CN103288749A - Amino sulfonylurea compounds capable of being used as herbicides - Google Patents
Amino sulfonylurea compounds capable of being used as herbicides Download PDFInfo
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- CN103288749A CN103288749A CN2013100867479A CN201310086747A CN103288749A CN 103288749 A CN103288749 A CN 103288749A CN 2013100867479 A CN2013100867479 A CN 2013100867479A CN 201310086747 A CN201310086747 A CN 201310086747A CN 103288749 A CN103288749 A CN 103288749A
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Abstract
Amino sulfonylurea compounds shown in formula (I) have high herbicidal activities for a variety of weeds. The invention relates to amino sulfonylurea compounds and salts thereof which have high herbicidal activities, a preparation method therefor and applications thereof in agriculture as herbicides for controlling weeds.
Description
Technical field
The present invention relates to the aminosulfonyl carbamide compounds, relate to aminosulfonyl carbamide compounds with efficient weeding activity, preparation method specifically and on agricultural as the purposes of weedicide controlling weeds.
Background technology
The present invention has found new aminosulfonyl carbamide compounds, and these compounds have weeding activity efficiently, highly selective and to the hypotoxicity of the crop of tool agronomical value.
Summary of the invention
Target of the present invention is the aminosulfonyl carbamide compounds with following formula (I):
Wherein:
R
1The expression hydrogen atom; C
1-C
4Straight chain, branched-chain alkyl or cycloalkyl;
R
2Expression C
1-C
4The straight or branched alkoxyl group; C
1-C
4The amido that straight or branched replaces; C
1-C
4Alkyl, halogen atom, C that the straight or branched halogen atom replaces
1-C
4The straight or branched alkylthio;
Z represents CH or nitrogen-atoms;
The specific examples of the aminosulfonyl carbamide compounds of the general formula that weeding activity merits attention (I) is:
1-[2-(N-ethyl-N-cyclohexyl-carbonyl) phenyl amino alkylsulfonyl]-3-(4,6-dimethyl pyrimidine-2-yl) urea (compound 1)
1-[2-(N-ethyl-N-cyclohexyl-carbonyl) phenyl amino alkylsulfonyl]-3-(4,6-dimethoxypyridin-2-yl) urea (compound 2)
1-[2-(N-ethyl-N-cyclohexyl-carbonyl) phenyl amino alkylsulfonyl]-3-(4,6-dimethoxy-1,3,5-triazines-2-methyl) urea (compound 3)
1-[2-(N-ethyl-N-cyclohexyl-carbonyl) phenyl amino alkylsulfonyl]-3-(4-methoxyl group-6-chloro-1,3,5-triazines-2-cyclopropyl) urea (compound 4)
1-[2-(N-ethyl-N-cyclohexyl-carbonyl) phenyl amino alkylsulfonyl]-3-(4-methoxyl group-6-methylthio group-1,3,5-triazines-2-cyclopropyl) urea (compound 5)
1-[2-(N-ethyl-N-cyclohexyl-carbonyl) phenyl amino alkylsulfonyl]-3-(4,6-diethoxy-1,3,5-triazines-2-methyl) urea (compound 6)
1-[2-(N-ethyl-N-cyclohexyl-carbonyl) phenyl amino alkylsulfonyl]-3-[4-(N, N-diethylin)-6-chloro-1,3,5-triazines-2-cyclopropyl] urea (compound 7)
1-[2-(N-ethyl-N-cyclohexyl-carbonyl) phenyl amino alkylsulfonyl]-3-(4-methoxyl group-6-Trifluoromethyl-1,3,5-triazine-2-yl) urea (compound 8)
The aminosulfonyl carbamide compounds of general formula of the present invention (I) has acidity, so they can generate salt and quaternary ammonium salt with alkaline matter such as basic metal, alkaline-earth metal, amine and other organic basess.The aminosulfonyl carbamide compounds of the general formula of salt form (I) is also contained in the scope of the present invention, constitutes another target of the present invention.
