CN1042690C - Herbicidal composition containing substituted pyridinesulfonamide compounds - Google Patents
Herbicidal composition containing substituted pyridinesulfonamide compounds Download PDFInfo
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- CN1042690C CN1042690C CN92100307A CN92100307A CN1042690C CN 1042690 C CN1042690 C CN 1042690C CN 92100307 A CN92100307 A CN 92100307A CN 92100307 A CN92100307 A CN 92100307A CN 1042690 C CN1042690 C CN 1042690C
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Abstract
A substituted pyridinesulfonamide compound and a salt thereof represented by the following general formula I, the groups have the meanings given in the description.
Description
The present invention relates to new, the pyridinsulfonamide compounds that replaces and salt thereof, with this compounds as the weed killer herbicide of active component and the method for preparing this compounds.
The characteristics of the pyridine sulfamide compound of replacement of the present invention are to have (being that substituting group is arranged on the nitrogen-atoms) amino carbonyl that a N-replaces on its pyridine ring.The pyridinsulfonamide compounds of this replacement is from being published in United States Patent (USP) 4,518, No. 776, european patent application disclose No. 101670 and United States Patent (USP) 4,521, No. 597 general formula is known, but the pyridine sulfonamide of replacement of the present invention does not disclose out in above-mentioned existing patent document particularly.United States Patent (USP) 4,435 has been introduced a kind of pyridine sulfamide compound of replacement in No. 206, but the amino carbonyl that replaces of N-not on the pyridine ring of this compound.People have developed a lot with the similar weed killer herbicide of sulfamide compound as active component, but also both develop cereal are not had tight security, and the weed killer herbicide of fine herbicide effect is arranged again.
The present inventor furthers investigate the chemical constitution of sulfamide compound and the relation between the physiologically active.Particularly, in order to seek a kind of weed killer herbicide that is used for cereal, the inventor makes further research.Consequently, the inventor has obtained as drawing a conclusion: it is the effective herbicide that has that can be used for paddy Tanaka that a kind of pyridinsulfonamide compounds is arranged, this compound has pyridine ring, have an amino carbonyl and a special substituting group (if any) that a N-replaces on this pyridine ring, this compound also has a sulfonamide part, has on the nitrogen-atoms of this part by the specific pyrimidine-2--amino carbonyl that substituting group replaced; The inventor has made this invention therefrom.
The invention provides a kind of pyridinsulfonamide compounds of replacement, its salt, the weed killer herbicide that contains them and their preparation method.The pyridinsulfonamide compounds of this replacement can be represented with following general formula:
In the formula, R represents base
R1 and R2 represent a hydrogen atom, alkyl, haloalkyl, thiazolinyl, alkynyl, alkoxyl, halogenated alkoxy, alkoxyalkyl, haloalkoxy alkyl, cycloalkyl, halogenated cycloalkyl, alkoxy carbonyl group, haloalkoxy carbonyl, phenyl or halogenophenyl independently of one another, condition is when having one to represent hydrogen atom among R1 and the R2, and then another represents a group except that hydrogen atom in the above-mentioned group; R1 and R2 can constitute a heterocycle with an adjacent nitrogen-atoms; Y represents a halogen atom, alkyl, haloalkyl, alkoxyl, halogenated alkoxy, alkylthio group, halogenated alkylthio, alkoxyalkyl, haloalkoxy alkyl or group
R3 and R4 represent a hydrogen atom or alkyl independently of one another): n is 0 or integer 1 or 2; X1 and X2 represent a methyl, methoxy or ethoxy independently of one another.
The salt of the pyridinsulfonamide compounds of replacement of the present invention comprises alkali metal salt (for example sodium salt and sylvite), alkali salt (for example magnesium salts and calcium salt) and amine salt (for example single methylamine salt, dimethylamine salt and triethylamine salt).These salt can prepare with conventional method.
In general formula (I), haloalkyl, halogenated alkoxy, haloalkoxy alkyl, haloalkoxy carbonyl by R1 and R2 representative, halogenated cycloalkyl or halogenophenyl, and can be by one or more halogen atoms replacements by haloalkyl, halogenated alkoxy, halogenated alkylthio or the haloalkoxy alkyl of Y representative.
Alkyl or moieties by R1, R2 in the general formula (I), R3, R4 and Y representative are the alkyl that contains 1～6 carbon atom, for example methyl, ethyl, propyl group and butyl.The thiazolinyl or the alkenyl part of R1 and R2 representative have 2～6 carbon atoms, for example acrylic and cyclobutenyl.Alkynyl or alkynyl partly have 2～6 carbon atoms, for example propinyl and butynyl.Said cycloalkyl has 3～6 carbon atoms, and example has cyclopropyl, cyclobutyl, cyclopenta and cyclohexyl.Halogen atom among R1, R2 and the Y for example is fluorine atom, chlorine atom, bromine atoms and iodine atom.R1 and R2 can constitute a heterocycle with described nitrogen-atoms.The example of this heterocycle has morpholine ring, ethylene imine ring, pyrrolidine ring and piperidine ring.
In the middle of the pyridinsulfonamide compounds of the represented replacement of general formula (I), be preferably as follows the compound and the salt thereof of general formula representative:
More preferred particular compound are described below:
(1) R1 represents a hydrogen atom or alkyl, preferably hydrogen atom or methyl, and R2 represents an alkyl, preferably methyl.
(2) Y represents halogen atom, alkyl, haloalkyl, alkoxyl or an alkoxyalkyl, preferably chlorine atom, bromine atoms, methyl or difluoromethyl, and wherein each all is connected on 6 of pyridine nucleus; And n is 0,1 or 2, preferably 0 or 1.
(3) X1 and X2 represent a methoxyl group independently of one another.
(4) more specifically get on very well preferred following compounds:
N-[(4,6-dimethoxypyridin-2-yl) amino carbonyl]-3-first aminocarbonyl-2-pyridine sulfonamide or N-[(4,6-dimethoxypyridin-2-yl) amino carbonyl]-3-diformazan aminocarbonyl-2-pyridine sulfonamide, or 6-chlorine (or bromine, difluoromethyl or methyl)-N-[(4,6-dimethoxypyridin-2-yl) amino carbonyl]-3-diformazan aminocarbonyl-2-pyridine sulfonamide.
According to the present invention, the pyridinsulfonamide compounds of the replacement of general formula (I) representative and salt thereof can prepare with following method.
Make a kind of pyridine compounds and their of general formula (II) representative and a kind of pyrimidines reaction of general formula (III) representative,
R-SO
2Z
1(II)
In the formula (II), the definition of R is the same, and Z1 represents group-NH
2,-NCO ,-NHCOCl or-NHCOOR5 (wherein R5 represents alkyl or aryl); In formula (III), on behalf of halogen atom, methyl, methoxy or ethoxy, Z2, X3 and X4 represent group-NH independently of one another
2, NCO ,-NHCOCl or-NHCOOR5 (wherein the definition of R5 is the same), condition is to represent group-NH as Z1
2The time, Z2 represent group-NCO ,-NHCOCl or-NHCOOR5; Represent group-NH and work as Z2
2The time, Z1 represent group-NCO ,-NHCOCl or-NHCOOR5.After this,, then carry out methoxylation or ethoxylation if X3 and/or X4 are halogen atoms.In addition, carrying out salify when needed handles.
Say that in particular above-mentioned pyridinsulfonamide compounds and derivative thereof can pass through method [A] to [G] preparation.
(Ⅱ-6)
In the reaction equation of [H], Hal represents halogen atom in method [A], and the definition of R, R5, X1, X2 and X3 is the same.The compound of general formula (II-5) representative can be by the step card preparation of method [A] to [F].Make compound and ammonia react, can make the compound of general formula (II-6) representative at an easy rate by general formula (II-2) to (II-4) representative.The aryl of R5 representative can be can be by one or more chlorine atoms or one or more methyl substituted naphthyl or phenyl in general formula (III-1) and (II-2).In method [A] and [D], in case of necessity, can add 1,8-diazabicylo [5.4.0] 11 carbon-7-alkene is to add fast response.In method [B], [C], [E] and [F], can add 1 in case of necessity, 4-diazabicylo [2.2.2.] octane in method [B], [C], [E] and [F], can add a kind of alkali, in case of necessity as triethylamine or pyridine.When using method [A] arrives [H], can in solvent, carry out if necessary.The example of solvent has: the aprotic solvent (for example methyl-sulfoxide (DMSO) and sulfolane) of aromatic hydrocarbons (for example benzene,toluene,xylene and chlorobenzene), ring-type or acyclic aliphatic hydrocarbon (for example chloroform, tetrahydro carbon, carrene, dichloroethane, trichloroethanes, hexane and cyclohexane), ether (for example ether, dioxane and oxolane), nitrile (for example acetonitrile, propionitrile and acrylonitrile) and polarity
(1) according to illustrating: can make by the method that route 1 and 2 is pointed out as the pyridine compounds and their (II-1 ') in the general formula (II-1) of anti-rock formula raw material.
Route 1
Route 2
Note: EG is an ethylene glycol, and MeOH is a methyl alcohol, and EtOH is an ethanol, and DMF is a dimethyl formamide, and DMSO is a methyl-sulfoxide, and Bz is a benzyl, and-Bu (t) is the tert-butyl group, and AcOH is an acetate.
Show according to diagram (route 3) that (2) Y in the general formula (II-1 ') is if the alkyl that is replaced by one or more fluorine atoms, then corresponding product also can make by the method that following route 3 is pointed out.
Note: raw material
Can use
Method according to route 1 and 2 makes.Q1 is hydrogen atom or halogen atom, and NBS is a N-bromosuccinimide, and BPO is a benzoyl peroxide.The meaning of other abbreviation and symbol is with aforementioned identical.
