CA2319053A1 - Substituted heteroarylmethyl compounds used as herbicides - Google Patents
Substituted heteroarylmethyl compounds used as herbicides Download PDFInfo
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- CA2319053A1 CA2319053A1 CA002319053A CA2319053A CA2319053A1 CA 2319053 A1 CA2319053 A1 CA 2319053A1 CA 002319053 A CA002319053 A CA 002319053A CA 2319053 A CA2319053 A CA 2319053A CA 2319053 A1 CA2319053 A1 CA 2319053A1
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- Prior art keywords
- substituted
- cyano
- halogen
- alkoxy
- chlorine
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
- C07D401/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings
- C07D401/12—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings linked by a chain containing hetero atoms as chain links
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/34—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom
- A01N43/40—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom six-membered rings
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
- A01N43/56—1,2-Diazoles; Hydrogenated 1,2-diazoles
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/64—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with three nitrogen atoms as the only ring hetero atoms
- A01N43/647—Triazoles; Hydrogenated triazoles
- A01N43/653—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
- A01N43/74—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms five-membered rings with one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,3
- A01N43/78—1,3-Thiazoles; Hydrogenated 1,3-thiazoles
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D417/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00
- C07D417/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings
- C07D417/12—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings linked by a chain containing hetero atoms as chain links
Abstract
The invention relates to novel substituted heteroarylmethyl compounds of general formula (I), wherein Q, X1, X2, Z1 and Z2 have the meanings given in the description, to a method for producing the same, and to their use as herbicides.
Description
> CA 02319053 2000-07-26 Le A 32 843-Foreign countries Kri/Ke/bo/W6 / V 10.07.1998 Substituted heteroarvlmethvl compounds The invention relates to novel substituted heteroarylmethyl compounds, to processes for their preparation and to their use as herbicides.
Substituted arylmethyl compounds are already known from the (patent) literature as potential herbicides (cf. DE-A-2526358, US-A-4249934, US-A-5262390, WO-A-9621647). However, these compounds have not attained any practical importance worth mentioning.
The present invention accordingly provides novel substituted heteroarylmethyl compounds of the general formula (I) Zz X' Xz ~ / Q (I) in which Q represents O, S, SO or S02, X 1 represents hydrogen, hydroxyl, mercapto, amino, nitro, formyl, carboxyl, cyano, carbamoyl, thiocarbamoyl, halogen, or represents in each case optionally cyano-, halogen- or alkoxy-substituted alkyl, alkoxy, alkylthio, alkylsulphinyl, alkylsulphonyl, alkylamino, dialkylamino, alkylcarbonyl, alkoxycarbonyl, alkylcarbonylamino, alkoxycarbonylamino or alkylsulphonylamino, X2 represents hydrogen or halogen, Le A 32 843-Foreign countries Z i represents optionally substituted heteroaryl from the series consisting of furyl, benzofuryl, pyrrolyl, pyrazolyl, imidazolyl, triazolyl, oxazolyl, isoxazolyl, benzoxazolyl, thiazolyl, isothiazolyl, benzothiazolyl, benzimidazolyl, pyridinyl, quinolinyl, isoquinolinyl, pyrimidinyl, pyrazinyl, pyridazinyl, quinazolinyl or quinoxalinyl, and Z2 represents one of the groupings below Q' Q' R' R' N- R ~ N- Q ~N R, I ~N
R~ RziN~N\ NuN\
Q' Q' IQI' IQI' R' Rz Rz R' w R' \ N R' NON Rz'~NiN O' RzwN~N
~ l ~ i N
' \ ' '~ \ ' \
R R Q Q
z R' R' O Q' I R' R' R' O' R' N R' \
N N ~ \
N R' Q' Rz R' Q' I
I~I ' ' O N Q' z ~ R~N~ ~ R N Q
RAN Q ~ Q
N /N~\ N N\ Rz/N N\
' Rz N--Q ~ ' O Q
where Q l represents O or S, Le A 32 843-Foreign countries R1 represents hydrogen, cyano, halogen, or represents in each case optionally cyano-, halogen- or alkoxy-substituted alkyl, alkoxy, alkylthio, alkylsulphinyl, alkylsulphonyl, alkylamino, dialkylamino, alkenyl, alkenyloxy, alkenylthio, alkenylamino, alkinyl, alkinyloxy, alkinylthio, cycloalkyl, cycloalkyloxy, cycloalkylthio or cycloalkylamino, or optionally together with an adjacent R1 represents alkanediyl (alkylene), and R2 represents hydrogen, cyano, formyl, or represents in each case optionally cyano-, halogen- or alkoxy-substituted alkyl, alkylcarbonyl, alkoxycarbonyl, alkenyl or alkinyl.
In the definitions, the hydrocarbon chains, such as alkyl - including in combination 1 S with heteroatoms, such as in alkoxy - are in each case straight-chain or branched.
The invention preferably provides compounds of the formula (I) in which Q represents O, S, SO or S02, X1 represents hydrogen, hydroxyl, mercapto, amino, nitro, formyl, carboxyl, cyano, carbamoyl, thiocarbamoyl, halogen, or represents in each case optionally cyano-, halogen- or C1-C4-alkoxy-substituted alkyl, alkoxy, alkylthio, alkylsulphinyl, alkylsulphonyl, alkylamino, dialkylamino, alkylcarbonyl, alkoxycarbonyl, alkylcarbonylamino, alkoxycarbonylamino or alkylsulphonylamino having in each case 1 to 6 carbon atoms in the alkyl groups, X2 represents hydrogen or halogen, Le A 32 843-Foreign countries Z1 represents optionally substituted heteroaryl from the series consisting of furyl, benzofuryl, pyrrolyl, pyrazolyl, imidazolyl, triazolyl, oxazolyl, isoxazolyl, benzoxazolyl, thiazolyl, isothiazolyl, benzothiazolyl, benzimidazolvl.
pyridinyl, quinolinyl, isoquinolinyl, pyrimidinyl, pyrazinyl, pyridazinyl, quinazolinyl or quinoxalinyl, where the possible substituents are preferably selected from the list below:
nitro, amino, hydroxyl, carboxyl, cyano, carbamoyl, thiocarbamoyl, sulpho, chlorosulphonyl, aminosulphonyl, halogen, in each case optionally cyano-, halogen- or C 1-C4-alkoxy-substituted alkyl, alkoxy, alkylthio, alkylsulphinyl, alkylsulphonyl, alkylamino, alkylcarbonyl, alkoxycarbonyl, alkylaminocarbonyl, alkylcarbonylamino, alkoxycarbonylamino or alkylsulphonylamino having in each case 1 to 4 carbon atoms in the alkyl groups or phenyl, and ZZ represents one of the groupings below Q~ Qi Ri R~
R~ Q~ Ri / vN- I \N- W N I w N
R~ Rz~N N~ N N~
Q' R' R2 RZ ' R
w R~ \ N R' NON RwN~N Q' RWN~N
-N
R R Q Q
Le A 32 843-Foreign countries z R' R~ O Q~ I R~ R~ R~ Q~
R~ N R~
N-N~ ~ ( / N\
N R~ ~N \
Q
R~ O~ Rz Rz ' I ' Q N Q' z ~ Rw ~ ~ R N Q
RwN Q ; Q
N z/N~~ - N N\ Rz/N N\
R N
Q \ Q~
Q
where Q 1 represents O or S, R1 represents hydrogen, cyano, haloben, represents in each case optionally cyano-, halogen- or Cl-C4-alkoxy-substituted alkyl, alkoxy, alkylthio, alkylsulphinyl, alkylsulphonyl, alkylamino or dialkylamino having in each case 1 to 6 carbon atoms in the alkyl groups, represents in each case optionally halogen-substituted alkenyl, alkenyloxy, alkenylthio, alkenylamino, alkinyl, alkinyloxy or alkinylthio having in each case 2 to 6 carbon atoms in the alkenyl or alkinyl groups, 1S represents in each case optionally cyano-, halogen- or C1-C4-alkyl-substituted cycloalkyl, cycloalkyloxy, cycloalkylthio or cycloalkylamino having in each case 3 to 6 carbon atoms in the cycloalkyl groups, or optionally together with an adjacent R1 represents alkanediyl (alkylene) having 3 to 5 carbon atoms, and R2 represents hydrogen, cyano, formyl, represents in each case optionally cyano-, halogen- or Cl-C4-alkoxy-substituted alkyl, alkylcarbonyl, alkoxycarbonyl having in each case 1 to 6 carbon atoms in the alkyl Le A 32 843-Foreign countries groups, or represents in each case optionally halogen-substituted alkenyl or alkinyl having in each case 3 to 6 carbon atoms.
The invention relates in particular to compounds of the formula (I) in which Q represents O, S, SO or 502, X 1 represents hydrogen, hydroxyl, mercapto, amino, nitro; formyl, carboxyl, cyano, carbamoyl, thiocarbamoyl, fluorine, chlorine, bromine, represents in each case optionally cyano-, fluorine-, chlorine-, methoxy- or ethoxy-substituted methyl, ethyl, n- or i-propyl, methoxy, ethoxy, n- or i-propoxy, methylthio, ethylthio, n- or i-propylthio, methylsulphinyl, ethylsulphinyl, methylsulphonyl, ethylsulphonyl, methylamino, ethylamino, n- or i-propylamino, dimethylamino, diethylamino, acetyl, propionyl, i S methoxycarbonyl, ethoxycarbonyl, acetylamino, propionylamino, methoxycarbonylamino, ethoxycarbonylamino, methylsulphonylamino, ethylsulphonylamino, n- or i-propylsulphonylamino, XZ represents hydrogen, fluorine, chlorine or bromine, Z1 represents optionally substituted heteroaryl from the series consisting of furyl, benzofuryl, pyrrolyl, pyrazolyl, imidazolyl, triazolyl, oxazolyl, isoxazolyl, benzoxazolyl, thiazolyl, isothiazolyl, benzothiazolyl, benzimidazolyl, pyridinyl, quinolinyl, isoquinolinyl, pyrimidinyl, pyrazinyl, pyridazinyl, quinazolinyl or quinoxalinyl, where the possible substituents are preferably selected from the list below:
nitro, amino, hydroxyl, carboxyl, cyano, carbamoyl, thiocarbamoyl, aminosulphonyl, fluorine, chlorine, bromine, in each case optionally cyano-, fluorine-, chlorine-, methoxy- or ethoxy-substituted methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, methoxy, ethoxy, n- or i-propoxy, n-, i-, s- or t-Le A 32 843-Foreign countries butoxy, methylthio, ethylthio, n- or i-propylthio, n-, i-, s- or t-butylthio, methylsulphinyl, ethylsulphinyl, methylsulphonyl, ethylsulphonyl, methylamino, ethylamino, n- or i-propylamino, n-, i-, s- or t-butylamino, acetyl, propionyl, n- or i-butyroyl, methoxycarbonyl, ethoxycarbonyl, n- or i-S propoxycarbonyl, methylaminocarbonyl, ethylaminocarbonyl, n- or i-propylaminocarbonyl, acetylamino, propionylamino, n- or i-butyroylamino, methoxycarbonylamino, ethoxycarbonylamino, n- or i-propoxycarbonylamino, methylsulphonylamino, ethylsulphonylamino, n- or i-propylsulphonylamino, n-, i-, s- or t-butylsulphonylamino or phenyl, and Z2 represents one of the groupings below Q' Q' R, R' \ R~ Q ~ N R~ ~ N
~N- I ~N- I I I
R~ ~ N N\ N N\
Rzi R' RZ RZ R' I I l R' \ N R' NON Rz~N~IV Q~ RwN~IV
W
~ l ~ i N
R R Q Q
R' R~ O Q~ ( R~ R~ R~ Q~
R~ N R~ \
N-N ~ N\
N R~
Q' Rz R' Q' Rz ( ' Q N Q' z , RzwN~Q, R N Q
R w N Q
N % ~~ N N\ Rz/N N\
RZ N -Q Qi Le A 32 843-Foreign countries -g_ where Q1 represents O or S, R1 represents hydrogen, cyano, fluorine, chlorine, bromine, represents in each case optionally cyano-, fluorine-, chlorine-, methoxy- or ethoxy-substituted methyl, ethyl, n- or i-propyl, methoxy, ethoxy, n- or i-propoxy, methylthio, ethylthio, n- or i-propylthio, methylsulphinyl, ethylsulphinyl, methylsulphonyl, ethylsulphonyl, methylamino, ethylamino, n- or i-propylamino, dimethylamino or diethylamino, represents in each case optionally fluorine-, chlorine- or bromine-substituted ethenyl, propenyl, propenyloxy, propenylthio, propenylamino, ethinyl, propinyl, propinyloxy or propinylthio, represents in each case optionally cyano-, fluorine-, chlorine-, methyl-, ethyl-, n- or i-propyl-substituted cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclopropyloxy, cyclobutyloxy, cyclopentyloxy, cyclohexyloxy, cyclopropylamino, cyclobutylamino, cyclopentylamino or cyclohexylamino, or optionally together with an adjacent R1 represents propane-1,3-diyl (trimethylene) or butane-1,4-diyl (tetramethylene), and R2 represents hydrogen, cyano, formyl, represents in each case optionally cyano-, fluorine-, chlorine-, methoxy- or ethoxy-substituted methyl, ethyl, n- or i-propyl, acetyl, propionyl, n- or i-butyroyl, methoxycarbonyl, ethoxycarbonyl, n- or i-propoxycarbonyl, or represents in each case optionally fluorine-, chlorine- or bromine-substituted propenyl, butenyl, propinyl or butinyl.
A very particularly preferred group are those compounds of the general formula (I) in which Z2 represents the heterocyclic grouping below and Q, XI, X2 and Zl and have the meanings given above as being particularly preferred.
