CN104341366A - Synthesis process of herbicide prosulfuron for removing gramineous weeds and broad-leaved weeds - Google Patents
Synthesis process of herbicide prosulfuron for removing gramineous weeds and broad-leaved weeds Download PDFInfo
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- CN104341366A CN104341366A CN201310346067.6A CN201310346067A CN104341366A CN 104341366 A CN104341366 A CN 104341366A CN 201310346067 A CN201310346067 A CN 201310346067A CN 104341366 A CN104341366 A CN 104341366A
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- prosulfuron
- trifluoro propyl
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- phenylsulfonic acid
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D251/00—Heterocyclic compounds containing 1,3,5-triazine rings
- C07D251/02—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings
- C07D251/12—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members
- C07D251/14—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with hydrogen or carbon atoms directly attached to at least one ring carbon atom
- C07D251/16—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with hydrogen or carbon atoms directly attached to at least one ring carbon atom to only one ring carbon atom
Abstract
The invention discloses a research method for green synthesis of herbicide prosulfuron for removing gramineous weeds and broad-leaved weeds. The synthesis method comprises steps of firstly synthesizing 2-(3,3,3-trifluoro-1-propenyl)-benzenesulfonic acid from o-aminobenzenesulfonic acid and 3,3,3-trifluoro-1-propylene, then implementing hydrogenation reduction to generated 2-(3,3,3-trifluoro-1-propenyl)-benzene sulfonate under palladium catalysis to obtain 2-(3,3,3-trifluoro propyl)-benzenesulfonic acid, and reacting with phosgene and ammonia gas to obtain 2-(3,3,3-trifluoro propyl)-benzene sulfonamide; and finally reacting with dimethyl carbonate, 2-amine-4-methoxy-6-methyl-1,3,5-triazine, thus generating prosulfuron. The research method disclosed by the invention is a relatively effective method for synthesizing prosulfuron; and by replacing phosgene through dimethyl carbonate at the last step, the method has the advantages of relatively low toxicity, being green and environment-friendly, etc.
Description
Technical field
The present invention relates to a kind of synthesis technique of sulfonylurea herbicide prosulfuron, belong to a kind of synthesis technique removing gramineous weeds and broadleaved herb agent.
Background technology
Prosulfuron is a kind of sulfonylurea herbicide of efficient, low toxicity, acts on gramineous weeds and the broadleaved herb of corn field.Prosulfuron consumption is 27 ~ 40g a.i/hm
2, consumption is few, is called as highy potent herbicide, and efficiency is 100-1000 times of traditional weedicide.3 ~ 5 leaf phases after maize seedling, broadleaved herb 2 ~ 4 leaf phase pesticide supplying effect are best, before dispenser 10d, be 5 can not use organic phosphorous insecticide after wanting.Prosulfuron is by suppressing weeds lactic acid synthetic enzyme, acetic acid hydroxy acid synthetic enzyme, stop branched-chain amino acid as the biosynthesizing of leucine, α-amino-isovaleric acid, destroy the synthesis of protein, interference DNA synthesis and cell fission and growth, finally cause weeds dead, owing to lacking the biosynthetic pathway of the branched-chain amino acids such as leucine, α-amino-isovaleric acid, Isoleucine in animal body, sulfonylurea herbicide is to suppress this type of amino acid whose biosynthetic weedicide, high to the security of animal.
Existing prosulfuron synthetic method mainly phosgenation:
The method final step uses phosgene, because phosgene gas is a kind of colourless hypertoxic gas, has strong impulse smell or stinkpot.Easily cause intoxicating phenomenon, although often have to phosgene as raw material in the industry, the severe toxicity of phosgene and highly corrosive by product make it face huge environmental protection pressure, a kind of to the extremely disagreeableness compound of environment, also can damage operative employee.So our selection methylcarbonate replaces phosgene and becomes except gramineous weeds and broadleaved herb agent prosulfuron.