Illustrate according to diagram (route 4) that (3) when the Y in the general formula (II-1 ') was alkoxyl, halogenated alkoxy, alkylthio group or halogenated alkylthio, corresponding product also can prepare by the method shown in the following route 4.
(on connect the 12nd page)
Note: R6 is alkyl or haloalkyl.The meaning of other abbreviation and symbol is the same.
Illustrate according to diagram (route 5) that (A.) when the Y in the general formula (II-1 ') was alkoxyl-methyl or haloalkoxy methyl, corresponding product also can make according to the method shown in the following route 5.
Route 5
Note: the meaning of each abbreviation and symbol is the same.
Illustrate according to diagram (route 6) that (5) Y in general formula (II-1 ') is a group
The time, corresponding product also can be made by the method shown in the following route 6.
Route 6
Note: the meaning of each abbreviation and symbol is the same.
Show according to diagram (route 7) that (6) when the Y in the general formula (II-1 ') was halogen atom, corresponding product also can be made by method shown in the following route 7.
Route 7
Note: the implication of each abbreviation and symbol is the same.
Illustrate according to diagram (route 8) that (7) the 3-pyridinsulfonamide compounds of general formula (II-1 ') representative also can be made by the method shown in the following route 8.
Illustrate according to diagram (route 9) that (8) (the N-pyridine oxide compounds of II-1 ") representative also can make by the method shown in the following route 9 general formula.Route 9
Illustrate according to diagram (route 10) that (9) general formula (II-2) can be by the method for following route 10 to each compound of (II-4) representative, each compound of being represented by general formula (II-1) makes.
Route 10
The reaction condition of preparation starting compound as reaction temperature, reaction time, the solvent that can selectively use arbitrarily, alkaline matter or the like, can suitably be selected according to the reaction condition of similar reaction traditionally.
The following stated be the synthetic embodiment of the intermediate of The compounds of this invention.
Intermediate synthesizes embodiment 1
2-amino-sulfonyl-5-chloro-N, N-dimethyl nicotinamide synthetic
[I] make 6.5 the gram 2, the 5-dichloro-nicotinic acid mix mutually with 24.7 milliliters of thionyl chlorides and under refluxad with its reaction 2 hours.After the reaction, steam and remove excessive thionyl chloride, in mixture, add 39 milliliters of carrene, add 2.77 gram dimethylamine hydrochlorides subsequently again.Splashed into 8.60 gram triethylamines with about 1 hour time, allow gained mixture about 1 hour in room temperature reaction.
After reaction is finished, in product impouring water, extract with carrene.Use the anhydrous sodium sulfate drying dichloromethane layer, the pressure reducing and steaming carrene.The gained residue is purified with silica gel column chromatography, makes 5.5 grams 2,5-two chloro-N, N-dimethyl nicotinamide, 120～122 ℃ of fusing points.
[II] is at 80 ℃, with about 1 hour time, 3.0 grams by method [I] make 2,5-two chloro-N, the mixtures of N-dimethyl nicotinamide, 1.70 gram benzyl mercaptans and 5 milliliters of methyl-sulfoxides are added drop-wise to 1.89 and restrain in the suspension of Anhydrous potassium carbonates in 28 milliliters of methyl-sulfoxides.Make the gained mixture 130～140 ℃ of reactions 30 minutes.
After reaction is finished, product is added in the entry, extract with carrene.Use the anhydrous sodium sulfate drying dichloromethane layer, remove carrene under reduced pressure.With silica gel column chromatography purification gained residue, make the 2-benzylthio-5-chloro-N of 2.18 gram oilies, the N-dimethyl nicotinamide.
[III] contains 2.36 gram 2-benzylthio-5-chloro-N at 0～5 ℃ at 20 milliliters, feeds chlorine in 50% acetic acid solution of N-dimethyl nicotinamide.When overflowing, excessive chlorine makes the stopping of reaction.
After reaction is finished, product is added in 150 gram ice and the 200 milliliters of carrene, tells dichloromethane layer.Wash dichloromethane layer with 300 milliliters of frozen water, make it be cooled to 0 ℃.Splash into tert-butylamine subsequently, till stirring gained mixture reaches room temperature to this layer temperature.Reactant liquor is through verifying as alkalescent, and reaction has so far just been finished.
After reaction is finished, product is added to the water, extracts with carrene.Tell the dichloromethane layer anhydrous sodium sulfate drying; Steam again and remove carrene.The gained residue is purified with silicon amine column chromatography, makes 1.21 gram 2-tert-butylamine sulphonyl-5-chloro-N, N-dimethyl nicotinamide, 143～145 ℃ of fusing points.
[IV] makes 1.0 grams with method [III] 2-tert-butylamine sulphonyl-5-chloro-N, the N-dimethyl nicotinamide is added in 10 milliliters of trifluoroacetic acids, and under refluxad allows the two react about 1 hour.
After reaction is finished, remove the trifluoroacetic acid in the product under reduced pressure.The gained residue obtains 0.71 gram 2-aminosulfonyl-5-chloro-N through the silica gel column chromatography purifying, and N-dimethyl nicotinamide, its fusing point are 155～157 ℃.
Intermediate synthesizes embodiment 2
2-aminosulfonyl-6-chloro-N, N-dimethyl nicotinamide synthetic
[I] is at 130～140 ℃, with about 1 hour time, restrain 7.0 by 2, the 6-dichloro-nicotinic acid, according to the same step of process [I] among the synthetic embodiment 1 of intermediate make 2,6-two chloro-N, the mixture of N-dimethyl nicotinamide (62.5～65 ℃ of fusing points), 3.8 gram phenmethylols and 20 milliliters of methyl-sulfoxides is added drop-wise to 6.6 and converts in the suspension of Anhydrous potassium carbonate in 50 milliliters of methyl-sulfoxides, allows the gained mixture about 2 hours of 150 ℃ of reactions.
After reaction is finished, product is added in the water, carries out carrene and extract.The dichloromethane layer anhydrous sodium sulfate drying removes carrene under reduced pressure.With silica gel column chromatography purification gained residue, get the 6-benzyloxy-2-chloro-N of 6.0 gram oilies, the N-dimethyl nicotinamide.
[II] is with 0.69 gram 6-benzyloxy-2-chloro-N, the N-dimethyl nicotinamide, 6-benzyloxy-2-benzylthio-the N that makes according to the same step of process [II] among the synthetic embodiment 1 of intermediate, N-dimethyl nicotinamide (oily product) mixes mutually with 6 milliliters of concentrated hydrochloric acids, and under agitation makes the gained mixture in room temperature reaction about 15 hours.
After reaction is finished, product is added in the water, extracts required product with carrene.The dichloromethane layer anhydrous sodium sulfate drying, the pressure reducing and steaming carrene.Gained residue silica gel column chromatography purifying gets 0.41 gram 2-benzylthio-N, N-dimethyl-6-hydroxy nicotinoyl amine, 52～60 ℃ of fusing points.
The 2-benzylthio-N of 1.0 grams by top process [II] preparation, N-dimethyl-6-hydroxy nicotinoyl amine and 0.3 milliliter of dimethyl formamide are added in 5 milliliters of thionyl chlorides, and the gained mixture was reacted about 1 hour [III].
After reaction is finished, product is added in the water, extracts required product with carrene.Dichloromethane layer washes with water, uses anhydrous sodium sulfate drying.The pressure reducing and steaming carrene, the gained residue is purified with silica gel chromatography, makes 0.45 gram 2-benzylthio-6-chloro-N, N-dimethyl nicotinamide grease.
[IV] uses above-mentioned product, and operates according to the same step of process [III] and [IV] among the synthetic embodiment 1 of intermediate, makes 2-aminosulfonyl-6-chloro-N, N-dimethyl nicotinamide, 171～173 ℃ of fusing points.
Intermediate synthesizes embodiment 3
2-aminosulfonyl-N, N-dimethyl-6-ethyoxyl vitamin PP synthetic
[I] is added to 0.231 gram sodium metal in 50 milliliters of absolute ethyl alcohols with the preparation alcohol sodium alcohol solution.In this solution, add 2.0 grams by intermediate synthesize that the same step of process [I] among the embodiment 1 makes 2,6-two chloro-N, N-dimethyl nicotinamide, and under refluxad allow mixture react about 1 hour.Reacted solution added in the entry and with carrene extract.The dichloromethane layer anhydrous sodium sulfate drying removes carrene under reduced pressure.Residue is purified with silica gel chromatography, obtains 1.95 gram 2-chloro-N, N-dimethyl-6-ethyoxyl vitamin PP grease.
The same step that [II] uses the said goods press process [II], [III] and [IV] among the synthetic embodiment 1 of intermediate is operated, and makes fusing point and be 2-aminosulfonyl-N of 150.5～151.5 ℃, N-dimethyl-6-ethyoxyl vitamin PP.
Intermediate synthesizes embodiment 4
2-aminosulfonyl-N, N-dimethyl-6-fluorine vitamin PP synthetic
[I] is 0.302 gram 2-tert-butylamine base sulphonyl-6-chloro-N, the N-dimethyl nicotinamide is added in 10 milliliters of dimethyl formamide pulpous state liquid, these slurries contain 0.116 gram through spray-dired potassium fluoride, under agitation make the gained mixture about 3 hours of 150 ℃ of reactions then.
Reaction is added to reactant liquor in 100 ml waters, and extracts with carrene after finishing.Extract is through using anhydrous sodium sulfate drying after the washing repeatedly.Remove carrene under reduced pressure, residue is purified with silica gel column chromatography, makes 0.204 gram 2-tert-butylamine base sulphonyl-N, N-dimethyl-6-fluorine vitamin PP.
The same step that [II] uses the said goods press process [IV] among the synthetic embodiment 1 of intermediate is operated, and makes fusing point and be 2-aminosulfonyl-N of 164～165 ℃, N-dimethyl-6-fluorine vitamin PP.
