CN87100436A - The pyridinsulfonamide compounds that replaces, the method that contains the weedicide of this compounds and prepare this compounds - Google Patents
The pyridinsulfonamide compounds that replaces, the method that contains the weedicide of this compounds and prepare this compounds Download PDFInfo
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- CN87100436A CN87100436A CN87100436.4A CN87100436A CN87100436A CN 87100436 A CN87100436 A CN 87100436A CN 87100436 A CN87100436 A CN 87100436A CN 87100436 A CN87100436 A CN 87100436A
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Abstract
A kind of new substituted pyridine sulfonyl amide, it has a pyridine ring [N-replacement aminocarbonyl, 1 or 2 Y group and a special substituent (if the words that have) are arranged on the ring] and a pyridine ring that has specified substituent, and pyridine ring is connected on 3 of sulfonylurea chain.The Y amino representing hydrogen atom, halogen atom, alkyl, alkoxyl group, alkylthio, alkoxyalkyl or do not replace or replace wherein.This compound is effective millet field weedicide.Also have above-claimed cpd salt, contain the weedicide of this compound or its salt and the method for producing above-claimed cpd or its salt.
Description
The present invention relates to new, the pyridinsulfonamide compounds that replaces and salt thereof, with this compounds as the weedicide of activeconstituents 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) aminocarboxyl 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 aminocarboxyl that replaces of N-not on the pyridine ring of this compound.People have developed a lot with the similar weedicide of sulfamide compound as activeconstituents, but also both develop cereal are not had tight security, and the weedicide of fine herbicide effect is arranged again.
The present inventor furthers investigate the chemical structure of sulfamide compound and the relation between the physiologically active.Particularly, in order to seek a kind of weedicide that is used for cereal, the contriver makes further research.Consequently, the contriver 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 aminocarboxyl and a special substituting group (if any) that a N-replaces on this pyridine ring, this compound also has a sulphonamide part, has on the nitrogen-atoms of this part by the specific pyrimidine-2--amino carbonyl that substituting group replaced; The contriver has made this invention therefrom.
The invention provides a kind of pyridinsulfonamide compounds of replacement, its salt, the weedicide that contains them and their preparation method.The pyridinsulfonamide compounds of this replacement can be used following general formula
R1 and R2 represent a hydrogen atom, alkyl, haloalkyl, thiazolinyl, alkynyl, alkoxyl group, halogenated alkoxy, alkoxyalkyl, haloalkoxy alkyl, cycloalkyl, halogenated cycloalkyl, carbalkoxy, 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 group, halogenated alkoxy, alkylthio, 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 an alkali metal salt (for example sodium salt and sylvite), alkaline earth 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 traditional method.
In logical formula I, by haloalkyl, halogenated alkoxy, haloalkoxy alkyl, haloalkoxy carbonyl, halogenated cycloalkyl or the halogenophenyl of R1 and R2 representative, 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, R3, R4 and Y representative in the logical formula I 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 propenyl and butenyl.Alkynyl or alkynyl partly have 2～6 carbon atoms, for example proyl and butynyl.Said cycloalkyl has 3～6 carbon atoms, and example has cyclopropyl, cyclobutyl, cyclopentyl 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.This heterocyclic example has morpholine ring, ethylene imine ring, pyrrolidine ring and piperidine ring.
In the middle of the pyridinsulfonamide compounds of the represented replacement of logical 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 group 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) aminocarboxyl]-3-first aminocarbonyl-2-pyridine sulfonamide or N-[(4,6-dimethoxypyridin-2-yl) aminocarboxyl]-3-diformazan aminocarbonyl-2-pyridine sulfonamide, or 6-chlorine (or bromine, difluoromethyl or methyl)-N-[(4,6-dimethoxypyridin-2-yl) aminocarboxyl]-3-diformazan aminocarbonyl-2-pyridine sulfonamide.
According to the present invention, the pyridinsulfonamide compounds of the replacement of logical formula I representative and salt thereof can prepare with following method.
Make a kind of pyridine compounds and their of logical formula II representative and a kind of pyrimidines reaction of logical formula III representative,
In the formula II, the definition of R is the same, and Z1 represents group-NH
2,-NCO ,-NHCOCl or-NHCOOR5(wherein R5 represent 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-wherein the definition of R5 is the same for NHCOOR5(), 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.