Another target of the present invention is the method for the aminosulfonyl carbamide compounds of preparation general formula (I), and the compound of general formula (I) can obtain by following method:
Have or do not have alkali and inert organic solvents in the presence of, with the halogen sulfonylurea of general formula (IV) and the aniline reaction of logical formula V:
Wherein:
R
1The expression hydrogen atom; C
1-C
4Straight chain, branched-chain alkyl or cycloalkyl;
R
2Expression C
1-C
4The straight or branched alkoxyl group; C
1-C
4The amido that straight or branched replaces; C
1-C
4Alkyl, halogen atom, C that the straight or branched halogen atom replaces
1-C
4The straight or branched alkylthio;
Z represents CH or nitrogen-atoms;
Employed inert organic solvents is aromatic hydrocarbon (as toluene, dimethylbenzene, benzene etc.), halohydrocarbon (as chlorobenzene, methylene dichloride, chloroform etc.) and ether compound (as ether, tetrahydrofuran (THF), 1,4-dioxane, methyl tertiary butyl ether etc.) in the above-mentioned steps; Employed alkali is organic bases (triethylamine, pyridine etc.) or mineral alkali (yellow soda ash, salt of wormwood etc.).
Above-mentioned temperature of reaction can be carried out to employed solvent boiling point at-70 degree, between preferred-10 to 30 degree.
The halogen sulfonylurea of general formula (IV) and the aniline of logical formula V are compounds as known in the art.
The aminosulfonyl carbamide compounds (The compounds of this invention) of general formula (I) has tangible biological activity, and especially the high herbicidal activity is applicable to the field-crop protection.Can before bud, plant unifacial leaf and broadleaf weed in bud rear defence Zhiduo County.Simultaneously useful crop there is not poisoning.
The aminosulfonyl carbamide compounds of general formula (I), the effectively example of controlling weeds: Echinochloa, Cyperus, lady's-grass, mouse tail are seen ma wheat, Tender Catchweed Bedstraw Herb, black nightshade, Amaranthus retroflexus, lamb's-quarters, little lamb's-quarters, Herba Salsolae Collinae, Herba hibisci trioni, summer cypress, shepherd's purse, penny cress, purslane, descurainia sophia (l.) webb ex prantl, Siberian cocklebur, veronica, Mai Lancai, Herba Bidentis Tripartitae, Herba Bidentis Bipinnatae, field thistle, chickweed, ox chickweed etc.
The metering of common compound is at 1-1, but the interior just controlling weeds of the scope of 000 gram/hectare.Can use the compound that contains one or more general formulas (I) in actual the use, it is free state or is the isomer mixture of the form of salt.
Can use the compound that exists with forms such as dry powder doses, wettable powder, missible oil, microemulsion, paste, granule, solution, suspension, or according to the composition of currently known methods preparation, for example in the presence of tensio-active agent, in solvent or solid dielectric, prepare by dissolving or dilution actives.
The operable material of solid inert diluents or carrier: clay, potter's clay, kaolin, diatomite, pyrophyllite, talcum powder etc.
Outside dewatering as inert liquid diluent, can also be organic solvent: benzene, dimethylbenzene, ethyl acetate, ethanol, methyl alcohol, mix benzene, solvent wet goods.
Tensio-active agent is: anion surfactant such as nonionogenic tenside such as the ester of polyoxyethylene groups and ether and alkylbenzene sulfonate.
Also can add dispersion agent such as alkylaryl sulphonate and formaldehyde condensation products thereof, sulfonated lignin, alkylphenol-polyethenoxy base ether formaldehyde condensation products, vitriol etc.; Wetting agent is as spaonin powder, the camellia oleosa seed cake powder that contains saponin and the lignosulfite that contains xylogen, and synthetic tensio-active agent such as polyoxyethylene groups alkyl aryl ether, polyoxyethylene groups alkyl oxide, alkylbenzene sulfonate, sulfonated alkyl naphathalene etc.; Spreader-sticker such as nonionic or anion surfactant, sulfonated lignin, lactic casein etc.