Intermediate synthesizes embodiment 5
Synthesizing of 2-aminosulfonyl-N-methylnicotinamide
[I] is saturated with 250 milliliters of dry methyl alcohol with hydrogen chloride gas, adds 250 ml methanol and 30 gram 2-sulfydryl nicotinic acid then therein.Allowing gained solution at room temperature react spends the night.
After the reaction, make reactant liquor become alkalescent, and remove methyl alcohol under reduced pressure with ammonia.Leach with after washing gained crystal and with it.The crystal that drying under reduced pressure leaches obtains 24 gram 2-sulfydryl methyl nicotinates, 136～140 ℃ of fusing points.
[II] is added to the 2-sulfydryl methyl nicotinate that 10 grams are made by process [I] in the suspension that makes with 50 milliliters of acetate and 50 ml waters.At 0 ℃ or more under the low temperature chlorine is fed in this reaction system, when excessive chlorine is overflowed, react and just finished.
After the reaction, gained solution is added in the mixture of 150 gram ice and 500 milliliters of carrene, isolates dichloromethane layer.Wash dichloromethane layer with 500 milliliters of frozen water it is cooled to 0 ℃.Subsequently 12.9 gram tert-butylamines are added drop-wise in the above-mentioned solution, and the temperature that is stirred to gained solution reaches till the room temperature.After stirring end, reactant liquor is added in 500 ml waters, extract with carrene then.Also steam except that after the carrene with anhydrous sodium sulfate drying, obtain 13 gram coarse crystals.This crystal with carrene and n-hexane recrystallization, is made 2-tert-butylamine base sulphonyl methyl nicotinate, 169～171 ℃ of fusing points.
[III] is added to 1 gram the said goods in 20 milliliters of absolute methanols that absorb excessive methylamine, stirs then 15 hours.
After reaction is finished, product is added in the water, and extracts with carrene.Extract the back and use the anhydrous sodium sulfate drying dichloromethane layer, and remove carrene wherein under reduced pressure, obtain 0.73 gram 2-tert-butylamine base sulphonyl-N-methylnicotinamide, 189～192 ℃ of fusing points.
[IV] uses this product to operate by the same step of process [IV] among the synthetic embodiment 1 of intermediate, makes the 2-aminosulfonyl-N-methylnicotinamide of 207～209.5 ℃ of fusing points.
Intermediate synthesizes embodiment 6
2-aminosulfonyl-N, N-dimethyl nicotinamide synthetic
[method A]
In blanket of nitrogen, at 10 ℃ or more under the low temperature, 10 milliliters of n-hexanes that contain 19% trimethyl aluminium are added in the following solution: this solution is dissolved in 1.3 milliliters of dimethylamine in 10 milliliters of anhydrous benzene and obtains [I].Allow the gained mixture react, till its temperature reaches room temperature.In this reactant liquor, splash into and 2-tert-butylamine base sulphonyl methyl nicotinate is dissolved in 40 milliliters of benzene and the 20 milliliters of carrene and in the solution that obtains.Under refluxad stirred the gained mixture subsequently about 9 hours.
Reaction is added to reactant liquor in the watery hydrochloric acid after finishing, and extracts with carrene.The extract anhydrous sodium sulfate drying removes carrene under reduced pressure, and residue silica gel column chromatography purifying obtains 1.0 gram 2-tert-butylamine base sulphonyl-N, the N-dimethyl nicotinamide.
[II] uses the same steps as operation of above product according to process [IV] among the synthetic embodiment 1 of intermediate, makes fusing point and be 2-aminosulfonyl-N of 209～211 ℃, the N-dimethyl nicotinamide.
[method B]
Chlorine is fed 2.7 gram 2-benzylthio-N, in the solution of N-dimethyl nicotinamide in 50 milliliter of 50% acetate, till having excessive chlorine to overflow.
After reaction finishes, reactant mixture is added in 200 milliliters of frozen water, and extract with 60 milliliters of carrene.Wash dichloromethane layer with 100 milliliters of frozen water subsequently, it is cooled to 0 ℃ simultaneously.In solution, feed ammonia, till changing it into alkaline solution.Steam and remove after the carrene, in residue, add 15 ml waters, stir the gained mixture again.The gained crystal is leached and wash with a small amount of.This crystal obtains 1.27 gram 2-aminosulfonyl-N, N-dimethyl nicotinamide, 209～211 ℃ of fusing points behind drying under reduced pressure.
Intermediate synthesizes embodiment 7
Synthesizing of 2-aminosulfonyl-N-ethyl-N-methylnicotinamide
[I] under refluxad reacted the mixture of 30 gram 2-chlorine apellagrins and thionyl chloride 4 hours.After removing thionyl chloride excessive in the reactant liquor under reduced pressure, in reactant liquor, add 500 milliliters of carrene, feed methylamine gas in room temperature again, become weakly alkaline solution to reactant liquor till.The methylamine hydrochloride that filtering forms, concentrated filtrate.The crystal of separating out obtains 27 gram 2-chloro-N-methylnicotinamides, 106～107 ℃ of fusing points with n-hexane and carrene recrystallization.
[II] is added to 2-chloro-N-methylnicotinamide the drips of solution in 10 milliliter dimethyl formamides of 5 grams by the same step preparation of process in the present embodiment [I] in the suspension that makes with the method for adding 117 gram 60% sodium hydrides in 50 milliliters of dimethyl formamides at 0～5 ℃.The gained mixture splashes into 3.5 gram bromoethanes in 0 ℃ again about 30 minutes of 0～5 ℃ of reaction.Gained solution at room temperature reacted 2.5 hours, then reactant liquor was added in the water, and extracted with carrene.The washing extract, with anhydrous sodium sulfate drying it.Pressure reducing and steaming carrene subsequently, residue silica gel column chromatography purifying makes 5.7 gram 2-chloro-N-ethyl-N-methylnicotinamides, is a grease.
[III] presses the same step operation that process [II] arrives [IV] among the synthetic embodiment 1 of intermediate with this product, makes 2-aminosulfonyl-N-ethyl-N-methylnicotinamide, and its fusing point is 202～203 ℃.
Intermediate synthesizes embodiment 8
2-aminosulfonyl-N, N-dimethyl-6-methylnicotinamide synthetic
[I] be dimethyl formamide of adding in the mixture of 1.35 gram 2-hydroxyl-6-methylnicotinic acids and 15 milliliters of thionyl chlorides, under refluxad allows about 2 hours of gained solution reaction then.The thionyl chloride that pressure reducing and steaming is excessive adds 50 milliliters of carrene in residue.The gained mixture is added drop-wise in the mixture of 30 milliliter 30% dimethylamine agueous solution and 50 milliliters of carrene, gained solution was at room temperature reacted 15 minutes.
After reaction is finished, reactant mixture is added in the entry, extract with carrene.The washing dichloromethane layer and with anhydrous sodium sulfate drying it.The pressure reducing and steaming carrene, residue is purified with silica gel column chromatography, obtains 1.57 gram 2-chloro-3-N, N-dimethylamino carbonyl-6-picoline (66～67.5 ℃ of fusing points).
[II] presses the same steps as operation of process [II] to [IV] among the synthetic embodiment 1 of intermediate with this product, makes fusing point and be 2-aminosulfonyl-N of 188.5～190.5 ℃, N-dimethyl-6-methylnicotinamide.
Intermediate synthesizes embodiment 9
2-aminosulfonyl-N, N-dimethyl-6-methoxyl group vitamin PP synthetic
[I] makes 33 grams 2, and the 6-dichloro-nicotinic acid mixes mutually with 100 milliliters of thionyl chlorides, and under refluxad reacts about 3 hours.
After reaction was finished, the thionyl chloride that pressure reducing and steaming is excessive added 500 milliliters of carrene again.Under the temperature of room temperature to 40 ℃, in this mixture, dripping absolute methanol.After dropwising, make the gained mixture under refluxad should be about 1 hour.
After finishing reaction, reactant liquor is added in 500 ml waters, separates with carrene again.With the dichloromethane layer washing and with behind the anhydrous sodium sulfate drying, the pressure reducing and steaming carrene.With the silica gel column chromatography residue of purifying, obtain 27 grams 2,6-dichloro-nicotinic acid methyl esters, 45.5～48.0 ℃ of fusing points.
[II] uses above product to operate by [I] of [method A] among process [II], the synthetic embodiment 6 of intermediate among process [I], the synthetic embodiment 1 of intermediate among the synthetic embodiment 3 of intermediate and the same step that intermediate synthesizes process [III] to [IV] among the embodiment 1, make 2-aminosulfonyl-N, N-dimethyl-6-methoxyl group vitamin PP.
Intermediate synthesizes embodiment 10
2-aminosulfonyl-6-difluoromethyl-N, N-dimethyl nicotinamide synthetic
[I] added hot reflux 3 hours with the mixture of following each material: 2-tert-butylamine base sulphonyl-6-methylnicotinic acid methyl esters that 11.5 grams make by the same step of process [I] and [II] among the synthetic embodiment 5 of intermediate, 186 milliliters of carbon tetrachloride, 14.84 restrain N-bromosuccinimides and 0.68 and restrain benzoyl peroxides.
After reaction is finished, filter reaction mixture, concentrated filtrate is purified with silica gel column chromatography, obtains 4.5 gram 2-tert-butylamine base sulphonyl-6-dibromo methylnicotinic acid methyl esters.
[II] is added to 3.7 gram silver nitrates in the mixture of being made up of 4.4 gram the said goods, 35 milliliters of ethanol and 29 ml waters, adds hot reflux gained mixture 3 hours then.
