CN110590836A - Synthesis method of glufosinate-ammonium intermediate - Google Patents
Synthesis method of glufosinate-ammonium intermediate Download PDFInfo
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- CN110590836A CN110590836A CN201910939838.XA CN201910939838A CN110590836A CN 110590836 A CN110590836 A CN 110590836A CN 201910939838 A CN201910939838 A CN 201910939838A CN 110590836 A CN110590836 A CN 110590836A
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- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic System
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/30—Phosphinic acids R2P(=O)(OH); Thiophosphinic acids, i.e. R2P(=X)(XH) (X = S, Se)
- C07F9/32—Esters thereof
- C07F9/3205—Esters thereof the acid moiety containing a substituent or a structure which is considered as characteristic
- C07F9/3211—Esters of acyclic saturated acids which can have further substituents on alkyl
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Abstract
The invention relates to a synthesis method of glufosinate-ammonium intermediate, which is used for synthesizing methyl propionaldehyde ethyl phosphate and NH4CN reacts in the presence of ammonium chloride and ammonia water to prepare glufosinate-ammonium aminonitrile as a glufosinate-ammonium intermediate. The method can effectively avoid the generation of mixed salt of ammonium chloride and sodium chloride in the traditional process, solves the problem of treating the mixed salt from the source, and can also avoid the use of expensive trimethylsilylcyanide as a cyaniding reagent.
Description
Technical Field
The invention particularly relates to a synthesis method of a glufosinate-ammonium intermediate.
Background
The glufosinate ammonium salt is developed and produced by German Hurst company in the last 80 century, and has the characteristics of high efficiency, low toxicity, easy degradation and the like besides the herbicidal activity.
Glufosinate-ammonium cyanamide is an important intermediate in the glufosinate-ammonium synthesis process, methyl phosphite and acrolein are subjected to addition reaction and then subjected to acidolysis, and then react with cyanide and ammonia/ammonium chloride to obtain intermediate glufosinate-ammonium cyanamide, the traditional cyanides are sodium cyanide and potassium cyanide, so that the problem of separation of ammonium chloride and sodium chloride or potassium chloride is faced, and CN109879910A discloses that trimethylsilyl cyanide is used as a cyaniding reagent, but the price is high, the atom economy is poor, and the industrial production is not suitable.
At present, ammonium cyanide is not reported to be used for synthesizing cyanamide as an intermediate of glufosinate-ammonium.
Disclosure of Invention
The invention aims to provide a method for synthesizing a glufosinate-ammonium intermediate with a cyanide reagent, which is cheap.
In order to solve the technical problems, the invention adopts the following technical scheme:
a synthetic method of glufosinate-ammonium intermediate, which is to make methyl propionaldehyde ethyl phosphate and NH4CN reacts in the presence of ammonium chloride and ammonia water to prepare glufosinate-ammonium aminonitrile as a glufosinate-ammonium intermediate.
The reaction equation of this step is:
preferably, said methylpropionaldehyde ethyl phosphate and said NH4The feeding molar ratio of CN is 1: 1-6, and the preferable ratio is 1: 1.5-3; more preferably 1: 1.5-2.5.
Preferably, the reaction temperature is 15-30 ℃.
Preferably, the feeding molar ratio of the methylpropionaldehyde ethyl phosphate to the ammonium chloride is 1: 1-6, further preferably 1: 1.5-3, and more preferably 1: 1.5-2.5.
Preferably, the feeding molar ratio of the methylpropionaldehyde ethyl phosphate to ammonia in the ammonia water is 1: 1-6, further preferably 1: 1.5-5.5, and more preferably 1: 1.5-4.5.
Preferably, after the reaction is finished, adding hydrochloric acid into the reaction solution, heating and refluxing, then cooling, introducing ammonia gas, filtering out ammonium chloride, adding methanol, and recrystallizing to obtain the glufosinate-ammonium aminonitrile.
