Note: Descriptions are shown in the official language in which they were submitted.
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y S ~9~,~, 1°HIS A~EN~B~D
~E~fi TRANSLATION
Substituted pyridylpyrazoles
The invention relates to novel substituted pyridylpyrazoles, to processes for
their
preparation and to their use as crop treatment agents, in particular as
herbicides, in
s secticides and acaricides.
A large number of substituted pyridylpyrazoles is already known from the
(Patent)
literature (cf. J. Med. Chem. 38 (1995), 3524-3535; DE 2623302; DE 1 9530606,
WO 93/07138; JP 08193067 - cited in Chem. Abstracts 125:247808). Some of them
are also known to be suitable for use as crop treatment agents, such as, for
example,
as fungicides, herbicides, insecticides or acaricides. However, these
compounds have
not attained any particular importance.
This invention, accordingly, provides the novel substituted pyridylpyrazoles
of the
general formula (I)
R'
I
R''
(R4)n
in which
m represents the number 0 or 1,
n represents the number 1, 2 or 3,
RI represents hydrogen, represents in each case optionally cyano-, halogen- or
C1-C4-alkoxy-substituted alkyl having 1 to 6 carbon atoms, or represents in
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each case optionally cyano- or halogen-substituted alkenyl or alkinyl having
in each case 2 to 6 carbon atoms,
R2 represents hydrogen, nitro, hydroxyl, mercapto, carboxyl, cyano, thio-
carbamoyl, halogen, represents cyano-, halogen- or C 1-C4-alkoxy-substituted
alkyl having 1 to 6 carbon atoms or represents in each case optionally cyano-,
halogen- or C1-C4-alkoxy-substituted alkoxy, alkoxycarbonyl, alkylthio,
alkylsulphinyl or alkylsulphonyl having in each case 1 to 6 carbon atoms,
R3 represents hydrogen, cyano, halogen or represents optionally cyano-,
halogen-
or C1-C4-alkoxy-substituted alkyl having 1 to 6 carbon atoms and
R4 represents nitro, cyano, carboxyl, carbamoyl, thiocarbamoyl, hydroxyl, mer-
capto, amino, hydroxyamino, halogen or represents one of the groupings -Q-
RS, -NH-R5, -NH-O-R5, -NH-S02-R5, -N(S02-RS)2, -CQ1-R5, -CQ1-Q2-
R5, -CQ1-NH-R5, -Q2-CQ1-R5, -NH-CQ1-R5, -N(S02-RS)(CQ1-RS),
-Q2-CQ1-Q2_R5~ _NH-CQ1-Q2-RS or -Q2-CQ1-NH-R5, where Q represents
O, S, SO or 502, Q1 and Q2 each represent oxygen or sulphur and
RS represents optionally cyano-, halogen-, C 1-C4-alkoxy-, C 1-C4-alkylthio-,
C 1-
C4-alkyl-carbonyl-, C1-C4-alkoxy-carbonyl- or C1-C4-alkylamino-carbonyl-
substituted alkyl having 1 to 6 carbon atoms,
RS furthermore represents in each case optionally cyano-, carboxyl-, halogen-,
C1-C4-alkyl-carbonyl-, C1-C4-alkoxy-carbonyl- or C1-C4-alkylamino-
carbonyl-substituted alkenyl or alkinyl having in each case 2 to 6 carbon at-
oms,
RS furthermore represents in each case optionally cyano-, carboxyl-, halogen-,
C 1-C4-alkyl-carbonyl- or C 1-C4-alkoxy-carbonyl-substituted cycloalkyl or
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cycloalkylalkyl having in each case 3 to 6 carbon atoms in the cycloalkyl
group and optionally 1 to 4 carbon atoms in the alkyl moiety,
RS furthermore represents in each case optionally hydroxyl-, mercapto-, amino-
,
cyano-, carboxyl-, carbamoyl-, thiocarbamoyl-, C 1-C4-alkyl-, C 1-C4-halo-
genoalkyl-, C 1-C4-alkoxy-, C 1-C4-halogenoalkoxy-, C 1-C4-alkylthio-, C 1-
C4-halogenoalkylthio-, C1-C4-alkylsulphinyl-, C1-C4-alkylsulphonyl-, C1-
C4-alkylamino- or dimethylamino-substituted aryl or arylalkyl having in each
case 6 or 10 carbon atoms in the aryl group and optionally 1 to 4 carbon at-
oms in the alkyl moiety, or
RS furthermore represents in each case optionally hydroxyl-, mercapto-, amino-
,
cyano-, carboxyl-, carbamoyl-, thiocarbamoyl-, C 1-C4-alkyl-, C 1-C4-haloge-
noalkyl-, C 1-C4-alkoxy-, C 1-C4-halogenoalkoxy-, C 1-C4-alkylthio-, C 1-C4-
halogenoalkylthio-, C 1-C4-alkylsulphinyl-, C 1-C4-alkylsulphonyl-, C 1-C4-
alkylamino- or dimethylamino-substituted heterocyclyl or heterocyclylalkyl
having 2 to 6 carbon atoms and 1 to 3 nitrogen atoms and/or 1 or 2 oxygen
atoms and/or one sulphur atom in the heterocyclyl group and optionally 1 to 4
carbon atoms in the alkyl moiety.
The novel substituted pyridylpyrazoles of the general formula (I) are obtained
when
hydrazine or its derivatives of the general formula (II)
H2N-NH-R1 (II)
in which
R1 is as defined above,
are reacted with substituted pyridyl-1,3-dicarbonyl compounds of the general
for-
mula (III)
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O R2
O~ R3 (III)
R4)n
N
I
(~)m
in which
m, n, R2 , R3 and R4 are each as defined above,
or with substituted pyridyl-carbonyl compounds of the general formula (IV)
R R
Q3 Q3
R3 (IV)
\~R4)n
~)m
in which
m, n, R3 and R4 are each as defined above,
Q3 represents oxygen or sulphur and
R represents hydrogen or alkyl,
- and/or, if appropriate, tautomers of the compounds of the formula (IV) -,
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y
-5-
if appropriate in the presence of a reaction auxiliary and if appropriate in
the presence
of a diluent,
and the resulting compounds of the formula (I) are, if desired, subjected to
further
conversions according to customary methods in the context of the above
definition of
substituents.
The compounds of the general formula (I) can be converted according to
customary
methods into other compounds of the general formula (I) according to the above
definition of substituents, for example by customary alkylation, acylation or
sulphonylation reactions (for example R1: H -~ CH3, CHF2, C2H5, CH2CH=CH2;
R4: OH ~ OCH3, OC2H5, OCHF2, OCH2CH=CH2, OCOCH3; SH -~ SCH3,
SC2H5; NH2 ~ NHC3H~, NHCOCH3, NHS02CH3), or by electrophilic or nucleo-
philic substitution reactions (for example R3: H ~ C1, Br; R4: F ~ OH, SH,
NH2) -
cf. also the Preparation Examples.
The novel substituted pyridylpyrazoles of the general formula (I) have
interesting
biological properties, which make it possible to use them as crop treatment
agents.
They have strong herbicidal, insecticidal and acaricidal activity and have in
particular
excellent and selective herbicidal action.
In the definitions, the saturated or unsaturated hydrocarbon radicals, such as
alkyl,
alkenyl or alkinyl, are in each straight-chain or branched.
Halogen generally represents fluorine, chlorine, bromine or iodine, preferably
fluo-
rine, chlorine or bromine, in particular fluorine or chlorine.