[A] R-SO
2NH
2+
(20～+ 100 ℃)/(0.1～24 hour) (I)
（Ⅲ-1）
[B] (II-1)+
(0～100 ℃)/(0.1～24 hour) (I)
（Ⅲ-2）
[C] (II-1)+
(10～+ 60 ℃)/(0.5～24 hour) (I)
（Ⅲ-3）
[D] R-SO
2NHCOOR
5+
(20～+ 100 ℃)/(0.1～24 hour) (I)
（Ⅱ-2）????（Ⅲ-4）
[E] R-SO
2NCO+(III-4) (0～100 ℃)/(0.1～24 hour) (I)
（Ⅱ-3）
[F] R-SO
2NHCOCl+(III-4) (10～+ 60 ℃)/(0.5～24 hour) (I)
（Ⅱ-4）
Can also adopt following method:
[H] R-SO
2NHCONH
2+ (III-4) (130～250 ℃)/(0.5～24 hour) (I)
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 prepare by the step 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 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: aromatic hydrocarbons (for example benzene,toluene,xylene and chlorobenzene), ring-type or acyclic aliphatic hydrocarbon (for example chloroform, tetrahydro-carbon, methylene dichloride, ethylene dichloride, trichloroethane, hexane and hexanaphthene), ether (for example ether, dioxane and tetrahydrofuran (THF)), nitrile (for example acetonitrile, propionitrile and vinyl cyanide) and polar aprotic solvent (for example methyl-sulphoxide (DMSO) and tetramethylene sulfone).
(1) according to graphic extension: 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 reaction formula raw material.
Note: EG is an ethylene glycol, and Me OH is a methyl alcohol, and Et OH is an ethanol, and DMF is a dimethyl formamide, and DMSO is a methyl-sulphoxide, and Bz is a benzyl ,-Bu(t) be the tertiary butyl, 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.
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 group, halogenated alkoxy, alkylthio or halogenated alkylthio, corresponding product also can prepare by the method shown in the following route 4.
Note: R6 is alkyl or haloalkyl.The meaning of other abbreviation and symbol is the same.
Illustrate according to diagram (route 5) that (4) 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.
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.
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.
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.
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.
The reaction conditions of preparation starting compound as temperature of reaction, reaction times, the solvent that can selectively use arbitrarily, alkaline matter or the like, can suitably be selected according to the reaction conditions 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 chloride and under refluxad with its reaction 2 hours.After the reaction, steam and remove excessive thionyl chloride, in mixture, add 39 milliliters of methylene dichloride, 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 reaction product impouring water, use dichloromethane extraction.With sky and water dried over sodium sulfate dichloromethane layer, pressure reducing and steaming methylene dichloride.The gained resistates 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 sulfhydrates and 5 milliliters of methyl-sulphoxides are added drop-wise to 1.89 and restrain in the suspension of Anhydrous potassium carbonates in 28 milliliters of methyl-sulphoxides.Make the gained mixture 130～140 ℃ of reactions 30 minutes.
After reaction is finished, reaction product is added in the entry, extract with methylene dichloride.Use the anhydrous sodium sulfate drying dichloromethane layer, remove methylene dichloride under reduced pressure.With silica gel column chromatography purification gained resistates, make 2.18 gram buttery 2-benzylthio--5-chloro-N, 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, reaction product is added in 150 gram ice and the 200 milliliters of methylene dichloride, tells dichloromethane layer.Wash dichloromethane layer with 300 milliliters of frozen water, make it be cooled to 0 ℃.Splash into TERTIARY BUTYL AMINE subsequently, till stirring gained mixture reaches room temperature to this layer temperature.Reaction solution is through verifying as weakly alkaline, and reaction has so far just been finished.
After reaction is finished, reaction product is added to the water, uses dichloromethane extraction.Tell the dichloromethane layer anhydrous sodium sulfate drying; Steam again and remove methylene dichloride.The gained resistates is purified with silica gel column chromatography, makes 1.21 gram 2-TERTIARY BUTYL AMINE sulphonyl-5-chloro-N, N-dimethyl nicotinamide, 143～145 ℃ of fusing points.
[IV] makes 1.0 grams with method [III] 2-TERTIARY BUTYL AMINE 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 reaction product under reduced pressure.The gained resistates 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 phenylcarbinols and 20 milliliters of methyl-sulphoxides is added drop-wise in the suspension of 6.6 gram Anhydrous potassium carbonates in 50 milliliters of methyl-sulphoxides, allows the gained mixture about 2 hours of 150 ℃ of reactions.
