CA1243674A - Process for producing sulfonylureas having a herbicidal action and an action regulating plant growth - Google Patents
Process for producing sulfonylureas having a herbicidal action and an action regulating plant growthInfo
- Publication number
- CA1243674A CA1243674A CA000434948A CA434948A CA1243674A CA 1243674 A CA1243674 A CA 1243674A CA 000434948 A CA000434948 A CA 000434948A CA 434948 A CA434948 A CA 434948A CA 1243674 A CA1243674 A CA 1243674A
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- Prior art keywords
- alkyl
- hydrogen
- halogen
- formula
- alkoxy
- Prior art date
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D521/00—Heterocyclic compounds containing unspecified hetero rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D251/00—Heterocyclic compounds containing 1,3,5-triazine rings
- C07D251/02—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings
- C07D251/12—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members
- C07D251/14—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with hydrogen or carbon atoms directly attached to at least one ring carbon atom
- C07D251/16—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with hydrogen or carbon atoms directly attached to at least one ring carbon atom to only one ring carbon atom
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic System
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/10—Compounds having one or more C—Si linkages containing nitrogen having a Si-N linkage
Abstract
Case 5-14064/=
A process for producing sulfonylureas having a herbicidal action and an action regulating Plant growth Abstract Process for producing hervicidal and plant-growth-regulating sulfonylureas of the general formula I
(I) wherein G is a radical of the formula or X is C1-C4-alkyl, C1-C4-haloalkyl, C1-C4-alkoxy, C1-C4-alkylthio, C1-C4-haloalkoxy, C1-C4-alkylamino or di-C1-C4-alkylamino, Y is C1-C4-alkyl, C1-C4-haloalkyl, C1-C4-alkoxy or C1-C4-haloalkoxy, and Z is nitrogen or the methine bridge, A is oxygen, sulfùr, -NR5- or -C=N-, R5 being hydrogen, C1-C4-alkyl or -CO-C1-C4-alkyl, R1 is hydrogen, halogen, nitro, -Q-Cl-C4-alkyl, C1-C4-alkyl, CF3, -SO2-di-C1-C4 alkylamino, -CO-Q-C3-C5-alkynyl, or -CO-Q-C1-c4-alkyl or -CO-Q-C3-C5-alkenyl each unsubstituted or substituted by halogen, cyano, C1-C4alkoxy or C1-C4-alkylthio, R2 is hydrogen, halogen, CF3, NO2, C1-C4-alkyl or C1-C4-alkoxy, R3 is hydrogen, fluorine or chlorine, R4 is hydrogen, halogen, nitro, CF3, C1-C4-alkyl, -CHR6R7, -SO2-di-C1-C4-alkylamino, -Q-C3-C5-alkynyl, -CO-T-C3-C5-alkynyl, or -Q-C1-C4-alkyl, -Q-C2-C5 alkenyl, -CO-T-C1-C4-alkyl or -CO-T-C3-C5-alkenyl each of which is unsubstituted or substituted by halogen, cyano, C1-C4-alkoxy or C1-C4-alkylthio, Q being an oxygen, sulfur, -SOn-, -NH- or N(C1-C4-alkyl)- bridge, n being zero, one or two, and T being an oxygen, sulfur, -NH- or -N(C1-C4-alkyl)- bridge, R6 is hydrogen, chlorine or methyl, and R7 is chlorine, cyano, methoxy, ethoxy or -SOn-C1-C4-alkyl, which process comprises reacting a sulfonamide of the formula II
G-SO2-NH2 (II), wherein G has the meaning defined above, with an N-pyrimidinylcarbamate or N-triazinylcarbamate of the formula III
A process for producing sulfonylureas having a herbicidal action and an action regulating Plant growth Abstract Process for producing hervicidal and plant-growth-regulating sulfonylureas of the general formula I
(I) wherein G is a radical of the formula or X is C1-C4-alkyl, C1-C4-haloalkyl, C1-C4-alkoxy, C1-C4-alkylthio, C1-C4-haloalkoxy, C1-C4-alkylamino or di-C1-C4-alkylamino, Y is C1-C4-alkyl, C1-C4-haloalkyl, C1-C4-alkoxy or C1-C4-haloalkoxy, and Z is nitrogen or the methine bridge, A is oxygen, sulfùr, -NR5- or -C=N-, R5 being hydrogen, C1-C4-alkyl or -CO-C1-C4-alkyl, R1 is hydrogen, halogen, nitro, -Q-Cl-C4-alkyl, C1-C4-alkyl, CF3, -SO2-di-C1-C4 alkylamino, -CO-Q-C3-C5-alkynyl, or -CO-Q-C1-c4-alkyl or -CO-Q-C3-C5-alkenyl each unsubstituted or substituted by halogen, cyano, C1-C4alkoxy or C1-C4-alkylthio, R2 is hydrogen, halogen, CF3, NO2, C1-C4-alkyl or C1-C4-alkoxy, R3 is hydrogen, fluorine or chlorine, R4 is hydrogen, halogen, nitro, CF3, C1-C4-alkyl, -CHR6R7, -SO2-di-C1-C4-alkylamino, -Q-C3-C5-alkynyl, -CO-T-C3-C5-alkynyl, or -Q-C1-C4-alkyl, -Q-C2-C5 alkenyl, -CO-T-C1-C4-alkyl or -CO-T-C3-C5-alkenyl each of which is unsubstituted or substituted by halogen, cyano, C1-C4-alkoxy or C1-C4-alkylthio, Q being an oxygen, sulfur, -SOn-, -NH- or N(C1-C4-alkyl)- bridge, n being zero, one or two, and T being an oxygen, sulfur, -NH- or -N(C1-C4-alkyl)- bridge, R6 is hydrogen, chlorine or methyl, and R7 is chlorine, cyano, methoxy, ethoxy or -SOn-C1-C4-alkyl, which process comprises reacting a sulfonamide of the formula II
G-SO2-NH2 (II), wherein G has the meaning defined above, with an N-pyrimidinylcarbamate or N-triazinylcarbamate of the formula III
Description
3~Z~3674 Case 5-14064/=
A process for_producing sulfon~lureas having a herbicidal action and an action re~ulatin~ plant ~rowth The present invention relates to a novel process for producing sulfonylureas having a herbicidal action and an action regulating plant growth, and also to novel pyrimidinyl- and triazinylcarbamates and trimethylsilyl-amino~pyrimidines and -triazines produced as intermediates.
The sulfonylureas to be produced by the novel process according to the invention are described together with their properties in the U.S. Patent Specifications Nos.
4,127,405, 4,301,286 and 4,302,241, and in the European Patent Applications Nos. 23422, 44807, 44808, 708Q2 and 72347.