Le A 32 843-Foreign countries Rz I
RzwNiN~O
-N
O
A further very particularly preferred group are those compounds of the general formula (I) in which Z2 represents the heterocyclic grouping below and Q, X1, and Z1 and R1 and R2 have the meanings given above as being particularly preferred.
Rz R, N ~
/N
R' Most preference is given to compounds of the formula (Ia) Zz \ x, Xz ~ / Q (Ia) in which Q, X1, X2, Z1 and ZZ have the meanings given in Table 1 (after the Preparation Examples) and to the compounds of Preparation Examples 1 and 2.
The abovementioned general or preferred radical definitions apply both to the end products 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 one another at will, i.e. including combinations between the given preferred ranges.
Le A 32 843-Foreign countries The novel substituted heteroarylmethyl compounds of the general formula (I) have strong and selective herbicidal activity.
S The novel substituted heteroarylmethyl compounds of the general formula (I) are obtained when (a) phthalic anhydride or 3,4,5,6-tetrahydro-phthalic anhydride is reacted with aminobenzene derivatives of the general formula (II) HzN X~
Xz I / Q (.II) in which Q, X1, X2 and Z1 are as defined above, 1 S if appropriate in the presence of a diluent and if appropriate in the presence of a reaction auxiliary, or when (b) heterocyclylarenes of the general formula (III) Zz X' Xz I / Q (III) I
H
in which Q, Xl, X2 and ZZ are as defined above, Le A 32 843-Foreign countries are reacted with heteroarylmethyl halides of the general formula (N) X3_CH2_Z1 (IV) S in which Z1 is as defined above and X3 represents halogen, if appropriate in the presence of a diluent and if appropriate in the presence of a reaction auxiliary, or when (c) heterocyclylarenes of the general formula (V) Z2 X, (V) XZ ~ Xa in which X1, X2 and Z2 are as defined above and X4 represents halogen, are reacted with heteroarenes of the general formula (VI) HQ-CH2-Z1 (VI) in which Le A 32 843-Forei>;rl countries Q and Z1 are as defined above, if appropriate in the presence of a diluent and if appropriate in the presence of a reaction auxiliary, and, if appropriate, electrophilic or nucleophilic substitution reactions or oxidation or reduction reactions within the scope of the definition of the substituents are subsequently carned out in a customary manner.
Using, for example, phthalic anhydride and 1-amino-2-fluoro-4-(3,5-dimethyl-isoxazol-4-yl-methoxy)-benzene as starting materials, the course of the reaction in the process (a) according to the invention can be illustrated by the following formula scheme:
F O
O F
HzN \ \
\ I / ~ I / .N \
O +
/ O
O \ CH3 I N
o I ~~N
O
Using, for example, 4-(5-chloro-2-fluoro-4-mercapto-phenyl)-1,2-dimethyl-1,2,4-triazoline-3,5-dione and 2-chloro-5-chloromethyl-thiazole as starting materials, the course of the reaction in the process (b) according to the invention can be illustrated by the following formula scheme:
H3CN 1 0 H3C n F
CI
HsC-N Il N ~ \ + ~ SCI HsC-N
O
S N
I
CI H CI
Le A 32 843-Foreign countries Using, for example, 3-(2,4-difluoro-S-nitro-phenyl)-4-bromo-1-methyl-S-trifluoromethyl-1H-pyrazole and furfuryl alcohol as starting materials, the course of the reaction in the process (c) according to the invention can be illustrated by the following formula scheme:
S
HsC HsC
N-N F N-N F
F3C ~ ~ \ -~ HO F3C ~ I \
O
Br ~ / ~ ~ Br ~ / O
-F
O
N Oz N Oz The compounds phthalic anhydride and 3,4,5,6-tetrahydro-phthalic anhydride to be used as starting materials in the process (a) according to the invention for preparing compounds of the formula (I) are known organic chemicals for synthesis.
The formula (II) provides a general definition of the aminobenzene derivatives further to be used as starting materials in the process (a) according to the invention for preparing compounds of the formula (I). In the formula (II), Q, X1, X2 and preferably or in particular have those meanings which have already been mentioned 1 S 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 Q, X1, X2 and Z1.
The starting materials of the general formula (II) are known and/or can be prepared by processes known per se (cf. Justus Liebigs Ann. Chem. 733 (1970), 125-140;
DE-A-2842186; US-A-5344812; US-A-5399543; WO-A-9S 17096; Preparation Examples).
The formula (III) provides a general definition of the heterocyclylarenes to be used as 2S starting materials in the process (b) according to the invention for preparing compounds of the formula (I). In the formula (III), Q, Xt, XZ and Z2 preferably or in Le A 32 843-Foreign countries 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 Q, X 1, X2 and Z2.
The starting materials of the general formula (III) are known and/or can be prepared by processes known per se (cf. EP-A-545206; JP-A-04178373; WO-A-9618618;
Preparation Examples).
The formula (IV) provides a general definition of the heteroarylmethyl halides further to be used as starting materials in the process (b) according to the invention. In the formula (N), Z1 preferably or in particular has 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 Z1; X3 preferably represents fluorine, chlorine, bromine or iodine, in particular chlorine or bromine.
The starting materials of the general formula (N) are known organic chemicals for synthesis.
The formula (V) provides a general definition of the heterocyclylarenes to be used as starting materials in the process (c) according to the invention for preparing compounds of the formula (I). In the formula (V), X1, X2 and Z2 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 X1, X2 and Z2; X4 preferably represents fluorine, chlorine or bromine, in particular fluorine or chlorine.
The starting materials of the general formula (V) are known and/or can be prepared by processes known per se (cf. US-A-5281571, WO-A-9206962; WO-A-9618618).
Le A 32 843-Foreign countries The formula (VI) provides a general definition of the heteroarenes further to be used as starting materials in the process (c) according to the invention. In the formula (VI), Q and Z1 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 Q and Z1.
The starting materials of the general formula (VI) are known organic chemicals for synthesis.
The processes according to the invention for preparing compounds of the general formula (I) are preferably carried out using diluents. Suitable diluents for carrying out the processes (a) to (c) according to the invention are especially inert organic solvents. These include, in particular, aliphatic, alicyclic or aromatic, optionally halogenated hydrocarbons, such as, for example, benzine, benzene, toluene, xylene, chlorobenzene, dichlorobenzene, petroleum ether, hexane, cyclohexane, dichloromethane, chloroform, carbon tetrachloride; ethers, such as diethyl ether, diisopropyl ether, dioxane, tetrahydrofuran or ethylene glycol dimethyl ether or ethylene glycol diethyl ether; ketones, such as acetone, butanone or methyl isobutyl ketone; 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, diethylene glycol monoethyl ether, mixtures thereof with water or pure water.
Suitable reaction auxiliaries for the processes (a) to (c) 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 acetate or calcium Le A 32 843-Foreign countries acetate, lithium amide, sodium amide, potassium amide or calcium amide, sodium carbonate, potassium carbonate or calcium carbonate, sodium bicarbonate, potassium bicarbonate or calcium bicarbonate, lithium hydride, sodium hydride, potassium hydride or calcium hydride, lithium hydroxide, sodium hydroxide, 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-propoxide, n-, i-, s- or t-butoxide; furthermore also basic organic nitrogen compounds, such as, for example, trimethylamine, triethylamine, tripropylamine, tributylamine, ethyl-diisopropylamine, N,N-dimethylcyclohexylamine, dicyclohexylamine, ethyl-dicyclohexylamine, 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, S-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-S-ene (DBN) or 1,8-diazabicyclo[5.4.0]-undec-7-ene (DBU).
When carrying out the processes (a) to (c) according to the invention, the reaction temperatures can be varied within a relatively wide range. In general, the processes are carried out at temperatures between 0°C and 200°C, preferably between 10°C
and 150°C.
The processes (a) to (c) according to the invention are generally carried out under atmospheric pressure. However, it is also possible to carry out the processes according to the invention under elevated or reduced pressure - generally between 0.1 bar and 10 bar.
For carrying out the processes (a) to (c) according to the invention, the starting materials are generally employed in approximately equimolar amounts. However, it is also possible for one of the components to be used in a relatively large excess. The reaction is generally carried out in a suitable diluent in the presence of a reaction auxiliary, and the reaction mixture is generally stirred at the required temperature for Le A 32 843-Foreign countries several hours. Work-up is carried out by customary methods (cf. the Preparation Examples).
The active compounds according to the invention can be used as defoliants, desiccants, haulm killers and, especially, as weed killers. By weeds in the broadest sense there 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 connection with the following plants:
Dicotyledonous weeds of the eg nera: Sinapis, Lepidium, Galium, Stellaria, Matricaria, Anthemis, Galinsoga; Chenopodium, Urtica, Senecio, Amaranthus, Portulaca, Xanthium, Convolvulus, Ipomoea, Polygonum, Sesbania, Ambrosia, Cirsium, Carduus, Sonchus, .Solanum, Rorippa, Rotala, Lindernia, Lamium, Veronica, Abutilon, Emex, Datura, Viola, Galeopsis, Papaver, Centaurea, Trifolium, Ranunculus, Taraxacum.
Dicoyledonous cress of the eg_ nera: Gossypium, Glycine, Beta, Daucus, Phaseolus, Pisum, Solanum, Linum, Ipomoea, Vicia, Nicotiana, Lycopersicon, Arachis, Brassica, Lactuca, Cucumis, Cucurbita.
Monocotyledonous weeds of the Qenera: Echinochloa, Setaria, Panicum, Digitaria, Phleum, Poa, Festuca, Eleusine, Brachiaria, Lolium, Bromus, Avena, Cyperus, Sorghum, Agropyron, Cynodon, Monochoria, Fimbristylis, Sagittaria, Eleocharis, Scirpus, Paspalum, Ischaemum, Sphenoclea, Dactyloctenium, Agrostis, Alopecurus, Apera.
Monocotyledonous crops of the eg nera: Oryza, Zea, Triticum, Hordeum, Avena, Seca.le, Sorghum, Panicum, Saccharum, Ananas, Asparagus, Allium.
Le A 32 843-Foreign countries 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.
Depending on the concentration, the compounds are suitable for total weed control, for example on industrial terrain and rail tracks and on paths and areas with or without tree growth. Equally, the compounds can be employed for controlling weeds in perennial crops, for example forests, ornamental tree plantings, orchards, vineyards, citrus groves, nut orchards, banana plantations, coffee plantations, tea plantations, rubber plantations, oil palm plantations, cocoa plantations, soft fruit plantings and hop fields, on lawns and turf and pastures and for selective weed control in annual crops.
The compounds of the formula (n according to the invention are particularly suitable 1 S for selective control of monocotyledonous and dicotyledonous weeds in monocotyledonous and dicotyledonous crops, both by the pre-emergence and by the post-emergence method.
The active compounds can be converted into the customary formulations, such as solutions, emulsions, wettable powders, suspensions, powders, dusts, pastes, soluble powders, granules, suspo-emulsion concentrates, natural and synthetic substances impregnated with active compound, and microencapsulations in polymeric substances.
These formulations are produced in a known manner, for example by mixing the active compounds with extenders, that is to say liquid solvents and/or solid earners, optionally with the use of surfactants, that is to say emulsifiers and/or dispersants and/or foam formers.
If the extender used is water, it is also possible to use, for example, organic solvents as auxiliary solvents. Liquid solvents which are mainly suitable are:
aromatics, such Le A 32 843-Foreign countries as xylene, toluene or alkylnaphthalenes, chlorinated aromatics and chlorinated aliphatic hydrocarbons, such as chlorobenzenes, chloroethylenes or methylene chloride, aliphatic hydrocarbons, such as cyclohexane or paraffins, for example petroleum fractions, mineral and vegetable oils, alcohols, such as butanol or glycol, and also their ethers and esters, ketones, such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, strongly polar solvents, such as dimethylformamide and dimethyl sulphoxide, and water.
Suitable solid carriers are: for example ammonium salts and ground natural minerals, such as kaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth, and ground synthetic minerals, such as finely divided silica, alumina and silicates; suitable solid carriers for granules are: for example crushed and fractionated natural rocks, such as calcite, marble, pumice, sepiolite, dolomite and synthetic granules of inorganic and organic meals, and granules of organic material, such as sawdust, coconut shells, maize cobs and tobacco stalks;
suitable emulsifiers and/or foam formers are: for-example nonionic and anionic emulsifiers, such as polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers, for example alkylaryl polyglycol ethers, alkylsulphonates, alkyl sulphates, arylsulphonates and protein hydrolysates; suitable dispersants are: for example lignosulphite waste liquors and methylcellulose.
Tackifiers, such as carboxymethylcellulose, natural and synthetic polymers in the form of powders, granules or latices, such as gum arabic, polyvinyl alcohol and polyvinyl acetate, and also natural phospholipids, such as cephalins and lecithins, and synthetic phospholipids can be used in the formulations. Other possible additives are mineral and vegetable oils.
It is possible to use dyestuffs, such as inorganic pigments, for example iron oxide, titanium oxide, Prussian blue, and organic dyestuffs, such as alizarin dyestuffs, azo dyestuffs and metal phthalocyanine dyestuffs, and trace nutrients, such as salts of iron, manganese, boron, copper, cobalt, molybdenum and zinc.