After reaction is finished, reaction product is added in the water, carries out dichloromethane extraction.The dichloromethane layer anhydrous sodium sulfate drying removes methylene dichloride under reduced pressure.With silica gel column chromatography purification gained resistates, get 6.0 gram buttery 6-benzyloxy-2-chloro-N, 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, reaction product is added in the water, with the required product of dichloromethane extraction.The dichloromethane layer anhydrous sodium sulfate drying, the pressure reducing and steaming methylene dichloride.Gained resistates silica gel column chromatography purifying gets 0.41 gram 2-benzylthio--N, N-dimethyl-6-hydroxy nicotinoyl amine, 52～60 ℃ of fusing points.
[III] 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 chloride, and under refluxad make the gained mixture reaction about 1 hour.
After reaction is finished, reaction product is added in the water, with the required product of dichloromethane extraction.Dichloromethane layer washes with water, uses anhydrous sodium sulfate drying.The pressure reducing and steaming methylene dichloride, the gained resistates is purified with silica gel chromatography, makes 0.45 gram 2-benzylthio--6-chloro-N, N-dimethyl nicotinamide oily matter.
[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-oxyethyl group niacinamide synthetic
[I] is added to 0.231 gram sodium Metal 99.5 in 50 milliliters of dehydrated 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 about 1 hour of mixture reaction.Add reacted solution in the entry and use dichloromethane extraction.Two sulphur methane layer anhydrous sodium sulfate drying remove methylene dichloride under reduced pressure.Resistates is purified with silica gel chromatography, obtains 1.95 gram 2-chloro-N, N-dimethyl-6-oxyethyl group niacinamide oily matter.
The same step that [II] uses the said products 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-oxyethyl group niacinamide.
Intermediate synthesizes embodiment 4
2-aminosulfonyl-N, N-dimethyl-6-fluorine niacinamide synthetic
0.302 gram 2-TERTIARY BUTYL AMINE base sulphonyl-6-chloro-N, the N-dimethyl nicotinamide is added in 10 milliliters of dimethyl formamide pulpous state liquid [I], and these slurries contain 0.116 gram through spray-dired Potassium monofluoride; Under agitation make the gained mixture about 3 hours of 150 ℃ of reactions then.
Reaction is added to reaction solution in 100 ml waters, and uses dichloromethane extraction after finishing.Extract is through using anhydrous sodium sulfate drying after the washing repeatedly.Remove methylene dichloride under reduced pressure, resistates is purified with silica gel column chromatography, makes 0.204 gram 2-TERTIARY BUTYL AMINE base sulphonyl-N, N-dimethyl-6-fluorine niacinamide.
The same step that [II] uses the said products 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 niacinamide.
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 reaction solution become weakly alkaline, 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 nicotinic acid methyl esters, 136～140 ℃ of fusing points.
[II] is added to the 2-sulfydryl nicotinic acid methyl ester 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 methylene dichloride, isolates dichloromethane layer.Wash dichloromethane layer with 500 milliliters of frozen water it is cooled to 0 ℃.Subsequently 12.9 gram TERTIARY BUTYL AMINE 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, reaction solution is added in 500 ml waters, use dichloromethane extraction then.Also steam except that after the methylene dichloride with anhydrous sodium sulfate drying, obtain 13 gram coarse crystals.This crystal with methylene dichloride and normal hexane recrystallization, is made 2-TERTIARY BUTYL AMINE base sulphonyl nicotinic acid methyl ester, 169～171 ℃ of fusing points.
[III] is added to 1 gram the said products in 20 milliliters of anhydrous methanols that absorb excessive methylamine, stirs then 15 hours.
After reaction is finished, reaction product is added in the water, and extracts with methylene dichloride.Extract the back and use the anhydrous sodium sulfate drying dichloromethane layer, and remove methylene dichloride wherein under reduced pressure, obtain 0.73 gram 2-TERTIARY BUTYL AMINE 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 nitrogen atmosphere, at 10 ℃ or more under the low temperature, 10 milliliters of normal 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 dry-out benzene and obtains [I].Allow the gained mixture reaction, till its temperature reaches room temperature.In this reaction solution, splash into and 2-TERTIARY BUTYL AMINE base sulphonyl nicotinic acid methyl ester is dissolved in 40 milliliters of benzene and the 20 milliliters of methylene dichloride and in the solution that obtains.Under refluxad stirred the gained mixture subsequently about 9 hours.