The known processes are disadvantageous either because the process involves the use of isocyanate or isothio-cyanate derivatives, the handling of which is difficult on account o1f the high reactivity of this class of compounds, or because ecologically undesirable by-products,.
for example phenols, occur during the synthesis from phenylcarbamates. ;
From the European Patent Application No. 5146~ there is:: :
known a process for producing similar sul~fonylureas,~:with :
which process: the above disadvantages are largely avoided.~
: ~:
.: .......
- :
.
1;243674 Sulfonylureas are produced in this process by reacting a sulfonamide with a pyrimidinyl- or triazinyl-methylcarbamate in the presence of at least equimolar amounts of trimethylaluminium. This process i9 disad-vantageous in that the trimethylaluminium used is pyrophoric, and is furthermore decomposed by air and moisture.
It is hence the obiect of the present invention to provide a process which avoids the use of compounds which are difficult to handle, and also the occurrence of environmentally unfavourable by-products.
It has now been established that surprisingly the reaction of sulfonamides with alkylcarbamates can also be performed without trialkylaluminium.
It is thus suggested according to the invention that the herbicidal and plant-growth-regulating sulfonylureas of the general formula I
G-502-NH-co-NR-~
wherein G is a radical of the formula RL~ - or X is Cl-C4-alkyl, Cl-C4-haloalkyl, Cl-C4-alkoxy, Cl-C4-alkylthio ~ Cl-C4-haloalkoxy 9 Cl-C4-a~kylamino or di-Cl-C4-alkylamino, Y is Cl-C4-alkyl, Cl-C4-haloalkyl, Cl-C4-alkoxy or ` Cl-C4-haloalkoxy, and , . . . ~
~24367~
Z is nitrogen or the methine bridge, A is oxygen, sulfur~ -NR5- or -C=N-, R5 being hydrogen, Cl-C4-alkyl or -CO-Cl-C4-alkyl, Rl is hydrogen, halogen, nit:ro, ~Q~Cl-C~-alkyl, cl-C4-alkyl, CF3, -S02-di-Cl-C4-alkylamino, -CO-Q-C3-C5-alkynyl, or -CO-Q-Cl-C4-alkyl or -CO-Q-C3-C5-alkenyl each unsubstituted or substituted by halogen, cyano, Cl~C4-alkoxy or Cl-C4-alkylthio, R2 is hydrogen9 halogen, CF3, N02, Cl-C4-alkyl or cl-C4-alkoxy, R3 is hydrogen, fluorine or chlorine, R4 is hydrogen, halogen, nitro, CF3, Cl-C4-alkyl, -CHR6R7, -S02-di-Cl-C4-alkylamino, -Q-C3-C5-alkynyl, -CO-T-C3-C5-alkynyl, or -Q-Cl-C4-alkyl~ -Q-C2-C5-alkenyl, -CO-T-Cl-C4-alkyl or -CO-T-C3-C5-alkenyl each oE which is unsubstituted or substituted by halogen, cyano, Cl-C4-alkoxy or Cl-C4-alkylthio, Q being oxygen, sulfur, ~SOn~, -NH- or -N(Cl-C4-alkyl)-, n being zero, one or two, and T being an oxygen, sulfur, -NH- or -N(Cl-C4-alkyl)- bridge, R6 is hydrogen~ chlorine or methyl, and R7 is chlorine, cyano, methoxy, ethoxy or -SOn-Cl-C4-alkyl, be produced by reacting a sulfonamide of the formula II
G-S02-NH2 . (II) wherein G has the meaning defined above, with an N-pyrimidinyl- or N-triazinylcarbamate of the formula III
R-o-C-N~ Z : (III) o wherein X, Y and Z have the meanings defined above,:and : :
R is methyl or ethyl.
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By halogen is meant within the scope of the above definition in general fluorine, chlorine, bromine or iodine, fluorine and chlorine being preferred~ Preferred as substituent of the radical G is particularly chlorine;
and as substituent of an alkyl group, which in its turn can be part of a radical, especially fluorine.
Examples of alkyl are: methyl, ethyl, n-propyl and i-propyl or the isomeric butyl groups. Alkyl is itself to be understood as being a substituent or as part of another substituent, for example alkoxy or alkylthio.
Preferred alkyl groups are in each case unbranched alkyl chains, especially however methyl and ethyl.
Preferred substituents of the radical G among the 1~ R2, R3j R4 and R5 are those selected from the group comprising: chlorine, methoxycarbonyl, nitro, dimethylsulfamoyl, trifluoromethyl, methylsulfonyl and n-propylsulfonyl.
By alkenyl is meant as a rule: allyl, 2-butenyl, 3-butenyl, 2-isobutenyl, isopropenyl, 2-pentenyl, 3-pentenyl and 4-pentenyl, particularly allyl and 4-pentenyl.
By alkynyl is meant in general: propargyl, 2-butynyl, 3-butynyl, methylpropargyl, 2-pentynyl, 3-pentynyl and 4-pentynyl.
The heterocycles which are covered by the definition of the radical G are: thiophene, furan, pyrrole and pyridine.
Preferred pyrimidine and ,riazine rings are those in which X is methyl, ethyl, fluoromethyl, trifluoromethyl, methoxy, ethoxy, i-propyloxy, methylthio, chlorine~
bromine, difluoromethoxy, 2,2,2-trifluoroetho~y, methylamino or dimethylamino, and Y is methyl, methoxy or difluoro-methoxy. ~ `
~:
- : , , . `' . . :
"
~Zg3G74 The carbamates of the formula III are reacted with the sulfonamides of the formula II by heating the mixture of both reactants wntil a detachment of the alcohol occurs. The reaction can be performed either without solvent or in the presence o an iner~ solvenk. The reaction mixture is generally heated up until the reaction in which the alcohol is detached commences, and is held at this temperature until a complete conversion has been obtained. The temperature is as a rule 20 to 200C, preferably 40 to 100C. Solvents which have proved suitable are: hydrocarbons, such as benzene, toluene, xylene, mesitylene, tetrahydronaphthalene, decalin, cyclohexane and higher-boiling ligroin fractions; ethers, such as tetrahydrofuran, dioxane, ethylene glycol dimethyl ether, diethyLeneglycoldimethyl ether and diphenyl ether;
nitriles, such as acetonitrile or propionitrile, ketones, such as ethyl methyl ketone, cyclohexanone and acetone;
amides, such as dimethylformamide or N-methylpyrrolidinone and dimethyl sulfoxide.
The addition of a base frequently proves advantageous in the reaction according to the invention. Particularly suitable bases for this purpose are: 1,5-diazabicyclo [4~3,0]non-5-ene SDBN) or 1,5-diazabicyclo [5,4,0) undec-5-ene (DBU). The reaction temperatures are as a rule between 20 and 200C, preferably between 40 and 100C.
In a preferred embodiment of the process according to the invention, the procedure therefore comprises heating a sulfonamide of the formula II, in the presence of a base, with a carbamate of the formula III in an inert solvent at 40 to 100C until the reaction in which the alcohol is detached is completed, and then isolating the product.