Reaction is added to reactant mixture in the water after finishing, and extracts with carrene.Extract washes with water, uses anhydrous sodium sulfate drying, boils off solvent wherein.Residue is purified with silica gel column chromatography, obtains 2.92 gram 2-tert-butylamine base sulphonyl-6-formyl methyl nicotinates.
[III] is added to the solution of 0.642 gram diethylin sulfur trifluoride in 5 milliliters of carrene in the 0.48 gram 2-tert-butylamine base sulphonyl-solution of 6-formyl methyl nicotinate in 19 milliliters of carrene, at room temperature stirs the mixture then 1 hour.
Reaction adds reactant mixture in the entry after finishing, and extracts with carrene.(dichloromethane layer) washes with water, uses anhydrous sodium sulfate drying.Then solvent is boiled off.Residue silica gel column chromatography purifying gets 0.25 gram 2-tert-butylamine base sulphonyl-6-dichloromethyl methyl nicotinate.
[IV] makes at room temperature to be reacted by 0.50 gram the said goods and 10 milliliters of mixtures of forming with the absolute methanol of the saturated mistake of dimethylamine and spends the night.
After reaction is finished, steam the solvent that removes in the reactant mixture,, obtain 0.15 gram 2-tert-butylamine base sulphonyl-6-difluoromethyl-N, the N-dimethyl nicotinamide then with silica gel column chromatography purifying residue.
[V] uses above product to press the same step operation of process [IV] among the synthetic embodiment 1 of intermediate, obtains 2-aminosulfonyl-6-difluoromethyl-N, the N-dimethyl nicotinamide.
Intermediate synthesizes embodiment 11
2-aminosulfonyl-6-bromo-N, N-dimethyl nicotinamide synthetic
[I] adds 1.2 gram 2-benzylthio-6-chloro-N with 5 milliliters of acetate, in the N-dimethyl nicotinamide, heats gained mixture to 70 ℃ then.Feed bromize hydrogen gas in this mixture, the feeding time is 30 minutes, and allows mixture react 30 minutes again.
After reaction is finished, with reactant mixture cooling and be added in the frozen water, extract with carrene.(dichloromethane layer) washed with sodium bicarbonate solution, and water Xian uses anhydrous sodium sulfate drying then.Steam and remove carrene, residue obtains 1.0 gram 2-benzylthio-6-bromo-N, N-dimethyl nicotinamide, 105～106 ℃ of fusing points with the pure system of silica gel column chromatography.
[II] uses above product, and the same step operation according to process [III] and [IV] among the synthetic embodiment 1 of intermediate makes 2-aminosulfonyl-6-bromo-N, N-dimethyl nicotinamide, 154～156 ℃ of fusing points.
Representative instance in the compound of general formula (II-1 ') representative is summarized in table 1.
Table 1
(table 1 brought forward)
| 11 | H | 3 | H | C 3H 7(different) | 2 | 152～153 |
| 12 | ″ | ″ | CH 3 | CH 3 | ″ | 209～211 |
| 13 | H | ″ | ″ | C 2H 5 | ″ | 202～203 |
| 14 | ″ | ″ | C 2H 5 | ″ | ″ | - |
| 15 | 5-Cl | ″ | CH 3 | CH 3 | ″ | 155～157 |
| 16 | 6-C 2H 5 | ″ | ″ | ″ | ″ | 153～154 |
| 17 | H | ″ | H | CH 2CH=CH 2 | ″ | 152～153.5 |
| 18 | ″ | ″ | ″ | CH 2CF 3 | ″ | 190～196 |
| 19 | ″ | ″ | ″ | Phenyl | ″ | 186～189 |
| 20 | 4,6(CH 3) 2 | ″ | CH 3 | CH 3 | ″ | 199～202 |
| 21 | 6-Br | ″ | H | C 2H 5 | ″ | - |
| 22 | H | ″ | ″ | CH 2CH 2OCH 3 | ″ | 170.5～172.5 |
| 23 | 6-CH 2OCH 3 | ″ | CH 3 | CH 3 | ″ | - |
| 24 | 5-Cl,6-OCH 3 | ″ | ″ | ″ | ″ | 212～214 |
| 25 | H | ″ | H | Cyclopropyl | ″ | 180～182 |
| 26 | ″ | ″ | ″ | CH 2C≡CH | ″ | 203～205 |
| 27 | ″ | ″ | -(CH 2) 4- | ″ | 206～209 | |
(table 1 brought forward)
| 28 | 6-Cl | 3 | CH 3 | CH 3 | 2 | 171～173 |
| 29 | 6-CH 3 | ″ | ″ | ″ | ″ | 188.5～190.5 |
| 30 | 6-OCH 3 | ″ | ″ | ″ | ″ | - |
| 31 | 6-C 2H 5 | ″ | ″ | ″ | ″ | 153～154 |
| 32 | 6-CH 3 | ″ | H | ″ | ″ | 230～231.5 |
| 33 | H | ″ | -CH 2CH 2OCH 2CH 2- | ″ | 236～238 | |
| 34 | 6-N(CH 3) 2 | ″ | CH 3 | CH 3 | ″ | - |
| 35 | 6-SCH 3 | ″ | ″ | ″ | ″ | 195.5～197 |
| 36 | 6-NHCH 3 | ″ | ″ | ″ | ″ | 212～213 |
| 37 | 6-CH 2F | ″ | ″ | ″ | ″ | - |
| 38 | 6-CHF 2 | ″ | ″ | ″ | ″ | - |
| 39 | H | ″ | ″ | 2, the 4-difluorophenyl | ″ | 232～237 |
| 40 | ″ | ″ | H | (CH 2) 3CH 3 | ″ | - |
| 41 | 6-CH 2OCH 2CF 3 | ″ | CH 3 | CH 3 | ″ | - |
| 42 | H | 4 | H | ″ | 3 | 239～241 |
| 43 | ″ | 2 | CH 3 | ″ | ″ | - |
| 44 | 6-OCH 2CF 3 | 3 | ″ | ″ | 2 | - |
(table 1 brought forward)
| 45 | 6-Br | 3 | CH 3 | CH 3 | 2 | 154～156 |
| 46 | 6-OCH 2CH 3 | 4 | ″ | ″ | ″ | - |
| 47 | H | ″ | ″ | ″ | ″ | - |
| 48 | ″ | 2 | ″ | ″ | 3 | 169～170 |
| 49 | 6-C 3H 7(different) | 3 | ″ | ″ | 2 | - |
| 50 | 5-CHF 2 | ″ | ″ | ″ | ″ | - |
| 51 | 6-CF 3 | ″ | ″ | ″ | ″ | 151～153 |
| 52 | ″ | ″ | ″ | C 2H 5 | ″ | - |
| 53 | ″ | ″ | H | CH 3 | ″ | - |
| 54 | 6-CH 3 | ″ | CH 3 | C 2H 5 | ″ | - |
| 55 | 6-Br | ″ | H | CH 3 | ″ | - |
| 56 | 6-Cl | ″ | ″ | ″ | ″ | - |
| 57 | 6-CHF 2 | ″ | ″ | ″ | ″ | - |
Below provide the embodiment of synthetic The compounds of this invention.
Synthetic embodiment 1
5-chloro-N-[(4,6-dimethoxypyridin-2-yl) amino carbonyl]-3-dimethylamino carbonyl-2-pyridine sulfonamide (9 compound) synthetic
With 0.30 gram 2-aminosulfonyl-5-chloro-N, N-dimethyl nicotinamide and 0.35 gram 2-carbonyl phenoxy amino-4, the 6-dimethoxypyridin is added in 10 milliliters of anhydrous acetonitriles, in gained suspension, add in 0.19 gram 1,8-diazabicylo [5 40] 11 carbon-7-alkene at room temperature reacted the gained mixture 45 minutes.
After reaction is finished, reactant mixture is added in the entry, leach insoluble matter., extract with carrene then solution weak acidization with concentrated hydrochloric acid.Subsequently with anhydrous sodium sulfate with the solution drying, and steam and to desolventize, 0.26 gram title compound, 152～155 ℃ of fusing points.
Synthetic embodiment 2～13
By the same step operation of synthetic embodiment 1, gained the results are shown in the table 2.
Table 2
Table 2 (continuing)
Table 2 (having continued)
Annotate: the compound number in the intermediate numbering in the pyridine compounds and their hurdle and the product hurdle respectively with table 1 and table 3 in consistent.
Synthetic embodiment 14
N-[(4,6-dimethoxypyridin-2-yl) amino carbonyl]-3-dimethylamino carbonyl-2-pyridine sulfonamide synthetic
Method 1
At 15 ℃, 250 milligrams of 2-amino-4,6-dimethoxy-pyridine, 0.65 gram triethylamine and 2.5 gram ethyl acetate threes' mixed solutions are added drop-wise to 6.3 and contain in the ethyl acetate solution of 20% phosgene, make composition remain on 15 ℃ and reacted 1 hour then.Then mixture is heated to 90 ℃, steams and remove excessive phosgene and ethyl acetate with oil bath.Then with 300 milligrams of 2-aminosulfonyl-N, the N-dimethyl nicotinamide is dissolved in that resulting drips of solution is added in the said mixture in 10 milliliters of acetonitriles, drips 0.2 gram triethylamine in addition again.The gained mixture was at room temperature reacted 1 hour.
After reaction is finished, product is added in the water, the acidifying of gained solution, filters the crystal of separating out then with hydrochloric acid.This crystal obtains 0.46 gram titled reference compound through water Xian and drying.