The invention preferably provides compounds of the formula (I) in which
m represents the number 0 or 1,
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n represents the numbers 1, 2 or 3,
R1 represents hydrogen, represents in each case optionally cyano-, fluorine-,
chlorine-, methoxy- or ethoxy-substituted methyl, ethyl, n- or i-propyl, n-, i-
,
s- or t-butyl, or represents in each case optionally cyano-, fluorine-,
chlorine-
or bromine-substituted propenyl, butenyl, propinyl or butinyl,
R2 represents hydrogen, nitro, hydroxyl, mercapto, carboxyl, cyano, thiocar-
bamoyl, fluorine, chlorine, bromine, represents in each case cyano-, fluorine-
,
chlorine-, methoxy- or ethoxy-substituted methyl, ethyl, n- or i-propyl, n-, i-
,
s- or t-butyl, or represents in each case optionally cyano-, fluorine-,
chlorine-,
methoxy- or ethoxy-substituted methoxy, ethoxy, n- or i-propoxy, n-, i-, s- or
t-butoxy, methoxycarbonyl, ethoxycarbonyl, methylthio, ethylthio, n- or i-
propylthio, n-, i-, s- or t-butylthio, methylsulphinyl, ethylsulphinyl, n- or
i-
propylsulphinyl, n-, i-, s- or t-butylsulphinyl, methylsulphonyl, ethyl-
sulphonyl, n- or i-propylsulphonyl, n-, i-, s- or t-butylsulphonyl,
R3 represents hydrogen, fluorine, chlorine, bromine, or represents optionally
cyano-, fluorine-, chlorine-, methoxy- or ethoxy-substituted methyl, ethyl, n-
or i-propyl, n-, i-, s- or t-butyl, and
R4 represents nitro, cyano, carboxyl, carbamoyl, thiocarbamoyl, hydroxyl, mer-
capto, amino, hydroxyamino, fluorine, chlorine, bromine, or represents one of
the groupings -Q-R5, -NH-R5, -NH-O-R5, -NH-S02-R5, -N(S02-RS)2, -
CQ 1 _R5~ _CQ 1 _Q2_RS ~ _CQ 1 _NH_R5~ _Q2_CQ 1 _RS _NH_CQ 1 _R5,
-N(S02-RS)(CQ 1-RS), -Q2-CQ 1-Q2-R5, -NH-CQ 1-Q2-RS or -Q2-CQ 1-NH-
-R5, where Q represents O, S, SO or 502, Q1 and Q2 each represent oxygen
or sulphur and
RS represents in each case optionally cyano-, fluorine-, chlorine-, methoxy-,
eth-
oxy-, methylthio-, ethylthio-, acetyl-, propionyl-, methoxycarbonyl-, ethoxy-
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carbonyl-, methylaminocarbonyl- or ethylaminocarbonyl-substituted methyl,
ethyl, n- or i-propyl, n-, i-, s- or t-butyl,
RS furthermore represents in each case optionally cyano-, carboxyl-, fluorine-
,
chlorine-, bromine-, acetyl-, propionyl-, methoxycarbonyl-, ethoxycarbonyl-,
methylaminocarbonyl- or ethylaminocarbonyl-substituted propenyl, butenyl,
propinyl or butinyl,
RS furthermore represents in each case optionally cyano-, carboxyl-, fluorine-
,
chlorine-, bromine-, acetyl-, propionyl-, methoxycarbonyl- or ethoxy-
carbonyl-substituted cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclo-
propylmethyl, cyclobutylmethyl, cyclopentylmethyl or cyclohexylmethyl,
RS furthermore represents in each case optionally hydroxyl-, mercapto-, amino-
,
cyano-, carboxyl-, carbamoyl-, thiocarbamoyl-, methyl-, ethyl-, n- or i-
propyl-, n-, i-, s- or t-butyl-, difluoromethyl-, trifluoromethyl-, methoxy-,
eth-
oxy-, n- or i-propoxy-, difluoromethoxy-, trifluoromethoxy-, methylthio-,
ethylthio-, difluoromethylthio-, trifluoromethylthio-, methylsulphinyl-, ethyl-
sulphinyl-, methylsulphonyl-, ethylsulphonyl-, methylamino-, ethylamino- or
dimethylamino-substituted phenyl, benzyl or phenylethyl, or
RS furthernlore represents in each case optionally hydroxyl-, mercapto-, amino-
,
cyano-, carboxyl-, carbamoyl-, thiocarbamoyl-, methyl-, ethyl-, n- or i-
propyl-, n-, i-, s- or t-butyl-, dichloromethyl-, trichloromethyl-, difluoro-
methyl-, trifluoromethyl-, chlorodifluoromethyl-, fluorodichloromethyl-,
methoxy-, ethoxy-, n- or i-propoxy-, difluoromethoxy-, trifluoromethoxy-,
methylthio-, ethylthio-, n- or i-propylthio-, difluoromethylthio-, trifluoro-
methylthio-, chlorodifluoromethylthio-, fluorodichloromethylthio-, methyl-
sulphinyl-, ethylsulphinyl-, methylsulphonyl-, ethylsulphonyl-, methyl-
amino-, ethylamino-, n- or i-propylamino- or dimethylamino-substituted het-
erocyclyl or heterocyclylalkyl from the group consisting of oxiranyl,
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oxetanyl, furyl, tetrahydrofuryl, dioxolanyl, thienyl, tetrahydrothienyl, pyr-
rolyl, pyrazolyl, imidazolyl, triazolyl, oxazolyl, isoxazolyl, thiazolyl,
isothi-
azolyl, oxadiazolyl, thiadiazolyl, pyridinyl, pyrimidinyl, triazinyl,
pyrazolyl-
methyl, furylmethyl, thienylmethyl, oxazolylmethyl, isoxazolylmethyl, thi-
s azolylmethyl, pyridinylmethyl, pyrimidinylmethyl.
The invention relates in particular to the compounds of the formula (I) in
which
m represents the number 0 or 1,
n represents the number 1, 2 or 3,
R1 represents in each case optionally cyano-, fluorine-, chlorine-, methoxy-
or
ethoxy-substituted methyl or ethyl,
R2 represents hydroxyl, mercapto, fluorine, chlorine, bromine, or represents
in
each case cyano-, fluorine-, chlorine-, methoxy- or ethoxy-substituted methyl,
ethyl, methoxy, ethoxy, methylthio, ethylthio, methylsulphinyl, ethyl-
sulphinyl, methylsulphonyl or ethylsulphonyl,
R3 represents fluorine, chlorine, bromine or optionally cyano-, fluorine-,
chlorine-, methoxy- or ethoxy-substituted methyl or ethyl, and
R4 represents nitro, cyano, carboxyl, carbamoyl, thiocarbamoyl, hydroxyl, mer-
capto, amino, hydroxyamino, halogen or represents one of the groupings -Q-
R5, -NH-R5, -NH-O-R5, -NH-S02-R5, -N(S02-RS)2, -CQI-R5,
-CQ1-Q2-R5, -CQ1-NH-R5, -Q2-CQ1-R5, -NH-CQ1-R5, -N(S02-RS)_
(CQ1-RS), -Q2-CQ1-Q2-R5, -NH-CQ1-Q2-RS or -Q2-CQ1-NH-R5, where Q
represents O, S, SO or 502, Q1 and Q2 each represent oxygen or sulphur and
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RS represents in each case optionally cyano-, fluorine-, chlorine-, methoxy-,
eth-
oxy-, methylthio-, ethylthio-, acetyl-, propionyl-, methoxycarbonyl-, ethoxy-
carbonyl-, methylaminocarbonyl- or ethylaminocarbonyl-substituted methyl,
ethyl, n- or i-propyl, n-, i-, s- or t-butyl,
RS furthermore represents in each case optionally cyano-, carboxyl-, fluorine-
,
chlorine-, bromine-, acetyl-, propionyl-, methoxycarbonyl-, ethoxycarbonyl-,
methylaminocarbonyl- or ethylaminocarbonyl-substituted propenyl, butenyl,
propinyl or butinyl,
RS furthermore represents in each case optionally cyano-, carboxyl-, fluorine-
,
chlorine-, bromine-, acetyl-, propionyl-, methoxycarbonyl- or ethoxy-
carbonyl-substituted cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclo-
propylmethyl, cyclobutylmethyl, cyclopentylmethyl or cyclohexylmethyl,
RS furthermore represents in each case optionally hydroxyl-, mercapto-, amino-
,