The starting compounds of the formula II are known or can be produced by methods analogous to known methods.
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~, . ~
The N-pyrimidinyl- and N-triazinylcarbamates of the formula III are in part known. They are produced by reaction of the aminopyrimidines or -triazines o~ khe formula IV
H2N ~ z (IV), --.
wherein X, Y and Z have the meanings defined in the foregoing, with a carbonic acid ester of the formula V
R - O - CO - OR (V), or with a chloroformic acid ester of the formula VI
Cl - CO - OR (VI) wherein R is methyL or ethyl.
Novel N-pyrimidinyl- and N-triazinylcarbamates correspond to the subformulae IIIa and IIIb R-O-C-NH-~ (IIIa), o \Y
wherein R, X and Y have the meanings defined under the formula III, with the proviso that R is ethyl when at the same time Y is methyl and X is methoxy; and ` /o-alkyl R-O-C-NH-~ (IIIb), o CH3 wherein R is as defined under the formula III, and alkyl is Cl-C4-alkyl.
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The novel compounds of the formulae IIIa and IIIb have been developed specially for the synthesis of the active substances o~ the formula I according to the invention, and therefore also form subject matter o ~he present invention.
The reaction of the aminopyrimidines and -triazines of the formula IV with the carboni~ acid esters of the formula V or with the chloroformic acid esters of the formula VI can be performed in the presence of a suitable inert aprotic solvent, or in the absence of a solvent.
The use of a solvent has however proved advantageous.
Suitable solvents are: hydrocarbonsg such as benzene, toluene and xylene, ethers such as diethyl ether, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, tetrahydrofuran and dioxane; ketones, such as acetone, ethyl methyl ketone and cyclohexanone; and nitriles, such as acetonitrile and propionitrile. The reaction is performed in the presence of at least equimolar amounts of a base. Suitable bases are carbonates, such as sodium and potassium carbonate, hydrogen carbonates, such as sodium and potassium hydrogen carbonate, oxides, such as calcium and magnesium oxide, and tertiary amines, such as trimethylamine, triethylamine, quinuclidine, quinoline 9 pyridine and tripropylamine. The base is advantageously used in excess. There are thus preferably used 1 to 5 mols of base, especially 1.1 to 1.5 mols, per mol of sulfonamide.
Larger excesses of base are used in particular when the reaction is performed without solvent, and the base9 preferably a liquid tertiary amine, simultaneously serves as reaction medium. The reaction temperatùres are as a rule between 0 and 140C, preferably between 10 and 80C.
It can in some cases be advantageous to produce~the carbamates of the formula III not by the process outlined ~J
: ~ :
~, ' `
~Z~367~
above but by the following process in order to obtain a higher yield. The N-pyrimidinyl- and N-triazinyl~
carbamates of the formula III are accordingly produced by converting an aminopyrimidine or -triazine o:E the formula III with a silylating agent into the silylamino-pyrimidines or -triazines of the formula VII
(CH3)3 Sl - NH _ ,~N ~Z (VII), and reacting these with the chloroformic acid esters of the formula VI.
Silylation is customarily performed by heating the aminopyrimidine or -triazine together with the silylating agent, such as N,0-bis-(trimethylsilyl)-acetamide, hexamethyldisilazane or trimethylchlorosilane, optionally in the presence of a catalyst, such as concentrated sulfuric acid or hydrogen chloride, in an inert solvent at 30 to 150C~ preferably at 40 to 80C. Suitable solvents are: hydrocarbons, such as benzene, toluene and xylene; ethers, such as diethyl ether, ethylene glycol dimethyl ether, diethyl ether, diethylene glycol dimethyl ether, tetrahydrofuran and dioxane; nitriles, such as acetonitrile and propionitrile; and dimethyl sulf~xide.
The further reaction of the silylaminopyrimidines or -triazines of the formula VII with the chloroformic acid esters of the formula VI to the N-pyrimidinyl- and N-triazinylcarbamates of the formula III is performed by heating at 30 to 120C, preferably at 40 to 80C. This reaction can be carried out without solvent or in an inert solvent, for example benzene, toluene, xylene, petroleum ether, cyclohexane, diethyl ether, dioxane or tetrahydrofuran.
' ' ' ~ ` :" , .;
~243~74 The process for producing the intermediates of the formula VII and also these intermediates are novel, and have been developed specially for the production process according to the invention. They therefore likewise form part of the present invention.
The starting materials o the formulae V and VI
are known and are obtainable commercially.
The following Examples serve to further illustrate the present invention.
Example 1: N-(2-Chlorophenyl-sulfonyl)-N'-(4-methoxy-6 methyl-1,3,5-triazin-2-yl) urea.
A mixture of 1.0 g of 2-chlorophenylsulfonamide, 1.0 g of N-(4-methoxy-6 methyl-1,3,5-triazin-2-yl)-methyl-carbamate and 1.0 g of 1,5-diazabicyclo [4,3,0lnon-5-ene in 10 ml of dioxane is stirred for 14 hours at 100C.
After the addition of 50 ml of water, the mixture is acidified with 10% hydrochloric acid and extracted with ethyl acetate. The organic phase is concentrated by evaporation, and the residue is crystaLlised from a methylene chloride/ether mixture to thus obtain 0.75 g of N-(2-chlorophenylsulfonyl)-N'-(4-methoxy-6-methyl-1,3,5-triazin-2 yl)-urea, m.p. 176-178C.
Example 2:
a) 4-Methoxy-6-methyl-2-trimethylsilylamino-1,3,5-triazine.
A mixture of 238.2 g of 2-amino-4-methoxy-6-methoxy-6-methyl-1,3,5-triazine, 505 ml of N,0-bis-(trimethylsilyl3-acetamide and 1150 ml of anhydrous acetonitrile is refluxed for 8 hours. Fractional distillation yields 296.4 g of~4-methoxy-6-methyl-2-trimethylsilylamino-1,3,5-triazine, b.p. 78C/0.053 mb.
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.., -~LZ43674 b) N-(4-Methoxy-6-methyl-1,3,5-triazin-2-yl)-methylcarbamate A mixture of 10.6 g of 4-methoxy-6-methyl-2-trimethylsilylamino-1,3,5-triazine and 14.2 g of chloroformic acid methyl ester is stirred for 20 hours at 65C. The volatile constituents are evaporated o~
in vacuo, and the residue is taken up with 30 ml o methylene chloride. After separation of the insoluble constituents, the solution is concentrated by evaporation and the residue is chromatographed on silica gel. The yield is 6.2 g of N-(4 methoxy-6-methyl-1,3,5-triazin-2-yl)-methylcarbamate, m.p. 102-104C.
Example 3: 4-~ifluoromethoxy-6-methyl-2-trimethylsilyl-pyrimidine.