Method 2
[I] at-5 ℃, and 2.13 gram 2-aminosulfonyl-N, the N-dimethyl nicotinamide is added in 5 milliliters of dimethyl formamide slurries that contain 60% sodium hydride, allows the gained mixture react about 1 hour.At-5 ℃, in above-mentioned solution, drip the solution of 2.14 gram diphenyl carbonates in 10 milliliters of dimethyl formamides.With 30 minutes this solution is heated to room temperature to finish reaction.Reactant liquor added in the entry and use carrene Xian.The water layer hcl acidifying extracts with carrene then.The dichloromethane layer anhydrous sodium sulfate drying, the pressure reducing and steaming carrene.The gained crystal obtains 0.91 gram N, N-dimethyl-2-carbonyl phenoxy aminosulfonyl vitamin PP, 189～194 ℃ of fusing points with ethyl acetate and hexane recrystallization.
[II] is the N of 0.28 gram by process [I] preparation, N-dimethyl-2-carbonyl phenoxy aminosulfonyl vitamin PP and 0.14 gram 2-amino-4-chloro-6-methoxy pyrimidine are added in 8 milliliters of anhydrous dioxanes, and the gained mixture was under refluxad reacted about 40 minutes.
After reaction is finished, reactant mixture is added in 200 ml waters, leaches the gained crystal, obtain 0.21 gram N-[(4-chloro-6-methoxy pyrimidine-2-yl) amino carbonyl]-3-diformazan aminocarbonyl-2-pyridine sulfonamide, 157～158.5 ℃ of fusing points.
[III] is added to 18.3 milligrams of sodium metals in 7 milliliters of absolute methanols, adds N-[(4-chloro-6-methoxy pyrimidine-2-yl that 0.11 gram makes by process [II] to it again) amino carbonyl]-3-diformazan aminocarbonyl-2-pyridine sulfonamide.The gained mixture added hot reflux 12 hours.
After reaction is finished, reactant mixture is added in the entry, make it acidifying with hydrochloric acid.Leach the crystal of separating out, washing, drying makes 70 milligrams of title compounds.
Typical compound and salt thereof by general formula [I] representative of the present invention is as shown in table 3.
Table 3
(table 3 brought forward)
| 8 | H | 3 | CH 3 | CH 2CF 3 | 2 | OCH 3 | OCH 3 | 171.5-173.5 |
| 9 | 5-Cl | ″ | ″ | CH 3 | ″ | ″ | ″ | 152～155 |
| 10 | H | ″ | H | Phenyl | ″ | ″ | ″ | 188～190 |
| 11 | 4,6-(CH 3) 2 | ″ | CH 3 | CH 3 | ″ | ″ | ″ | 201～204 |
| 12 | 5-Cl,6-OCH 3 | ″ | ″ | ″ | ″ | ″ | ″ | 166～168 |
| 13 | H | ″ | H | CH 2C≡CH | ″ | ″ | ″ | 154.5～157 |
| 14 | ″ | ″ | -(CH 2) 4- | ″ | ″ | ″ | 158～162 | |
| 15 | 6-Cl | ″ | CH 3 | CH 3 | ″ | ″ | ″ | 183～186 |
| 16 | H | ″ | ″ | COOCH 3 | ″ | ″ | ″ | 162～164 |
| 17 | 6-OC 2H 5 | ″ | ″ | CH 3 | ″ | ″ | ″ | 208～209 |
| 18 | 6-C 2H 5 | ″ | ″ | ″ | ″ | ″ | ″ | 193～194.5 |
| 19 | 6-CH 2OCH 3 | ″ | ″ | ″ | ″ | ″ | ″ | 183～185 |
| 20 | 4,6-(CH 3) 2 | ″ | H | ″ | ″ | ″ | ″ | 179～181 |
| 21 | 6-F | ″ | CH 3 | ″ | ″ | ″ | ″ | 115～124 |
| 22 | 6-Br | ″ | H | C 2H 5 | ″ | ″ | ″ | - |
| 23 | 6-CH 3 | ″ | CH 3 | C 3H 7(just) | ″ | ″ | ″ | - |
| 24 | 6-Cl | ″ | ″ | CH 3 | ″ | CH 3 | ″ | - |
(table 3 brought forward)
| 25 | H | 3 | H | CH 3 | 2 | OCH 3 | OCH 3 | 147～149.5 |
| 26 | ″ | ″ | ″ | C 2H 5 | ″ | ″ | ″ | 163～168 |
| 27 | ″ | ″ | ″ | C 3H 7(different) | ″ | ″ | ″ | 166.5～168.5 |
| 28 | 6-C 2H 5 | ″ | ″ | CH 3 | ″ | ″ | ″ | - |
| 29 | H | ″ | CH 3 | ″ | ″ | ″ | ″ | 169～173 |
| 30 | 6-C 3H 7(different) | ″ | ″ | ″ | ″ | ″ | ″ | - |
| 31 | 6-I | ″ | ″ | ″ | ″ | ″ | ″ | - |
| 32 | H | ″ | C 2H 5 | C 2H 5 | ″ | CH 3 | ″ | - |
| 33 | ″ | ″ | CH 3 | ″ | ″ | OCH 3 | ″ | 170.5～172 |
| 34 | 6-CH 3 | ″ | ″ | CH 3 | ″ | ″ | ″ | 170～174 |
| 35 | 6-OCH 3 | ″ | ″ | ″ | ″ | ″ | ″ | 206～207.5 |
| 36 | 5-CHF 2 | ″ | ″ | ″ | ″ | ″ | ″ | - |
| 37 | H | ″ | C 2H 5 | C 2H 5 | ″ | ″ | ″ | 109～111 |
| 38 | 6-CH 3 | ″ | H | CH 3 | ″ | ″ | ″ | 183～185 |
| 39 | 6-CF 3 | ″ | CH 3 | ″ | ″ | ″ | ″ | 189～191 |
| 40 | 6-Br | ″ | ″ | C 2H 5 | ″ | ″ | ″ | - |
| 41 | 6-N(CH 3) 2 | ″ | ″ | CH 3 | ″ | ″ | ″ | 199～201.5 |
(table 3 brought forward)
| 42 | 6-SCH 3 | 3 | CH 3 | CH 3 | 2 | OCH 3 | OCH 3 | 200～201.5 |
| 43 | H | ″ | ″ | ″ | ″ | CH 3 | ″ | 177～185 |
| 44 | 6-NHCH 3 | ″ | ″ | ″ | ″ | OCH 3 | ″ | 183～185 |
| 45 | 6-Br | ″ | ″ | ″ | ″ | ″ | ″ | 201.5～203.5 |
| 46 | H | ″ | ″ | ″ | ″ | ″ | OC 2H 5 | 111～114 (decomposition) |
| 47 | ″ | ″ | H | (CH 2) 3CH 3 | ″ | ″ | OCH 3 | 156～158 |
| 48 | 6-CH 2F | ″ | CH 3 | CH 3 | ″ | ″ | ″ | 180～181 |
| 49 | 6-CHF 2 | ″ | ″ | ″ | ″ | ″ | ″ | 194～195 |
| 50 | H | ″ | ″ | 2, the 4-difluorophenyl | ″ | ″ | ″ | 156～158 |
| 51 | ″ | ″ | ″ | The 4-chlorphenyl | ″ | ″ | ″ | 241～243 |
| 52 | The N-pyridine oxide homologue of No. 29 compounds | 169.5～171 | ||||||
| 53 | 6-CF 3 | 3 | CH 3 | C 2H 5 | 2 | OCH 3 | OCH 3 | - |
| 54 | 6- CH 2OCH 2CF 3 | ″ | ″ | CH 3 | ″ | ″ | ″ | 179～180 |
| 55 | H | 2 | ″ | ″ | 3 | ″ | ″ | 196～198 |
| 56 | ″ | 4 | H | ″ | ″ | ″ | ″ | 129～132 |
| 57 | ″ | 2 | ″ | ″ | ″ | ″ | ″ | 122～125 |
| 58 | 6-OCH 2CF 3 | 3 | CH 3 | ″ | 2 | ″ | ″ | 186.5～189 |
(table 3 brought forward)
| 59 | The sodium salt of No. 29 compounds | 195～215 (decomposition) | ||||||
| 60 | Single methylamine salt of No. 29 compounds | 125～128 | ||||||
| 61 | The N-pyridine oxide homologue of No. 34 compounds | 163～164.5 | ||||||
| 62 | The sylvite of No. 25 compounds | - | ||||||
| 63 | 6-I | 3 | H | CH 3 | 2 | OCH 3 | OCH 3 | - |
| 64 | 6-CF 3 | ″ | ″ | ″ | ″ | ″ | ″ | - |
| 65 | 6-CH 3 | ″ | CH 3 | C 2H 5 | ″ | ″ | ″ | - |
| 66 | 6-Br | ″ | H | CH 3 | ″ | ″ | ″ | - |
| 67 | 6-Cl | ″ | ″ | ″ | ″ | ″ | ″ | - |
| 68 | 6-CHF 2 | ″ | ″ | ″ | ″ | ″ | ″ | - |
| 69 | The sodium salt of No. 15 compounds | |||||||
| 70 | The sodium salt of No. 25 compounds | |||||||
| 71 | The sodium salt of No. 34 compounds | |||||||
| 72 | The sodium salt of No. 45 compounds | |||||||
| 73 | The sodium salt of No. 49 compounds | |||||||
| 74 | The dimethylamine salt of No. 34 compounds | |||||||
Compound of the present invention has herbicidal effect to following various weeds: cyperus weeds (Cyperaceae), as rice nutgrass flatsedge [rice flatsedge] (Cyperus iria), Japanese common rush (Scirpus juncoides) and purple nutsedge (Cyperusrotundus); Grassy weed (Gramineae) is as barnyard grass (Echinochloacrus-galli), lady's-grass (Digitaria adscendens), green foxtail (Setariaviridis), yard grass (Eleusine indica), wild oat (Avena fatua), stone thatch Chinese sorghum (Sorghum halepensc) and roegneria kamoji (Agropyron repens); And broad leaved weed, as piemarker (Abutilon theophrasti), high plant (tall) is towards face flower (Ipomoea purpurea), common lamb's-quarters class plant (Chenopodium album), thorniness brocade last of the ten Heavenly stems (Sida spinosa), kitchen garden (Portulaca oleracea), elongated Amaranthus (Amaranthus viridis), Canada's wall cress (Cassia tora), black nightshade (Solanum nigrum), knotweed car grass (Polygonum longisetum), chickweed (Stellaria media), common Siberian cocklebur (Xanthium strumarium) and the wavy mustard of cracking rice (Cardamine flexuosa).So weed killer herbicide of the present invention can for example used in the farm, highland, can also be applied to many other occasions, as farming district (for example orchard and mulberry field) and non-farming district (for example forest, farming district road, pleasure ground, factory district and meadow).Herbicidal combinations of the present invention can be handled as soil treatment or leaf as required.