cyano-, carboxyl-, carbamoyl-, thiocarbamoyl-, methyl-, ethyl-, n- or i-
propyl-, n-, i-, s- or t-butyl-, difluoromethyl-, trifluoromethyl-, methoxy-,
eth-
oxy-, n- or i-propoxy-, difluoromethoxy-, trifluoromethoxy-, methylthio-,
ethylthio-, difluoromethylthio-, trifluoromethylthio-, methylsulphinyl-, ethyl-
sulphinyl-, methylsulphonyl-, ethylsulphonyl-, methylamino-, ethylamino- or
dimethylamino-substituted phenyl, benzyl or phenylethyl, or
RS furthermore represents in each case optionally hydroxyl-, mercapto-, amino-
,
cyano-, carboxyl-, carbamoyl-, thiocarbamoyl-, methyl-, ethyl-, n- or i-
propyl-, n-, i-, s- or t-butyl-, dichloromethyl-, trichloromethyl-, difluo-
romethyl-, trifluoromethyl-, chlorodifluoromethyl-, fluorodichloromethyl-,
methoxy-, ethoxy-, n- or i-propoxy-, difluoromethoxy-, trifluoromethoxy-,
methylthio-, ethylthio-, n- or i-propylthio-, difluoromethylthio-, trifluo-
romethylthio-, chlorodifluoromethylthio-, fluorodichloromethylthio-, methyl-
sulphinyl-, ethylsulphinyl-, methylsulphonyl-, ethylsulphonyl-, methyl-
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amino-, ethylamino-, n- or i-propylamino- or dimethylamino-substituted het-
erocyclyl or heterocyclylalkyl from the group consisting of oxiranyl,
oxetanyl, furyl, tetrahydrofuryl, dioxolanyl, thienyl, tetrahydrothienyl, pyr-
rolyl, pyrazolyl, imidazolyl, triazolyl, oxazolyl, isoxazolyl, thiazolyl,
isothi-
azolyl, oxadiazolyl, thiadiazolyl, pyridinyl, pyrimidinyl, triazinyl,
pyrazolyl-
methyl, furylmethyl, thienylmethyl, oxazolylmethyl, isoxazolylmethyl, thi-
azolylmethyl, pyridinylmethyl, pyrimidinylmethyl.
A particularly preferred group of compounds of the general formula (I) are com-
pounds of the formula (Ia),
R'
R2 NON
R3 N
Ra)
n
in which
(la)
n, R1, R2, R3 and R4 each have the meanings given above as being particularly
pre-
ferred.
A further particularly preferred group of compounds of the general formula (I)
are
compounds of the formula (Ib),
R'
I
RZ N~
N
R3
Ni R4y
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in which
n, R1, R2, R3 and R4 each have the meanings given above as being particularly
pre-
y ferred.
A further particularly preferred group of compounds of the general formula (I)
are
compounds of the formula (Ic),
R'
R'
(Ic)
R
in which
n, R1, R2, R3 and R4 each have the meanings given above as being particularly
pre-
ferred.
The general or preferred radical definitions given above apply both to the end
prod-
ucts of the formula (I) and, correspondingly, to the starting materials or
intermediates
required in each case for the preparation. These radical definitions can be
combined
with each other as desired, i.e. including combinations between the given
preferred
ranges.
Using, for example, methylhydrazine and 2-chloro-1-(4-cyano-3-methoxy-pyridin-
2-
yl)-4,4-difluoro-butane-1,3-dione as starting materials, the course of the
reaction in
the process according to the invention can be illustrated by the following
formula
scheme:
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H3C CHFz
N
CH3 N
Nhi + -~ ~ CI
NHz
N
~OCH3
CN
The formula (II) provides a general definition of the hydrazine derivatives to
be used
as starting materials in the process according to the invention for preparing
com-
pounds of the formula (I). In the formula (II), R1 preferably or in particular
has that
meaning which has already been mentioned above in connection with the
description
of the compounds of the formula (I) according to the invention as being
preferred or
as being particularly preferred for R1.
The starting materials of the general formula (II) are known chemical for
synthesis.
The formula (III) provides a general definition of the substituted pyridyl-1,3-
di-
carbonyl compounds further to be used as starting materials in the process
according
to the invention. In the formula (III), n, R2, R3 and R4 each preferably or in
particu-
lar have those meanings which have already been mentioned above in connection
with the description of the compounds of the formula (I) according to the
invention
as being preferred or as being particularly preferred for n, R2, R3 and R4.
The formula (IV) provides a general definition of the substituted pyridyl-
carbonyl
compounds further to be used as starting materials in the process according to
the
invention. In the formula (IV), n, R3 and R4 each preferably or in particular
have
those meanings which have already been mentioned above in connection with the
description of the compounds of the formula (I) according to the invention as
being
preferred or as being particularly preferred for n, R3 and R4; Q3 preferably
repre-
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sents oxygen or sulphur and R preferably represents hydrogen or C1-C4-alkyl,
in
particular hydrogen, methyl or ethyl.
The starting materials of the-formulae (III) and (IV) are known and/or can be
pre-
y pared by known processes (cf. J. Chem. Soc. C 1969, 2738-2747; loc. cit. C
1970,
796-800; J. Chem. Soc., Perkin Trans. I 1988, 2785-2789; J. Heterocycl. Chem.
30
(1993), 855-859; J. Med. Chem. 33 (1990), 1859-1865; J. Org. Chem. 47 (1982),
3027-3038; loc. cit. 49 (1984), 3733-3742; Pharmazie 23 (1968), 557-560;
Synthesis
1993, 290-292; DE 2458808; DE 4031798; DE 4425650; EP 206294; EP 306251;
US 4026900; US 4980357; Preparation Examples).
Suitable diluents for carrying out the process according to the invention for
preparing
the novel compounds of the formula (I) are especially organic solvents. These
in-
clude, in particular, aliphatic, alicyclic or aromatic, optionally halogenated
hydrocar-
bons, such as, for example, benzine, benzene, toluene, xylene, chlorobenzene,
dichlo-
robenzene, petroleum ether, hexane, cyclohexane, dichloromethane, chloroform,
car-
bon tetrachloride; ethers, such as diethyl ether, diisopropyl ether, dioxane,
tetra-
hydrofuran or ethylene glycol dimethyl ether or ethylene glycol diethyl ether;
ke-
tones, such as acetone, butanone or methyl isobutyl ketone; carboxylic acids,
such as,
for example, acetic acid or propionic acid, nitriles, such as acetonitrile,
propionitrile
or butyronitrile; amides, such as N,N-dimethylformamide, N,N-
dimethylacetamide,
N-methyl-formanilide, N-methyl-pyrrolidone or hexamethylphosphoric triamide;
esters, such as methyl acetate or ethyl acetate, sulphoxides, such as dimethyl
sulphoxide, alcohols, such as methanol, ethanol, n- or i-propanol, ethylene
glycol
monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol
monomethyl
ether or diethylene glycol monoethyl ether.