The object of the invention is to provide a kind of toxicity less, the environment amenable synthesis technique removing gramineous weeds and broadleaved herb agent prosulfuron.Because methylcarbonate is a kind of important organic chemical industry's intermediate, containing carbonyl, methyl, methoxyl group and carbomethoxy in its molecule, thus the organic synthesis such as carbonylation can be widely used in.Poisonous phosgene etc. can be replaced to use as carbonyl agent, and form carbonyl compound, byproduct is methyl alcohol, can improve the security of production operation, reduces environmental pollution." new foundation stone " that current methylcarbonate is considered to organic synthesis has vast potential for future development.
Summary of the invention
The present invention is directed to above-mentioned phosgene is the disagreeableness gas of a kind of environment, uses methylcarbonate instead and originates as carbonyl.Object is to provide a kind of toxicity less, the environment amenable synthesis technique removing gramineous weeds and broadleaved herb agent prosulfuron.
The technical solution used in the present invention is for this reason: 1) first is Material synthesis 2-(3 with ORTHO AMINO PHENOL SULPHONIC and the fluoro-1-propylene of 3,3,3-tri-, 3,3 ,-three fluoro-1-propenyl)-Phenylsulfonic acid,
2) then by fluoro-for generated 2-(3,3,3-tri-1-propenyl)-Phenylsulfonic acid hydrogenating reduction under palladium chtalyst is 2-(3,3,3-trifluoro propyl)-Phenylsulfonic acid,
3) 2-(3 that will generate, 3,3-trifluoro propyl)-Phenylsulfonic acid photoreactive gas, ammonia is anti-, DMF should generate 2-(3,3,3-trifluoro propyl)-Ben sulphonamide
4) 2-(3 that finally will generate, 3,3-trifluoro propyl)-Ben sulphonamide and methylcarbonate, 2-amine-4-methoxyl group-6-methyl isophthalic acid, 3,5-triazine is reacted, and finally generates prosulfuron.
[synthesis 2-(3,3,3 ,-three fluoro-1-propenyl)-Phenylsulfonic acid, with pd(dba)
2for catalyzer, amyl nitrite, sodium-acetate is that reactant is to carry out in the solvent of water, amylalcohol composition.The ratio of its each material is the mol ratio of ORTHO AMINO PHENOL SULPHONIC and sodium-acetate is 1:2 ~ 4, the mol ratio of ORTHO AMINO PHENOL SULPHONIC and amyl nitrite is 1:1 ~ 3, ORTHO AMINO PHENOL SULPHONIC and 3,3, the mol ratio of the fluoro-1-propylene of 3-tri-is 1:1 ~ 2, temperature of reaction is 15 DEG C-30 DEG C, makees solvent with the water of 10%.
Preparation 2-(3,3,3-trifluoro propyl)-Phenylsulfonic acid, with the solution of isopropyl alcohol and water composition for solvent, 2-(3,3,3 ,-three fluoro-1-propenyl) mol ratio of-Phenylsulfonic acid and carbon is 10:1 ~ 3, logical hydrogen 4 ~ 8 hours, temperature of reaction is 35 ~ 40 DEG C, logical hydrogen under 1 ~ 2bar air pressure.
Preparation 2-(3,3,3-trifluoro propyl)-Ben sulphonamide, with chlorobenzene and water for solvent, 2-(3,3,3-trifluoro propyl) mol ratio of-Phenylsulfonic acid photoreactive gas is 1:2 ~ 4, the mol ratio of phosgene and DMF is 1:0.05 ~ 0.15, temperature of reaction is 85 DEG C ~ 105 DEG C, at least 5 hours reaction times.The ammonia soln of 30%, 2-(3,3,3-trifluoro propyl) mol ratio of-Phenylsulfonic acid and ammonia is 1:3 ~ 8, temperature of reaction is 60 DEG C ~ 70 DEG C, and the reaction times is more than 0.5h.Then continue to stir at least 2h.