Reaction is added to reaction solution in the dilute hydrochloric acid after finishing, and extracts with methylene dichloride.The extracting solution anhydrous sodium sulfate drying removes methylene dichloride under reduced pressure, and resistates silica gel column chromatography purifying obtains 1.0 gram 2-TERTIARY BUTYL AMINE 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, reaction mixture is added in 200 milliliters of frozen water, and with 60 milliliters of dichloromethane extraction.Wash dichloromethane layer with 100 milliliters of frozen water subsequently, it is cooled to 0 ℃ simultaneously.In solution, feed ammonia, till changing it into basic solution.Steam and remove after the methylene dichloride, in resistates, add 15 ml waters, restir gained mixture.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 makes the mixture reaction 4 hours of 30 gram 2-chlorine apellagrins and thionyl chloride.After removing thionyl chloride excessive in the reaction solution under reduced pressure, in reaction solution, add 500 milliliters of methylene dichloride, feed methylamine gas in room temperature again, become weakly alkaline solution to reaction solution 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 normal hexane and methylene dichloride 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 monobromethanes in 0 ℃ again about 30 minutes of 0～5 ℃ of reaction.Gained solution at room temperature reacted 2.5 hours, then reaction solution was added in the water, and extracted with methylene dichloride.The washing extracting solution, with anhydrous sodium sulfate drying it.Pressure reducing and steaming methylene dichloride subsequently, resistates silica gel column chromatography purifying makes 5.7 gram 2-chloro-N-ethyl-N-methylnicotinamides, for-oily matter.
[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 chloride, 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 methylene dichloride in resistates.The gained mixture is added drop-wise in the mixture of 30 milliliter 30% dimethylamine agueous solution and 50 milliliters of methylene dichloride, gained solution was at room temperature reacted 15 minutes.
After reaction is finished, reaction mixture is added in the entry, use dichloromethane extraction.The washing dichloromethane layer and with anhydrous sodium sulfate drying it.The pressure reducing and steaming methylene dichloride, resistates 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 niacinamide synthetic
[I] makes 33 grams 2, and the 6-dichloro-nicotinic acid mixes mutually with 100 milliliters of thionyl chloride, 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 methylene dichloride again.Under the temperature of room temperature to 40 ℃, in this mixture, dripping anhydrous methanol.After dropwising, make the gained mixture under refluxad should be about 1 hour.
After finishing reaction, reaction solution is added in 500 ml waters, separates with methylene dichloride again.With the dichloromethane layer washing and with behind the anhydrous sodium sulfate drying, the pressure reducing and steaming methylene dichloride.With the silica gel column chromatography resistates 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 niacinamide.
Intermediate synthesizes embodiment 10
2-aminosulfonyl-6-difluoromethyl-N, N-dimethyl nicotinamide synthetic
[I] refluxes the mixture heating up of following each material 3 hours: 2-TERTIARY BUTYL AMINE 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 tetracol phenixin, 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-TERTIARY BUTYL AMINE 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 products, 35 milliliters of ethanol and 29 ml waters, and reflux gained mixture is 3 hours then.
Reaction is added to reaction mixture in the water after finishing, and uses dichloromethane extraction.Extract washes with water, uses anhydrous sodium sulfate drying, boils off solvent wherein.Resistates is purified with silica gel column chromatography, obtains 2.92 gram 2-TERTIARY BUTYL AMINE base sulphonyl-6-formyl nicotinic acid methyl esters.
[III] is added to the solution of 0.642 gram diethylin sulfur trifluoride in 5 milliliters of methylene dichloride in the 0.48 gram 2-TERTIARY BUTYL AMINE base sulphonyl-solution of 6-formyl nicotinic acid methyl ester in 19 milliliters of methylene dichloride, at room temperature stirs the mixture then 1 hour.
Reaction adds reaction mixture in the entry after finishing, and extracts with methylene dichloride.(dichloromethane layer) washes with water, uses anhydrous sodium sulfate drying.Then solvent is boiled off.Resistates silica gel column chromatography purifying obtains 0.25 gram 2-TERTIARY BUTYL AMINE base sulphonyl-6-dichloromethyl nicotinic acid methyl ester.
[IV] makes at room temperature to be reacted by 0.50 gram the said products and 10 milliliters of mixtures of forming with the anhydrous methanol of the saturated mistake of dimethylamine and spends the night.
After reaction is finished, steam the solvent that removes in the reaction mixture,, obtain 0.15 gram 2-TERTIARY BUTYL AMINE base sulphonyl-6-difluoromethyl-N, the N-dimethyl nicotinamide then with silica gel column chromatography purifying resistates.