Suitable reaction auxiliaries for the process according to the invention are
in general
the customary inorganic or organic bases or acid acceptors. These preferably
include
alkali metal or alkaline earth metal acetates, amides, carbonates,
bicarbonates,
hydrides, hydroxides or alkoxides, such as, for example, sodium acetate,
potassium
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acetate or calcium acetate, lithium amide, sodium amide, potassium amide or
calcium
amide, sodium carbonate, potassium carbonate or calcium carbonate, sodium bi-
carbonate, potassium bicarbonate or calcium bicarbonate, lithium hydride,
sodium
hydride, potassium hydride or calcium hydride, lithium hydroxide, sodium
hydrox-
ide, potassium hydroxide or calcium hydroxide, sodium methoxide, ethoxide n-
or i-
propoxide, n-, i-, s- or t-butoxide or potassium methoxide, ethoxide, n- or i-
propox-
ide, n-, i-, s- or t-butoxide; furthermore also basic organic nitrogen
compounds, such
as, for example, trimethylamine, triethylamine, tripropylamine, tributylamine,
ethyl-
diisopropylamine, N,N-dimethyl-cyclohexylamine, dicyclohexylamine, ethyl-di-
cyclohexylamine, N,N-dimethyl-aniline, N,N-dimethyl-benzylamine, pyridine, 2-
methyl-, 3-methyl-, 4-methyl-, 2,4-dimethyl-, 2,6-dimethyl-, 3,4-dimethyl- and
3,5-
dimethyl-pyridine, 5-ethyl-2-methyl-pyridine, 4-dimethylamino-pyridine, N-
methyl-
piperidine, 1,4-diazabicyclo[2.2.2]-octane (DABCO), 1,5-diazabicyclo[4.3.0]-
non-5-
ene (DBN), or 1,8-diazabicyclo[5.4.0]-undec-7-ene (DBU).
When carrying out the process according to the invention, the reaction
temperatures
can be varied within a relatively wide range. In general, the process is
carried out at
temperatures between 0°C and 150°C, preferably between
20°C and 120°C.
The process according to the invention is generally carried out under
atmospheric
pressure. However, it is also possible to carry out the process according to
the inven-
tion under elevated or reduced pressure - in general between 0.1 bar and 10
bar.
To carry out the process according to the invention, the starting materials
are gener-
ally employed in approximately equimolar amounts. However, it is also possible
to
use one of the components in a relatively large excess. The reaction is
generally car-
ried out in a suitable diluent in the presence of a reaction auxiliary, and
the reaction
mixture is generally stirred for several hours at the temperature required.
Work-up is
carried out according to customary methods (cf. the Preparation Examples).
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The active compounds according to the invention can be used as defoliants,
desic
cants, haulm-killers and, especially, as weed-killers. By weeds, in the
broadest sense,
are to be understood all plants which grow in locations where they are
undesired.
Whether the substances according to the invention act as total or selective
herbicides
depends essentially on the amount used.
The active compounds according to the invention can be used, for example, in
con-
nection with the following plants:
Dicotyledonous weeds of the genera: Sinapis, Lepidium, Galium, Stellaria,
Matri
caria, Anthemis, Galinsoga, Chenopodium, Urtica, Senecio, Amaranthus,
Portulaca,
Xanthium, Convolvulus, Ipomoea, Polygonum, Sesbania, Ambrosia, Cirsium,
Carduus, Sonchus, Solanum, Rorippa, Rotala, Lindernia, Lamium, Veronica, Abuti
lon, Emex, Datura, Viola, Galeopsis, Papaver, Centaurea, Trifolium, Ranunculus
and
Taraxacum.
Dicotyledonous crops of the genera: Gossypium, Glycine, Beta, Daucus,
Phaseolus,
Pisum, Solanum, Linum, Ipomoea, Vicia, Nicotiana, Lycopersicon, Arachis, Bras-
sica, Lactuca, Cucumis and Cucurbita.
Monocotyledonous weeds of the genera: Echinochloa, Setaria, Panicum,
Digitaria,
Phleum, Poa, Festuca, Eleusine, Brachiaria, Lolium, Bromus, Avena, Cyperus,
Sor
ghum, Agropyron, Cynodon, Monochoria, Fimbristylis, Sagittaria, Eleocharis,
Scir
pus, Paspalum, Ischaemum, Sphenoclea, Dactyloctenium, Agrostis, Alopecurus and
Apera.
Monocotyledonous crops of the genera: Oryza, Zea, Triticum, Hordeum, Avena, Se-
cale, Sorghum, Panicum, Saccharum, Ananas, Asparagus and Allium.
However, the use of the active compounds according to the invention is in no
way
restricted to these genera, but also extends in the same manner to other
plants.
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The compounds are suitable, depending on the concentration, for the total
control of
weeds, for example on industrial terrain and rail tracks, and on paths and
squares
with or without tree plantings. Equally, the compounds can be employed for
control-
s ling weeds in perennial cultures, for example forests, decorative tree
plantings, or-
chards, vineyards, citrus groves, nut orchards, banana plantations, coffee
plantations,
tea plantations, rubber plantations, oil palm plantations, cocoa plantations,
soft fruit
plantings and hopfields, on lawns, turf and pasture-land, and for the
selective control
of weeds in annual crops.
The compounds of the formula (I) according to the invention are particularly
suitable
for the selective control of monocotyledonous and dicotyledonous weeds in mono-
cotyledonous and dicotyledenous crops by both the pre- and the post-emergence
method.
The active compounds are suitable for controlling animal pests, preferably
arthropods
and nematodes, in particular insects and arachnids, which are encountered in
agri-
culture, in forestry, in the protection of stored products and of materials,
and in the
hygiene sector. They are active against normally sensitive and resistant
species and
against all or some stages of development. The abovementioned pests include:
From the order of the Isopoda, for example, Oniscus asellus, Armadillidium
vulgare
and Porcellio scaber.
From the order of the Diplopoda, for example, Blaniulus guttulatus.
From the order of the Chilopoda, for example, Geophilus carpophagus and
Scutigera
spec.
From the order of the Symphyla, for example, Scutigerella immaculate.
From the order of the Thysanura, for example, Lepisma saccharine.
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From the order of the Collembola, for example, Onychiurus armatus.
From the order of the Orthoptera, for example, Blatta orientalis, Periplaneta
ameri-
cana, Leucophaea maderae, Blatella germanica, Acheta domesticus, Gryllotalpa
spp.,
Locusts migratoria migratorioides, Melanoplus differentialis and Schistocerca
gre-
garia.
From the order of the Dermaptera, for example, Forficula auricularia.
From the order of the Isoptera, for example, Reticulitermes spp.
From the order of the Anoplura, for example, Pediculus humanus corporis,
Haematopinus spp. and Linognathus spp.
From the order of the Mallophaga, for example, Trichodectes spp. and Damalinea
spp.
From the order of the Thysanoptera, for example, Hercinothrips femoralis and
Thrips
tabaci.
From the order of the Heteroptera, for example, Eurygaster spp., Dysdercus
interme-
thus, Piesma quadrata, Cimex lectularius, Rhodnius prolixus and Triatoma spp.
From the order of the Homoptera, for example, Aleurodes brassicae, Bemisia
tabaci,
Trialeurodes vaporariorum, Aphis gossypii, Brevicoryne brassicae, Cryptomyzus
ribis, Aphis fabae, Aphis pomi, Eriosoma lanigerum, Hyalopterus arundinis,
Macro-
siphum avenae, Myzus spp., Pemphigus spp., Phorodon humuli, Phylloxera
vastatrix,
Rhopalosiphum path, Empoasca spp., Euscelis bilobatus, Nephotettix cincticeps,
Lecanium corni, Saissetia oleae, Laodelphax striatellus, Nilaparvata lugens,
Aonidi-
ella aurantii, Aspidiotus hederae, Pseudococcus spp. and Psylla spp.
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From the order of the Lepidoptera, for example, Pectinophora gossypiella,
Bupalus
piniarius, Cheimatobia brumata, Lithocolletis blancardella, Hyponomeuta
padella,
Plutella maculipennis, Malacosoma neustria, Euproctis chrysorrhoea, Lymantria
spp.,
Bucculatrix thurberiella, Phyllocnistis citrella, Agrotis spp., Euxoa spp.,
Feltia spp.,
Earias insulana, Heliothis spp., Spodoptera exigua, Mamestra brassicae,
Panolis
flammea, Prodenia litura, Spodoptera spp., Trichoplusia ni, Carpocapsa
pomonella,
Pieris spp., Chilo spp., Pyrausta nubilalis, Ephestia kuehniella, Galleria
mellonella,
Tineola bisselliella, Tinea pellionella, Hofmannophila pseudospretella,
Cacoecia
podana, Capua reticulana, Choristoneura fumiferana, Clysia ambiguella, Homona
magnanima and Tortrix viridana.