A mixture of 21.0 g of 2-amino-4-difluoromethoxy-6-methyl-pyrimidine and 0.27 ml of cancentrated sulfuric acid is heated in 90 ml of anhydrous toluene to 60C, and a mixture of 12.5 ml of hexamethyldisilazane and 7.6 ml of trimethylchlorosilane is added within 10 minutes.
The formed suspension is stirred at 60C for 24 hoursg it is subsequently cooled to 20 to 25G, filtered and fractionally distilled. The yield is 26 g of 4-difluoro-methoxy-6-methyl-2-trimethylsilyl-pyrimidine, b.p. 95C/ll mb.
Example 4:
a) 4-Methoxy-6-methyl-2-trimethylsilylamino-pyrimidine.
A mixture of 27.9 g of 2-amino-4-methoxy-6-methyl-pyrimidine and 48.8 g of N,0-bis-(trimethylsilyl)-acetamide in 250 ml of acetonitrile is refluxed for 7 hours. After cooling, the insoluble sediment is separated off and the filtrate is fractionally distilled. The yield is 36.3 g of 4-methoxy-6-methyl-2-trimethylsilylamino-pyrimidine, b.p. 62-640C/o.026 mb.
b) N-(4-Methoxy-6-methyl-pyrimidin-2-yl)-methylcarbamate.
A mixture of 10.6 g of 4-methoxy-6-methyl-2-trimethyl-.
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lZ~367~
silylamino-pyrimidine and 47 g of chloroformic acid methyl ester is stirred in 120 ml of petroleum ether at 50C for 7 hours. As the solution cools, 5.5 g o~
N-(4-methoxy-6-methyl-pyrimidin-2-yl)-methylcarbamate, m.p. 92-95C, crystallise out.
The intermediates listed in the following Tables are obtained in an analogous manner.
Table 1 ~N_ ./X
R-O-CO-NH ~ \N /Z
\Y
_ . _ . ___ .
No. R x Y . Z Physical data .
1.1 ~ OCH3 C33 N m.p. 102-104C
1. 2 CH 3 OCH 3 OCH 3 N
1. 3 CH 3 OCH 3 CH3~ CH m . p . 92- 95 C
1. 4 CH 3 OCH 3 OCH3 CH
, 1. 5 CH 3 CH3 CH 3 CH m . p . 96- 98 C
l . 6 . CH 3 CH 3 CH3 N
1. 7 CH 3 OCHF2 CH3 CH
1. 8 C2H5 OCHF2 CH3 CH m . p . 86-89 C
1. 9 CH3 OCHF2 OCH3 CH
1. lO CH3 OCHF2 OCHF2 CH
l. ll C2H5 OCH3 CH3 N m . p. 73-74C
1 .1 2 C2H5 OCH3 OCH3 N
1 .1 3 C2H5 OCH3 CH3 CH
1 .1 4 C2H5 OCH3 OCH3 CH
1.15 C2H5 CH3 CH3 CH m.p. 68-69C
l.l6 ~ C~3 L ~
Table 2:
/ X
(C1~3)3Si ~ NH - ~ /Z
. y No. Z I Physical data
A process for_producing sulfon~lureas having a herbicidal action and an action re~ulatin~ plant ~rowth The present invention relates to a novel process for producing sulfonylureas having a herbicidal action and an action regulating plant growth, and also to novel pyrimidinyl- and triazinylcarbamates and trimethylsilyl-amino~pyrimidines and -triazines produced as intermediates.
The sulfonylureas to be produced by the novel process according to the invention are described together with their properties in the U.S. Patent Specifications Nos.
4,127,405, 4,301,286 and 4,302,241, and in the European Patent Applications Nos. 23422, 44807, 44808, 708Q2 and 72347.
The known processes are disadvantageous either because the process involves the use of isocyanate or isothio-cyanate derivatives, the handling of which is difficult on account o1f the high reactivity of this class of compounds, or because ecologically undesirable by-products,.
for example phenols, occur during the synthesis from phenylcarbamates. ;
From the European Patent Application No. 5146~ there is:: :
known a process for producing similar sul~fonylureas,~:with :
which process: the above disadvantages are largely avoided.~
: ~:
.: .......
- :
.
1;243674 Sulfonylureas are produced in this process by reacting a sulfonamide with a pyrimidinyl- or triazinyl-methylcarbamate in the presence of at least equimolar amounts of trimethylaluminium. This process i9 disad-vantageous in that the trimethylaluminium used is pyrophoric, and is furthermore decomposed by air and moisture.
It is hence the obiect of the present invention to provide a process which avoids the use of compounds which are difficult to handle, and also the occurrence of environmentally unfavourable by-products.
It has now been established that surprisingly the reaction of sulfonamides with alkylcarbamates can also be performed without trialkylaluminium.
It is thus suggested according to the invention that the herbicidal and plant-growth-regulating sulfonylureas of the general formula I
G-502-NH-co-NR-~
wherein G is a radical of the formula RL~ - or X is Cl-C4-alkyl, Cl-C4-haloalkyl, Cl-C4-alkoxy, Cl-C4-alkylthio ~ Cl-C4-haloalkoxy 9 Cl-C4-a~kylamino or di-Cl-C4-alkylamino, Y is Cl-C4-alkyl, Cl-C4-haloalkyl, Cl-C4-alkoxy or ` Cl-C4-haloalkoxy, and , . . . ~
~24367~
Z is nitrogen or the methine bridge, A is oxygen, sulfur~ -NR5- or -C=N-, R5 being hydrogen, Cl-C4-alkyl or -CO-Cl-C4-alkyl, Rl is hydrogen, halogen, nit:ro, ~Q~Cl-C~-alkyl, cl-C4-alkyl, CF3, -S02-di-Cl-C4-alkylamino, -CO-Q-C3-C5-alkynyl, or -CO-Q-Cl-C4-alkyl or -CO-Q-C3-C5-alkenyl each unsubstituted or substituted by halogen, cyano, Cl~C4-alkoxy or Cl-C4-alkylthio, R2 is hydrogen9 halogen, CF3, N02, Cl-C4-alkyl or cl-C4-alkoxy, R3 is hydrogen, fluorine or chlorine, R4 is hydrogen, halogen, nitro, CF3, Cl-C4-alkyl, -CHR6R7, -S02-di-Cl-C4-alkylamino, -Q-C3-C5-alkynyl, -CO-T-C3-C5-alkynyl, or -Q-Cl-C4-alkyl~ -Q-C2-C5-alkenyl, -CO-T-Cl-C4-alkyl or -CO-T-C3-C5-alkenyl each oE which is unsubstituted or substituted by halogen, cyano, Cl-C4-alkoxy or Cl-C4-alkylthio, Q being oxygen, sulfur, ~SOn~, -NH- or -N(Cl-C4-alkyl)-, n being zero, one or two, and T being an oxygen, sulfur, -NH- or -N(Cl-C4-alkyl)- bridge, R6 is hydrogen~ chlorine or methyl, and R7 is chlorine, cyano, methoxy, ethoxy or -SOn-Cl-C4-alkyl, be produced by reacting a sulfonamide of the formula II
G-S02-NH2 . (II) wherein G has the meaning defined above, with an N-pyrimidinyl- or N-triazinylcarbamate of the formula III
R-o-C-N~ Z : (III) o wherein X, Y and Z have the meanings defined above,:and : :
R is methyl or ethyl.