[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, leading to the time is 30 minutes, and allows mixture react 30 minutes again.
After reaction is finished, with reaction mixture cooling and be added in the frozen water, extract with methylene dichloride.(dichloromethane layer) washed with sodium hydrogen carbonate solution, and anhydrous sodium sulfate drying is used in washing then.Steam and remove methylene dichloride, resistates 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.
Below provide the embodiment of synthetic The compounds of this invention.
Synthetic embodiment 1
5-chloro-N-[(4,6-dimethoxypyridin-2-yl) aminocarboxyl]-3-dimethylin 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 [5.4.0] 11 carbon-7-alkene at room temperature reacted the gained mixture 45 minutes.
After reaction is finished, reaction mixture is added in the entry, leach insolubles., extract with methylene dichloride then solution weak acidization with concentrated hydrochloric acid.Subsequently with anhydrous sodium sulphate 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.
Synthetic embodiment 14
N-[(4,6-dimethoxypyridin-2-yl) aminocarboxyl]-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' mixing solutionss are added drop-wise to 6.3 and contain in the ethyl acetate solution of 20% carbonyl chloride, make composition remain on 15 ℃ and reacted 1 hour then.Then with oil bath mixture heating up to 90 ℃, steam and remove excessive carbonyl chloride and ethyl acetate.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 washing and dry.
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, allow about 1 hour of gained mixture reaction.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.Reaction solution added in the entry and with methylene dichloride wash.The water layer hcl acidifying is used dichloromethane extraction then.The dichloromethane layer anhydrous sodium sulfate drying, the pressure reducing and steaming methylene dichloride.The gained crystal obtains 0.91 gram N, N-dimethyl-2-carbonyl phenoxy aminosulfonyl niacinamide, 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 niacinamide 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, reaction mixture is added in 200 ml waters, leaches the gained crystal, obtain 0.21 gram N-[(4-chloro-6-methoxy pyrimidine-2-yl) aminocarboxyl]-3-diformazan aminocarbonyl-2-pyridine sulfonamide, 157～158.5 ℃ of fusing points.
[III] is added to 18.3 milligrams of sodium Metal 99.5s in 7 milliliters of anhydrous methanols, adds N-[(4-chloro-6-methoxy pyrimidine-2-yl that 0.11 gram makes by process [II] to it again) aminocarboxyl]-3-diformazan aminocarbonyl-2-pyridine sulfonamide.The gained mixture heating up refluxed 12 hours.
After reaction is finished, reaction 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.
Compound of the present invention has herbicidal effect to following various weeds: cyperus weeds (Cyperaceae), as rice nutgrass flatsedge [rice flatsedge] (Cyperus iria), Japanese Rush (Scirpus juncoides) and purple nutsedge(Cyperusrotundus); Gramineous weeds (Gramineae) is as barnyard grass (Echinochloacrus-galli), lady's-grass (Digitaria adscendens), Herba Setariae Viridis (Setariaviridis), yard grass (Eleusine indica), wild avena sativa (Avena fatua), stone thatch Chinese sorghum (Sorghum halepense) and roegneria kamoji (Agropyron repens); And broadleaf weeds, 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), purslane (Portulaca oleracea), elongated Amaranthus (Amaranthus viridis), Canada's alpine rockcress (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 weedicide 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 composition 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.Herbicidal compound of the present invention is to use with the form of granule, wettable 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, emulsifying agent, dispersion agent or tensio-active agent) as required.Active ingredient and one or more agricultural assistant agents mutually the suitable weight ratio of blended 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, edaphic 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 composition 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.Can with herbicidal composition of the present invention other herbicidal compound of blended such as following listed mutually.In some cases, can produce synergistic effect.