From the order of the Coleoptera, for example, Anobium punctatum, Rhizopertha
dominica, Acanthoscelides obtectus, Bruchidius obtectus, Hylotrupes bajulus,
Agelastica alni, Leptinotarsa decemlineata, Phaedon cochleariae, Diabrotica
spp.,
Psylliodes chrysocephala, Epilachna varivestis, Atomaria spp., Oryzaephilus
surina-
mensis, Anthonomus spp., Sitophilus spp., Otiorrhynchus sulcatus, Cosmopolites
sordidus, Ceuthorrhynchus assimilis, Hypera postica, Dermestes spp.,
Trogoderma
spp., Anthrenus spp., Attagenus spp., Lyctus spp., Meligethes aeneus, Ptinus
spp.,
Niptus hololeucus, Gibbium psylloides, Tribolium spp., Tenebrio molitor,
Agriotes
spp., Conoderus spp., Melolontha melolontha, Amphimallon solstitialis and
Costely-
tra zealandica.
From the order of the Hymenoptera, for example, Diprion spp., Hoplocampa spp.,
Lasius spp., Monomorium pharaonis and Vespa spp.
From the order of the Diptera, for example, Aedes spp., Anopheles spp., Culex
spp.,
Drosophila melanogaster, Musca spp., Fannia spp., Calliphora erythrocephala,
Lucilia spp., Chrysomyia spp., Cuterebra spp., Gastrophilus spp., Hyppobosca
spp.,
Stomoxys spp., Oestrus spp., Hypoderma spp., Tabanus spp., Tannia spp., Bibio
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hortulanus, Oscinella frit, Phorbia spp., Pegomyia hyoscyami, Ceratitis
capitata,
Dacus oleae and Tipula paludosa.
From the order of the Siphonaptera, for example, Xenopsylla cheopis and Cerato-
phyllus spp.
From the order of the Arachnida, for example, Scorpio maurus and Latrodectus
mactans.
From the order of the Acarina, for example, Acarus situ, Argas spp.,
Ornithodoros
spp., Dermanyssus gallinae, Eriophyes ribis, Phyllocoptruta oleivora,
Boophilus spp.,
Rhipicephalus spp., Amblyomma spp., Hyalomma spp., Ixodes spp., Psoroptes
spp.,
Chorioptes spp., Sarcoptes spp., Tarsonemus spp., Bryobia praetiosa,
Panonychus
spp. and Tetranychus spp.
The phytoparasitic nematodes include, for example, Pratylenchus spp.,
Radopholus
spp., Ditylenchus spp., Tylenchulus spp., Heterodera spp., Globodera spp.,
Meloido-
gyne spp., Aphelenchoides spp., Longidorus spp., Xiphinema spp., Trichodorus
spp.,
Tylenchus spp., Helicotylenchus spp., Rotylenchus spp. and Tylenchulus spp..
The active compounds can be converted into the customary formulations, such as
solu-
tions, emulsions, wettable powders, suspensions, powders, dusting agents,
pastes, solu-
ble powders, granules, suspo-emulsion concentrates, natural and synthetic
materials
impregnated with active compound, and very fine capsules in polymeric
substances.
These formulations are produced in a known manner, for example by mixing the
active
compounds with extenders, that is liquid solvents and/or solid carriers,
optionally with
the use of surface-active agents, that is emulsifying agents and/or dispersing
agents
and/or foam-forming agents.
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If the extender used is water, it is also possible to employ for example
organic solvents
as auxiliary solvents. Suitable liquid solvents are in the main: aromatics,
such as xy-
lene, toluene or alkylnaphthalenes, chlorinated aromatics and chlorinated
aliphatic hy-
drocarbons, such as chlorobenzenes, chloroethylenes or methylene chloride,
aliphatic
hydrocarbons, such as cyclohexane or paraffins, for example petroleum
fractions, min-
eral and vegetable oils, alcohols, such as butanol or glycol and also their
ethers and
esters, ketones, such as acetone, methyl ethyl ketone, methyl isobutyl ketone
or cyclo-
hexanone, strongly polar solvents, such as dimethylformamide and dimethyl
sulph-
oxide, and also water.
Suitable solid carriers are: for example ammonium salts and ground natural
minerals,
such as kaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite or
diatomaceous
earth, and ground synthetic minerals, such as finely divided silica, alumina
and sili-
cates, suitable solid carriers for granules are: for example crushed and
fractionated
natural rocks such as calcite, marble, pumice, sepiolite and dolomite, and
also synthetic
granules of inorganic and organic meals, and granules of organic material such
as saw-
dust, coconut shells, maize cobs and tobacco stalks; suitable emulsifiers
and/or foam-
forming agents are: for example non-ionic and anionic emulsifiers, such as
polyoxyeth-
ylene fatty acid esters, polyoxyethylene fatty alcohol ethers, for example
alkylaryl
polyglycol ethers, alkylsulphonates, alkyl sulphates, arylsulphonates and also
protein
hydrolysates; suitable dispersants are: for example lignin-sulphite waste
liquors and
methylcellulose.
Tackifiers such as carboxymethylcellulose and natural and synthetic polymers
in the
form of powders, granules or latices, such as gum arabic, polyvinyl alcohol
and polyvi-
nyl acetate, and also natural phospholipids, such as cephalins and lecithins,
and syn-
thetic phospholipids, can be used in the formulations. Further additives can
be mineral
and vegetable oils.
It is possible to use colorants such as inorganic pigments, for example iron
oxide, tita-
nium oxide and Prussian Blue, and organic dyes, such as alizarin dyes, azo
dyes and
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metal phthalocyanine dyes, and trace nutrients such as salts of iron,
manganese, boron,
copper, cobalt, molybdenum and zinc.
The formulations in general comprise between 0.1 and 95 per cent by weight of
active
compound, preferably between 0.5 and 90%.
For controlling weeds, the active compounds according to the invention, as
such or in
the form of their formulations, can also be used as mixtures with known
herbicides,
ready-to-use formulations or tank mixes being possible.