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- . . ~
~Z4367~
By halogen is meant within the scope of the above definition in general fluorine, chlorine, bromine or iodine, fluorine and chlorine being preferred~ Preferred as substituent of the radical G is particularly chlorine;
and as substituent of an alkyl group, which in its turn can be part of a radical, especially fluorine.
Examples of alkyl are: methyl, ethyl, n-propyl and i-propyl or the isomeric butyl groups. Alkyl is itself to be understood as being a substituent or as part of another substituent, for example alkoxy or alkylthio.
Preferred alkyl groups are in each case unbranched alkyl chains, especially however methyl and ethyl.
Preferred substituents of the radical G among the 1~ R2, R3j R4 and R5 are those selected from the group comprising: chlorine, methoxycarbonyl, nitro, dimethylsulfamoyl, trifluoromethyl, methylsulfonyl and n-propylsulfonyl.
By alkenyl is meant as a rule: allyl, 2-butenyl, 3-butenyl, 2-isobutenyl, isopropenyl, 2-pentenyl, 3-pentenyl and 4-pentenyl, particularly allyl and 4-pentenyl.
By alkynyl is meant in general: propargyl, 2-butynyl, 3-butynyl, methylpropargyl, 2-pentynyl, 3-pentynyl and 4-pentynyl.
The heterocycles which are covered by the definition of the radical G are: thiophene, furan, pyrrole and pyridine.
Preferred pyrimidine and ,riazine rings are those in which X is methyl, ethyl, fluoromethyl, trifluoromethyl, methoxy, ethoxy, i-propyloxy, methylthio, chlorine~
bromine, difluoromethoxy, 2,2,2-trifluoroetho~y, methylamino or dimethylamino, and Y is methyl, methoxy or difluoro-methoxy. ~ `
~:
- : , , . `' . . :
"
~Zg3G74 The carbamates of the formula III are reacted with the sulfonamides of the formula II by heating the mixture of both reactants wntil a detachment of the alcohol occurs. The reaction can be performed either without solvent or in the presence o an iner~ solvenk. The reaction mixture is generally heated up until the reaction in which the alcohol is detached commences, and is held at this temperature until a complete conversion has been obtained. The temperature is as a rule 20 to 200C, preferably 40 to 100C. Solvents which have proved suitable are: hydrocarbons, such as benzene, toluene, xylene, mesitylene, tetrahydronaphthalene, decalin, cyclohexane and higher-boiling ligroin fractions; ethers, such as tetrahydrofuran, dioxane, ethylene glycol dimethyl ether, diethyLeneglycoldimethyl ether and diphenyl ether;
nitriles, such as acetonitrile or propionitrile, ketones, such as ethyl methyl ketone, cyclohexanone and acetone;
amides, such as dimethylformamide or N-methylpyrrolidinone and dimethyl sulfoxide.
The addition of a base frequently proves advantageous in the reaction according to the invention. Particularly suitable bases for this purpose are: 1,5-diazabicyclo [4~3,0]non-5-ene SDBN) or 1,5-diazabicyclo [5,4,0) undec-5-ene (DBU). The reaction temperatures are as a rule between 20 and 200C, preferably between 40 and 100C.
In a preferred embodiment of the process according to the invention, the procedure therefore comprises heating a sulfonamide of the formula II, in the presence of a base, with a carbamate of the formula III in an inert solvent at 40 to 100C until the reaction in which the alcohol is detached is completed, and then isolating the product.
The starting compounds of the formula II are known or can be produced by methods analogous to known methods.
. .
- ~
......... ,.,,.. , - .
~, . ~
The N-pyrimidinyl- and N-triazinylcarbamates of the formula III are in part known. They are produced by reaction of the aminopyrimidines or -triazines o~ khe formula IV
H2N ~ z (IV), --.
wherein X, Y and Z have the meanings defined in the foregoing, with a carbonic acid ester of the formula V
R - O - CO - OR (V), or with a chloroformic acid ester of the formula VI
Cl - CO - OR (VI) wherein R is methyL or ethyl.
Novel N-pyrimidinyl- and N-triazinylcarbamates correspond to the subformulae IIIa and IIIb R-O-C-NH-~ (IIIa), o \Y
wherein R, X and Y have the meanings defined under the formula III, with the proviso that R is ethyl when at the same time Y is methyl and X is methoxy; and ` /o-alkyl R-O-C-NH-~ (IIIb), o CH3 wherein R is as defined under the formula III, and alkyl is Cl-C4-alkyl.
: . -, ~L24~6~7~
The novel compounds of the formulae IIIa and IIIb have been developed specially for the synthesis of the active substances o~ the formula I according to the invention, and therefore also form subject matter o ~he present invention.
The reaction of the aminopyrimidines and -triazines of the formula IV with the carboni~ acid esters of the formula V or with the chloroformic acid esters of the formula VI can be performed in the presence of a suitable inert aprotic solvent, or in the absence of a solvent.
The use of a solvent has however proved advantageous.
Suitable solvents are: hydrocarbonsg such as benzene, toluene and xylene, ethers such as diethyl ether, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, tetrahydrofuran and dioxane; ketones, such as acetone, ethyl methyl ketone and cyclohexanone; and nitriles, such as acetonitrile and propionitrile. The reaction is performed in the presence of at least equimolar amounts of a base. Suitable bases are carbonates, such as sodium and potassium carbonate, hydrogen carbonates, such as sodium and potassium hydrogen carbonate, oxides, such as calcium and magnesium oxide, and tertiary amines, such as trimethylamine, triethylamine, quinuclidine, quinoline 9 pyridine and tripropylamine. The base is advantageously used in excess. There are thus preferably used 1 to 5 mols of base, especially 1.1 to 1.5 mols, per mol of sulfonamide.
Larger excesses of base are used in particular when the reaction is performed without solvent, and the base9 preferably a liquid tertiary amine, simultaneously serves as reaction medium. The reaction temperatùres are as a rule between 0 and 140C, preferably between 10 and 80C.