Preparing prosulfuron, take water as solvent, 2-amine-4-methoxyl group-6-methyl isophthalic acid, and the mol ratio of 3,5-triazine and sodium methylate is 1:1 ~ 2, and 2-amine-4-methoxyl group-6-methyl isophthalic acid, the mol ratio of 3,5-triazine and methylcarbonate is 1:1 ~ 2, adds a certain amount of hydrochloric acid.Then 2-(3 is being added, 3,3-trifluoro propyl) mixture of-benzsulfamide and acetonitrile, 2-(3,3,3-trifluoro propyl)-benzsulfamide and 2-amine-4-methoxyl group-6-methyl isophthalic acid, the mol ratio of 3,5-triazine is 1:1 ~ 2, add a certain amount of DBU, mix, at room temperature stir 1.5 ~ 3h.
Advantage of the present invention is: the present invention by reasonable selection to raw material, the conservative control of each parameter, define one of synthesis prosulfuron comparatively effectively, the synthetic method of little, the environmental protection of toxicity.
Embodiment
Embodiment 1
(1) get the round-bottomed flask that 250mL is clean, under being placed in low temperature, temperature controls at 15 DEG C ~ 20 DEG C, add 100mL amylalcohol and 10mL water, add 9.35g ORTHO AMINO PHENOL SULPHONIC 6.14g amyl nitrite, add acetic anhydride and 12.3g sodium-acetate, stir 90min at 20 ~ 30 DEG C.Then add the palladium catalyst of 1%, then add the fluoro-1-propylene of 4.8g 3,3,3-tri-, continue to stir 5h, until raw material reaction is complete, products obtained therefrom carries out hydrogenation.
(2) the Schlenk pipe getting 50mL is placed in the oil bath pan of 35 DEG C ~ 40 DEG C, add the solution of the first step, add 0.6g carbon, control Schlenk overpressure is the air pressure of 1 ~ 2bar, passes into hydrogen 6 hours, after reaction terminates, suspended matter is filtered, and in order to remove sodium-acetate and byproduct, washes amyl alcohol solution with water and NaOH, amylalcohol part is distilled, and adds water and makes amylalcohol by component distillation.Obtain product solution in water, for next step.
(3) get 250mL round-bottomed flask, add second aqueous solution, water is distilled removing, adds chlorobenzene and water is removed by component distillation.Add 12.4g phosgene, control oil bath temperature at 85 ~ 105 DEG C.Add 0.9g DMF, react temperature after 5 hours and be down to 60 DEG C.In 1 hour, add the ammonia solution of 11.3g 30%, then continue to stir 2h.Throw out is leached after cooling.
(4) get 250mL round-bottomed flask, add 7g 2-amine-4-methoxyl group-6-methyl isophthalic acid, 3,5-triazine, 2.7g sodium methylate and 6.75g methylcarbonate, 100mL water, as solvent, adds appropriate hydrochloric acid.Stirring at room temperature aftertreatment in 3 hours obtains product.Getting 250mL round-bottomed flask, add the 2-(3 of 0.02mol the said products and 0.02mol, 3,3-trifluoro propyl)-benzsulfamide, add the acetonitrile of 100mL drying, add 1, the 8-diazabicylo [5.4.0] 11 carbon-7-alkene (DBU) of 3mL at room temperature 1 minute, at room temperature stir 1.5 hours.Then dilute with the hydrochloric acid soln of 40mL water and 5%, wash rear collecting by filtration product with water and ether, dry, obtain prosulfuron finished product.
Embodiment 2
(1) get the round-bottomed flask that 500mL is clean, under being placed in low temperature, temperature controls at 15 DEG C ~ 20 DEG C, add 200mL amylalcohol and 20mL water, add 18.7g ORTHO AMINO PHENOL SULPHONIC 12.28g amyl nitrite, add acetic anhydride and 24.6g sodium-acetate, stir 90min at 20 ~ 30 DEG C.Then add the palladium catalyst of 1%, then add the fluoro-1-propylene of 9.6g 3,3,3-tri-, continue to stir 5h, until raw material reaction is complete, products obtained therefrom carries out hydrogenation.
(2) the Schlenk pipe getting 100mL is placed in the oil bath pan of 35 DEG C ~ 40 DEG C, add the solution of the first step, add 1.2g carbon, control Schlenk overpressure is the air pressure of 1 ~ 2bar, passes into hydrogen 6 hours, after reaction terminates, suspended matter is filtered, and in order to remove sodium-acetate and byproduct, washes amyl alcohol solution with water and NaOH, amylalcohol part is distilled, and adds water and makes amylalcohol by component distillation.Obtain product solution in water, for next step.