For improving the sphere of action of above-mentioned composition, can add other activeconstituentss, other weedicides that add are: 2, the 4-d butyl ester, 2 first, 4 chlorine, 2,4-drips propionic acid, Vi par, 2,4-Embutox, Dicamba, chloramben, dinoben, tribac, chlorthal, enemy's grass is dead, tricamba, fluazifop-p-butyl, smart quizalofopethyl, high lid, the prestige despot, diclofop-methyl, quizalofopPethyl, galloping horse, trifluralin, dibutalin, weeding is logical, G-30027, simazine, prometryn, bladex, sencorex, simetryn, molinate, thiobencarb, Wei Nong, the oat fear, the ring grass is special, phenmedipham, metolachlor (all you, Jin Douer), propisochlor (Probiotics), acetochlor, the third careless amine (auspicious fly spy), Butachlor technical 92, Stam F-34, the Da Hui profit, monuron, methoxydiuron, isoproturon, beautiful farming is happy, thiameturonmethyl, pyrazosulfuronmethyl (careless jinx), chlorine sulphur is grand, metsulfuron-methyl, superstar's (broad-leaved is clean), benbbensulfuronmethyl (Nongdeshi, the prestige farming), pyrazosulfuronmethyl (careless jinx, Mercury), chlorimuronethyl (beans sulphur is grand), thifensulfuronmethyl, glyphosate, grass fourth phosphorus, two propylamine phosphorus, imazethapyr (Pu Shite, Imazethapyr), the weed eradication quinoline, sethoxydim (Sethoxydin), methoxyphenone, clethodim, ethoxy ether (if so), weeds are burnt, fomesafen, restrain wealthy pleasure, fluoroglycofenethyl, Paraquat, diquat, bromoxynil, two cyanophenyls, quinclorac, difenzoquat, Guangmieling, celestial being is controlled, bentazone etc.
Specific implementation method
Following examples further specify content of the present invention, but should not be construed as limitation of the present invention.
Embodiment 1
1-[2-(N-ethyl-N-cyclohexyl-carbonyl) phenyl amino alkylsulfonyl]-3-(4,6-dimethoxypyridin-2-yl) urea synthetic
With 2-amino-4,6-dimethoxypyridin 1.5g (0.01mol) and methylene dichloride 30ml put in the 250mL four-hole boiling flask, under the cryogenic liquid recycle pump, system are cooled to-1～0 ℃.Slowly drip the mixed solution of chloro sulfonyl isocyanate 1.4g (0.01mol) and methylene dichloride 15mL under this temperature with constant pressure funnel, temperature is not higher than 0 ℃ in the dropping process, drips about 30 minutes, drips and finishes, and insulation is 2 hours under this temperature.Under-1～0 ℃, slowly drip 2.4g (0.01mol) 2-amino-N-ethyl-N-phenylcyclohexane methane amide with constant pressure funnel, the mixed solution of triethylamine 1.3g (0.013mol) and 30mL methylene dichloride, see temperature control rate of addition, dripped about 1 hour, drip and finish, stirred 30 minutes at 0 ℃, move on to again and stirred under the room temperature 15 hours, add twice of 50ml washing, layering changes reaction unit into water distilling apparatus, takes off most methylene dichloride and water, cooling, add methyl alcohol 10mL, stir and make its dissolving, pour 50mL single port flask again into, put into refrigerator-freezer, after treating that product is separated out, suction filtration is poured the methyl alcohol that freezes in advance into single port flask suction filtration again, dry white solid 2.8g, yield 55.3%.Fusing point: 91～93 ℃.
Embodiment 2
Adopt similar method to synthesize following product:
1-[2-(N-ethyl-N-cyclohexyl-carbonyl) phenyl amino alkylsulfonyl]-3-(4,6-dimethyl pyrimidine-2-yl) urea (compound 1) fusing point: 107～109 ℃.
1-[2-(N-ethyl-N-cyclohexyl-carbonyl) phenyl amino alkylsulfonyl]-3-(4,6-dimethoxy-1,3,5-triazines-2-methyl) urea (compound 3) fusing point: 123～125 ℃.
1-[2-(N-ethyl-N-cyclohexyl-carbonyl) phenyl amino alkylsulfonyl]-3-(4-methoxyl group-6-chloro-1,3,5-triazines-2-cyclopropyl) urea (compound 4) fusing point: 99～102 ℃.
1-[2-(N-ethyl-N-cyclohexyl-carbonyl) phenyl amino alkylsulfonyl]-3-(4-methoxyl group-6-methylthio group-1,3,5-triazines-2-cyclopropyl) urea (compound 5) fusing point: 98～101 ℃.