It can in some cases be advantageous to produce~the carbamates of the formula III not by the process outlined ~J
: ~ :
~, ' `
~Z~367~
above but by the following process in order to obtain a higher yield. The N-pyrimidinyl- and N-triazinyl~
carbamates of the formula III are accordingly produced by converting an aminopyrimidine or -triazine o:E the formula III with a silylating agent into the silylamino-pyrimidines or -triazines of the formula VII
(CH3)3 Sl - NH _ ,~N ~Z (VII), and reacting these with the chloroformic acid esters of the formula VI.
Silylation is customarily performed by heating the aminopyrimidine or -triazine together with the silylating agent, such as N,0-bis-(trimethylsilyl)-acetamide, hexamethyldisilazane or trimethylchlorosilane, optionally in the presence of a catalyst, such as concentrated sulfuric acid or hydrogen chloride, in an inert solvent at 30 to 150C~ preferably at 40 to 80C. Suitable solvents are: hydrocarbons, such as benzene, toluene and xylene; ethers, such as diethyl ether, ethylene glycol dimethyl ether, diethyl ether, diethylene glycol dimethyl ether, tetrahydrofuran and dioxane; nitriles, such as acetonitrile and propionitrile; and dimethyl sulf~xide.
The further reaction of the silylaminopyrimidines or -triazines of the formula VII with the chloroformic acid esters of the formula VI to the N-pyrimidinyl- and N-triazinylcarbamates of the formula III is performed by heating at 30 to 120C, preferably at 40 to 80C. This reaction can be carried out without solvent or in an inert solvent, for example benzene, toluene, xylene, petroleum ether, cyclohexane, diethyl ether, dioxane or tetrahydrofuran.
' ' ' ~ ` :" , .;
~243~74 The process for producing the intermediates of the formula VII and also these intermediates are novel, and have been developed specially for the production process according to the invention. They therefore likewise form part of the present invention.
The starting materials o the formulae V and VI
are known and are obtainable commercially.
The following Examples serve to further illustrate the present invention.
Example 1: N-(2-Chlorophenyl-sulfonyl)-N'-(4-methoxy-6 methyl-1,3,5-triazin-2-yl) urea.
A mixture of 1.0 g of 2-chlorophenylsulfonamide, 1.0 g of N-(4-methoxy-6 methyl-1,3,5-triazin-2-yl)-methyl-carbamate and 1.0 g of 1,5-diazabicyclo [4,3,0lnon-5-ene in 10 ml of dioxane is stirred for 14 hours at 100C.
After the addition of 50 ml of water, the mixture is acidified with 10% hydrochloric acid and extracted with ethyl acetate. The organic phase is concentrated by evaporation, and the residue is crystaLlised from a methylene chloride/ether mixture to thus obtain 0.75 g of N-(2-chlorophenylsulfonyl)-N'-(4-methoxy-6-methyl-1,3,5-triazin-2 yl)-urea, m.p. 176-178C.
Example 2:
a) 4-Methoxy-6-methyl-2-trimethylsilylamino-1,3,5-triazine.
A mixture of 238.2 g of 2-amino-4-methoxy-6-methoxy-6-methyl-1,3,5-triazine, 505 ml of N,0-bis-(trimethylsilyl3-acetamide and 1150 ml of anhydrous acetonitrile is refluxed for 8 hours. Fractional distillation yields 296.4 g of~4-methoxy-6-methyl-2-trimethylsilylamino-1,3,5-triazine, b.p. 78C/0.053 mb.
.
- "
.., -~LZ43674 b) N-(4-Methoxy-6-methyl-1,3,5-triazin-2-yl)-methylcarbamate A mixture of 10.6 g of 4-methoxy-6-methyl-2-trimethylsilylamino-1,3,5-triazine and 14.2 g of chloroformic acid methyl ester is stirred for 20 hours at 65C. The volatile constituents are evaporated o~
in vacuo, and the residue is taken up with 30 ml o methylene chloride. After separation of the insoluble constituents, the solution is concentrated by evaporation and the residue is chromatographed on silica gel. The yield is 6.2 g of N-(4 methoxy-6-methyl-1,3,5-triazin-2-yl)-methylcarbamate, m.p. 102-104C.
Example 3: 4-~ifluoromethoxy-6-methyl-2-trimethylsilyl-pyrimidine.
A mixture of 21.0 g of 2-amino-4-difluoromethoxy-6-methyl-pyrimidine and 0.27 ml of cancentrated sulfuric acid is heated in 90 ml of anhydrous toluene to 60C, and a mixture of 12.5 ml of hexamethyldisilazane and 7.6 ml of trimethylchlorosilane is added within 10 minutes.
The formed suspension is stirred at 60C for 24 hoursg it is subsequently cooled to 20 to 25G, filtered and fractionally distilled. The yield is 26 g of 4-difluoro-methoxy-6-methyl-2-trimethylsilyl-pyrimidine, b.p. 95C/ll mb.
Example 4:
a) 4-Methoxy-6-methyl-2-trimethylsilylamino-pyrimidine.
A mixture of 27.9 g of 2-amino-4-methoxy-6-methyl-pyrimidine and 48.8 g of N,0-bis-(trimethylsilyl)-acetamide in 250 ml of acetonitrile is refluxed for 7 hours. After cooling, the insoluble sediment is separated off and the filtrate is fractionally distilled. The yield is 36.3 g of 4-methoxy-6-methyl-2-trimethylsilylamino-pyrimidine, b.p. 62-640C/o.026 mb.
b) N-(4-Methoxy-6-methyl-pyrimidin-2-yl)-methylcarbamate.
A mixture of 10.6 g of 4-methoxy-6-methyl-2-trimethyl-.
.
lZ~367~
silylamino-pyrimidine and 47 g of chloroformic acid methyl ester is stirred in 120 ml of petroleum ether at 50C for 7 hours. As the solution cools, 5.5 g o~
N-(4-methoxy-6-methyl-pyrimidin-2-yl)-methylcarbamate, m.p. 92-95C, crystallise out.
The intermediates listed in the following Tables are obtained in an analogous manner.
Table 1 ~N_ ./X
R-O-CO-NH ~ \N /Z
\Y
_ . _ . ___ .
No. R x Y . Z Physical data .