Compound of the present invention has herbicidal effect especially to the injurious weed in the cereal field, thereby can use effectively.Herbicides compounds of the present invention is to use with the form of granule, wetting powder, emulsifiable concentrate or the aqueous solution.These medicaments are made by The compounds of this invention is mixed mutually with a kind of carrier and various additive (as thinner, solvent, emulsifier, dispersant or surfactant) as required.The suitable weight ratio that active ingredient and one or more agricultural assistant agents mix mutually is at 1: 99 to 90: 10, preferably in 5: 95 to 60: 40 scope.The optimum spraying amount of active ingredient can't be clear and definite given, this is because it depends on multiple factor, as climatic condition, weather condition, soil condition, pharmaceutical formulation, the similar and time of application of ruderal species that will control, but the consumption of active ingredient is generally every are (100 square metres) 0.1～100 gram, better be 0.2～50 gram, be more preferably 0.5～10 gram.
Herbicidal combinations of the present invention can mix mutually with all gases agricultural chemicals, fertilizer, soil or safener or use simultaneously.Use can obtain better effect or effect like this.Other herbicides compounds that can mix mutually with Herbicidal combinations of the present invention such as following listed.In some cases, can produce synergistic effect.
3,6-two chloro-2-methoxy benzoic acids
2,5-two chloro-3-aminobenzoic acids
(2,4 dichloro benzene oxygen base) acetate
(4-chloro-2-methylphenoxy) acetate
2-chloro-4, two (the ethylamino-)-1,3,5-triazines of 6-
2-chloro-4-ethylamino--6-isopropylamine base-1,3,5-triazines
2-(4-chloro-6-ethylamino--1,3,5-triazines-2-base is amino)-2-methyl propionitrile
2-ethylamino--4-isopropylamine base-6-methyl mercapto-1,3,5-triazines
2-chloro-2 ', 6 '-diethyl-N-(methoxyl methyl)-monoacetylaniline
2-chloro-6 '-ethyl-N-(2-methoxyl group-1-Methylethyl)-N-acetyl ortho-aminotoluene
2-chloro-N-isopropyl-monoacetylaniline
2-chloro-N, N-two-2-acrylic acetamide
Dipropyl thiocarbamic acid-S-ethyl ester
The diisobutyl dithiocarbamate-s-ethyl
Dipropyl thiocarbamic acid-S-propyl ester
N-(1-ethyl propyl)-2,6-dinitro-3,4-dimethylaniline
α, α, α-three fluoro-2,6-dinitro-N, N-dipropyl p-toluidine
2-(3, the 5-dichlorophenyl)-2-(2,2,2-three chloroethyls) oxirane
The 3-isopropyl-(1H)-benzo-2,1,3-thiadiazine-4-ketone-2,2-dioxide
3-(3, the 4-dichlorophenyl)-1-methoxyl group-1-methyl urea
3,5-two bromo-4-4-hydroxy-benzonitriles
2-chloro-4-trifluoromethyl-3-ethyoxyl-4-nitrobenzophenone ether
For instance, N-[(4,6-dimethoxypyridin-2-yl) amino carbonyl]-3-methylamine carbonyl (or dimethylamino carbonyl)-2-pyridine sulfonamide or 6-chloro-(or bromo-, difluoromethyl-or methyl-) N-[(4,6-dimethoxypyridin-2-yl) amino carbonyl]-3-dimethylamino carbonyl-2-pyridine sulfonamide can unite use with following each compound: 2-chloro-4-ethylamino--6-isopropylamine base-1,3, the 5-triazine, 2-(4-chloro-6-ethylamino--1,3,5-triazine-2-base is amino)-2-methyl propionitrile, 2-chloro-2 ', 6 '-diethyl-N-(methoxyl methyl)-monoacetylaniline, 2-chloro-6 '-ethyl-N-(2-methoxyl group-1-(Methylethyl) acetyl ortho-aminotoluene or N-(1-ethyl propyl)-2,6-dinitro-3, the 4-dimethylaniline.The weed killer herbicide that is mixed and made into like this is harmless to cereal, and can fully eliminate weeds basically.
Test example 1
The mountain soil of in the little basin of 1/1500 are of some area, packing into, and the seed of planting the various test plants of scheduled volume.Each test plant is long respectively during to developmental stage of being scheduled to [that is: to be 2.2～3.5 leaf stages to corn (Zea mays), (Triticum aestium) was 2.0～3.5 leaf stages to wheat, being listed as common cocklebur was 2.0～3.5 leaf stages, being listed as high plant was 0.5～1.2 leaf stage towards the face flower, to knotweed car grass was 0.5～1.2 leaf stage, to the thorniness high mallow was 0.1～1.5 leaf stage, to elongated Amaranthus is that 0.1～1.5 leaf is educated the stage, to barnyard grass was 2.0～2.5 leaf stages], prepare a kind of aqueous dispersions, method is to contain a kind of wetting powder of each test compound of scheduled volume with the dilution of 5 liters/are water, and adds certain dispersant of 0.2% in this aqueous solution.With a miniaturised nebuliser resulting solution is sprayed onto on the leaf of test plant.After the dispenser 22～37 days, perusal was through the development degree of the test plant of above-mentioned processing.The evaluation of weeds control action is divided into 10 grades, and wherein 10 expression test plants are all killed, and not influence of 1 expression is shown in following table 4.
Table 4
| Compound number | The amount of active component (gram/are) | Weeds control action grade | Term day | |||||||
| Corn | Wheat | Common Siberian cocklebur | High plant is towards the face flower | The thorniness high mallow | Knotweed car grass | Elongated Amaranthus | Barnyard grass | |||
| 1 | 5 | 1 | 9 | 10 | 9 | 5 | 8 | 7 | 10 | The 24th day |
| 1.25 | 1 | 7 | 9 | 7 | 4 | 7 | 5 | 7 | ||
| 2 | 5 | 1 | 3 | 10 | 8 | 7 | 6 | 7 | 8 | The 25th day |
| 1.25 | 1 | 2 | 9 | 6 | 5 | 4 | 5 | 8 | ||
| 3 | 5 | 1 | 5 | 9 | 9 | 5 | 7 | 8 | 6 | The 28th day |
| 1.25 | 1 | 1 | 6 | 6 | 4 | 5 | 6 | 3 | ||
| 4 | 5 | 1 | 9 | 10 | 9 | 7 | 9 | 8 | 10 | The 25th day |
| 1.25 | 1 | 7 | 9 | 9 | 6 | 8 | 6 | 10 | ||
| 5 | 5 | 1 | 3 | 8 | 9 | 6 | 4 | 10 | 5 | The 28th day |
| 1.25 | 1 | 1 | 7 | 7 | 4 | 4 | 7 | 4 | ||
| 6 | 5 | 1 | 6 | 10 | 9 | 8 | 8 | 10 | 9 | The 28th day |
| 1.25 | 1 | 7 | 10 | 9 | 6 | 8 | 10 | 10 | ||
| 7 | 5 | 1 | 6 | 10 | 7 | 6 | 10 | 7 | 6 | The 24th day |
| 1.25 | 1 | 4 | 9 | 6 | 6 | 7 | 7 | 4 | ||
Table 4 (continuing)
| Compound number | The amount of active component (gram/are) | Weeds control action grade | Term day | |||||||
| Corn | Wheat | Common Siberian cocklebur | High plant is towards the face flower | The thorniness high mallow | Knotweed car grass | Elongated Amaranthus | Barnyard grass | |||
| 8 | 5 | 1 | 6 | 9 | 9 | 5 | 7 | 5 | 7 | The 24th day |
| 1.25 | 1 | 5 | 9 | 7 | 4 | 6 | 4 | 7 | ||
| 9 | 5 | 1 | 10 | 10 | 10 | 8 | 9 | 10 | 10 | The 28th day |
| 1.25 | 1 | 9 | 10 | 8 | - | - | 10 | 10 | ||
| 10 | 5 | 1 | 4 | 10 | 8 | 5 | 10 | 10 | - | The 37th day |
| 1.25 | 1 | 1 | 10 | 8 | - | 7 | 8 | - | ||