3,6-two chloro-2-methoxy benzoic acids
2,5-two chloro-3-benzaminic acid
(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-methylthio group-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 Toluidine
2-chloro-N-sec.-propyl-monoacetylaniline
2-chloro-N, N-two-2-propenyl ethanamide
Dipropyl thiocarbamate-S-ethyl ester
The diisobutyl dithiocarbamate-s-ethyl
Dipropyl thiocarbamate-S-propyl ester
The N-(1-ethyl propyl)-2,6-dinitrobenzene-3,4-xylidine
α, α, α-three fluoro-2,6-dinitrobenzene-N, N-dipropyl p-toluidine
2-(3, the 5-dichlorophenyl)-2-(2,2,2-three chloroethyls) oxyethane
The 3-sec.-propyl-(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-oxyethyl group-4-nitrophenyl ether
For instance, N-[(4,6-dimethoxypyridin-2-yl) aminocarboxyl]-3-methylamine carbonyl (or dimethylin carbonyl)-2-pyridine sulfonamide or 6-chloro-(or bromo-, difluoromethyl-or methyl-) N-[(4,6-dimethoxypyridin-2-yl) aminocarboxyl]-3-dimethylin 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 Toluidine or N-(1-ethyl propyl)-2,6-dinitrobenzene-3, the 4-xylidine.The weedicide 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 during to stage of development of being scheduled to respectively [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, it was 2.0～3.5 leaf stages to common cocklebur, be 0.5～1.2 leaf stage to high plant towards the face flower, it was 0.5～1.2 leaf stage to knotweed car grass, it was 0.1～1.5 leaf stage to the thorniness high mallow, be that 0.1～1.5 leaf is educated the stage to elongated Amaranthus, it was 2.0～2.5 leaf stages to barnyard grass], prepare a kind of aqueous dispersions, method is to contain a kind of wettable 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, visually observe the development degree through 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 impact of 1 expression is shown in following table 4.
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, weigh up a certain amount of a kind of with medicament for the treatment of to 2 with during 0.5 leaf stage in that the test plant of lady's-grass and black nightshade is long respectively, make wherein that contained active ingredient amount is scheduled volume, then with 5 premium on currency/ares this medicament is diluted. Add 0.2% agricultural dispersants in the obtained aqueous solution, then gained solution is sprayed with a kind of miniaturised nebuliser. Behind the spray medicine the 23rd day, with the naked eye estimate the speed of growth of lady's-grass and black nightshade; Identical in the evaluation method of weeds control action and the test example 1. The results are shown in the table 5.
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, then with 5 premium on currency/ares this medicament is diluted. 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.
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 purple njutsedge is long, make wherein that the amount of active ingredient is scheduled volume, then with 5 premium on currency/ares this medicament is diluted. In addition, add 0.2% agricultural dispersants in this aqueous solution, and gained solution is sprayed onto on the leaf of above-mentioned plant. The spray medicine visually observed the control effect to purple nutsedge after 51 days. The evaluation method of weeds control action is with test example 1, and it the results are shown in following table 7.
The below provides the preparation embodiment of Herbicidal combinations of the present invention.
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 wettable 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 wettable 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 wettable 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 wettable powder.
Claims (20)
1, the pyridine sulfamide compound and the salt thereof of a kind of replacement of logical formula I representative:
R1 and R2 represent a hydrogen atom independently of one another, alkyl, haloalkyl, thiazolinyl, alkynyl, alkoxyl group, halogenated alkoxy, alkoxyalkyl, the haloalkoxy alkyl, cycloalkyl, halogenated cycloalkyl, carbalkoxy, the haloalkoxy carbonyl, phenyl or halogenophenyl, condition is when having one to represent hydrogen atom among R1 and the R2, then another represents a group except that hydrogen atom in the above-mentioned group, R2 and R1 can constitute a heterocycle with an adjacent nitrogen-atoms, and Y represents a halogen atom, alkyl, haloalkyl, alkoxyl group, halogenated alkoxy, alkylthio, halogenated alkylthio, alkoxyalkyl, haloalkoxy alkyl or group
(R3 and R4 cause representing independently a hydrogen atom or alkyl), n is 0 or integer 1 or 2, and X1 and X2 represent a methyl, methoxy or ethoxy independently of one another.
According to described a kind of compound of claim 1, it is characterized in that 2, this pyridine sulfamide compound and salt thereof are by the pyridine sulfonamide of a kind of replacement of following general formula representative and salt thereof:
R1, R2Y, n, X1 and X2 are with described in the claim 1 in the formula.
3, a kind of compound according to claim 2 and salt thereof is characterized in that, R1 is hydrogen atom or alkyl, R2 is an alkyl, Y is the plain atom of fontanel, alkyl, fontanel substituted alkyl, alkoxyl group or alkoxyalkyl, and n is 0 or 1, and each all is methoxyl group independently among X1 and the X2.
4, a kind of compound according to claim 2 and salt thereof is characterized in that, R1 is hydrogen atom or methyl, R2 is a methyl, and Y is chlorine atom, bromine atoms, methyl or difluoromethyl, and Y is on 6 of pyridine nucleus, n is 0 or 1, and each all is methoxyl group independently among X1 and the X2.
