER, JOACHIM MERZIGER STR. 24, 67063 LUDWIGSHAFEN
2 STRATHMANN, SIEGFRIED DONNERSBERGSTR. 9, 67117 LIMBURGERHOF
3 SCHIEWECK, FRANK LINDENWEG 4, 67258 HESSHEIM
4 SCHWOGLER, ANJA HEINRICH-LANZ-STR. 3, 68165 MANNHEIM
5 LOHMANN, JAN KLAAS LENAUSTR. 20, 68167 MANNHEIM
6 SCHAFER, PETER ROMERSTR. 1, 67308 OTTERSHEIM
7 GEWEHR, MARKUS GOETHESTR. 21, 56288 KASTELLAUN
8 GROTE, THOMAS IM HOHNHAUSEN 18, 67157 WACHENHEIM
9 BLETTNER, CARSTEN UNIT A, 4/F, NO. 23 REPULSE BAY ROAD, HONG KONG
10 GRAMMENOS, WASSILIOS ALEXANDER-FLEMING-STR. 13, 67071 LUDWIGSHAFEN
11 HUNGER, UDO UHLANDSTR. 14, 68167 MANNHEIM
12 MULLER, BERND STOCKINGER STR. 7, 67227 FRANKENTHAL
13 STIERL, REINHARD JAHNSTR.8, 67251 FREINSHEIM
14 DIETZ, JOCHEN SPELZENSTR. 2A, 68167 MANNHEIM
PCT International Classification Number C07D 231/14
PCT International Application Number PCT/EP2006/050962
PCT International Filing date 2006-02-15
PCT Conventions:
# PCT Application Number Date of Convention Priority Country
1 102005007160.0 2005-02-16 Germany