Possible components for the mixtures are known herbicides, for example
acetochlor, acifluorfen(-sodium), aclonifen, alachlor, alloxydim(-sodium),
ametryne,
amidochlor, amidosulphuron, asulam, atrazine, azimsulphuron, benazolin, ben-
furesate, bensulphuron(-methyl), bentazon, benzofenap, benzoylprop(-ethyl),
biala-
phos, bifenox, bromobutide, bromofenoxim, bromoxynil, butachlor, butylate,
cafen-
strole, carbetamide, chlomethoxyfen, chloroamben, chloroidazon, chloro-
imuron(-ethyl), chloronitrofen, chlorosulphuron, chlorotoluron, cinmethylin,
cino-
sulphuron, clethodim, clodinafop(-propargyl), clomazone, clopyralid,
clopyrasul-
phuron, cloransulam(-methyl), cumyluron, cyanazine, cycloate,
cyclosulphamuron,
cycloxydim, cyhalofop(-butyl), 2,4-D, 2,4-DB, 2,4-DP, desmedipham, diallate,
di-
camba, diclofop(-methyl), difenzoquat, diflufenican, dimefuron, dimepiperate,
di-
methachlor, dimethametryn, dimethenamid, dinitramine, diphenamid, diquat,
dithio-
pyr, diuron, dymron, EPTC, esprocarb, ethalfluralin, ethametsulphuron(-
methyl),
ethofumesate, ethoxyfen, etobenzanid, fenoxaprop-ethyl, flamprop(-isopropyl),
flam-
prop(-isopropyl-L), flamprop(-methyl), flazasulphuron, fluazifop(-butyl),
flumet-
sulam, flumiclorac(-pentyl), flumioxazin, flumipropyn, fluometuron, fluoro-
chloridone, fluoroglycofen(-ethyl), flupoxam, flupropacil, flurenol,
fluridone, flur-
oxypyr, flurprimidol, flurtamone, fomesafen, glufosinate(-ammonium),
glyphosate(-
isopropylammonium), halosafen, haloxyfop(-ethoxyethyl), hexazinone, imazametha-
benz(-methyl), imazamethapyr, imazamox, imazapyr, imazaquin, imazethapyr,
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imazosulphuron, ioxynil, isopropalin, isoproturon, isoxaben, isoxaflutole,
isoxapyri-
fop, lactofen, lenacil, linuron, MCPA, MCPP, mefenacet, metamitron,
metazachlor,
methabenzthiazuron, metobenzuron, metobromuron, metolachlor, metosulam, metox-
uron, metsulphuron(-methyl), metribuzin, molinate, monolinuron, naproanilide,
napropamide, neburon, nicosulphuron, norflurazon orbencarb, oryzalin,
oxadiazon,
oxyfluorfen, paraquat, pendimethalin, phenmedipham, piperophos, pretilachlor,
primisulphuron(-methyl), prometryn, propachlor, propanil, propaquizafop,
propyz-
amide, prosulphocarb, prosulphuron, pyrazolate, pyrazosulphuron(-ethyl),
pyrazoxy-
fen, pyributicarb, pyridate, pyrithiobac(-sodium), quinchlorac, quinmerac,
quizalo-
fop(-ethyl), quizalofop(-p-tefuryl), rimsulphuron, sethoxydim, simazine,
simetryn,
sulcotrione, sulphentrazone, sulphometuron(-methyl), sulphosate, tebutam,
tebuthi-
uron, terbuthylazine, terbutryn, thenylchlor, thiafluamide, thiazopyr,
thidiazimin,
thifensulphuron(-methyl), thiobencarb, tiocarbazil, tralkoxydim, triallate,
triasul-
phuron, tribenuron(-methyl), triclopyr, tridiphane, trifluralin and
triflusulphuron.
Mixtures with other known active compounds, such as fungicides, insecticides,
acaricides, nematicides, bird repellents, plant nutrients and agents which
improve soil
structure, are also possible.
The active compounds can be used as such, in the form of their formulations or
in the
use forms prepared therefrom by further dilution, such as ready-to-use
solutions, sus-
pensions, emulsions, powders, pastes and granules. They are used in a
customary man-
ner, for example by watering, spraying, atomizing or scattering.
The active compounds according to the invention can be applied either before
or after
emergence of the plants. They can also be incorporated into the soil before
sowing.
The amount of active compound used can vary within a substantial range. It
depends
essentially on the nature of the desired effect. In general, the amounts used
are between
1 g and 10 kg of active compound per hectare of soil surface, preferably
between 5 g
and 5 kg per ha.
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The preparation and use of the active compounds according to the invention can
be
seen from the examples below.
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Preparation Examples:
Example 1
HO
CI
20.2 g (89 mmol) of ethyl 3-(6-chloro-pyridin-3-yl)-3-oxo-propionate are
initially
charged in 40 ml of acetic acid and, at an internal temperature of
approximately
40°C, admixed dropwise with 5.8 g (126 mmol) of methylhydrazine. The
mixture is
subsequently heated at from 90°C to 100°C for approximately 90
minutes, and a
brown solid precipitates out. The cold mixture is poured into 300 ml of water
and the
precipitated solid is filtered off, washed with water and dried at 50°C
under a reduced
pressure.
This gives 13.6 g (73% of theory) of 5-(6-chloro-pyridin-3-yl)-2-methyl-2H-
pyrazol-
3-0l of melting point 220°C.
Example 2
H
i
FsC N.N
N
CI
8.0 g (160 mmol) of hydrazine hydrate and 16.3 g (160 mmol) of acetic
anhydride
are added successively to a solution of 33.5 g (133 mmol) of 1-(6-chloro-
pyridin-3-
yl)-4,4,4-trifluorobutane-1,3-dione in 160 ml of acetic acid. The reaction
mixture is
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heated at from 90°C to 100°C for one hour and the cold mixture
is poured into
800 ml of ice-water. The precipitated solid is filtered off, washed with water
and
dried at SO°C under a reduced pressure.
S This gives 29.8 g (90% of theory) of 2-chloro-S-(S-trifluoromethyl-1H-
pyrazol-3-yl)-
pyridine of melting point 183°C.
Example 3
CH3
i
F2CH0 N' N
N
CI
A mixture of 12,6 g (60 mmol) of S-(6-chloro-pyridin-3-yl)-2-methyl-2H-pyrazol-
3-
ol and 100 ml of N,N-dimethyl-formamide is admixed with 16.5 g of potassium
carbonate and heated at SO°C for approximately 60 minutes. At a
temperature be-
tween 60°C and 70°C, approximately 30 g (0.35 mol) of
chlorodifluoromethane are
1 S then introduced over a period of one hour. The reaction mixture is cooled
to room
temperature, poured into 1.3 litres of water and acidified using 2N
hydrochloric acid.
The precipitated solid is filtered off with suction, dissolve in
dichloromethane,
washed successively with saturated aqueous sodium bicarbonate solution and
satu-
rated aqueous sodium chloride solution, dried with magnesium sulphate and
filtered.
The filtrate is concentrated under water pump vacuum and the residue is
separated by
column chromatography using toluene/ethyl acetate (Vol.: l:l).
In the main fraction, 6.S g (42% of theory) of 2-chloro-S-(S-difluoro-methoxy-
1-
methyl-1H-pyrazol-3-yl)-pyridine of melting point 102°C are obtained.
2S
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Example 4
CH3
i
F2CH0 N' N
CI
N
CI
At room temperature (approximately 20°C), 2.2 g (1.63 mmol) of
sulphuryl chloride
are added with stirring to a solution of 3.6 g (13.9 mmol) of 2-chloro-5-(5-
difluo-
romethoxy-1-methyl-1H-pyrazol-3-yl)-pyridine in 15 ml of dichloromethane. The
mixture is stirred at approximately 20°C for three hours, diluted with
20 ml of di-
chloromethane, washed with saturated aqueous sodium bicarbonate solution and
with
saturated aqueous sodium chloride solution, dried with magnesium sulphate and
fil-
tered. The solvent is carefully distilled off from the filtrate under water
pump vac-
uum.
This gives 4.05 g (99% of theory) of 2-chloro-5-(4-chloro-5-difluoromethoxy-1-
methyl-1H-pyrazol-3-yl)-pyridine of melting point 42°C.
Using, instead of sulphuryl chloride, a corresponding solution of bromine in
dichlo-
romethane, 2-chloro-5-(4-bromo-5-difluoromethoxy-1-methyl-1H-pyrazol-3-yl)-
pyridine ("Example 11") of melting point 60°C is obtained in a similar
yield.
Example 5
CH3
i
FsC N . N
N
CI
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At approximately 20°C, 18.3 g (129 mmol) if iodomethane are added over
a period
of approximately two minutes to a solution of 10.1 g (40 mmol) of 2-chloro-5-
(5-tri-
fluoromethyl-1H-pyrazol-3-yl)-pyridine and 8.4 g (60 mmol) of potassium
carbonate
in 150 ml of acetonitrile. The reaction mixture is stirred at 40°C for
3 hours and, after
cooling, concentrated under water pump vacuum. The residue is taken up in 100
ml
of dichloromethane and 200 ml of water, and the organic phase is separated
off,
washed with water, dried with magnesium sulphate and filtered. The filtrate is
con-
centrated under water pump vacuum and the residue is separated by column chro-
matography using n-hexane/ethyl acetate (Vol.: 2:1).
This gives 6.6 g (50,5% of theory) of 2-chloro-5-(1-methyl-5-trifluoromethyl-
1H-
pyrazol-3-yl)-pyridine of melting point 95°C.