| 11 | 5 | 1 | 6 | 10 | 10 | 6 | 10 | 10 | - | The 37th day |
| 1.25 | 1 | 5 | 10 | 9 | 6 | 9 | 10 | - | ||
| 12 | 5 | 1 | 8 | 10 | 10 | 6 | 10 | 10 | 9 | The 28th day |
| 1.25 | 1 | 7 | 10 | 10 | - | 9 | 8 | 7 | ||
| 13 | 5 | 1 | 9 | 10 | 10 | 5 | 10 | 10 | 9 | The 37th day |
| 1.25 | 1 | 9 | 10 | 9 | 4 | 10 | 9 | 9 | ||
| 14 | 5 | 2 | 9 | 9 | 10 | 8 | 8 | 10 | 10 | The 28th day |
| 1.25 | 1 | 8 | 8 | 8 | 7 | 7 | 9 | 8 | ||
Table 4 (continuing)
| Compound number | The amount of active component (gram/are) | Weeds control action grade | Term day | |||||||
| Corn | Wheat | Common Siberian cocklebur | High plant is towards the face flower | The thorniness high mallow | Knotweed car grass | Elongated Amaranthus | Barnyard grass | |||
| 15 | 5 | 1 | 10 | 10 | 10 | 9 | 10 | 10 | 10 | The 29th day |
| 1.25 | 1 | 10 | 10 | 10 | 6 | 10 | 10 | 10 | ||
| 16 | 5 | 1 | 9 | 9 | 9 | 8 | 9 | 8 | 7 | The 28th day |
| 1.25 | 1 | 4 | 8 | 7 | 6 | 8 | 6 | 6 | ||
| 17 | 5 | 1 | 7 | 10 | 10 | 6 | 10 | 9 | 8 | The 28th day |
| 1.25 | 1 | 7 | 10 | 10 | 6 | 10 | 9 | 5 | ||
| 18 | 5 | 1 | - | 10 | 9 | 6 | 10 | 10 | 8 | The 28th day |
| 1.25 | 1 | - | 10 | 9 | 4 | 10 | 10 | 6 | ||
| 19 | 5 | 1 | 10 | 10 | 10 | 9 | 10 | 10 | 10 | The 25th day |
| 1.25 | 1 | 10 | 10 | 10 | 7 | 10 | 10 | 10 | ||
| 20 | 5 | 1 | 10 | 10 | 10 | 6 | 9 | 10 | 7 | The 37th day |
| 1.25 | 1 | 5 | 7 | 9 | 5 | 9 | 9 | 5 | ||
| 21 | 5 | 1 | - | 10 | 10 | 6 | 10 | 10 | 10 | The 28th day |
| 1.25 | 1 | - | 7 | 9 | 5 | 10 | 10 | 10 | ||
Table 4 (continuing)
| Compound number | The amount of active component (gram/are) | Weeds control action grade | Term day | |||||||
| Corn | Wheat | Common Siberian cocklebur | High plant is towards the face flower | The thorniness high mallow | Knotweed car grass | Elongated Amaranthus | Barnyard grass | |||
| 25 | 5 | 1 | 10 | 10 | 10 | 10 | 10 | 10 | 10 | The 30th day |
| 1.25 | 1 | 8 | 10 | 9 | 7 | 10 | 10 | 10 | ||
| 26 | 5 | 1 | 8 | 10 | 10 | 7 | 8 | 9 | 10 | The 24th day |
| 1.25 | 1 | 8 | 9 | 7 | 7 | 7 | 9 | 9 | ||
| 27 | 5 | 1 | 7 | 10 | 8 | 7 | 8 | 10 | 10 | The 24th day |
| 1.25 | 1 | 6 | 7 | 8 | 7 | 7 | 8 | 9 | ||
| 29 | 5 | 2 | 10 | 9 | 9 | 9 | 9 | 9 | 9 | The 24th day |
| 1.25 | 1 | 8 | 10 | 8 | 7 | 8 | 10 | 10 | ||
| 33 | 5 | 2 | 10 | 10 | 9 | 9 | 9 | 10 | 10 | The 25th day |
| 1.25 | 1 | 9 | 10 | 9 | 8 | 9 | 9 | 10 | ||
| 34 | 5 | 1 | 10 | 10 | 9 | 9 | 10 | 10 | 10 | The 25th day |
| 1.25 | 1 | 10 | 10 | 9 | 8 | 10 | 10 | 9 | ||
| 35 | 5 | 1 | 9 | 10 | 10 | 7 | 10 | 10 | 10 | The 24th day |
| 1.25 | 1 | 10 | 9 | 9 | 5 | 10 | 10 | 9 | ||
Table 4 (continuing)
| Compound number | The amount of active component (gram/are) | Weeds control action grade | Term day | |||||||
| Corn | Wheat | Common Siberian cocklebur | High plant is towards the face flower | The thorniness high mallow | Knotweed car grass | Elongated Amaranthus | Barnyard grass | |||
| 37 | 5 | 1 | 5 | 10 | 9 | 6 | 8 | 10 | 9 | The 28th day |
| 1.25 | 1 | 6 | 9 | 8 | 6 | 8 | 10 | 9 | ||
| 38 | 5 | 1 | 8 | 10 | 10 | 9 | 10 | 10 | 10 | The 28th day |
| 1.25 | 1 | 9 | 10 | 9 | 6 | 9 | 9 | 9 | ||
| 41 | 5 | 3 | 10 | 10 | 10 | 9 | 10 | 10 | 10 | The 31st day |
| 1.25 | 1 | 8 | 10 | 9 | 8 | 10 | 10 | 9 | ||
| 42 | 5 | 1 | - | 10 | 9 | 6 | 10 | 10 | 8 | The 28th day |
| 1.25 | 1 | - | 10 | 9 | 4 | 10 | 10 | 6 | ||
| 43 | 5 | 2 | - | 8 | 7 | 6 | 8 | 8 | 7 | The 22nd day |
| 1.25 | 1 | - | 7 | 7 | 3 | 7 | 8 | 7 | ||
| 44 | 5 | 2 | - | 10 | 10 | 8 | 10 | 9 | 10 | The 22nd day |
| 1.25 | 1 | - | 10 | 7 | 7 | 9 | 4 | 9 | ||
| 45 | 5 | 1 | 10 | 10 | 9 | 7 | 10 | 9 | 10 | The 29th day |
| 1.25 | 1 | 10 | 10 | 9 | 6 | 9 | 10 | 10 | ||
Table 4 (continuing)
| Compound number | The amount of active component (gram/are) | Weeds control action grade | Term day | |||||||
| Corn | Wheat | Common Siberian cocklebur | High plant is towards the face flower | The thorniness high mallow | Knotweed car grass | Elongated Amaranthus | Barnyard grass | |||
| 46 | 5 | 4 | 10 | 7 | 9 | 7 | 10 | 1 0 | 10 | The 29th day |
| 1.25 | 1 | 5 | 5 | 9 | 5 | 9 | 10 | 9 | ||
| 47 | 5 | 1 | 9 | 10 | 9 | 5 | 6 | 7 | 6 | The 25th day |
| 1.25 | 1 | 7 | 9 | 7 | 2 | 4 | 5 | 5 | ||
| 48 | 5 | 1 | - | 10 | 9 | 6 | 10 | 10 | 10 | The 26th day |
| 1.25 | 1 | - | 8 | 7 | 5 | 10 | 7 | 10 | ||
| 49 | 5 | 2 | 10 | 10 | 10 | 7 | 9 | 10 | 10 | The 29th day |
| 1.25 | 1 | 10 | 10 | 10 | 6 | 9 | 9 | 10 | ||
| 50 | 5 | 1 | 10 | 10 | 6 | 4 | 7 | 7 | 6 | The 29th day |
| 1.25 | 1 | 4 | 10 | 6 | 3 | 4 | 6 | 5 | ||
| 52 | 5 | 1 | - | 9 | 9 | 4 | 9 | 10 | 10 | The 36th day |
| 1.25 | 1 | - | 9 | 8 | 4 | 9 | 9 | 10 | ||
| 54 | 5 | 2 | - | 9 | 10 | 7 | 6 | 8 | 10 | The 36th day |
| 1.25 | 1 | - | 9 | 7 | 4 | 5 | 5 | 6 | ||
Table 4 (having continued)
| Compound number | The amount of active component (gram/are) | Weeds control action grade | Term day | |||||||
| Corn | Wheat | Common Siberian cocklebur | High plant is towards the face flower | The thorniness high mallow | Knotweed car grass | Elongated Amaranthus | Barnyard grass | |||
| 55 | 5 | 1 | 4 | 10 | 10 | - | 9 | 10 | 8 | The 28th day |
| 1.25 | 1 | 3 | 10 | 10 | 7 | - | - | 8 | ||
| 56 | 5 | 1 | 4 | 9 | 9 | 8 | 9 | 9 | 6 | The 25th day |
| 1.25 | 1 | 3 | 7 | 8 | 6 | 8 | 7 | 6 | ||
| 57 | 5 | 4 | 6 | 10 | 10 | 9 | 10 | 10 | 10 | The 28th day |
| 1.25 | 1 | 4 | 9 | 10 | 8 | 9 | 10 | 9 | ||
| 58 | 5 | 1 | - | 10 | 9 | 2 | 8 | 5 | 7 | The 22nd day |
| 1.25 | 1 | - | 9 | 8 | 1 | 6 | 3 | 4 | ||
| 59 | 1.25 | 1 | 10 | 10 | 10 | 6 | 9 | 10 | 10 | The 24th day |
| 60 | 1.25 | 1 | 10 | 9 | 9 | 5 | 9 | 10 | 10 | The 24th day |
Test example 2
In area is each little basin of 1/10000 are, be respectively charged into mountain soil, and plant the seed of lady's-grass and black nightshade.After this, when the test plant of lady's-grass and black nightshade grows to 2 and 0.5 leaf stage respectively, weigh up a certain amount of a kind of with medicament for the treatment of, making wherein contained active ingredient amount is scheduled volume, with 5 premium on currency/ares this medicament is diluted then.The agricultural dispersants of adding 0.2% is sprayed gained solution then with a kind of miniaturised nebuliser in obtained aqueous solution.Behind the spray medicine the 23rd day, with the naked eye estimate the growth rate of lady's-grass and black nightshade; The evaluation method of weeds control action is identical in the example 1 with test.The results are shown in the table 5.