5, a kind of compound according to claim 2 is characterized in that, this compound is 6-bromo-N-[(4,6-dimethoxypyridin-2-yl) aminocarbonyl]-3-diformazan aminocarbonyl-2-pyridine sulfonamide.
6, a kind of compound according to claim 2 is characterized in that, this compound is 6-difluoromethyl-N-[(4,6-dimethoxypyridin-2-yl) aminocarbonyl]-3-diformazan aminocarbonyl-2-pyridine sulfonamide.
7, a kind of compound according to claim 2 is characterized in that, this compound is N-[(4,6-dimethoxypyridin-2-yl) aminocarbonyl]-3-diformazan aminocarbonyl-2-pyridine sulfonamide.
8, a kind of compound according to claim 2 is characterized in that, this compound is N-[(4,6-dimethoxypyridin-2-yl) aminocarbonyl]-3-diformazan aminocarbonyl-6-methyl-2-pyridine sulfonamide.
9, a kind of compound according to claim 2 is characterized in that, this compound is 6-chloro-N-[(4,6-dimethoxypyridin-2-yl) aminocarbonyl]-3-diformazan aminocarbonyl-2-pyridine sulfonamide.
10, a kind of compound according to claim 2 is characterized in that, this compound is N-[(4,6-dimethoxypyridin-2-yl) aminocarbonyl]-3-first aminocarbonyl-2-pyridine sulfonamide.
11, a kind of compound according to claim 2 is characterized in that, the salt of this compound is N-[(4,6-dimethoxypyridin-2-yl) aminocarbonyl]-sodium salt of 3-diformazan aminocarbonyl-2-pyridine sulfonamide.
12, a kind of herbicidal composition, the defined compound or its salt of a kind of claim 1 and the agricultural that wherein mainly contain herbicidally effective amount go up acceptable assistant agent.
13, a kind of herbicidal composition according to claim 12 is characterized in that, the pyridinsulfonamide compounds of replacement or its salt are 1: 99～90: 1 with the ratio of mixture that agricultural goes up acceptable assistant agent.
14, a kind of by using the method that the described composition of claim 12 kills paddy Tanaka injurious weed, the amount of application of said composition is calculated as 0.1～100 gram/are by active ingredient wherein.
15, a kind of method of producing the pyridinsulfonamide compounds of the replacement of leading to the formula I representative,
R1 and R2 represent a hydrogen atom independently of one another, alkyl, haloalkyl, thiazolinyl, alkynyl, alkoxyl group, halogenated alkoxy, alkoxyalkyl, the haloalkoxy alkyl, cycloalkyl, halogenated cycloalkyl, carbalkoxy, the haloalkoxy carbonyl, phenyl or halogenophenyl, condition is when having one to represent hydrogen atom among R1 and the R2, then another represents a group except that hydrogen atom in the above-mentioned group, R2 and R3 can constitute a heterocycle with an adjacent nitrogen-atoms, and Y represents a halogen atom, alkyl, haloalkyl, alkoxyl group, halogenated alkoxy, alkylthio, 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,
This method comprises: a kind of pyridine compounds and their that makes following general formula representative
[meaning of R is same as above in the formula, and Z1 represents group-NH
2,-NCO ,-NHCOCl or-NHCOOR
5(wherein R5 represents an alkyl or aryl)] react with a kind of pyrimidines of following general formula representative,
On behalf of halogen atom, methyl, methoxy or ethoxy, Z2, each in the following formula among X3 and the X4 all independently represent group-NH
2,-NCO ,-NHCOCl or-NHCOOR5(wherein the meaning of R5 with above-mentioned), condition is to represent group-NH as Z1
2The time, Z2 represent group-NCO ,-NHCOCl or-NHCOOR5, and represent group-NH as Z2
2The time,
Then Z1 represent group-NCO ,-NHCOCl or-NHCOOR5, when X3 and/or X4 represent a halogen atom, carry out methoxylation or ethoxylation then, and carry out salify when needed and handle.
According to a kind of method of claim 15, it is characterized in that 16, Z1 represents one-NH
2Group, and Z2 represent group-NCO ,-NHCOCl or-NHCOOR5.
17, according to a kind of method of claim 15, it is characterized in that, Z1 represent group-NCO ,-NHCOCl or-NHCOOR5, and Z2 represents one-NH
2Group.
According to a kind of method of claim 15, it is characterized in that 18, the temperature of reaction of condensation reaction is-20～+ 100 ℃.