Le A 32 843-Foreign countries The formulations generally 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, finished 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, amidosulfuron, anilofos, asulam, atrazine, azafenidin, azimsulfuron, benazolin(-ethyl), benfuresate, bensulfuron(-methyl), bentazone, benzofenap, benzoylprop(-ethyl), bialaphos, bifenox, bispyribac(-sodium), bromobutide, bromofenoxim, bromoxynil, butachlor, butroxydim, butylate, cafenstrole, c:aloxydim, carbetamide, carfentrazone(-ethyl), chlomethoxyfen, chloramben, chloridazon, chlorimuron(-ethyl), chlornitrofen, chlorsulfuron, chlorotoluron, cinmethylin, cinosulfuron, clethodim, clodinafop(-propargyl), clomazone, clomeprop, clopyralid, clopyrasulfuron(-methyl), cloransulam(-methyl), cumyluron, cyanazine, cycloate, cyclosulfamuron, cycloxydim, cyhalofop(-butyl), 2,4-D, 2,4-DB, 2,4-DP, desmedipham, diallate, dicamba, diclofop(-methyl), diclosulam, diethatyl(-ethyl), difenzoquat, diflufenican, diflufenzopyr, dimefuron, dimepiperate, dimethachlor, dimethametryn, dimethenamid, dimexyflam, dinitramine, diphenamid, diquat, dithiopyr, diuron, dymron, epoprodan, EPTC, esprocarb, ethalfluralin, ethametsulfuron(-methyl), ethofumesate, ethoxyfen, ethoxysulfuron, etobenzanid, fenoxaprop-(-P-ethyl), flamprop(-isopropyl), flamprop(-isopropyl-L), flam-prop(-methyl), flazasulfuron, fluazifop(-P-butyl), flumetsulam, flumiclorac(-pentyl), flumioxazin, flumipropyn, flumetsulam, fluometuron, fluorochloridone, fluoroglycofen(-ethyl), flupoxam, flupropacil, flurpyrsulfuron(-methyl, -sodium), flurenol(-butyl), fluridone, fluroxypyr(-meptyl), flurprimidol, flurtamone, fluthi-acet(-methyl), fluthiamide, fomesafen, glufosinate(-ammonium), glyphosate-Le A 32 843-Foreign countries (-isopropylammonium), halosafen, haloxyfop(-ethoxyethyl), haloxyfop(-p-methyl), hexazinone, imazamethabenz-(-methyl), imazamethapyr, imazamox, imazapyr, imazaquin, imazethapyr, imazosulfuron, ioxynil, isopropalin, isoproturon, isouron, isoxaben, isoxaflutole, isoxapyrifop, lactofen, lenacil, linuron, MCPA, MCPP, S mefenacet, metamitron, metazachlor, methabenzthiazuron, metobenzuron, metobromuron, (alpha-)metolachlor, metosulam, metoxuron, metribuzin, metsulfuron(-methyl), molinate, monolinuron, naproanilide, napropamide, neburon, nicosulfuron, norflurazon, orbencarb, oryzalin, oxadiargyl, oxadiazon, oxasulfuron, oxaziclomefone, oxyfluorfen, paraquat, pelargonic acid, pendimethalin, pentoxazone, phenmedipham, piperophos, pretilachlor, primisulfuron(-methyl), prometryn, propachlor, propanil, propaquizafop, propisochlor, propyzamide, prosulfocarb, prosulfuron, pyraflufen(-ethyl), pyrazolate, pyrazosulfuron(-ethyl), pyrazoxyfen, pyribenzoxim, pyributicarb, pyridate, pyriminobac-(-methyl), pyrithiobac(-sodium), quinchlorac, quinmerac, quinoclamine, quizalofop(-P-ethyl), quizalofop(-P-tefuryl), rimsulfuron, sethoxydim, simazine, simetryn, sulcotrione, sulfentrazone, sulfometuron(-methyl). sulfosate, sulfosulfuron, tebutam, tebuthiuron, terbuthylazine, terbutryn, thenylchlor, thiafluamide, thiazopyr, thidiazimin, thifensulfuron(-methyl), thiobencarb, tiocarbazil, tralkoxydim, triallate, triasulfuron, tribenuron(-methyl), triclopyr, tridiphane, trifluralin and triflusulfuron.
A mixture with other known active compounds, such as fungicides, insecticides, acaricides, nematicides, bird repellents, plant nutrients and agents which improve soil structure, is 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, suspensions, emulsions, powders, pastes and granules. They are used in the customary manner, for example by watering, spraying, atomizing, scattering.
Le A 32 843-Foreign countries The active compounds according to the invention can be applied both before and after emergence of the plants. They can also be incorporated into the soil before sowing.
S The amount of active compound used can vary within a relatively wide 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 S g and 5 kg per ha.
The preparation and the use of the active compounds according to the invention can be seen from the examples below.
Le A 32 843-Foreign countries Preparation Examples:
Example 1 O
N
O
F / O ~ ~N
CI
(Process (a)) A mixture of 2.0 g (8 mmol) of 1-amino-2-fluoro-4-(2-chloro-pyridin-S-yl-methoxy)-benzene, 1.2 g (8 mmol) of phthalic anhydride and 50 ml of acetic acid is heated under reflux for 5 hours, then stirred at room temperature for 18 hours and subsequently heated under reflux for another 4 hours. The mixture is then concentrated under water pump vacuum, the residue is shaken with water/ethyl acetate and the organic phase is separated off, washed with water, dried with sodium sulphate and filtered. The filtrate is concentrated under water pump vacuum, the 1 S residue is digested with diisopropyl ether and the crystalline product is isolated by filtration with suction.
This gives 1.9 g (62% of theory) of N-(2-fluoro-(2-chloro-pyridin-5-yl-methoxy)-phenyl]-phthalimide of melting point 183°C.
Le A 32 843-Foreign countries Example 2 FZHC O
N
Fi3C N' 'N
O
F / O ~ ~N
CI
(Process (b)) A mixture of 0.90 g (3.3 mmol) of 4-(2-fluoro-4-hydroxy-phenyl)-2-difluoromethyl-1-methyl-1,2,4-triazoline-3,5-dione, 0.65 g (3.3 mmol) of 2-chloro-5-chloromethyl-pyridine, 0.55 g of potassium carbonate and 10 ml of N,N-dimethyl-formamide is stirred at 80°C for 3 hours. After slight cooling, the mixture is then poured into a solvent mixture of 1N hydrochloric acid and diethyl ether which has been admixed with ice beforehand. After thorough stirring, the crystalline product is isolated by filtration with suction.
This gives 0.35 g (26.5% of theory) of 4-[2-fluoro-4-(2-chloro-pyridin-S-yl methoxy)-phenyl)-2-difluoromethyl-1-methyl-1,2,4-triazoline-3,5-dione of melting point 134°C.
Analogously to Preparation Examples 1 and 2 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 (Ia) listed in Table 1 below.
Zz \ X' XZ ~ / Q (Ia) ~Z' Le A 32 843-Forei>;n countries Table 1: Examples of the compounds of the formula (Ia) Ex. Q Xl XZ Zl Z2 Melting point No. (C) 3 O H F w N (amorphous) N-/ CI
O
4 O H F ~ N cH3 73 CI
5 O H F ~ N (amorphous) /
CI ~ N
N
CI
6 O N02 F ~ N CH3 170 / F3C Nw CI ~ ~N
CI
Substituted arylmethyl compounds are already known from the (patent) literature as potential herbicides (cf. DE-A-2526358, US-A-4249934, US-A-5262390, WO-A-9621647). However, these compounds have not attained any practical importance worth mentioning.
The present invention accordingly provides novel substituted heteroarylmethyl compounds of the general formula (I) Zz X' Xz ~ / Q (I) in which Q represents O, S, SO or S02, X 1 represents hydrogen, hydroxyl, mercapto, amino, nitro, formyl, carboxyl, cyano, carbamoyl, thiocarbamoyl, halogen, or represents in each case optionally cyano-, halogen- or alkoxy-substituted alkyl, alkoxy, alkylthio, alkylsulphinyl, alkylsulphonyl, alkylamino, dialkylamino, alkylcarbonyl, alkoxycarbonyl, alkylcarbonylamino, alkoxycarbonylamino or alkylsulphonylamino, X2 represents hydrogen or halogen, Le A 32 843-Foreign countries Z i represents optionally substituted heteroaryl from the series consisting of furyl, benzofuryl, pyrrolyl, pyrazolyl, imidazolyl, triazolyl, oxazolyl, isoxazolyl, benzoxazolyl, thiazolyl, isothiazolyl, benzothiazolyl, benzimidazolyl, pyridinyl, quinolinyl, isoquinolinyl, pyrimidinyl, pyrazinyl, pyridazinyl, quinazolinyl or quinoxalinyl, and Z2 represents one of the groupings below Q' Q' R' R' N- R ~ N- Q ~N R, I ~N
R~ RziN~N\ NuN\
Q' Q' IQI' IQI' R' Rz Rz R' w R' \ N R' NON Rz'~NiN O' RzwN~N
~ l ~ i N
' \ ' '~ \ ' \
R R Q Q
z R' R' O Q' I R' R' R' O' R' N R' \
N N ~ \
N R' Q' Rz R' Q' I
I~I ' ' O N Q' z ~ R~N~ ~ R N Q
RAN Q ~ Q
N /N~\ N N\ Rz/N N\
' Rz N--Q ~ ' O Q
where Q l represents O or S, Le A 32 843-Foreign countries R1 represents hydrogen, cyano, halogen, or represents in each case optionally cyano-, halogen- or alkoxy-substituted alkyl, alkoxy, alkylthio, alkylsulphinyl, alkylsulphonyl, alkylamino, dialkylamino, alkenyl, alkenyloxy, alkenylthio, alkenylamino, alkinyl, alkinyloxy, alkinylthio, cycloalkyl, cycloalkyloxy, cycloalkylthio or cycloalkylamino, or optionally together with an adjacent R1 represents alkanediyl (alkylene), and R2 represents hydrogen, cyano, formyl, or represents in each case optionally cyano-, halogen- or alkoxy-substituted alkyl, alkylcarbonyl, alkoxycarbonyl, alkenyl or alkinyl.
In the definitions, the hydrocarbon chains, such as alkyl - including in combination 1 S with heteroatoms, such as in alkoxy - are in each case straight-chain or branched.
The invention preferably provides compounds of the formula (I) in which Q represents O, S, SO or S02, X1 represents hydrogen, hydroxyl, mercapto, amino, nitro, formyl, carboxyl, cyano, carbamoyl, thiocarbamoyl, halogen, or represents in each case optionally cyano-, halogen- or C1-C4-alkoxy-substituted alkyl, alkoxy, alkylthio, alkylsulphinyl, alkylsulphonyl, alkylamino, dialkylamino, alkylcarbonyl, alkoxycarbonyl, alkylcarbonylamino, alkoxycarbonylamino or alkylsulphonylamino having in each case 1 to 6 carbon atoms in the alkyl groups, X2 represents hydrogen or halogen, Le A 32 843-Foreign countries Z1 represents optionally substituted heteroaryl from the series consisting of furyl, benzofuryl, pyrrolyl, pyrazolyl, imidazolyl, triazolyl, oxazolyl, isoxazolyl, benzoxazolyl, thiazolyl, isothiazolyl, benzothiazolyl, benzimidazolvl.
pyridinyl, quinolinyl, isoquinolinyl, pyrimidinyl, pyrazinyl, pyridazinyl, quinazolinyl or quinoxalinyl, where the possible substituents are preferably selected from the list below:
nitro, amino, hydroxyl, carboxyl, cyano, carbamoyl, thiocarbamoyl, sulpho, chlorosulphonyl, aminosulphonyl, halogen, in each case optionally cyano-, halogen- or C 1-C4-alkoxy-substituted alkyl, alkoxy, alkylthio, alkylsulphinyl, alkylsulphonyl, alkylamino, alkylcarbonyl, alkoxycarbonyl, alkylaminocarbonyl, alkylcarbonylamino, alkoxycarbonylamino or alkylsulphonylamino having in each case 1 to 4 carbon atoms in the alkyl groups or phenyl, and ZZ represents one of the groupings below Q~ Qi Ri R~
R~ Q~ Ri / vN- I \N- W N I w N
R~ Rz~N N~ N N~
Q' R' R2 RZ ' R
w R~ \ N R' NON RwN~N Q' RWN~N
-N
R R Q Q
Le A 32 843-Foreign countries z R' R~ O Q~ I R~ R~ R~ Q~
R~ N R~
N-N~ ~ ( / N\
N R~ ~N \
Q
R~ O~ Rz Rz ' I ' Q N Q' z ~ Rw ~ ~ R N Q
RwN Q ; Q
N z/N~~ - N N\ Rz/N N\
R N
Q \ Q~
Q
where Q 1 represents O or S, R1 represents hydrogen, cyano, haloben, represents in each case optionally cyano-, halogen- or Cl-C4-alkoxy-substituted alkyl, alkoxy, alkylthio, alkylsulphinyl, alkylsulphonyl, alkylamino or dialkylamino having in each case 1 to 6 carbon atoms in the alkyl groups, represents in each case optionally halogen-substituted alkenyl, alkenyloxy, alkenylthio, alkenylamino, alkinyl, alkinyloxy or alkinylthio having in each case 2 to 6 carbon atoms in the alkenyl or alkinyl groups, 1S represents in each case optionally cyano-, halogen- or C1-C4-alkyl-substituted cycloalkyl, cycloalkyloxy, cycloalkylthio or cycloalkylamino having in each case 3 to 6 carbon atoms in the cycloalkyl groups, or optionally together with an adjacent R1 represents alkanediyl (alkylene) having 3 to 5 carbon atoms, and R2 represents hydrogen, cyano, formyl, represents in each case optionally cyano-, halogen- or Cl-C4-alkoxy-substituted alkyl, alkylcarbonyl, alkoxycarbonyl having in each case 1 to 6 carbon atoms in the alkyl Le A 32 843-Foreign countries groups, or represents in each case optionally halogen-substituted alkenyl or alkinyl having in each case 3 to 6 carbon atoms.