1-[2-(N-ethyl-N-cyclohexyl-carbonyl) phenyl amino alkylsulfonyl]-3-(4,6-diethoxy-1,3,5-triazines-2-methyl) urea (compound 6) fusing point: 105～107 ℃
1-[2-(N-ethyl-N-cyclohexyl-carbonyl) phenyl amino alkylsulfonyl]-3-[4-(N, N-diethylin)-6-chloro-1,3,5-triazines-2-cyclopropyl] urea (compound 7) fusing point: 107～109 ℃.
1-[2-(N-ethyl-N-cyclohexyl-carbonyl) phenyl amino alkylsulfonyl]-3-(4-methoxyl group-6-Trifluoromethyl-1,3,5-triazine-2-yl) urea (compound 8) fusing point: 145～148 ℃.
Embodiment 3
1-[2-(N-ethyl-N-cyclohexyl-carbonyl) phenyl amino alkylsulfonyl]-preparation of 3-(4,6-dimethoxypyridin-2-yl) urea list sodium salt
The methanol solution that will contain the 0.01mol sodium methylate joins 1-[2-(N-ethyl-N-cyclohexyl-carbonyl) phenyl amino alkylsulfonyl]-3-(4; 6-dimethoxypyridin-2-yl) in the 50ml dichloromethane solution of urea; stirring at room 20 hours; remove solvent under reduced pressure and get 1-[2-(N-ethyl-N-cyclohexyl-carbonyl) phenyl amino alkylsulfonyl]-3-(4,6-dimethoxypyridin-2-yl) urea list sodium salt.
Embodiment 4
The mensuration of weeding activity
Canister is cultivated weeds: barnyard grass grass, lady's-grass, Tender Catchweed Bedstraw Herb.To contain the The compounds of this invention of aequum and (0.5%) water/acetone dispersion liquor (20%) of Tween20 and handle 20 days postevaluation weeding activity.Divide 10 grades of evaluations, 10 represents weeds is killed fully, 1 represent be untreated identical.
Table 1
Claims (10)
1. the aminosulfonyl carbamide compounds that has following general formula (I):
Wherein:
R
1The expression hydrogen atom; C
1-C
4Straight chain, branched-chain alkyl or cycloalkyl;
R
2Expression C
1-C
4The straight or branched alkoxyl group; C
1-C
4The amido that straight or branched replaces; C
1-C
4Alkyl, halogen atom, C that the straight or branched halogen atom replaces
1-C
4The straight or branched alkylthio;
Z represents CH or nitrogen-atoms.
2. preparation is according to the method for the aminosulfonyl carbamide compounds of the general formula (I) of aforesaid right requirement 1, and this method comprises:
2.1, in the presence of inert organic solvents, with the heterocyclic amine of following general formula (II),
R wherein
1, R
2, Z definition is the same
With the halosulfonyl isocyanate reaction of following general formula (III),
X-SO
2-NCO (III)
Wherein X is halogen atom,
Obtain the halogen sulfonylurea of following general formula (IV) thus,
R wherein
1, R
2, Z definition is the same
2.2, have or do not have alkali and inert organic solvents in the presence of, with the halogen sulfonylurea of general formula (IV) and the aniline reaction of logical formula V:
Wherein:
R
1The expression hydrogen atom; C
1-C
4Straight chain, branched-chain alkyl or cycloalkyl;
R
2Expression C
1-C
4The straight or branched alkoxyl group; C
1-C
4The amido that straight or branched replaces; C
1-C
4Alkyl, halogen atom, C that the straight or branched halogen atom replaces
1-C
4The straight or branched alkylthio;
Z represents CH or nitrogen-atoms.
3. according to the method for claim 2, the inert organic solvents that wherein can be used for step 2.1 can be aromatic hydrocarbon, halohydrocarbon and ether compound.
4. according to the method for claim 2 or 3, wherein can be used for the optional fat amine compound of inertia organic bases of step 2.2.
5. according to the method for claim 2, wherein can be used for step 2.1 and carry out to employed solvent boiling point at-70 degree.