19, a kind of as intermediate, by the pyridine compounds and their of following general formula representative,
R1 and R2 represent a hydrogen atom independently of one another, alkyl, haloalkyl, thiazolinyl, alkynyl, alkoxyl group, halogenated alkoxy, alkoxyalkyl, the haloalkoxy alkyl, cycloalkyl, halogenated cycloalkyl, carbalkoxy, the haloalkoxy carbonyl, phenyl or halogenophenyl, condition is when having one to represent hydrogen atom among R1 and the R2, then another represents a group except that hydrogen atom in the above-mentioned group, R2 and R3 can constitute a heterocycle with an adjacent nitrogen-atoms, and Y represents a halogen atom, alkyl, haloalkyl, alkoxyl group, halogenated alkoxy, alkylthio, 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, and Z1 is group-NH
2,-NCO ,-NHCOCl or-NHCOOR5(wherein R5 be an alkyl or aryl).
According to a kind of compound of claim 19, it is characterized in that 20, R is a group
(wherein R1, R2, Y and n are with identical described in the claim 19).
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN92100307A CN1042690C (en) | 1986-01-30 | 1992-01-18 | Herbicidal composition containing substituted pyridinesulfonamide compounds |
| CN 92100308 CN1032137C (en) | 1986-01-30 | 1992-01-18 | Process for preparing substituted pyridinsulfonamide compounds |
Applications Claiming Priority (7)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1900686 | 1986-01-30 | ||
| JP19006/86 | 1986-01-30 | ||
| JP61019863 | 1986-01-31 | ||
| JP19863/86 | 1986-01-31 | ||
| JP86847/86 | 1986-04-15 | ||
| JP178489/86 | 1986-07-29 | ||
| JP17848986 | 1986-07-29 |
Related Child Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 92100308 Division CN1032137C (en) | 1986-01-30 | 1992-01-18 | Process for preparing substituted pyridinsulfonamide compounds |
| CN92100307A Division CN1042690C (en) | 1986-01-30 | 1992-01-18 | Herbicidal composition containing substituted pyridinesulfonamide compounds |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN87100436A true CN87100436A (en) | 1987-08-12 |
| CN1016661B CN1016661B (en) | 1992-05-20 |
Family
ID=27282458
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 87100436 Expired CN1016661B (en) | 1986-01-30 | 1987-01-27 | Herbicidal composition containing pyridinesulfonamide |
Country Status (2)
| Country | Link |
|---|---|
| CN (1) | CN1016661B (en) |
| BR (1) | BR8708013B1 (en) |
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| CN101805286A (en) * | 2010-03-25 | 2010-08-18 | 江苏丰山集团有限公司 | Method for synthesizing midbody sulfamide of nicosulfuron |
| CN102993176A (en) * | 2012-11-02 | 2013-03-27 | 安徽丰乐农化有限责任公司 | Novel synthetic process of nicosulfuron |
| CN103483318A (en) * | 2013-09-25 | 2014-01-01 | 安徽丰乐农化有限责任公司 | Environment-friendly novel technology for synthesizing high content nicosulfuron |
| CN103951655A (en) * | 2014-05-15 | 2014-07-30 | 天津市华宇农药有限公司 | Nicosulfuron derivative, herbicide containing same, preparation methods of nicosulfuron derivative and herbicide and application of herbicide |
| CN104151294A (en) * | 2008-04-18 | 2014-11-19 | 石原产业株式会社 | Method for producing pyrimidine compound |
| CN105330649A (en) * | 2015-12-09 | 2016-02-17 | 安徽久易农业股份有限公司 | Preparation method of hingosulfuron-methyl |
| CN109757504A (en) * | 2018-12-28 | 2019-05-17 | 京博农化科技有限公司 | Oil-suspending agent and preparation method thereof can be dispersed in a kind of nicosulfuron |
| CN113387928A (en) * | 2021-06-15 | 2021-09-14 | 淄博新农基作物科学有限公司 | Method for circularly producing nicosulfuron technical by using byproduct phenol |
| CN114539165A (en) * | 2022-02-21 | 2022-05-27 | 江苏瑞邦农化股份有限公司 | Preparation method of mesosulfuron-methyl |
-
1987
- 1987-01-27 CN CN 87100436 patent/CN1016661B/en not_active Expired
- 1987-01-27 BR BR8708013A patent/BR8708013B1/en active IP Right Grant
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Also Published As
| Publication number | Publication date |
|---|---|
| BR8708013B1 (en) | 2011-07-12 |
| CN1016661B (en) | 1992-05-20 |
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