The invention relates in particular to compounds of the formula (I) in which Q represents O, S, SO or 502, X 1 represents hydrogen, hydroxyl, mercapto, amino, nitro; formyl, carboxyl, cyano, carbamoyl, thiocarbamoyl, fluorine, chlorine, bromine, represents in each case optionally cyano-, fluorine-, chlorine-, methoxy- or ethoxy-substituted methyl, ethyl, n- or i-propyl, methoxy, ethoxy, n- or i-propoxy, methylthio, ethylthio, n- or i-propylthio, methylsulphinyl, ethylsulphinyl, methylsulphonyl, ethylsulphonyl, methylamino, ethylamino, n- or i-propylamino, dimethylamino, diethylamino, acetyl, propionyl, i S methoxycarbonyl, ethoxycarbonyl, acetylamino, propionylamino, methoxycarbonylamino, ethoxycarbonylamino, methylsulphonylamino, ethylsulphonylamino, n- or i-propylsulphonylamino, XZ represents hydrogen, fluorine, chlorine or bromine, Z1 represents optionally substituted heteroaryl from the series consisting of furyl, benzofuryl, pyrrolyl, pyrazolyl, imidazolyl, triazolyl, oxazolyl, isoxazolyl, benzoxazolyl, thiazolyl, isothiazolyl, benzothiazolyl, benzimidazolyl, pyridinyl, quinolinyl, isoquinolinyl, pyrimidinyl, pyrazinyl, pyridazinyl, quinazolinyl or quinoxalinyl, where the possible substituents are preferably selected from the list below:
nitro, amino, hydroxyl, carboxyl, cyano, carbamoyl, thiocarbamoyl, aminosulphonyl, fluorine, chlorine, bromine, in each case optionally cyano-, fluorine-, chlorine-, methoxy- or ethoxy-substituted methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, methoxy, ethoxy, n- or i-propoxy, n-, i-, s- or t-Le A 32 843-Foreign countries butoxy, methylthio, ethylthio, n- or i-propylthio, n-, i-, s- or t-butylthio, methylsulphinyl, ethylsulphinyl, methylsulphonyl, ethylsulphonyl, methylamino, ethylamino, n- or i-propylamino, n-, i-, s- or t-butylamino, acetyl, propionyl, n- or i-butyroyl, methoxycarbonyl, ethoxycarbonyl, n- or i-S propoxycarbonyl, methylaminocarbonyl, ethylaminocarbonyl, n- or i-propylaminocarbonyl, acetylamino, propionylamino, n- or i-butyroylamino, methoxycarbonylamino, ethoxycarbonylamino, n- or i-propoxycarbonylamino, methylsulphonylamino, ethylsulphonylamino, n- or i-propylsulphonylamino, n-, i-, s- or t-butylsulphonylamino or phenyl, and Z2 represents one of the groupings below Q' Q' R, R' \ R~ Q ~ N R~ ~ N
~N- I ~N- I I I
R~ ~ N N\ N N\
Rzi R' RZ RZ R' I I l R' \ N R' NON Rz~N~IV Q~ RwN~IV
W
~ l ~ i N
R R Q Q
R' R~ O Q~ ( R~ R~ R~ Q~
R~ N R~ \
N-N ~ N\
N R~
Q' Rz R' Q' Rz ( ' Q N Q' z , RzwN~Q, R N Q
R w N Q
N % ~~ N N\ Rz/N N\
RZ N -Q Qi Le A 32 843-Foreign countries -g_ where Q1 represents O or S, R1 represents hydrogen, cyano, fluorine, chlorine, bromine, represents in each case optionally cyano-, fluorine-, chlorine-, methoxy- or ethoxy-substituted methyl, ethyl, n- or i-propyl, methoxy, ethoxy, n- or i-propoxy, methylthio, ethylthio, n- or i-propylthio, methylsulphinyl, ethylsulphinyl, methylsulphonyl, ethylsulphonyl, methylamino, ethylamino, n- or i-propylamino, dimethylamino or diethylamino, represents in each case optionally fluorine-, chlorine- or bromine-substituted ethenyl, propenyl, propenyloxy, propenylthio, propenylamino, ethinyl, propinyl, propinyloxy or propinylthio, represents in each case optionally cyano-, fluorine-, chlorine-, methyl-, ethyl-, n- or i-propyl-substituted cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclopropyloxy, cyclobutyloxy, cyclopentyloxy, cyclohexyloxy, cyclopropylamino, cyclobutylamino, cyclopentylamino or cyclohexylamino, or optionally together with an adjacent R1 represents propane-1,3-diyl (trimethylene) or butane-1,4-diyl (tetramethylene), and R2 represents hydrogen, cyano, formyl, represents in each case optionally cyano-, fluorine-, chlorine-, methoxy- or ethoxy-substituted methyl, ethyl, n- or i-propyl, acetyl, propionyl, n- or i-butyroyl, methoxycarbonyl, ethoxycarbonyl, n- or i-propoxycarbonyl, or represents in each case optionally fluorine-, chlorine- or bromine-substituted propenyl, butenyl, propinyl or butinyl.
A very particularly preferred group are those compounds of the general formula (I) in which Z2 represents the heterocyclic grouping below and Q, XI, X2 and Zl and have the meanings given above as being particularly preferred.
Le A 32 843-Foreign countries Rz I
RzwNiN~O
-N
O
A further very particularly preferred group are those compounds of the general formula (I) in which Z2 represents the heterocyclic grouping below and Q, X1, and Z1 and R1 and R2 have the meanings given above as being particularly preferred.
Rz R, N ~
/N
R' Most preference is given to compounds of the formula (Ia) Zz \ x, Xz ~ / Q (Ia) in which Q, X1, X2, Z1 and ZZ have the meanings given in Table 1 (after the Preparation Examples) and to the compounds of Preparation Examples 1 and 2.
The abovementioned general or preferred radical definitions apply both to the end products 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 one another at will, i.e. including combinations between the given preferred ranges.
Le A 32 843-Foreign countries The novel substituted heteroarylmethyl compounds of the general formula (I) have strong and selective herbicidal activity.
S The novel substituted heteroarylmethyl compounds of the general formula (I) are obtained when (a) phthalic anhydride or 3,4,5,6-tetrahydro-phthalic anhydride is reacted with aminobenzene derivatives of the general formula (II) HzN X~
Xz I / Q (.II) in which Q, X1, X2 and Z1 are as defined above, 1 S if appropriate in the presence of a diluent and if appropriate in the presence of a reaction auxiliary, or when (b) heterocyclylarenes of the general formula (III) Zz X' Xz I / Q (III) I
H
in which Q, Xl, X2 and ZZ are as defined above, Le A 32 843-Foreign countries are reacted with heteroarylmethyl halides of the general formula (N) X3_CH2_Z1 (IV) S in which Z1 is as defined above and X3 represents halogen, if appropriate in the presence of a diluent and if appropriate in the presence of a reaction auxiliary, or when (c) heterocyclylarenes of the general formula (V) Z2 X, (V) XZ ~ Xa in which X1, X2 and Z2 are as defined above and X4 represents halogen, are reacted with heteroarenes of the general formula (VI) HQ-CH2-Z1 (VI) in which Le A 32 843-Forei>;rl countries Q and Z1 are as defined above, if appropriate in the presence of a diluent and if appropriate in the presence of a reaction auxiliary, and, if appropriate, electrophilic or nucleophilic substitution reactions or oxidation or reduction reactions within the scope of the definition of the substituents are subsequently carned out in a customary manner.
Using, for example, phthalic anhydride and 1-amino-2-fluoro-4-(3,5-dimethyl-isoxazol-4-yl-methoxy)-benzene as starting materials, the course of the reaction in the process (a) according to the invention can be illustrated by the following formula scheme:
F O
O F
HzN \ \
\ I / ~ I / .N \
O +
/ O
O \ CH3 I N
o I ~~N
O
Using, for example, 4-(5-chloro-2-fluoro-4-mercapto-phenyl)-1,2-dimethyl-1,2,4-triazoline-3,5-dione and 2-chloro-5-chloromethyl-thiazole as starting materials, the course of the reaction in the process (b) according to the invention can be illustrated by the following formula scheme:
H3CN 1 0 H3C n F
CI
HsC-N Il N ~ \ + ~ SCI HsC-N
O
S N
I
CI H CI
Le A 32 843-Foreign countries Using, for example, 3-(2,4-difluoro-S-nitro-phenyl)-4-bromo-1-methyl-S-trifluoromethyl-1H-pyrazole and furfuryl alcohol as starting materials, the course of the reaction in the process (c) according to the invention can be illustrated by the following formula scheme:
S
HsC HsC
N-N F N-N F
F3C ~ ~ \ -~ HO F3C ~ I \
O
Br ~ / ~ ~ Br ~ / O
-F
O
N Oz N Oz The compounds phthalic anhydride and 3,4,5,6-tetrahydro-phthalic anhydride to be used as starting materials in the process (a) according to the invention for preparing compounds of the formula (I) are known organic chemicals for synthesis.
The formula (II) provides a general definition of the aminobenzene derivatives further to be used as starting materials in the process (a) according to the invention for preparing compounds of the formula (I). In the formula (II), Q, X1, X2 and preferably or in particular have those meanings which have already been mentioned 1 S 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 Q, X1, X2 and Z1.
The starting materials of the general formula (II) are known and/or can be prepared by processes known per se (cf. Justus Liebigs Ann. Chem. 733 (1970), 125-140;
DE-A-2842186; US-A-5344812; US-A-5399543; WO-A-9S 17096; Preparation Examples).
The formula (III) provides a general definition of the heterocyclylarenes to be used as 2S starting materials in the process (b) according to the invention for preparing compounds of the formula (I). In the formula (III), Q, Xt, XZ and Z2 preferably or in Le A 32 843-Foreign countries 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 Q, X 1, X2 and Z2.
The starting materials of the general formula (III) are known and/or can be prepared by processes known per se (cf. EP-A-545206; JP-A-04178373; WO-A-9618618;
Preparation Examples).
The formula (IV) provides a general definition of the heteroarylmethyl halides further to be used as starting materials in the process (b) according to the invention. In the formula (N), Z1 preferably or in particular has 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 Z1; X3 preferably represents fluorine, chlorine, bromine or iodine, in particular chlorine or bromine.
The starting materials of the general formula (N) are known organic chemicals for synthesis.
The formula (V) provides a general definition of the heterocyclylarenes to be used as starting materials in the process (c) according to the invention for preparing compounds of the formula (I). In the formula (V), X1, X2 and Z2 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 X1, X2 and Z2; X4 preferably represents fluorine, chlorine or bromine, in particular fluorine or chlorine.
The starting materials of the general formula (V) are known and/or can be prepared by processes known per se (cf. US-A-5281571, WO-A-9206962; WO-A-9618618).
Le A 32 843-Foreign countries The formula (VI) provides a general definition of the heteroarenes further to be used as starting materials in the process (c) according to the invention. In the formula (VI), Q and Z1 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 Q and Z1.
The starting materials of the general formula (VI) are known organic chemicals for synthesis.
The processes according to the invention for preparing compounds of the general formula (I) are preferably carried out using diluents. Suitable diluents for carrying out the processes (a) to (c) according to the invention are especially inert organic solvents. These include, in particular, aliphatic, alicyclic or aromatic, optionally halogenated hydrocarbons, such as, for example, benzine, benzene, toluene, xylene, chlorobenzene, dichlorobenzene, petroleum ether, hexane, cyclohexane, dichloromethane, chloroform, carbon tetrachloride; ethers, such as diethyl ether, diisopropyl ether, dioxane, tetrahydrofuran or ethylene glycol dimethyl ether or ethylene glycol diethyl ether; ketones, such as acetone, butanone or methyl isobutyl ketone; 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, diethylene glycol monoethyl ether, mixtures thereof with water or pure water.
Suitable reaction auxiliaries for the processes (a) to (c) 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 acetate or calcium Le A 32 843-Foreign countries acetate, lithium amide, sodium amide, potassium amide or calcium amide, sodium carbonate, potassium carbonate or calcium carbonate, sodium bicarbonate, potassium bicarbonate or calcium bicarbonate, lithium hydride, sodium hydride, potassium hydride or calcium hydride, lithium hydroxide, sodium hydroxide, 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-propoxide, n-, i-, s- or t-butoxide; furthermore also basic organic nitrogen compounds, such as, for example, trimethylamine, triethylamine, tripropylamine, tributylamine, ethyl-diisopropylamine, N,N-dimethylcyclohexylamine, dicyclohexylamine, ethyl-dicyclohexylamine, 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, S-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-S-ene (DBN) or 1,8-diazabicyclo[5.4.0]-undec-7-ene (DBU).
When carrying out the processes (a) to (c) according to the invention, the reaction temperatures can be varied within a relatively wide range. In general, the processes are carried out at temperatures between 0°C and 200°C, preferably between 10°C
and 150°C.
The processes (a) to (c) according to the invention are generally carried out under atmospheric pressure. However, it is also possible to carry out the processes according to the invention under elevated or reduced pressure - generally between 0.1 bar and 10 bar.
For carrying out the processes (a) to (c) according to the invention, the starting materials are generally employed in approximately equimolar amounts. However, it is also possible for one of the components to be used in a relatively large excess. The reaction is generally carried out in a suitable diluent in the presence of a reaction auxiliary, and the reaction mixture is generally stirred at the required temperature for Le A 32 843-Foreign countries several hours. Work-up is carried out by customary methods (cf. the Preparation Examples).