Table 5
| Compound number | Active ingredient consumption (gram/are) | Weeds control action grade | |
| Lady's-grass | Black nightshade | ||
| 25 | 5.0 | 8 | 10 |
| 2.5 | 7 | 10 | |
| 29 | 5.0 | 10 | 10 |
| 2.5 | 10 | 10 | |
Test example 3
In area is 1/3000 are little basin, and it is grown in the greenhouse.During the leaf stage, weigh up a certain amount of a kind of with medicament for the treatment of to 4-5 when Johnson grass is long, make the active ingredient that wherein contains scheduled volume, with 5 premium on currency/ares this medicament is diluted then.In addition, in this aqueous solution, add 0.2% agricultural dispersants, and gained solution is sprayed onto on the leaf and stem of Johnson grass plant.Behind the spray medicine 35 days, with the naked eye estimate for the weeds of lady's-grass control effect.The evaluation method of weeds control action is with test example 1, and the result is as shown in table 6.
Table 6
| Compound number | Active ingredient consumption (gram/are) | Weeds control action grade |
| 2.5 | 5.0 | 9 |
| 2.5 | 8～9 | |
| 1.25 | 7 | |
| 0.625 | 4 | |
| 29 | 2.5 | 9～10 |
| 1.25 | 9～10 | |
| 0.625 | 8～9 | |
| 0.313 | 7 | |
| 34 | 2.5 | 9 |
| 1.25 | 9 | |
| 0.625 | 8 | |
| 0.313 | 6～7 |
Test example 4
In area is 1/10000 are little basin, and it is grown in the greenhouse.During the leaf stage, weigh up a certain amount of with medicament for the treatment of to 3-4 when fragrant head grass is long, make wherein that the amount of active ingredient is a scheduled volume, with 5 premium on currency/ares this medicament is diluted then.In addition, in this aqueous solution, add 0.2% agricultural dispersants, and gained solution is sprayed onto on the leaf of above-mentioned plant.The spray medicine is after 51 days, and perusal is to the control effect of fragrant head grass.The evaluation method of weeds control action is with test example 1, and it the results are shown in following table 7.
Table 7
| Compound number | Active ingredient consumption (gram/are) | Weeds control action grade |
| 15 | 5.0 | 10 |
| 3.5 | 10 | |
| 1.25 | 10 | |
| 0.625 | 10 | |
| 21 | 5.0 | 10 |
| 2.5 | 10 | |
| 1.25 | 9 | |
| 0.625 | 8 | |
| 29 | 2.5 | 10 |
| 1.25 | 10 | |
| 0.625 | 10 | |
| 0.313 | 8 | |
| 34 | 5.0 | 10 |
| 2.5 | 10 | |
| 1.25 | 10 | |
| 0.625 | 9 |
Provide the preparation embodiment of Herbicidal combinations of the present invention below.
Preparation embodiment 1
Parts by weight
(1) the kaolinite powder 97
(2) NONIN HS 240 2
(3) No. 15 compounds 1
Above-mentioned each composition is mixed, and be ground into pulvis.
Preparation embodiment 2
Parts by weight
(1) water soluble starch 55
(2) wooden sodium sulfonate 5
(3) No. 59 compounds 40
Above-mentioned each composition is mixed mutually, pulverize, make the aqueous solution.
Preparation embodiment 3
Parts by weight
(1) kaolin 78
(2) condensation product 2 of sodium naphthalene sulfonate and formaldehyde
(3) polyxyethylated allyl sulfate 5
(4) the silica micro mist 15
Mixture by 9: 1 mixes with The compounds of this invention mutually than with composition (1)～(4), makes a kind of wetting powder.
Preparation embodiment 4
Parts by weight
(1) diatomite 63
(2) the polyoxyethylene alkylphenyl sulfonic acid ammonium salt 5
(3) dialkyl sulfosuccinate (dialkylsulfosuccinate) 2
(4) No. 29 compounds 30
Above-mentioned each composition is mixed mutually, make wetting powder.
Preparation embodiment 5
Parts by weight
(1) the talcum micro mist 33
(2) dialkyl sulfosuccinate 3
(3) laureth sulfate 4
(4) No. 34 compounds 60
Above-mentioned each composition is mixed, make a kind of wetting powder.
Preparation embodiment 6
Parts by weight
(1) benzene sulfonic acid sodium salt 4
(2) polycarboxylic acid sodium (sodium polycarboxylate) 3
(3) alkylaryl sodium sulfonate 1
(4) kaolin 12
(5) No. 25 compounds 80
Above-mentioned composition and water are mixed, and dry and disintegration becomes a kind of wetting powder.
Claims (2)
1. Herbicidal combinations, it comprises pyridine sulfamide compound or its salt and the agricultural agent of replacement of general formula (I) representative of herbicidally effective amount,
In the formula, R represents group
Or group
R
1And R
2Represent hydrogen atom, C independently of one another
1-6Alkyl, halo C
1-6Alkyl, C
2-6Thiazolinyl, C
2-6Alkynyl, C
1-6Alkoxyl, halo C
1-6Alkoxyl, C
1-6Alkoxy C
1-6Alkyl, halo C
1-6Alkoxy C
1-6Alkyl, C
3-6Cycloalkyl, halo C
3-6Cycloalkyl, C
1-6Alkoxy carbonyl group, halo C
1-6Alkoxy carbonyl group, phenyl or halogenophenyl, condition are to work as R
1And R
2In when having one to represent hydrogen atom, then another represents a group except that hydrogen atom in the above-mentioned group, Y represents halogen atom, C
1-6Alkyl, halo C
1-6Alkyl, C
1-6Alkoxyl, halo C
1-6Alkoxyl, C
1-6Alkylthio group, halo C
1-6Alkylthio group, C
1-6Alkoxy C
1-6Alkyl, halo C
1-6Alkoxy C
1-6Alkyl or group
Wherein middle R
3And R
4Represent hydrogen atom or C respectively
1-6Alkyl, n are 0 or integer 1 or 2, X
1And X
2Represent methylidene, methoxy or ethoxy independently of one another, condition is to work as X
1And X
2When being all methoxyl group, R is not 3-dimethylamino carbonyl pyridine-2-base, and the mixing ratio of its Chinese style I compound or its salt and agricultural agent is: 1: 99-90: 10.
2. the purposes of Herbicidal combinations in agricultural that require of claim 1, wherein the active ingredient amount is the 0.1-100g/ are.
Applications Claiming Priority (7)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP19006/86 | 1986-01-30 | ||
| JP1900686 | 1986-01-30 | ||
| JP19863/86 | 1986-01-31 | ||
| JP86847/86 | 1986-04-15 | ||
| JP178489/86 | 1986-07-29 | ||
| JP17848986 | 1986-07-29 | ||
| CN 87100436 CN1016661B (en) | 1986-01-30 | 1987-01-27 | Herbicidal composition containing pyridinesulfonamide |
Related Parent Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 87100436 Division CN1016661B (en) | 1986-01-30 | 1987-01-27 | Herbicidal composition containing pyridinesulfonamide |
| CN87100436 Division | 1987-01-27 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1062263A CN1062263A (en) | 1992-07-01 |
| CN1042690C true CN1042690C (en) | 1999-03-31 |
Family
ID=27178862
Family Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN92100307A Expired - Lifetime CN1042690C (en) | 1986-01-30 | 1992-01-18 | Herbicidal composition containing substituted pyridinesulfonamide compounds |
| CN 92100308 Expired - Lifetime CN1032137C (en) | 1986-01-30 | 1992-01-18 | Process for preparing substituted pyridinsulfonamide compounds |
Family Applications After (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 92100308 Expired - Lifetime CN1032137C (en) | 1986-01-30 | 1992-01-18 | Process for preparing substituted pyridinsulfonamide compounds |
Country Status (1)
| Country | Link |
|---|---|
| CN (2) | CN1042690C (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101671327B (en) * | 2009-09-28 | 2011-04-06 | 南京第一农药集团有限公司 | Method for synthesizing nicosulfuron |
| CN104803982A (en) * | 2015-04-20 | 2015-07-29 | 安徽久易农业股份有限公司 | Method for preparing nicosulfuron |
| CN106749183A (en) * | 2016-11-12 | 2017-05-31 | 江苏长青生物科技有限公司 | The synthesis technique of nicosulfuron active compound |
| CN114163383A (en) * | 2021-12-24 | 2022-03-11 | 江苏丰山集团股份有限公司 | Green production process of nicosulfuron intermediate nicotinamide and sulfamide |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0101670A2 (en) * | 1982-08-23 | 1984-02-29 | Ciba-Geigy Ag | Process for the preparation of herbicides and plant growth regulating sulfonyl ureas |
| US4435206A (en) * | 1978-12-04 | 1984-03-06 | E. I. Du Pont De Nemours And Company | Agricultural pyridinesulfonamides |
| US4518776A (en) * | 1982-07-19 | 1985-05-21 | Ciba Geigy Corporation | Process for producing sulfonylureas |
| US4521597A (en) * | 1982-10-25 | 1985-06-04 | Ciba Geigy Corporation | Process for producing sulfonylureas having a herbicidal action |
-
1992
- 1992-01-18 CN CN92100307A patent/CN1042690C/en not_active Expired - Lifetime
- 1992-01-18 CN CN 92100308 patent/CN1032137C/en not_active Expired - Lifetime
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4435206A (en) * | 1978-12-04 | 1984-03-06 | E. I. Du Pont De Nemours And Company | Agricultural pyridinesulfonamides |
| US4518776A (en) * | 1982-07-19 | 1985-05-21 | Ciba Geigy Corporation | Process for producing sulfonylureas |
| EP0101670A2 (en) * | 1982-08-23 | 1984-02-29 | Ciba-Geigy Ag | Process for the preparation of herbicides and plant growth regulating sulfonyl ureas |
| US4521597A (en) * | 1982-10-25 | 1985-06-04 | Ciba Geigy Corporation | Process for producing sulfonylureas having a herbicidal action |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1062352A (en) | 1992-07-01 |
| CN1062263A (en) | 1992-07-01 |
| CN1032137C (en) | 1996-06-26 |
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