(3) get 500mL round-bottomed flask, add second aqueous solution, water is distilled removing, adds chlorobenzene and water is removed by component distillation.Add 24.8g phosgene, control oil bath temperature at 85 ~ 105 DEG C.Add 1.8g DMF, react temperature after 5 hours and be down to 60 DEG C.In 1 hour, add the ammonia solution of 22.6g 30%, then continue to stir 2h.Throw out is leached after cooling.
(4) get 500mL round-bottomed flask, add 14g 2-amine-4-methoxyl group-6-methyl isophthalic acid, 3,5-triazine, 5.4g sodium methylate and 13.5g methylcarbonate, 200mL water, as solvent, adds appropriate hydrochloric acid.Stirring at room temperature aftertreatment in 3 hours obtains product.Getting 500mL round-bottomed flask, add the 2-(3 of 0.04mol the said products and 0.04mol, 3,3-trifluoro propyl)-benzsulfamide, add the acetonitrile of 200mL drying, add 1, the 8-diazabicylo [5.4.0] 11 carbon-7-alkene (DBU) of 6mL at room temperature 1 minute, at room temperature stir 1.5 hours.Then dilute with the hydrochloric acid soln of 80mL water and 5%, wash rear collecting by filtration product with water and ether, dry, obtain prosulfuron finished product.
Claims (5)
1., except the synthesis technique of gramineous weeds and broadleaved herb agent prosulfuron, it is characterized in that, 1) be first Material synthesis 2-(3,3,3 ,-three fluoro-1-propenyl)-Phenylsulfonic acid with ORTHO AMINO PHENOL SULPHONIC and the fluoro-1-propylene of 3,3,3-tri-,
2) be then 2-(3,3,3-trifluoro propyl)-Phenylsulfonic acid by generated 2-(the fluoro-1-propenyl of 3,3,3-tri-)-Phenylsulfonic acid hydrogenating reduction under palladium chtalyst,
3) by 2-(3,3,3-the trifluoro propyl)-Phenylsulfonic acid photoreactive gas of generation, ammonia instead, DMF should generate 2-(3,3,3-trifluoro propyl)-Ben sulphonamide,
4) finally by 2-(3,3,3-the trifluoro propyl)-Ben sulphonamide of generation and methylcarbonate, 2-amine-4-methoxyl group-6-methyl isophthalic acid, 3,5-triazine is reacted, and finally generates prosulfuron
2. the synthesis technique of prosulfuron according to claim 1, is characterized in that synthesizing 2-(3,3,3 ,-three fluoro-1-propenyl)-Phenylsulfonic acid, with pd (dba)
2for catalyzer, amyl nitrite, sodium-acetate is that reactant is to carry out in the solvent of water, amylalcohol composition, the ratio of its each material is the mol ratio of ORTHO AMINO PHENOL SULPHONIC and sodium-acetate is 1: 2 ~ 4, and the mol ratio of ORTHO AMINO PHENOL SULPHONIC and amyl nitrite is 1: 1 ~ 3, ORTHO AMINO PHENOL SULPHONIC and 3,3, the mol ratio of the fluoro-1-propylene of 3-tri-is 1: 1 ~ 2, and temperature of reaction is 15 DEG C-30 DEG C, makees solvent with the water of 10%.
3. the synthesis technique removing gramineous weeds and broadleaved herb agent prosulfuron according to claim 1, it is characterized in that preparing 2-(3,3,3-trifluoro propyl)-Phenylsulfonic acid, with the solution of isopropyl alcohol and water composition for solvent, 2-(3,3,3,-three fluoro-1-propenyl) mol ratio of-Phenylsulfonic acid and carbon is 10: 1 ~ 3, logical hydrogen 4 ~ 8 hours, temperature of reaction is 35 ~ 40 DEG C, logical hydrogen under 1 ~ 2bar air pressure.