The active compounds according to the invention can be used as defoliants, desiccants, haulm killers and, especially, as weed killers. By weeds in the broadest sense there 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 connection with the following plants:
Dicotyledonous weeds of the eg nera: Sinapis, Lepidium, Galium, Stellaria, Matricaria, Anthemis, Galinsoga; Chenopodium, Urtica, Senecio, Amaranthus, Portulaca, Xanthium, Convolvulus, Ipomoea, Polygonum, Sesbania, Ambrosia, Cirsium, Carduus, Sonchus, .Solanum, Rorippa, Rotala, Lindernia, Lamium, Veronica, Abutilon, Emex, Datura, Viola, Galeopsis, Papaver, Centaurea, Trifolium, Ranunculus, Taraxacum.
Dicoyledonous cress of the eg_ nera: Gossypium, Glycine, Beta, Daucus, Phaseolus, Pisum, Solanum, Linum, Ipomoea, Vicia, Nicotiana, Lycopersicon, Arachis, Brassica, Lactuca, Cucumis, Cucurbita.
Monocotyledonous weeds of the Qenera: Echinochloa, Setaria, Panicum, Digitaria, Phleum, Poa, Festuca, Eleusine, Brachiaria, Lolium, Bromus, Avena, Cyperus, Sorghum, Agropyron, Cynodon, Monochoria, Fimbristylis, Sagittaria, Eleocharis, Scirpus, Paspalum, Ischaemum, Sphenoclea, Dactyloctenium, Agrostis, Alopecurus, Apera.
Monocotyledonous crops of the eg nera: Oryza, Zea, Triticum, Hordeum, Avena, Seca.le, Sorghum, Panicum, Saccharum, Ananas, Asparagus, Allium.
Le A 32 843-Foreign countries 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.
Depending on the concentration, the compounds are suitable for total weed control, for example on industrial terrain and rail tracks and on paths and areas with or without tree growth. Equally, the compounds can be employed for controlling weeds in perennial crops, for example forests, ornamental tree plantings, orchards, vineyards, citrus groves, nut orchards, banana plantations, coffee plantations, tea plantations, rubber plantations, oil palm plantations, cocoa plantations, soft fruit plantings and hop fields, on lawns and turf and pastures and for selective weed control in annual crops.
The compounds of the formula (n according to the invention are particularly suitable 1 S for selective control of monocotyledonous and dicotyledonous weeds in monocotyledonous and dicotyledonous crops, both by the pre-emergence and by the post-emergence method.
The active compounds can be converted into the customary formulations, such as solutions, emulsions, wettable powders, suspensions, powders, dusts, pastes, soluble powders, granules, suspo-emulsion concentrates, natural and synthetic substances impregnated with active compound, and microencapsulations in polymeric substances.
These formulations are produced in a known manner, for example by mixing the active compounds with extenders, that is to say liquid solvents and/or solid earners, optionally with the use of surfactants, that is to say emulsifiers and/or dispersants and/or foam formers.
If the extender used is water, it is also possible to use, for example, organic solvents as auxiliary solvents. Liquid solvents which are mainly suitable are:
aromatics, such Le A 32 843-Foreign countries as xylene, toluene or alkylnaphthalenes, chlorinated aromatics and chlorinated aliphatic hydrocarbons, such as chlorobenzenes, chloroethylenes or methylene chloride, aliphatic hydrocarbons, such as cyclohexane or paraffins, for example petroleum fractions, mineral and vegetable oils, alcohols, such as butanol or glycol, and also their ethers and esters, ketones, such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, strongly polar solvents, such as dimethylformamide and dimethyl sulphoxide, and water.
Suitable solid carriers are: for example ammonium salts and ground natural minerals, such as kaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth, and ground synthetic minerals, such as finely divided silica, alumina and silicates; suitable solid carriers for granules are: for example crushed and fractionated natural rocks, such as calcite, marble, pumice, sepiolite, dolomite and synthetic granules of inorganic and organic meals, and granules of organic material, such as sawdust, coconut shells, maize cobs and tobacco stalks;
suitable emulsifiers and/or foam formers are: for-example nonionic and anionic emulsifiers, such as polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers, for example alkylaryl polyglycol ethers, alkylsulphonates, alkyl sulphates, arylsulphonates and protein hydrolysates; suitable dispersants are: for example lignosulphite waste liquors and methylcellulose.
Tackifiers, such as carboxymethylcellulose, natural and synthetic polymers in the form of powders, granules or latices, such as gum arabic, polyvinyl alcohol and polyvinyl acetate, and also natural phospholipids, such as cephalins and lecithins, and synthetic phospholipids can be used in the formulations. Other possible additives are mineral and vegetable oils.
It is possible to use dyestuffs, such as inorganic pigments, for example iron oxide, titanium oxide, Prussian blue, and organic dyestuffs, such as alizarin dyestuffs, azo dyestuffs and metal phthalocyanine dyestuffs, and trace nutrients, such as salts of iron, manganese, boron, copper, cobalt, molybdenum and zinc.
Le A 32 843-Foreign countries The formulations generally 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, finished 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, amidosulfuron, anilofos, asulam, atrazine, azafenidin, azimsulfuron, benazolin(-ethyl), benfuresate, bensulfuron(-methyl), bentazone, benzofenap, benzoylprop(-ethyl), bialaphos, bifenox, bispyribac(-sodium), bromobutide, bromofenoxim, bromoxynil, butachlor, butroxydim, butylate, cafenstrole, c:aloxydim, carbetamide, carfentrazone(-ethyl), chlomethoxyfen, chloramben, chloridazon, chlorimuron(-ethyl), chlornitrofen, chlorsulfuron, chlorotoluron, cinmethylin, cinosulfuron, clethodim, clodinafop(-propargyl), clomazone, clomeprop, clopyralid, clopyrasulfuron(-methyl), cloransulam(-methyl), cumyluron, cyanazine, cycloate, cyclosulfamuron, cycloxydim, cyhalofop(-butyl), 2,4-D, 2,4-DB, 2,4-DP, desmedipham, diallate, dicamba, diclofop(-methyl), diclosulam, diethatyl(-ethyl), difenzoquat, diflufenican, diflufenzopyr, dimefuron, dimepiperate, dimethachlor, dimethametryn, dimethenamid, dimexyflam, dinitramine, diphenamid, diquat, dithiopyr, diuron, dymron, epoprodan, EPTC, esprocarb, ethalfluralin, ethametsulfuron(-methyl), ethofumesate, ethoxyfen, ethoxysulfuron, etobenzanid, fenoxaprop-(-P-ethyl), flamprop(-isopropyl), flamprop(-isopropyl-L), flam-prop(-methyl), flazasulfuron, fluazifop(-P-butyl), flumetsulam, flumiclorac(-pentyl), flumioxazin, flumipropyn, flumetsulam, fluometuron, fluorochloridone, fluoroglycofen(-ethyl), flupoxam, flupropacil, flurpyrsulfuron(-methyl, -sodium), flurenol(-butyl), fluridone, fluroxypyr(-meptyl), flurprimidol, flurtamone, fluthi-acet(-methyl), fluthiamide, fomesafen, glufosinate(-ammonium), glyphosate-Le A 32 843-Foreign countries (-isopropylammonium), halosafen, haloxyfop(-ethoxyethyl), haloxyfop(-p-methyl), hexazinone, imazamethabenz-(-methyl), imazamethapyr, imazamox, imazapyr, imazaquin, imazethapyr, imazosulfuron, ioxynil, isopropalin, isoproturon, isouron, isoxaben, isoxaflutole, isoxapyrifop, lactofen, lenacil, linuron, MCPA, MCPP, S mefenacet, metamitron, metazachlor, methabenzthiazuron, metobenzuron, metobromuron, (alpha-)metolachlor, metosulam, metoxuron, metribuzin, metsulfuron(-methyl), molinate, monolinuron, naproanilide, napropamide, neburon, nicosulfuron, norflurazon, orbencarb, oryzalin, oxadiargyl, oxadiazon, oxasulfuron, oxaziclomefone, oxyfluorfen, paraquat, pelargonic acid, pendimethalin, pentoxazone, phenmedipham, piperophos, pretilachlor, primisulfuron(-methyl), prometryn, propachlor, propanil, propaquizafop, propisochlor, propyzamide, prosulfocarb, prosulfuron, pyraflufen(-ethyl), pyrazolate, pyrazosulfuron(-ethyl), pyrazoxyfen, pyribenzoxim, pyributicarb, pyridate, pyriminobac-(-methyl), pyrithiobac(-sodium), quinchlorac, quinmerac, quinoclamine, quizalofop(-P-ethyl), quizalofop(-P-tefuryl), rimsulfuron, sethoxydim, simazine, simetryn, sulcotrione, sulfentrazone, sulfometuron(-methyl). sulfosate, sulfosulfuron, tebutam, tebuthiuron, terbuthylazine, terbutryn, thenylchlor, thiafluamide, thiazopyr, thidiazimin, thifensulfuron(-methyl), thiobencarb, tiocarbazil, tralkoxydim, triallate, triasulfuron, tribenuron(-methyl), triclopyr, tridiphane, trifluralin and triflusulfuron.
A mixture with other known active compounds, such as fungicides, insecticides, acaricides, nematicides, bird repellents, plant nutrients and agents which improve soil structure, is 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, suspensions, emulsions, powders, pastes and granules. They are used in the customary manner, for example by watering, spraying, atomizing, scattering.
Le A 32 843-Foreign countries The active compounds according to the invention can be applied both before and after emergence of the plants. They can also be incorporated into the soil before sowing.
S The amount of active compound used can vary within a relatively wide 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 S g and 5 kg per ha.
The preparation and the use of the active compounds according to the invention can be seen from the examples below.
Le A 32 843-Foreign countries Preparation Examples:
Example 1 O
N
O
F / O ~ ~N
CI
(Process (a)) A mixture of 2.0 g (8 mmol) of 1-amino-2-fluoro-4-(2-chloro-pyridin-S-yl-methoxy)-benzene, 1.2 g (8 mmol) of phthalic anhydride and 50 ml of acetic acid is heated under reflux for 5 hours, then stirred at room temperature for 18 hours and subsequently heated under reflux for another 4 hours. The mixture is then concentrated under water pump vacuum, the residue is shaken with water/ethyl acetate and the organic phase is separated off, washed with water, dried with sodium sulphate and filtered. The filtrate is concentrated under water pump vacuum, the 1 S residue is digested with diisopropyl ether and the crystalline product is isolated by filtration with suction.
This gives 1.9 g (62% of theory) of N-(2-fluoro-(2-chloro-pyridin-5-yl-methoxy)-phenyl]-phthalimide of melting point 183°C.
Le A 32 843-Foreign countries Example 2 FZHC O
N
Fi3C N' 'N
O
F / O ~ ~N
CI
(Process (b)) A mixture of 0.90 g (3.3 mmol) of 4-(2-fluoro-4-hydroxy-phenyl)-2-difluoromethyl-1-methyl-1,2,4-triazoline-3,5-dione, 0.65 g (3.3 mmol) of 2-chloro-5-chloromethyl-pyridine, 0.55 g of potassium carbonate and 10 ml of N,N-dimethyl-formamide is stirred at 80°C for 3 hours. After slight cooling, the mixture is then poured into a solvent mixture of 1N hydrochloric acid and diethyl ether which has been admixed with ice beforehand. After thorough stirring, the crystalline product is isolated by filtration with suction.
This gives 0.35 g (26.5% of theory) of 4-[2-fluoro-4-(2-chloro-pyridin-S-yl methoxy)-phenyl)-2-difluoromethyl-1-methyl-1,2,4-triazoline-3,5-dione of melting point 134°C.
Analogously to Preparation Examples 1 and 2 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 (Ia) listed in Table 1 below.
Zz \ X' XZ ~ / Q (Ia) ~Z' Le A 32 843-Forei>;n countries Table 1: Examples of the compounds of the formula (Ia) Ex. Q Xl XZ Zl Z2 Melting point No. (C) 3 O H F w N (amorphous) N-/ CI
O
4 O H F ~ N cH3 73 CI
5 O H F ~ N (amorphous) /
CI ~ N
N
CI
6 O N02 F ~ N CH3 170 / F3C Nw CI ~ ~N
CI
7 O NH2 F w N ~H3 116 CI
8 O H F ~ N FZH ~ ~H3 1 O8 / p CI
Br Le A 32 843-Foreign countries Ex. Q X1 X2 Zl Z2 Melting point No. (°C) 9 O H F ~ N FZHC CH3 90 p Nw CI ~ ~N
CI
O H F ~N FZH ; ~ H3 106 p Nw S---~ ~ ~N
CI
11 O H F ~N FZH ; CH3 81 N~
S--C ~ I N
CI CI
12 O H F ~ ~H3 107 N
C ~N/N
SCI
CI
The compound listed in Table 1 as Example No. 6 can, for example, be prepared as follows:
FsC NOz O ~ ~N
CI
0.56 g ( 14 mmol) of 60% sodium hydride in mineral oil is added to a solution of 2.3 g ( 15 mmol) of 2-chloro-5-hydroxymethyl-pyridine in 20 ml of acetonitrile. The 10 mixture is stirred at room temperature (about 20°C) for 15 minutes, and then admixed with 3.4 g (10 mmol) of 4-chloro-3-(2,4-difluoro-5-nitro-phenyl)-1-methyl-Le A 32 843-Foreign countries 5-trifluoromethyl-1H-pyrazole and stirred at room temperature for 4 hours. The mixture is then diluted with approximately equal amounts of water and ethyl acetate to about three times its volume and acidified with 2N hydrochloric acid. The organic phase is separated off, washed with saturated aqueous sodium bicarbonate solution S and with saturated sodium chloride solution, dried with sodium sulphate and filtered.
The solvent is carefully distilled off from the filtrate under water pump vacuum.