6. according to the method for claim 2, the inert organic solvents that wherein can be used for step 2.2 can be aromatic hydrocarbon, halohydrocarbon and ether compound.
7. according to the method for claim 2, wherein heterocyclic amine and halosulfonyl isocyanate reaction make the halogen sulfonylurea of general formula (IV), and the halogen sulfonylurea needn't separate with system, and the aniline that can directly add logical formula V in same reactor reacts with it.
8. contain one or more according to the herbicidal composition of the aminosulfonyl carbamide compounds of claim 1, described composition or contain described aminosulfonyl carbamide compounds to the greatest extent perhaps contains solid carrier, liquid diluent, tensio-active agent or other activeconstituentss.
9. the composition with weeding activity according to Claim 8, wherein the concentration of activeconstituents is between 1%-90%.
10. according to the salt of basic metal, alkaline-earth metal, optional alkylating ammonium or the organic amine of general formula (I) the aminosulfonyl carbamide compounds of claim 1.
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Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4515620A (en) * | 1982-01-12 | 1985-05-07 | Ciba Geigy Corporation | Triaza compounds |
| US4718937A (en) * | 1983-07-09 | 1988-01-12 | Hoechst Aktiengesellschaft | N-alkoxyaminosulfonylureas and N-alkylsulfonylaminosulfonylureas |
| US5009699A (en) * | 1990-06-22 | 1991-04-23 | American Cyanamid Company | 1-{[O-(cyclopropylcarbonyl)phenyl]sulfamoyl}-3-(4,6-dimethoxy-2-pyrimidinyl)urea herbicidal composition and use |
| US5214206A (en) * | 1990-11-07 | 1993-05-25 | Warner-Lambert Company | Aminosulfonyl urea acat inhibitors |
| CN1081815A (en) * | 1992-08-14 | 1994-02-16 | 孟山都公司 | Safe with pyrazolyl sulfonylureas of activity of weeding |
| JPH09249652A (en) * | 1995-10-27 | 1997-09-22 | Isagro Ricerca Srl | Aminosulfonylurea |
| CN1252062A (en) * | 1997-03-13 | 2000-05-03 | 伊萨罗里斯卡公司 | Aminosulfonylureas with herbicidal activity |
| CN1368971A (en) * | 1999-08-06 | 2002-09-11 | 拜尔公司 | Substituted thineyl (amino) sulfonylureas |
-
2013
- 2013-03-04 CN CN2013100867479A patent/CN103288749A/en active Pending
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4515620A (en) * | 1982-01-12 | 1985-05-07 | Ciba Geigy Corporation | Triaza compounds |
| US4718937A (en) * | 1983-07-09 | 1988-01-12 | Hoechst Aktiengesellschaft | N-alkoxyaminosulfonylureas and N-alkylsulfonylaminosulfonylureas |
| US5009699A (en) * | 1990-06-22 | 1991-04-23 | American Cyanamid Company | 1-{[O-(cyclopropylcarbonyl)phenyl]sulfamoyl}-3-(4,6-dimethoxy-2-pyrimidinyl)urea herbicidal composition and use |
| US5214206A (en) * | 1990-11-07 | 1993-05-25 | Warner-Lambert Company | Aminosulfonyl urea acat inhibitors |
| CN1081815A (en) * | 1992-08-14 | 1994-02-16 | 孟山都公司 | Safe with pyrazolyl sulfonylureas of activity of weeding |
| JPH09249652A (en) * | 1995-10-27 | 1997-09-22 | Isagro Ricerca Srl | Aminosulfonylurea |
| CN1252062A (en) * | 1997-03-13 | 2000-05-03 | 伊萨罗里斯卡公司 | Aminosulfonylureas with herbicidal activity |
| CN1368971A (en) * | 1999-08-06 | 2002-09-11 | 拜尔公司 | Substituted thineyl (amino) sulfonylureas |
Non-Patent Citations (2)
| Title |
|---|
| 张广良: "新型磺酰脲类化合物的设计、合成及除草活性", 《吉林大学博士学位论文》 * |
| 李吉来 等: "磺酰脲类化合物除草活性的QSAR研究", 《高等学校化学学报》 * |
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Application publication date: 20130911 |