1.1 ~ OCH3 C33 N m.p. 102-104C
1. 2 CH 3 OCH 3 OCH 3 N
1. 3 CH 3 OCH 3 CH3~ CH m . p . 92- 95 C
1. 4 CH 3 OCH 3 OCH3 CH
, 1. 5 CH 3 CH3 CH 3 CH m . p . 96- 98 C
l . 6 . CH 3 CH 3 CH3 N
1. 7 CH 3 OCHF2 CH3 CH
1. 8 C2H5 OCHF2 CH3 CH m . p . 86-89 C
1. 9 CH3 OCHF2 OCH3 CH
1. lO CH3 OCHF2 OCHF2 CH
l. ll C2H5 OCH3 CH3 N m . p. 73-74C
1 .1 2 C2H5 OCH3 OCH3 N
1 .1 3 C2H5 OCH3 CH3 CH
1 .1 4 C2H5 OCH3 OCH3 CH
1.15 C2H5 CH3 CH3 CH m.p. 68-69C
l.l6 ~ C~3 L ~
Table 2:
/ X
(C1~3)3Si ~ NH - ~ /Z
. y No. Z I Physical data
2.1 OCH3 CH3 N b.p. 78C/0.053 mb 2.2OCHF2 CH3 CH b.p. 95C/ 11 mb 2.3OCH3 CH3 CH b.p. 62-64C/0.026 mb 2.4OCH3 OCH3 N
2.5OGH3 CH2F CH
2.6OCHF2 CH3 N
2.7OCH3 OCH3 CH
2.8CH3 CH3 N
2.9CH3 CH3 CH
2.10OCHF2 - OCH3 ~ CH
2,11OCHF2 OCHF2 CH . .. ~ .... . .
.. .. ..... . - l -. . . , '` .- :: : :
- ~
2.5OGH3 CH2F CH
2.6OCHF2 CH3 N
2.7OCH3 OCH3 CH
2.8CH3 CH3 N
2.9CH3 CH3 CH
2.10OCHF2 - OCH3 ~ CH
2,11OCHF2 OCHF2 CH . .. ~ .... . .
.. .. ..... . - l -. . . , '` .- :: : :
- ~
Claims (8)
1. A process for producing N-arylsulfonyl-N -pyrimidinyl-and -triazinylureas of the general formula I
(I) wherein G is a radical of the formula or X is C1-C4-alkyl, C1-C4-haloalkyl, C1-C4-alkoxy, C1-C4-alkylthio, C1-C4-haloalkoxy, C1-C4-alkylamino or di-C1-C4-alkylamino, Y is C1-C4-alkyl, C1-C4-haloalkyl, C1-C4-alkoxy or C1-C4-haloalkoxy, and Z is nitrogen or the methine bridge, A is oxygen, sulfur, -NR5- or -C=N-, R5 being hydrogen, C1-C4-alkyl or -CO-C1-C4-alkyl Rl is hydrogen, halogen, nitro, -Q-C1-C4-alkyl, C1-C4-alkyl, CF3, SO2-di-C1-C4-alkylamino, -CO-Q-C3-C5-alkynyl, or -CO-Q-C1-C4-alkyl or -CO-Q-C3-C5-alkenyl each unsubstituted or substituted by halogen, cyano, C1-C4-alkoxy or C1-C4-alkylthio, R2 is hydrogen, halogen, CF3, NO2, C1-C4-alkyl or C1-C4-alkoxy, R3 is hydrogen, fluorine or chlorine, R4 is hydrogen, halogen, nitro, CF3, C1-C4-alkyl, -CHR6R7, -SO2-di-C1-C4-alkylamino, -Q-C3-C5-alkynyl, -CO-T-C3-C5-alkynyl, or -Q-C1-C4-alkyl, -Q-C2-C5-alkenyl, -CO-T-C1-C4-alkyl or -CO-T-C3-C5-alkenyl each of which is unsubstituted or substituted by halogen, cyano, C1-C4-alkoxy or C1-C4-alkylthio, Q being an oxygen, sulfur, -SOn-, -NH- or N(C1-C4-alkyl)- bridge, n being zero, one or two, and T being an oxygen, sulfur, -NH- or -N(C1-C4-alkyl) bridge, R6 is hydrogen, chlorine or methyl, and R7 is chlorine, cyano, methoxy, ethoxy or -SOn-C1-C4-alkyl, which process comprises reacting a sulfonamide of the formula II
G-SO2-NH2 (II), wherein G has the meaning defined above, with an N-pyrimidinylcarbamate or N-triazinylcarbamate of the formula III
(III) wherein X, Y and Z have the meanings defined above, and R is methyl or ethyl.
(I) wherein G is a radical of the formula or X is C1-C4-alkyl, C1-C4-haloalkyl, C1-C4-alkoxy, C1-C4-alkylthio, C1-C4-haloalkoxy, C1-C4-alkylamino or di-C1-C4-alkylamino, Y is C1-C4-alkyl, C1-C4-haloalkyl, C1-C4-alkoxy or C1-C4-haloalkoxy, and Z is nitrogen or the methine bridge, A is oxygen, sulfur, -NR5- or -C=N-, R5 being hydrogen, C1-C4-alkyl or -CO-C1-C4-alkyl Rl is hydrogen, halogen, nitro, -Q-C1-C4-alkyl, C1-C4-alkyl, CF3, SO2-di-C1-C4-alkylamino, -CO-Q-C3-C5-alkynyl, or -CO-Q-C1-C4-alkyl or -CO-Q-C3-C5-alkenyl each unsubstituted or substituted by halogen, cyano, C1-C4-alkoxy or C1-C4-alkylthio, R2 is hydrogen, halogen, CF3, NO2, C1-C4-alkyl or C1-C4-alkoxy, R3 is hydrogen, fluorine or chlorine, R4 is hydrogen, halogen, nitro, CF3, C1-C4-alkyl, -CHR6R7, -SO2-di-C1-C4-alkylamino, -Q-C3-C5-alkynyl, -CO-T-C3-C5-alkynyl, or -Q-C1-C4-alkyl, -Q-C2-C5-alkenyl, -CO-T-C1-C4-alkyl or -CO-T-C3-C5-alkenyl each of which is unsubstituted or substituted by halogen, cyano, C1-C4-alkoxy or C1-C4-alkylthio, Q being an oxygen, sulfur, -SOn-, -NH- or N(C1-C4-alkyl)- bridge, n being zero, one or two, and T being an oxygen, sulfur, -NH- or -N(C1-C4-alkyl) bridge, R6 is hydrogen, chlorine or methyl, and R7 is chlorine, cyano, methoxy, ethoxy or -SOn-C1-C4-alkyl, which process comprises reacting a sulfonamide of the formula II
G-SO2-NH2 (II), wherein G has the meaning defined above, with an N-pyrimidinylcarbamate or N-triazinylcarbamate of the formula III
(III) wherein X, Y and Z have the meanings defined above, and R is methyl or ethyl.
2. A process according to Claim 1, wherein the reaction is performed at a temperature of 20° to 200°C.
3. A process according to Claim 2, wherein the reaction temperature is 40° to 100°C.
4. A process according to Claim 1, wherein the reaction is performed in an inert solvent.
5. A process according to Claim 4, wherein the solvent is selected from the group comprising hydrocarbons, ethers, nitriles, ketones or dimethyl sulfoxide.
6. A process according to Claim 1, wherein the reaction is performed in the presence of a base.
7. A process according to Claim 6, wherein the base is selected from the group comprising 1,5-diazabicyclo [4,3,0]non-5-ene and 1,5-diazabicyclo[5,4,0]undec-5-ene.