This gives 4.6 g (99% of theory) of 4-chloro-3-[4-[(2-chloro-pyridin-5-yl)-methoxy]
2-fluoro-5-nitro-phenyl]-1-methyl-S-trifluoromethyl-1H-pyrazole of melting point 170°C.
The compound listed in Table 1 as Example No. 7 can, for example, be prepared as follows:
N~N
F3C ~ ' ~ NHZ
CI ~ /~
F- v _O ~ N
CI
At from 80°C to 90°C, a suspension of 27 g (58 mmol) of 4-chloro-3-[4-[(2-chloro-pyridin-5-yl)-methoxy]-2-fluoro-S-nitro-phenyl]-1-methyl-5-tri fluoromethyl-1 H-pyrazole in a mixture of 120 ml of acetic acid and 60 ml of ethyl acetate is slowly metered into a suspension of 32.3 g (0.58 mol) of iron (powder) and 72 ml of 5%
strength aqueous acetic acid. The reaction mixture is stirred at room temperature (about 20°C) for 150 minutes and then filtered through Celite~ (filter aid based on kieselguhr). The filtration residue is washed with water and ethyl acetate and the organic phases are separated off and pooled, washed with saturated aqueous sodium bicarbonate solution and saturated aqueous sodium chloride solution, dried with sodium sulphate and filtered. The solvent is carefully distilled off from the filtrate under water pump vacuum.
a Le A 32 843-Foreign countries This gives 24.8 g (98% of theory) of 4-chloro-3-[5-amino-4-[(2-chloro-pyridin-5-yl)-methoxy]-2-fluoro-phenyl)-1-methyl-5-trifluoromethyl-1H-pyrazole of melting point 116°C.
The compound listed in Table 1 as Example No. 4 can, for example, be prepared as follows:
N~N
CI
F / O ~ ~N
CI
r1 solution of 2.8 g (6.4 mmol) of 4-chloro-3-[5-amino-4-[(2-chloro-pyridin-S-yl)-methoxy]-2-fluoro-phenyl)-1-methyl-5-trifluoromethyl-1H-pyrazole in 20 ml of tetrahydrofuran is heated to reflux, with dropwise addition of 1.7 ml (12:8 mmol) of n-pentyl nitrite. The complete reaction mixture is heated under reflux for another 30 minutes and then concentrated under water pump vacuum. The oily residue is purified by column chromatography (silica gel, dichloromethane/methanol, vol.:
100:1 ).
This gives 0.65 g (24% of theory) of 4-chloro-3-[4-[(2-chloro-pyridin-5-yl)-methoxy]-2-fluoro-phenyl]-1-methyl-5-trifluoromethyl-1H-pyrazole of melting point 73°C.
1x A 32 843-Foreign countries Starting materials of the formula (II):
Example (II-1) F / O ~ ~N
CI
Step 1 OZN
F / O ~ ~N
CI
A mixture of 8.65 g (55 mmol) of 3-fluoro-4-nitro-phenol, 9.72 g (60 mmol) of chloro-S-chloromethyl-pyridine, 8.3 g (60 mmol) of potassium carbonate and 1~0 ml of butanone is heated at 80°C for 10 hours and then concentrated under water pump vacuum. The residue is stirred with a solvent mixture of aqueous 2N
hydrochloric acid, ethyl acetate and diethyl ether, and the crystalline product is isolated by filtration with suction.
This gives 9.8 g (63% of theory) of 2-chloro-5-(3-fluoro-4-nitro-phenoxymethyl)-pyridine of melting point 174°C.
St_ ep 2 HzN
F / O ~ ~N
CI
9.5 g (33.6 mmol) of 2-chloro-5-(3-fluoro-4-nitro-phenoxymethyl)-pyridine are initially charged in a mixture of 150 ml of acetic acid and 10 ml of water, and the Le A 32 843-Foreign countries mixture is heated to 50°C. 9.5 g of iron (powder) are then added a little at a time, and the reaction mixture is stirred for about 60 minutes at from 20°C
to 25°C and then filtered. The filtrate is concentrated, the residue is shaken with water/ethyl acetate and the organic phase is washed with water, dried with sodium sulphate and S filtered. The filtrate is concentrated under water pump vacuum, the residue is digested with petroleum ether and the crystalline product is isolated by filtration with suction.
This gives 7.3 g (86% of theory) of 2-chloro-S-(4-amino-3-fluoro-phenoxymethyl)-pyridine of melting point 101 °C.
Le A 32 843-Foreign countries Starting materials of the formula (III):
Example (III-1 ) FZHC O
N
HsC N II N
\
O /
F OH
Step 1 O
HsC2wO~NiH
I
~N~O
H3 'I~C
H'N ~ \
15.0 g (106.4 mmol) of 1-amino-2-fluoro-4-methoxy-benzene are initially charged in 400 ml of ethyl acetate and, at room temperature, admixed dropwise with stirring with 47 g of trichloromethyl chloroformate ("diphosgene"). The mixture is then heated under reflux for two hours and subsequently concentrated under water pump vacuum. The residue is taken up in 200 ml of acetonitrile and admixed with 23 g of 2-methyl-1-ethoxycarbonyl-hydrazine and 9.8 g of sodium bicarbonate. This mixture is then heated under reflux for 16 hours and subsequently concentrated under water pump vacuum. The residue is stirred with a mixture of 1N-hydrochloric acid and diethyl ether and the crystalline product is isolated by filtration with suction.
This gives 21.5 g (71% of theory) of 4-(2-fluoro-4-methoxy-phenyl)-1-ethoxycarbonyl-2-methyl-semicarbazide.
1H-NMR (DMSO-D6, 8, ppm): 2.98 (N-CH3).
Le A 32 843-Foreign countries Sten 2 H
'-O
~I//
HsC_N~N \
O
A mixture of 21.0 g (83.7 mmol) of 4-(2-fluoro-4-methoxy-phenyl)-1-ethoxycarbonyl-2-methyl-semicarbazide and 210 ml of 4N aqueous sodium hydroxide solution is heated at 80°C for 20 minutes and then cooled to 10°C and subsequently admixed with 70 ml of cone. hydrochloric acid. The mixture is then shaken with methylene chloride, and the organic phase is washed with water, dried with sodium sulphate and filtered. The filtrate is concentrated under water pump vacuum, the residue is digested with diethyl ether and the crystalline product is isolated by filtration with suction.
This gives 13.9 g (79% of theory) of 4-(2-fluoro-4-methoxy-phenyl)-1-methyl-1,2,3-triazoline-3,5-dione.
1H-NMR (DMSO-D6, 8, ppm): 3.81 (O-CH3).
Step 3 FZHC O
N
HsC-N II N \
O ( /
Chlorodifluoromethane is passed through a mixture, heated to 100°C, of 14.0 g (58.6 mmol) of 4-(2-fluoro-4-methoxy-phenyl)-1-methyl-1,2,3-triazoline-3,5-dione, 8.5 g of potassium carbonate and 50 ml of N,N-dimethyl-formamide for three hours.
After slight cooling, the mixture is poured into ice-water, acidified with 2N
Le A 32 843-Foreign countries hydrochloric acid and shaken with ethyl acetate. The organic phase is separated off, washed with water, dried with sodium sulphate and filtered. The filtrate is concentrated under water pump vacuum and the residue is separated by column chromatography (silica gel, ethyl acetate/hexane, vol. 1:2).
This gives (as second fraction) 4.0 g (24% of theory) of 4-(2-fluoro-4-methoxy-phenyl)-2-difluoromethyl-1-methyl-1,2,3-triazoline-3,5-dione of melting point 88°C.
Step 4 FZHC O
N
HsC_N~N \
O ~ /
F OH
2.0 g (6.9 mmol) of 4-(2-fluoro-4-methoxy-phenyl)-2-difluoromethyl-1-methyl-1,2,3-triazoline-3,5-dione are dissolved in 30 ml of methylene chloride, and this mixture is added dropwise with stirnng to a solution of 3 g of boron trifluoride in 30 ml of methylene chloride. The reaction mixture is then stirred at room temperature for 6 hours. After addition of 50 ml of water, the organic phase is separated off, washed with water, dried with sodium sulphate and filtered. The solvent is carefully distilled off from the filtrate under water pump vacuum.
This gives 1.6 g (84% of theory) of 4-(2-fluoro-4-hydroxy-phenyl)-2-difluoromethyl-1-methyl-1,2,3-triazoline-3,5-dione of melting point 141°C.
Le A 32 843-Foreign countries 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 emulsifier is added and the concentrate is diluted with water to the desired concentration.
Seeds of the test plants are sown in normal soil. After about 24 hours, the soil is sprayed with the preparation of active compound such that the particular amounts of active compound desired are applied per unit area. The concentration of the spray liquor is chosen so that the particular amounts of active compound desired are applied in 10001 of water/ha.
After three weeks, the degree of damage to the plants is rated in % damage in comparison to the development of the untreated control.
The figures denote:
0 % - no effect (like untreated control) 100 % - total destruction In this test, for example, the compounds of Preparation Example l, 2, 3 and 4 exhibit strong activity against weeds, and some of them are tolerated well by crop plants, such as, for example, maize and wheat.
Le A 32 843-Foreign countries Example B
Post-emergence test Solvent: 5 parts by weight of acetone Emulsifier: 1 part by weight of alkylaryl polyglycol ether To produce a suitable preparation of active compound, 1 part by weight of active compound is mixed with the stated amount of solvent, the stated amount of emulsifier is added and the concentrate is diluted with water to the desired concentration.
Test plants of a height of 5 - 15 cm are sprayed with the preparation of active compound such that the particular amounts of active compound desired are applied per unit area. The concentration of the spray liquor is chosen so that the particular arr~ounts of active compound desired are applied in 10001 of water/ha.
After three weeks, the degree of damage to the plants is rated in % damage in comparison to the development of the untreated control.
The figures denote:
0% = no effect (like untreated control) 100% = total destruction In this test, for example, the compounds of Preparation Example 2, 3, 4 and 5 exhibit strong activity against weeds, and some of them are tolerated well by crop plants, such as, for example, wheat.
Br Le A 32 843-Foreign countries Ex. Q X1 X2 Zl Z2 Melting point No. (°C) 9 O H F ~ N FZHC CH3 90 p Nw CI ~ ~N
CI
O H F ~N FZH ; ~ H3 106 p Nw S---~ ~ ~N
CI
11 O H F ~N FZH ; CH3 81 N~
S--C ~ I N
CI CI
12 O H F ~ ~H3 107 N
C ~N/N
SCI
CI
The compound listed in Table 1 as Example No. 6 can, for example, be prepared as follows:
FsC NOz O ~ ~N
CI
0.56 g ( 14 mmol) of 60% sodium hydride in mineral oil is added to a solution of 2.3 g ( 15 mmol) of 2-chloro-5-hydroxymethyl-pyridine in 20 ml of acetonitrile. The 10 mixture is stirred at room temperature (about 20°C) for 15 minutes, and then admixed with 3.4 g (10 mmol) of 4-chloro-3-(2,4-difluoro-5-nitro-phenyl)-1-methyl-Le A 32 843-Foreign countries 5-trifluoromethyl-1H-pyrazole and stirred at room temperature for 4 hours. The mixture is then diluted with approximately equal amounts of water and ethyl acetate to about three times its volume and acidified with 2N hydrochloric acid. The organic phase is separated off, washed with saturated aqueous sodium bicarbonate solution S and with saturated sodium chloride solution, dried with sodium sulphate and filtered.
The solvent is carefully distilled off from the filtrate under water pump vacuum.
This gives 4.6 g (99% of theory) of 4-chloro-3-[4-[(2-chloro-pyridin-5-yl)-methoxy]
2-fluoro-5-nitro-phenyl]-1-methyl-S-trifluoromethyl-1H-pyrazole of melting point 170°C.
The compound listed in Table 1 as Example No. 7 can, for example, be prepared as follows:
N~N
F3C ~ ' ~ NHZ
CI ~ /~
F- v _O ~ N
CI
At from 80°C to 90°C, a suspension of 27 g (58 mmol) of 4-chloro-3-[4-[(2-chloro-pyridin-5-yl)-methoxy]-2-fluoro-S-nitro-phenyl]-1-methyl-5-tri fluoromethyl-1 H-pyrazole in a mixture of 120 ml of acetic acid and 60 ml of ethyl acetate is slowly metered into a suspension of 32.3 g (0.58 mol) of iron (powder) and 72 ml of 5%
strength aqueous acetic acid. The reaction mixture is stirred at room temperature (about 20°C) for 150 minutes and then filtered through Celite~ (filter aid based on kieselguhr). The filtration residue is washed with water and ethyl acetate and the organic phases are separated off and pooled, washed with saturated aqueous sodium bicarbonate solution and saturated aqueous sodium chloride solution, dried with sodium sulphate and filtered. The solvent is carefully distilled off from the filtrate under water pump vacuum.
a Le A 32 843-Foreign countries This gives 24.8 g (98% of theory) of 4-chloro-3-[5-amino-4-[(2-chloro-pyridin-5-yl)-methoxy]-2-fluoro-phenyl)-1-methyl-5-trifluoromethyl-1H-pyrazole of melting point 116°C.
The compound listed in Table 1 as Example No. 4 can, for example, be prepared as follows:
N~N
CI
F / O ~ ~N
CI
r1 solution of 2.8 g (6.4 mmol) of 4-chloro-3-[5-amino-4-[(2-chloro-pyridin-S-yl)-methoxy]-2-fluoro-phenyl)-1-methyl-5-trifluoromethyl-1H-pyrazole in 20 ml of tetrahydrofuran is heated to reflux, with dropwise addition of 1.7 ml (12:8 mmol) of n-pentyl nitrite. The complete reaction mixture is heated under reflux for another 30 minutes and then concentrated under water pump vacuum. The oily residue is purified by column chromatography (silica gel, dichloromethane/methanol, vol.:
100:1 ).