Example 6
CH3
i
FsC N . N
CI
N
CI
At from 75°C to 85°C, 10 g (141 mmol) of chlorine gas are
introduced with stirring
over a period of 2 hours in a solution of 2.0 g (7.6 mmol) of 2-chloro-5-(1-
methyl-5-
trifluoromethyl-1H-pyrazol-3-yl)-pyridine in 40 ml of acetic acid. The
reaction mix-
ture is cooled, poured into 100 ml of ice-water and extracted with ethyl
acetate. The
organic phase is separated off and washed successively with saturated aqueous
so-
dium bicarbonate solution and saturated aqueous sodium chloride solution,
dried
with magnesium sulphate and filtered. The filtrate is concentrated under water
pump
vacuum.
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This gives 2.05 g (91% of theory) of 2-chloro-5-(4-chloro-1-methyl-5-trifluoro-
methyl-1H-pyrazol-3-yl)-pyridine of melting point SS°C.
Example 7
H3C-S~ CH3
N
/N
/N
CI
At approximately 20°C, 10.3 g (224 mmol) of methylhydrazine are added
to a solu-
tion of 23.0 g (88.6 mmol) of 1-(6-chloro-pyridin-3-yl)-3,3-bis-methylthio-2-
propen-
1-one in 145 ml of acetonitrile. The reaction mixture is heated under reflux
for 120
minutes and then poured into ice-water. The precipitated solid is filtered off
with
suction, washed with water and dried under reduced pressure.
This gives 17.9 g (84% of theory) of 3-(6-chloro-pyridin-3-yl)-1-methyl-5-
methyl-
thin-1H-pyrazole of melting point 93°C.
Example 8
H3C-S~ CH3
N
CI ~ N
/N
I
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At 0°C, a drop of acetic acid and 1.8 g (9 mmol) of 1,3-dichloro-5,5-
dimethyl-hy-
dantoin are added successively to a solution of 3.8 g (16 mmol) of 3-(6-chloro-
pyr-
idin-3-yl)-1-methyl-5-methylthio-1H-pyrazole in 30 ml of diethyl ether. The
reaction
mixture is stirred at room temperature (approximately 20°C) for 18
hours and ad-
mixed successively with 20 ml of water and 20 ml of ethyl acetate. The organic
phase is separated off, washed successively with saturated aqueous sodium
bicarbon-
ate solution and saturated aqueous sodium chloride solution, dried with
magnesium
sulphate and filtered. The filtrate is concentrated under water pump vacuum.
This gives 3.8 g (87% of theory) of 4-chloro-3-(6-chloro-pyridin-3-yl)-1-
methyl-5-
methylthio-1 H-pyrazole as an amorphous residue.
Example 9
H3C
At 0°C, 7.5 g (30 mmol) of 3-chloro-perbenzoic acid are added with
stirring to a so-
lution of 1.9 g (7.7 mmol) of 4-chloro-3-(6-chloro-pyridin-3-yl)-1-methyl-5-
methyl-
thio-1H-pyrazol in 30 ml of dichloromethane. The reaction mixture is stirred
at room
temperature (approximately 20°C) for 18 hours, the precipitated solid
is filtered off
and the filtrate is washed successively with saturated sodium thiosulphate
solution,
with saturated sodium bicarbonate solution and saturated sodium chloride
solution,
dried with magnesium sulphate and filtered. The filtrate is concentrated under
water
pump vacuum.
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This gives 2.0 g (81% of theory) of 4-chloro-3-(6-chloro-1-oxy-pyridin-3-yl)-1-
methyl-5-methylsulphonyl-1H-pyrazole as an amorphous residue.
By the methods of Preparation Examples 1 to 9, and in accordance with the
general
description of the preparation processes according to the invention, it is
also possible
to prepare, for example, the compounds of the formula (I) listed in Table 1
below.
R'
R2 NON
R3 \ 4
~R ~n
N
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Table 1: Examples of compounds of the formula (I)
Ex. No. R R R ~ Melting
" point (°C)
I
~~~m
CH3 S02CH3 Cl ~ 169
N CI
11 CH3 OCHF2 Br ~ 60
N CI
12 CH3 SCH3 Br ~ 95
N CI
13 CH3 S02CH3 Br
N CI
14 CH3 SOCH3 Cl
N CI
CH3 SOCH3 Br ~ 184
i
N CI
16 CH3 CN Cl
N CI
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Table 1: (Continued)
Ex. No. R1 R~ R~ . ~ Melting
" point (°C)
I
~~~m
17 CH3 CN Br
N CI
18 CH3 OCHF2 CH3
N CI
19 CH3 OCHF2 CH2F
N CI
20 CH3 CF3 CH3
N CI
21 CH3 OCHF2 CH3
N Br
22 CH3 CF3 CH3
N Br
23 CH3 SCH3 CH3
N Br
24 CH3 CN CH3
N Br
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Table 1: (Continued)
Ex. No. R1 Rz R ~ Melting
N~(R4>" point (°C)
I
~~~m
25 CH3 CN CH3
N CI
26 CH3 S02CH3 CH3
N Br
27 CH3 S02CH3 CH3 ~ 126
N CI
28 CH3 OCHF2 C1 ~ 90
N CN
29 CH3 CF3 C1
N CN
30 CH3 CF3 Br
N CN
31 CH3 OCHF2 Br ~ 120
N CN
32 CH3 SCH3 C1
N CN
33 CH3 CN C1
N CN
34 CH3 S02CH3 Cl
N CN
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Table 1: (Continued)
Ex. No. R1 R~ R-~ ~ Melting
" point (°C)
I
~~~m
35 CH3 SCH3 Br
N CN
36 CH3 CN Br
i
N CN
37 CH3 S02CH3 Br
N CN
38 CH3 OCHF2 CH3
N CN
39 CH3 OCHF2 CH2F
N CI
40 CH3 CF3 CH3
N CN
41 CH3 CN CH3
N CN
42 CH3 CF3 CH2F
N CI
43 CH3 CF3 C1
N CI
b
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Table 1: (Continued)
Ex. No. R1 Rl R ~ Melting
1" point (C)
~~~m
44 CH3 OCHF2 Cl ~ 141
N CI
45 CH3 CF3 Br
i
N
I
C
46 CH3 OCHF2 Br ~ 127
N CI
b
47 CH3 CN C1
N
CI
48 CH3 CN Br
i
N CI
b
49 CH3 S02CH3 CH3
N
I
C
50 CH3 S02CH3 Br ~ 178
N CI
b
51 CH3 S02CH3 CH3
N
Br
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Table 1: (Continued)
Ex. No. RI R R ~ Melting
" point (C)
I
~~~m
52 H CF3 Cl ~~~ 146
N CI
53 CH3 SCH3 H ~~~ 93
N CI
54 CH3 OH H ~~~ 236
N CN
55 CH3 OCHF2 H ~~~ 102
N CN
56 CH3 SCH3 CH3
N C
I
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Starting materials of the formula (III):
Example (III-1)
i2Hs
O O
O
/N
I
At from 10°C to 15°C, 50.5 g (0.5 mol) of triethylamine and 58.8
g (0.617 mol) of
anhydrous magnesium chloride are added successively to a mixture of 89.3 g
(0.525 mol) of potassium monoethyl malonate in 500 ml of acetonitrile. The
mixture
is stirred at approximately 20°C for 150 minutes, cooled to from -
10°C to -5°C and,
at this temperature, admixed successively with 88.0 g (0.50 mol) of 2-chloro-
pyridin-
5-carbonyl chloride and 5.05 g (0.05 mol) of triethylamine. The reaction
mixture is
stirred at approximately 20°C for 18 hours and then concentrated. The
residue is
stirred with 500 ml of toluene and admixed slowly with 240 ml of 33% strength
hy-
drochloric acid. The mixture is stirred at room temperature for 3 hours, the
precipi-
fated solid is filtered off and the organic phase is separated off from the
filtrate. The
organic phase is washed with dilute hydrochloric acid and with water, dried
with
magnesium sulphate and filtered. The filtrate is concentrated under water pump
vac-
uum and the residue is separated by column chromatography using dichlo-
romethane/methanol (Vol.: 9:1).