8. A process according to Claim 1, wherein the sulfonamide of the formula II is heated with a carbamate of the formula III in the presence of a base in an inert solvent at 40° to 100°C until the reaction by which the alcohol is detached is completed, and the product is then isolated.
Priority Applications (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA000495271A CA1243676A (en) | 1982-08-23 | 1985-11-13 | N-triazinyl carbonates |
| CA000495270A CA1243678A (en) | 1982-08-23 | 1985-11-13 | N-pyrimidinyl carbamates |
| CA000495269A CA1243675A (en) | 1982-08-23 | 1985-11-13 | Trimethylsilylamino-pyrimidines and triazines |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CH499982 | 1982-08-23 | ||
| CH4999/82-0 | 1982-08-23 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000495271A Division CA1243676A (en) | 1982-08-23 | 1985-11-13 | N-triazinyl carbonates |
| CA000495270A Division CA1243678A (en) | 1982-08-23 | 1985-11-13 | N-pyrimidinyl carbamates |
| CA000495269A Division CA1243675A (en) | 1982-08-23 | 1985-11-13 | Trimethylsilylamino-pyrimidines and triazines |
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|---|---|
| CA1243674A true CA1243674A (en) | 1988-10-25 |
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ID=4286204
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000434948A Expired CA1243674A (en) | 1982-08-23 | 1983-08-19 | Process for producing sulfonylureas having a herbicidal action and an action regulating plant growth |
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| Country | Link |
|---|---|
| EP (1) | EP0101670B1 (en) |
| JP (1) | JPH062752B2 (en) |
| AT (1) | ATE32892T1 (en) |
| CA (1) | CA1243674A (en) |
| DE (1) | DE3375916D1 (en) |
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| US5221315A (en) * | 1990-05-30 | 1993-06-22 | Ciba-Geigy Corporation | Sulfonylureas |
| US5342823A (en) * | 1992-02-20 | 1994-08-30 | Ciba-Geigy Corporation | Sulfonylureas |
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| US5532203A (en) * | 1992-12-02 | 1996-07-02 | Ciba-Geigy Corporation | Selective safened herbicidal composition |
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| AU4789685A (en) * | 1984-09-28 | 1986-04-10 | E.I. Du Pont De Nemours And Company | Heterocyclic sulphonamide derivatives |
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| US5296453A (en) * | 1988-11-21 | 1994-03-22 | E. I. Du Pont De Nemours And Company | Process for the interconversion of two seperate crystal forms of a herbicidal pyridine sulfonamide |
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| DE4029484A1 (en) * | 1990-09-18 | 1992-03-19 | Basf Ag | HERBICIDES (((1,3,5-TRIAZIN-2-YL) AMINOCARBONYL) AMINOSULFONYL) BENZOESE ACID ESTERS, PROCESS FOR THEIR PREPARATION AND THEIR USE |
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| IE34211B1 (en) * | 1969-05-09 | 1975-03-05 | Novo Terapeutisk Labor As | Improvements in or relating to sulphonylureas |
| CA1330438C (en) * | 1980-07-17 | 1994-06-28 | Willy Meyer | N-phenylsulfonyl-n'-pyrimidinyl-and-triazinylureas |
| US4369320A (en) * | 1980-11-03 | 1983-01-18 | E. I. Du Pont De Nemours And Company | N-[Heterocyclicaminocarbonyl]-8-quinolinesulfonamides |
| BR8204028A (en) * | 1981-07-16 | 1983-07-05 | Du Pont | HERBICIDE COMPOUND SUITABLE COMPOSITION AND PROCESS TO CONTROL THE GROWTH OF UNWANTED VEGETATION |
| BR8206012A (en) * | 1981-10-16 | 1983-09-13 | Du Pont | COMPOUND; SUITABLE COMPOSITION AND PROCESS TO CONTROL GROWTH OF VEGETATION; PROCESS TO SYNTHESIZE COMPOUNDS |
| BR8300016A (en) * | 1982-01-07 | 1983-08-30 | Du Pont | COMPOUNDS; ADEQUATE COMPOSITION AND PROCESS FOR UNWANTED VEGETATION GROWTH CONTROL |
| JPS58206573A (en) * | 1982-05-12 | 1983-12-01 | イ−・アイ・デユポン・デ・ニモアス・アンド・カンパニ− | Herbicidal o-alkoxybenzene sulfonamide |
| JPS5948465A (en) * | 1982-08-12 | 1984-03-19 | イ−・アイ・デユポン・デ・ニモアス・アンド・カンパニ− | Alkylsulfonylsulfonamides |
-
1983
- 1983-08-17 DE DE8383810366T patent/DE3375916D1/en not_active Expired
- 1983-08-17 EP EP83810366A patent/EP0101670B1/en not_active Expired
- 1983-08-17 AT AT83810366T patent/ATE32892T1/en not_active IP Right Cessation
- 1983-08-19 CA CA000434948A patent/CA1243674A/en not_active Expired
- 1983-08-23 JP JP58153996A patent/JPH062752B2/en not_active Expired - Lifetime
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5221315A (en) * | 1990-05-30 | 1993-06-22 | Ciba-Geigy Corporation | Sulfonylureas |
| US5209771A (en) * | 1991-01-25 | 1993-05-11 | Ciba-Geigy Corporation | Sulfonylureas |
| US5412107A (en) * | 1991-01-25 | 1995-05-02 | Ciba-Geigy Corporation | Phenylsulfonylchloride intermediates useful for the preparation of herbicidally active sulfonylureas |
| US5552368A (en) * | 1991-01-25 | 1996-09-03 | Ciba-Geigy Corporation | Sulfonylureas |
| US5597779A (en) * | 1991-01-25 | 1997-01-28 | Ciba-Geigy Corporation | Sulfonylureas |
| US5342823A (en) * | 1992-02-20 | 1994-08-30 | Ciba-Geigy Corporation | Sulfonylureas |
| US5369083A (en) * | 1992-07-30 | 1994-11-29 | Ciba-Geigy Corporation | Sulfonylureas |
| US5532203A (en) * | 1992-12-02 | 1996-07-02 | Ciba-Geigy Corporation | Selective safened herbicidal composition |
| US5612288A (en) * | 1992-12-02 | 1997-03-18 | Ciba Geigy Corporation | Selective herbicidal composition |
Also Published As
| Publication number | Publication date |
|---|---|
| ATE32892T1 (en) | 1988-03-15 |
| DE3375916D1 (en) | 1988-04-14 |
| JPH062752B2 (en) | 1994-01-12 |
| JPS5959671A (en) | 1984-04-05 |
| EP0101670A3 (en) | 1985-05-29 |
| EP0101670A2 (en) | 1984-02-29 |
| EP0101670B1 (en) | 1988-03-09 |
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Legal Events
| Date | Code | Title | Description |
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| MKEX | Expiry |