This gives 0.65 g (24% of theory) of 4-chloro-3-[4-[(2-chloro-pyridin-5-yl)-methoxy]-2-fluoro-phenyl]-1-methyl-5-trifluoromethyl-1H-pyrazole of melting point 73°C.
1x A 32 843-Foreign countries Starting materials of the formula (II):
Example (II-1) F / O ~ ~N
CI
Step 1 OZN
F / O ~ ~N
CI
A mixture of 8.65 g (55 mmol) of 3-fluoro-4-nitro-phenol, 9.72 g (60 mmol) of chloro-S-chloromethyl-pyridine, 8.3 g (60 mmol) of potassium carbonate and 1~0 ml of butanone is heated at 80°C for 10 hours and then concentrated under water pump vacuum. The residue is stirred with a solvent mixture of aqueous 2N
hydrochloric acid, ethyl acetate and diethyl ether, and the crystalline product is isolated by filtration with suction.
This gives 9.8 g (63% of theory) of 2-chloro-5-(3-fluoro-4-nitro-phenoxymethyl)-pyridine of melting point 174°C.
St_ ep 2 HzN
F / O ~ ~N
CI
9.5 g (33.6 mmol) of 2-chloro-5-(3-fluoro-4-nitro-phenoxymethyl)-pyridine are initially charged in a mixture of 150 ml of acetic acid and 10 ml of water, and the Le A 32 843-Foreign countries mixture is heated to 50°C. 9.5 g of iron (powder) are then added a little at a time, and the reaction mixture is stirred for about 60 minutes at from 20°C
to 25°C and then filtered. The filtrate is concentrated, the residue is shaken with water/ethyl acetate and the organic phase is washed with water, dried with sodium sulphate and S filtered. The filtrate is concentrated under water pump vacuum, the residue is digested with petroleum ether and the crystalline product is isolated by filtration with suction.
This gives 7.3 g (86% of theory) of 2-chloro-S-(4-amino-3-fluoro-phenoxymethyl)-pyridine of melting point 101 °C.
Le A 32 843-Foreign countries Starting materials of the formula (III):
Example (III-1 ) FZHC O
N
HsC N II N
\
O /
F OH
Step 1 O
HsC2wO~NiH
I
~N~O
H3 'I~C
H'N ~ \
15.0 g (106.4 mmol) of 1-amino-2-fluoro-4-methoxy-benzene are initially charged in 400 ml of ethyl acetate and, at room temperature, admixed dropwise with stirring with 47 g of trichloromethyl chloroformate ("diphosgene"). The mixture is then heated under reflux for two hours and subsequently concentrated under water pump vacuum. The residue is taken up in 200 ml of acetonitrile and admixed with 23 g of 2-methyl-1-ethoxycarbonyl-hydrazine and 9.8 g of sodium bicarbonate. This mixture is then heated under reflux for 16 hours and subsequently concentrated under water pump vacuum. The residue is stirred with a mixture of 1N-hydrochloric acid and diethyl ether and the crystalline product is isolated by filtration with suction.
This gives 21.5 g (71% of theory) of 4-(2-fluoro-4-methoxy-phenyl)-1-ethoxycarbonyl-2-methyl-semicarbazide.
1H-NMR (DMSO-D6, 8, ppm): 2.98 (N-CH3).
Le A 32 843-Foreign countries Sten 2 H
'-O
~I//
HsC_N~N \
O
A mixture of 21.0 g (83.7 mmol) of 4-(2-fluoro-4-methoxy-phenyl)-1-ethoxycarbonyl-2-methyl-semicarbazide and 210 ml of 4N aqueous sodium hydroxide solution is heated at 80°C for 20 minutes and then cooled to 10°C and subsequently admixed with 70 ml of cone. hydrochloric acid. The mixture is then shaken with methylene chloride, and the organic phase is washed with water, dried with sodium sulphate and filtered. The filtrate is concentrated under water pump vacuum, the residue is digested with diethyl ether and the crystalline product is isolated by filtration with suction.
This gives 13.9 g (79% of theory) of 4-(2-fluoro-4-methoxy-phenyl)-1-methyl-1,2,3-triazoline-3,5-dione.
1H-NMR (DMSO-D6, 8, ppm): 3.81 (O-CH3).
Step 3 FZHC O
N
HsC-N II N \
O ( /
Chlorodifluoromethane is passed through a mixture, heated to 100°C, of 14.0 g (58.6 mmol) of 4-(2-fluoro-4-methoxy-phenyl)-1-methyl-1,2,3-triazoline-3,5-dione, 8.5 g of potassium carbonate and 50 ml of N,N-dimethyl-formamide for three hours.
After slight cooling, the mixture is poured into ice-water, acidified with 2N
Le A 32 843-Foreign countries hydrochloric acid and shaken with ethyl acetate. The organic phase is separated off, washed with water, dried with sodium sulphate and filtered. The filtrate is concentrated under water pump vacuum and the residue is separated by column chromatography (silica gel, ethyl acetate/hexane, vol. 1:2).
This gives (as second fraction) 4.0 g (24% of theory) of 4-(2-fluoro-4-methoxy-phenyl)-2-difluoromethyl-1-methyl-1,2,3-triazoline-3,5-dione of melting point 88°C.
Step 4 FZHC O
N
HsC_N~N \
O ~ /
F OH
2.0 g (6.9 mmol) of 4-(2-fluoro-4-methoxy-phenyl)-2-difluoromethyl-1-methyl-1,2,3-triazoline-3,5-dione are dissolved in 30 ml of methylene chloride, and this mixture is added dropwise with stirnng to a solution of 3 g of boron trifluoride in 30 ml of methylene chloride. The reaction mixture is then stirred at room temperature for 6 hours. After addition of 50 ml of water, the organic phase is separated off, washed with water, dried with sodium sulphate and filtered. The solvent is carefully distilled off from the filtrate under water pump vacuum.
This gives 1.6 g (84% of theory) of 4-(2-fluoro-4-hydroxy-phenyl)-2-difluoromethyl-1-methyl-1,2,3-triazoline-3,5-dione of melting point 141°C.
Le A 32 843-Foreign countries 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 emulsifier is added and the concentrate is diluted with water to the desired concentration.
Seeds of the test plants are sown in normal soil. After about 24 hours, the soil is sprayed with the preparation of active compound such that the particular amounts of active compound desired are applied per unit area. The concentration of the spray liquor is chosen so that the particular amounts of active compound desired are applied in 10001 of water/ha.
After three weeks, the degree of damage to the plants is rated in % damage in comparison to the development of the untreated control.
The figures denote:
0 % - no effect (like untreated control) 100 % - total destruction In this test, for example, the compounds of Preparation Example l, 2, 3 and 4 exhibit strong activity against weeds, and some of them are tolerated well by crop plants, such as, for example, maize and wheat.
Le A 32 843-Foreign countries Example B
Post-emergence test Solvent: 5 parts by weight of acetone Emulsifier: 1 part by weight of alkylaryl polyglycol ether To produce a suitable preparation of active compound, 1 part by weight of active compound is mixed with the stated amount of solvent, the stated amount of emulsifier is added and the concentrate is diluted with water to the desired concentration.
Test plants of a height of 5 - 15 cm are sprayed with the preparation of active compound such that the particular amounts of active compound desired are applied per unit area. The concentration of the spray liquor is chosen so that the particular arr~ounts of active compound desired are applied in 10001 of water/ha.
After three weeks, the degree of damage to the plants is rated in % damage in comparison to the development of the untreated control.
The figures denote:
0% = no effect (like untreated control) 100% = total destruction In this test, for example, the compounds of Preparation Example 2, 3, 4 and 5 exhibit strong activity against weeds, and some of them are tolerated well by crop plants, such as, for example, wheat.
Claims (8)
1. Substituted heteroarylmethyl compounds of the general formula (I) in which Q represents O, S, SO or SO2, X1 represents hydrogen, hydroxyl, mercapto, amino, nitro, formyl, carboxyl, cyano, carbamoyl, thiocarbamoyl, halogen, or represents in each case optionally cyano-, halogen- or alkoxy-substituted alkyl, alkoxy, alkylthio, alkylsulphinyl, alkylsulphonyl, alkylamino, dialkylamino, alkylcarbonyl, alkoxycarbonyl, alkylcarbonylamino, alkoxycarbonylamino or alkylsulphonylamino, X2 represents hydrogen or halogen, Z1 represents optionally substituted heteroaryl from the series consisting of furyl, benzofuryl, pyrrolyl, pyrazolyl, imidazolyl, triazolyl, oxazolyl, isoxazolyl, benzoxazolyl, thiazolyl, isothiazolyl, benzothiazolyl, benzimidazolyl, pyridinyl, quinolinyl, isoquinolinyl, pyrimidinyl, pyrazinyl, pyridazinyl, quinazolinyl or quinoxalinyl, and Z2 represents one of the groupings below where Q1 represents O or S, R1 represents hydrogen, cyano, halogen, or represents in each case optionally cyano-, halogen- or alkoxy-substituted alkyl, alkoxy, alkylthio, alkylsulphinyl, alkylsulphonyl, alkylamino, dialkylamino, alkenyl, alkenyloxy, alkenylthio, alkenylamino, alkinyl, alkinyloxy, alkinylthio, cycloalkyl, cycloalkyloxy, cycloalkylthio or cycloalkylamino, or optionally together with an adjacent R1 represents alkanediyl (alkylene), and R2 represents hydrogen, cyano, formyl, or represents in each case optionally cyano-, halogen- or alkoxy-substituted alkyl, alkylcarbonyl, alkoxycarbonyl, alkenyl or alkinyl.
2. Substituted alkenyl compounds according to Claim 1, characterized in that Q represents O, S, SO or SO2, X1 represents hydrogen, hydroxyl, mercapto, amino, nitro, formyl, carboxyl, cyano, carbamoyl, thiocarbamoyl, halogen, or represents in each case optionally cyano-, halogen- or C1-C4-alkoxy-substituted alkyl, alkoxy, alkylthio, alkylsulphinyl, alkylsulphonyl, alkylamino, dialkylamino, alkylcarbonyl, alkoxycarbonyl, alkylcarbonylamino, alkoxycarbonylamino or alkylsulphonylamino having in each case 1 to 6 carbon atoms in the alkyl groups, X2 represents hydrogen or halogen, Z1 represents optionally substituted heteroaryl from the series consisting of furyl, benzofuryl, pyrrolyl, pyrazolyl, imidazolyl, triazolyl, oxazolyl, isoxazolyl, benzoxazolyl, thiazolyl, isothiazolyl, benzothiazolyl, benzimidazolyl, pyridinyl, quinolinyl, isoquinolinyl, pyrimidinyl, pyrazinyl, pyridazinyl, quinazolinyl or quinoxalinyl, where the possible substituents are preferably selected from the list below:
nitro, amino, hydroxyl, carboxyl, cyano, carbamoyl, thiocarbamoyl, sulpho, chlorosulphonyl, aminosulphonyl, halogen, in each case optionally cyano-, halogen- or C1-C4-alkoxy-substituted alkyl, alkoxy, alkylthio, alkylsulphinyl, alkylsulphonyl, alkylamino, alkylcarbonyl, alkoxycarbonyl, alkylaminocarbonyl, alkylcarbonylamino, alkoxycarbonylamino or alkylsulphonylamino having in each case 1 to 4 carbon atoms in the alkyl groups or phenyl, and Z2 represents one of the groupings below where Q1 represents O or S, R1 represents hydrogen, cyano, halogen, represents in each case optionally cyano-, halogen- or C1-C4-alkoxy-substituted alkyl, alkoxy, alkylthio, alkylsulphinyl, alkylsulphonyl, alkylamino or dialkylamino having in each case 1 to 6 carbon atoms in the alkyl groups, represents in each case optionally halogen-substituted alkenyl, alkenyloxy, alkenylthio, alkenylamino, alkinyl, alkinyloxy or alkinylthio having in each case 2 to 6 carbon atoms in the alkenyl or alkinyl groups, represents in each case optionally cyano-, halogen- or C1-C4-alkyl-substituted cycloalkyl, cycloalkyloxy, cycloalkylthio or cycloalkylamino having in each case 3 to 6 carbon atoms in the cycloalkyl groups, or optionally together with an adjacent R1 represents alkanediyl (alkylene) having 3 to 5 carbon atoms, and R2 represents hydrogen, cyano, formyl, represents in each case optionally cyano-, halogen- or C1-C4-alkoxy-substituted alkyl, alkylcarbonyl, alkenyl having in each case 1 to 6 carbon atoms in the alkyl groups, or represents in each case optionally halogen-substituted alkenyl or alkinyl having in each case 3 to 6 carbon atoms.
nitro, amino, hydroxyl, carboxyl, cyano, carbamoyl, thiocarbamoyl, sulpho, chlorosulphonyl, aminosulphonyl, halogen, in each case optionally cyano-, halogen- or C1-C4-alkoxy-substituted alkyl, alkoxy, alkylthio, alkylsulphinyl, alkylsulphonyl, alkylamino, alkylcarbonyl, alkoxycarbonyl, alkylaminocarbonyl, alkylcarbonylamino, alkoxycarbonylamino or alkylsulphonylamino having in each case 1 to 4 carbon atoms in the alkyl groups or phenyl, and Z2 represents one of the groupings below where Q1 represents O or S, R1 represents hydrogen, cyano, halogen, represents in each case optionally cyano-, halogen- or C1-C4-alkoxy-substituted alkyl, alkoxy, alkylthio, alkylsulphinyl, alkylsulphonyl, alkylamino or dialkylamino having in each case 1 to 6 carbon atoms in the alkyl groups, represents in each case optionally halogen-substituted alkenyl, alkenyloxy, alkenylthio, alkenylamino, alkinyl, alkinyloxy or alkinylthio having in each case 2 to 6 carbon atoms in the alkenyl or alkinyl groups, represents in each case optionally cyano-, halogen- or C1-C4-alkyl-substituted cycloalkyl, cycloalkyloxy, cycloalkylthio or cycloalkylamino having in each case 3 to 6 carbon atoms in the cycloalkyl groups, or optionally together with an adjacent R1 represents alkanediyl (alkylene) having 3 to 5 carbon atoms, and R2 represents hydrogen, cyano, formyl, represents in each case optionally cyano-, halogen- or C1-C4-alkoxy-substituted alkyl, alkylcarbonyl, alkenyl having in each case 1 to 6 carbon atoms in the alkyl groups, or represents in each case optionally halogen-substituted alkenyl or alkinyl having in each case 3 to 6 carbon atoms.