As main fraction, 82.9 g (73% of theory) of ethyl 3-(6-chloro-pyridin-3-yl)-3-
oxo-
propionate of melting point 48°C are obtained.
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Example (III-2)
FsC O
O
~N
CI
Step 1
H3C O
N
CI
A solution of 40 g (0.176 mol) of ethyl 3-(6-chloro-pyridin-3-yl)-3-oxo-
propionate in
60 ml of acetic acid is admixed successively with 40 ml of water and 7.5 ml of
conc.
sulphuric acid and then heated at approximately 80°C for 90 minutes.
The reaction
mixture is allowed to cool to room temperature and poured into 600 ml of ice-
water.
The resulting suspension is neutralized using dilute aqueous sodium hydroxide
solu-
tion and extracted with dichloromethane. The organic phase is washed with
saturated
aqueous sodium chloride solution, dried with magnesium sulphate and filtered.
The
solvent is carefully distilled off from the filtrate under water pump vacuum.
This gives 21.4 g (78% of theory) of 5-acetyl-2-chloro-pyridine of melting
point
98°C.
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Step 2
FsC O
O
N
CI
Initially, at approximately 20°C, 20.7 g (0.146 mol) of ethyl
trifluoroacetate and
then, at -5°C, 30.2 g (0.168 mol) of 30% strength methanolic sodium
methoxide so-
lution are added successively to a solution of 17.4 g (0.112 mol) of 5-acetyl-
2-chloro-
pyridine in 200 ml of diethyl ether. The reaction mixture is stirred at
0°C for two
hours and then poured into 200 ml of ice-water, and the pH is adjusted to
between 2
and 3 using 1N hydrochloric acid. The organic phase is then separated off,
washed
with saturated aqueous sodium chloride solution, dried with magnesium sulphate
and
filtered. The solvent is carefully distilled off from the filtrate under water
pump vac-
uum..
This gives 27.1 g (96% of theory) of 1-(6-chloro-pyridin-3-yl)-4,4,4-
trifluorobutane-
1,3-dione of melting point 54°C.
Example (III-3)
~S S
HsC ~ wCH3
O
N
CI
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At -40°C, a solution of 23.3 g (0.15 mol) of 5-acetyl-2-chloro-pyridin
in 50 ml of
tetrahydrofuran is added dropwise over a period of 1 S minutes to a suspension
of
33.6 g (0,3 mol) of potassium t-butoxide in 210 ml of tetrahydrofuran. The
mixture is
stirred at -40°C for 30 minutes and then admixed with 11.4 g (0.15 mol)
of carbon
disulphide. After a further 30 minutes, 42.6 g (0.3 mol) of methyl iodide are
added,
and the reaction mixture is allowed to warm to room temperature over a period
of
two hours. The reaction mixture is poured into 1.5 1 of ice-water, adjusted to
a pH
between 2 and 3 using 1N hydrochloric acid and extracted with 1.5 litres of
ethyl
acetate. The organic phase is washed with sodium chloride solution, dried over
mag-
nesium sulphate and freed from the solvent under reduced pressure. The
resulting
crude product is stirred with approximately 100 ml of diethyl ether and the
precipi-
tated solid is filtered off and dried.
This gives 24.3 g (62% of theory) of 1-(6-chloro-pyridin-3-yl)-3,3-bis-
methylthio-2-
propen-1-one as a crystalline light-yellow solid of melting point
145°C.
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Use examples:
Example A
Pre-emergence test
Solvent: 5 parts by weight of acetone
Emulsifier: 1 part by weight of alkylaryl polyglycol ether
To produce a suitable preparation of active compound, 1 part by weight of
active
compound is mixed with the stated amount of solvent, the stated amount of
emulsi-
fier is added and the concentrate is diluted with water to the desired
concentration.
Seeds of the test plants are sown in normal soil. After approximately 24
hours, the
soil is watered with the preparation of active compound. The amount of water
per
unit area is advantageously kept constant. The concentration of active
compound in
the preparation is immaterial, only the active compound application rate per
unit area
matters.
After three weeks, the degree of damage to the plants is rated in % damage in
com-
parison with the development of the untreated control.
The figures denote:
0% - no effect (like untreated control)
100% - total destruction
In this test, for example, the compounds of Preparation Examples 4, 6 and 7
exhibit,
at application rates of from 60 to 2000 g/ha, very strong activity against
weeds such
as Digitaria (100%), Sorghum (95%), Amaranthus (100%); Chenopodium (100%),
Solanum (100%), Avena fatua (80-100%), Setaria (100%), Abutilon (100%), Galium
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(90-100%), and Sinapis (80-100%), while being tolerated well by crop plants,
such
as, for example, cotton (0%).
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Example B
Pre-emergence test
Solvent: 5 parts by weight of acetone
Emulsifier: 1 part by weight of alkylaryl polyglycol ether
To produce a suitable preparation of active compound, 1 part by weight of
active
compound is mixed with the stated amount of solvent, the stated amount of
emulsi-
fier is added and the concentrate is diluted with water to the desired
concentration.
Test plants which have a height of 5 - 15 cm are sprayed with the preparation
of ac-
tive compound such that the particular desired amounts of active compound are
ap-
plied per unit area . The concentration of the spray liquor is chosen so that
the par-
ocular desired amounts of active compound are applied in 10001 of water/ha.
After three weeks, the degree of damage to the plants is rated in % damage in
com-
parison with the development of the untreated control.
The figures denote:
0% - no effect (like untreated control)
100% - total destruction
In this test, for example, the compounds of Preparation Examples 4, 6 and 7
exhibit,
at application rates from 15 to 2000 g/ha, very strong activity against weeds,
such as
Alopecurus (100%), Avena fatua (100%), Setaria (100%), Abutilon (100%), Ama-
ranthus (100%), Galium (100%), Ipomoea (100%), Polygonum (100%) and Solanum
(100%), and they are tolerated well by crop plants, such as, for example,
wheat
( 10%).
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Example C
Tetranychus test (OP resistant/dip treatment)
Solvent: 3 parts by weight of dimethylformamide
Emulsifier: 1 part by weight of alkylaryl polyglycol ether
To produce a suitable preparation of active compound, 1 part by weight of
active
compound is mixed with the stated amount of solvent and the stated amount of
emul-
sifter, and the concentrate is diluted with water to the desired
concentrations.
Bean plants (Phaseolus vulgaris) which are heavily infested by all stages of
the
greenhouse red spider mite (Tetranychus urticae) are dipped into a preparation
of
active compound of the desired concentration.
After the desired period of time, the effect in % is determined. 100% means
that all
spider mites have been killed; 0% means that none of the spider mites have
been
killed.
In this test, for example, the compound of Preparation Example 1 exhibits, at
an ac-
tive compound concentration of 0.01%, a kill of 95% after 7 days.
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Example D
Spodoptera frugiperda test/synthetic feed
Solvent: 100 parts by weight of acetone
1900 parts by weight of methanol
To produce a suitable preparation of active compound, 1 part by weight of
active
compound is mixed with the stated amount of solvent, and the concentrate is
diluted
with methanol to the desired concentrations.
A stated amount of the preparation of active compound of the desired
concentration
is pipetted onto a standardized amount of synthetic feed. After the methanol
has
evaporated, in each case one larvae (L2-L3) of the army worm (Spodoptera fru-
giperda) is placed onto the feed, in three replications.
After the desired period of time, the effect in % is determined. 100% means
that all
animals have been killed; 0% means that none of the animals have been killed.
In this test, for example, the compound of Preparation Example 2 exhibits, at
an ac-
tive compound concentration of 0.05%, a kill of 100% after 7 days.
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