4. the synthesis technique removing gramineous weeds and broadleaved herb agent prosulfuron according to claim 1, it is characterized in that preparing 2-(3, 3, 3-trifluoro propyl)-Ben sulphonamide, with chlorobenzene and water for solvent, 2-(3, 3, 3-trifluoro propyl) mol ratio of-Phenylsulfonic acid photoreactive gas is 1: 2 ~ 4, phosgene and N, the mol ratio of dinethylformamide is 1: 0.05 ~ 0.15, temperature of reaction is 85 DEG C ~ 105 DEG C, at least 5 hours reaction times, the ammonia soln of 30%, 2-(3, 3, 3-trifluoro propyl) mol ratio of-Phenylsulfonic acid and ammonia is 1: 3 ~ 8, temperature of reaction is 60 DEG C ~ 70 DEG C, reaction times is more than 0.5h, then continue to stir at least 2h.
5. the synthesis technique removing gramineous weeds and broadleaved herb agent prosulfuron according to claim 1, it is characterized in that preparing prosulfuron, take water as solvent, 2-amine-4-methoxyl group-6-methyl isophthalic acid, 3, the mol ratio of 5-triazine and sodium methylate is 1: 1.5, 2-amine-4-methoxyl group-6-methyl isophthalic acid, 3, the mol ratio of 5-triazine and methylcarbonate is 1: 1 ~ 2, add a certain amount of hydrochloric acid, then 2-(3 is being added, 3, 3-trifluoro propyl) mixture of-Ben sulphonamide and acetonitrile, 2-(3, 3, 3-trifluoro propyl)-Ben sulphonamide and 2-amine-4-methoxyl group-6-methyl isophthalic acid, 3, the mol ratio of 5-triazine is 1: 1 ~ 2, add a certain amount of DBU, mix, at room temperature stir 1.5h.
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| CN201310346067.6A CN104341366A (en) | 2013-08-10 | 2013-08-10 | Synthesis process of herbicide prosulfuron for removing gramineous weeds and broad-leaved weeds |
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| CN201310346067.6A CN104341366A (en) | 2013-08-10 | 2013-08-10 | Synthesis process of herbicide prosulfuron for removing gramineous weeds and broad-leaved weeds |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| RU2815938C1 (en) * | 2023-08-16 | 2024-03-25 | Акционерное общество "Щелково Агрохим" | Method of producing sulphonylurea herbicides containing a 4-methoxy-6-methyl-1,3,5-triazine fragment |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1083480A (en) * | 1992-08-18 | 1994-03-09 | 希巴-盖吉股份公司 | The preparation method of substituted benzene or Phenylsulfonic acid and derivative thereof and N, the preparation method of N '-replacement urea |
| US5508402A (en) * | 1992-08-18 | 1996-04-16 | Ciba-Geigy Corporation | Process for the preparation of N,N'-substituted ureas |
-
2013
- 2013-08-10 CN CN201310346067.6A patent/CN104341366A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1083480A (en) * | 1992-08-18 | 1994-03-09 | 希巴-盖吉股份公司 | The preparation method of substituted benzene or Phenylsulfonic acid and derivative thereof and N, the preparation method of N '-replacement urea |
| US5508402A (en) * | 1992-08-18 | 1996-04-16 | Ciba-Geigy Corporation | Process for the preparation of N,N'-substituted ureas |
Non-Patent Citations (2)
| Title |
|---|
| 何良年: "碳酸二甲酯在农药与医药合成工艺绿色化中的应用", 《华中师范大学学报（自然科学版）》, vol. 39, no. 4, 31 December 2005 (2005-12-31), pages 495 - 499 * |
| 潘鹤林等: "未来碳酸二甲醋替代光气在农药工业上的应用", 《化学推进剂与高分子材料》, no. 68, 31 December 1999 (1999-12-31), pages 5 - 10 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| RU2815938C1 (en) * | 2023-08-16 | 2024-03-25 | Акционерное общество "Щелково Агрохим" | Method of producing sulphonylurea herbicides containing a 4-methoxy-6-methyl-1,3,5-triazine fragment |
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