3. Substituted heteromethyl compounds according to Claim 1, characterized in that Q represents O, S, SO or SO2, X1 represents hydrogen, hydroxyl, mercapto, amino, nitro, formyl, carboxyl, cyano, carbamoyl, thiocarbamoyl, fluorine, chlorine, bromine, represents in each case, optionally cyano-, fluorine-, chlorine-, methoxy- or ethoxy-substituted methyl, ethyl, n- or i-propyl, methoxy, ethoxy, n- or i-propoxy, methylthio, ethylthio, n- or i-propylthio, methylsulphinyl, ethylsulphinyl, methylsulphonyl, ethylsulphonyl, methylamino, ethylamino, n- or i-propylamino, dimethylamino, diethylamino, acetyl, propionyl, methoxycarbonyl, ethoxycarbonyl, acetylamino, propionylamino, methoxycarbonylamino, ethoxycarbonylamino, methylsulphonylamino, ethylsulphonylamino, n- or i-propylsulphonylamino, X2 represents hydrogen, fluorine, chlorine or bromine, Z1 represents optionally substituted heteroaryl from the series consisting of furyl, benzofuryl, pyrrolyl, pyrazolyl, imidazolyl, triazolyl, oxazolyl, isoxazolyl, benzoxazolyl, thiazolyl, isothiazolyl, benzothiazolyl, benzimidazolyl, pyridinyl, quinolinyl, isoquinolinyl, pyrimidinyl, pyrazinyl, pyridazinyl, quinazolinyl or quinoxalinyl, where the possible substituents are preferably selected from the list below:
nitro, amino, hydroxyl, carboxyl, cyano, carbamoyl, thiocarbamoyl, aminosulphonyl, fluorine, chlorine, bromine, in each case optionally cyano-, fluorine-, chlorine-, methoxy- or ethoxy-substituted methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, methoxy, ethoxy, n- or i-propoxy, n-, i-, s- or t-butoxy, methylthio, ethylthio, n- or i-propylthio, n-, i-, s- or t-butylthio, methylsulphinyl, ethylsulphinyl, methylsulphonyl, ethylsulphonyl, methylamino, ethylamino, n- or i-propylamino, n-, i-, s- or t-butylamino, acetyl, propionyl, n- or i-butyroyl, methoxycarbonyl, ethoxycarbonyl, n- or i-propoxycarbonyl, methylaminocarbonyl, ethylaminocarbonyl, n- or i-propylaminocarbonyl, acetylamino, propionylamino, n- or i-butyroylamino, methoxycarbonylamino, ethoxycarbonylamino, n- or i-propoxycarbonylamino, methylsulphonylamino, ethylsulphonylamino, n- or i-propylsulphonylamino, n-, i-, s- or t-butylsulphonylamino or phenyl, and Z2 represents one of the groupings below where Q1 represents O or S, R1 represents hydrogen, cyano, fluorine, chlorine, bromine, represents in each case optionally cyano-, fluorine-, chlorine-, methoxy- or ethoxy-substituted methyl, ethyl, n- or i-propyl, methoxy, ethoxy, n- or i-propoxy, methylthio, ethylthio, n- or i-propylthio, methylsulphinyl, ethylsulphinyl, methylsulphonyl, ethylsulphonyl, methylamino, ethylamino, n- or i-propylamino, dimethylamino or diethylamino, represents in each case optionally fluorine-, chlorine- or bromine-substituted ethenyl, propenyl, propenyloxy, propenylthio, propenylamino, ethinyl, propinyl, propinyloxy or propinylthio, represents in each case optionally cyano-, fluorine-, chlorine-, methyl-, ethyl-, n- or i-propyl-substituted cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclopropyloxy, cyclobutyloxy, cyclopentyloxy, cyclohexyloxy, cyclopropylamino, cyclobutylamino, cyclopentylamino or cyclohexylamino, or optionally together with an adjacent R1 represents propane-1,3-diyl (trimethylene) or butane-1,4-diyl (tetramethylene), and R2 represents hydrogen, cyano, formyl, represents in each case optionally cyano-, fluorine-, chlorine-, methoxy- or ethoxy-substituted methyl, ethyl, n- or i-propyl, acetyl, propionyl, n- or i-butyroyl, methoxycarbonyl, ethoxycarbonyl, n- or i-propoxycarbonyl, or represents in each case optionally fluorine-, chlorine- or bromine-substituted propenyl, butenyl, propinyl or butinyl.
nitro, amino, hydroxyl, carboxyl, cyano, carbamoyl, thiocarbamoyl, aminosulphonyl, fluorine, chlorine, bromine, in each case optionally cyano-, fluorine-, chlorine-, methoxy- or ethoxy-substituted methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, methoxy, ethoxy, n- or i-propoxy, n-, i-, s- or t-butoxy, methylthio, ethylthio, n- or i-propylthio, n-, i-, s- or t-butylthio, methylsulphinyl, ethylsulphinyl, methylsulphonyl, ethylsulphonyl, methylamino, ethylamino, n- or i-propylamino, n-, i-, s- or t-butylamino, acetyl, propionyl, n- or i-butyroyl, methoxycarbonyl, ethoxycarbonyl, n- or i-propoxycarbonyl, methylaminocarbonyl, ethylaminocarbonyl, n- or i-propylaminocarbonyl, acetylamino, propionylamino, n- or i-butyroylamino, methoxycarbonylamino, ethoxycarbonylamino, n- or i-propoxycarbonylamino, methylsulphonylamino, ethylsulphonylamino, n- or i-propylsulphonylamino, n-, i-, s- or t-butylsulphonylamino or phenyl, and Z2 represents one of the groupings below where Q1 represents O or S, R1 represents hydrogen, cyano, fluorine, chlorine, bromine, represents in each case optionally cyano-, fluorine-, chlorine-, methoxy- or ethoxy-substituted methyl, ethyl, n- or i-propyl, methoxy, ethoxy, n- or i-propoxy, methylthio, ethylthio, n- or i-propylthio, methylsulphinyl, ethylsulphinyl, methylsulphonyl, ethylsulphonyl, methylamino, ethylamino, n- or i-propylamino, dimethylamino or diethylamino, represents in each case optionally fluorine-, chlorine- or bromine-substituted ethenyl, propenyl, propenyloxy, propenylthio, propenylamino, ethinyl, propinyl, propinyloxy or propinylthio, represents in each case optionally cyano-, fluorine-, chlorine-, methyl-, ethyl-, n- or i-propyl-substituted cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclopropyloxy, cyclobutyloxy, cyclopentyloxy, cyclohexyloxy, cyclopropylamino, cyclobutylamino, cyclopentylamino or cyclohexylamino, or optionally together with an adjacent R1 represents propane-1,3-diyl (trimethylene) or butane-1,4-diyl (tetramethylene), and R2 represents hydrogen, cyano, formyl, represents in each case optionally cyano-, fluorine-, chlorine-, methoxy- or ethoxy-substituted methyl, ethyl, n- or i-propyl, acetyl, propionyl, n- or i-butyroyl, methoxycarbonyl, ethoxycarbonyl, n- or i-propoxycarbonyl, or represents in each case optionally fluorine-, chlorine- or bromine-substituted propenyl, butenyl, propinyl or butinyl.
4. Substituted heteromethyl compounds according to any of Claims 1 to 3, characterized in that Z2 represents the heterocyclic grouping below and Q, X1, X2 and Z1 and R2 are as defined in any of Claims 1 to 3:
-44-~
-44-~
5. Substituted heteromethyl compounds according to any of Claims 1 to 3, characterized in that Z2 represents the heterocyclic grouping below and Q, X1, X2 and Z1 and R1 and R2 are as defined in any of Claims 1 to 3:
6. Process for preparing substituted heteroarylmethyl compounds according to any of Claims 1 to 3, characterized in that (a) phthalic anhydride or 3,4,5,6-tetrahydro-phthalic anhydride is reacted with aminobenzene derivatives of the general formula (II) in which Q, X1, X2 and Z1 are as defined in any of Claims 1 to 3, if appropriate in the presence of a diluent and if appropriate in the presence of a reaction auxiliary, or that (b) heterocyclylarenes of the general formula (III) in which Q, X1. X2 and Z2 are as defined in any of Claims 1 to 3 are reacted with heteroarylmethyl halides of the general formula (IV) X3-CH2-Z1 ~~~(IV) in which Z1 is as defined above and X3 represents halogen, if appropriate in the presence of a diluent and if appropriate in the presence of a reaction auxiliary, or that (c) heterocyclylarenes of the general formula (V) in which X1, X2 and Z2 are as defined in any of Claims 1 to 3 and X4 represents halogen are reacted with heteroarenes of the general formula (VI) HQ-CH2-Z1 (VI) in which Q and Z1 are as defined in any of Claims 1 to 3, if appropriate in the presence of a diluent and if appropriate in the presence of a reaction auxiliary, and, if appropriate, electrophilic or nucleophilic substitution reactions or oxidation or reduction reactions within the scope of the definition of the substituents are subsequently carried out in a customary manner.
7. Use of at least one substituted heteroarylmethyl compound according to any of Claims 1 to 5 for controlling undesirable plants.
8. Herbicidal composition, characterized in that it comprises at least one substituted heteroarylmethyl compound according to any of Claims 1 to 5 and customary extenders.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19803395.8 | 1998-01-29 | ||
| DE19803395A DE19803395A1 (en) | 1998-01-29 | 1998-01-29 | Substituted heteroarylmethyl compounds |
| PCT/EP1999/000238 WO1999038861A1 (en) | 1998-01-29 | 1999-01-16 | Substituted heteroarylmethyl compounds used as herbicides |
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| Publication Number | Publication Date |
|---|---|
| CA2319053A1 true CA2319053A1 (en) | 1999-08-05 |
Family
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002319053A Abandoned CA2319053A1 (en) | 1998-01-29 | 1999-01-16 | Substituted heteroarylmethyl compounds used as herbicides |
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| Country | Link |
|---|---|
| EP (1) | EP1051414A1 (en) |
| JP (1) | JP2002501917A (en) |
| KR (1) | KR20010033804A (en) |
| CN (1) | CN1289330A (en) |
| AU (1) | AU2421599A (en) |
| BR (1) | BR9908341A (en) |
| CA (1) | CA2319053A1 (en) |
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| WO (1) | WO1999038861A1 (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| IT1313601B1 (en) * | 1999-08-05 | 2002-09-09 | Isagro Ricerca Srl | HERBICIDE ACTIVITY PHENYLPIRAZOLI |
| AR096816A1 (en) * | 2013-07-08 | 2016-02-03 | Bayer Cropscience Ag | ARILSULFIDE AND ARILSULPHOXIDE DERIVATIVES OF SIX MEMBERS LINKED TO C-N AS AGENTS TO COMBAT PARASITES |
| CN111187213B (en) * | 2018-11-15 | 2021-09-07 | 华中师范大学 | Polyhalogenated 5- (2-hydroxyphenyl) pyrazole compound and preparation method and application thereof |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4332944A (en) * | 1981-07-09 | 1982-06-01 | Zoecon Corporation | Compositions and use |
| BR9106737A (en) * | 1990-08-06 | 1993-08-31 | Monsanto Co | ARIL ALQUILSULFONIL PIRAZOIS REPLACED HERBICIDES |
| DE19728125A1 (en) * | 1997-07-02 | 1999-01-07 | Bayer Ag | Substituted aryluracile |
-
1998
- 1998-01-29 DE DE19803395A patent/DE19803395A1/en not_active Withdrawn
-
1999
- 1999-01-16 WO PCT/EP1999/000238 patent/WO1999038861A1/en not_active Application Discontinuation
- 1999-01-16 EP EP99903637A patent/EP1051414A1/en not_active Withdrawn
- 1999-01-16 KR KR1020007007356A patent/KR20010033804A/en not_active Application Discontinuation
- 1999-01-16 CA CA002319053A patent/CA2319053A1/en not_active Abandoned
- 1999-01-16 CN CN99802547A patent/CN1289330A/en active Pending
- 1999-01-16 BR BR9908341-8A patent/BR9908341A/en not_active Application Discontinuation
- 1999-01-16 AU AU24215/99A patent/AU2421599A/en not_active Abandoned
- 1999-01-16 JP JP2000529329A patent/JP2002501917A/en active Pending
Also Published As
| Publication number | Publication date |
|---|---|
| BR9908341A (en) | 2001-10-02 |
| JP2002501917A (en) | 2002-01-22 |
| WO1999038861A1 (en) | 1999-08-05 |
| CN1289330A (en) | 2001-03-28 |
| KR20010033804A (en) | 2001-04-25 |
| AU2421599A (en) | 1999-08-16 |
| DE19803395A1 (en) | 1999-08-05 |
| EP1051414A1 (en) | 2000-11-15 |
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