Preferably, said NH4CN is fed in the form of an ammonium cyanide aqueous solution, wherein the mass content of the ammonium cyanide in the ammonium cyanide aqueous solution is 20-35%.
Preferably, said NH4The preparation method of CN comprises the following steps: mixing NaCN and ammonium bicarbonate in water, stirring and reacting at 10-20 ℃ to form sodium bicarbonate precipitate, and filtering to obtain NH4And (3) CN aqueous solution.
Preferably, the preparation method of the methyl propionaldehyde ethyl phosphate comprises the following steps: the methyl diethyl phosphite and acrolein are subjected to Michael reaction in the presence of ethanol, and then are hydrolyzed under acidic conditions to generate the methyl propionaldehyde ethyl phosphate.
The reaction equation of this step is:
further preferably, the feeding molar ratio of the diethyl methylphosphite to the acrolein is 1: 1-1.2.
Further preferably, the feeding temperature of the reaction is controlled to be 10-20 ℃, and the reaction temperature is controlled to be 20-50 ℃.
The invention takes methyl diethyl phosphite as a raw material to perform Michael reaction with acrolein to obtain intermediate acetal, the acetal is hydrolyzed under acidic condition to produce phosphor-aldehyde, and the phosphor-aldehyde is reacted in NH4And performing Strecker reaction in ammonia water solution of CN and ammonium chloride to obtain the key intermediate of glufosinate-ammonium aminonitrile. The synthetic route has the advantages of few steps, short reaction period, simple and convenient operation, cheap raw materials, reaction cost reduction, avoidance of mixed salt generation of ammonium chloride and sodium chloride, suitability for large-scale industrial production and capability of solving the problem that waste salt cannot be treated from the source.
Due to the implementation of the technical scheme, compared with the prior art, the invention has the following advantages:
the method can effectively avoid the generation of mixed salt of ammonium chloride and sodium chloride in the traditional process, solves the problem of treating the mixed salt from the source, and can also avoid the use of expensive trimethylsilylcyanide as a cyaniding reagent.
Detailed Description
The present invention will be described in further detail with reference to specific examples. It is to be understood that these embodiments are provided to illustrate the basic principles, essential features and advantages of the present invention, and the present invention is not limited by the following embodiments. The implementation conditions used in the examples can be further adjusted according to specific requirements, and the implementation conditions not indicated are generally the conditions in routine experiments. The contents are all mass contents.
Example 1
The synthesis steps of the ammonium cyanide aqueous solution are as follows: dissolving 45g of sodium cyanide in 100g of water, adding 73g of ammonium bicarbonate in batches, stirring for 1h at 10-20 ℃ after the addition is finished, and filtering out the sodium bicarbonate to obtain an ammonium cyanide aqueous solution, wherein the mass content of ammonium cyanide is about 27%.
Example 2
Adding 150ml of ethanol and diethyl methylphosphite (68g, 0.5mol) into a reaction flask in sequence, dropwise adding acrolein (28g, 0.5mol) at 15 ℃ under the protection of nitrogen, controlling the dropwise adding time to be 2h, reacting at 25 ℃ for 2-3 h after the dropwise adding is finished, and distilling under reduced pressure to obtain the residue 3- (methylethoxy) phosphoryl acetal diethanol after the reaction is finished. Dropwise adding 50g of 5% hydrochloric acid into the residue at 15 ℃, controlling the dropwise adding time to be 2h, preserving the temperature at 20 ℃ for 2h after the dropwise adding is finished, and carrying out reduced pressure distillation after the reaction is finished to obtain 78g of methyl propionaldehyde ethyl phosphate, wherein the content is 97.9%, and the yield is 93.1%.
Example 3
A reaction flask was charged with 27% aqueous ammonium cyanide solution (containing 5.26g of ammonium cyanide, 119.4mmol) prepared in example 1, ammonium chloride (6.45g, 119.4mmol) and 10g of 20% aqueous ammonia (containing NH)3119.4mmol), dropping methyl propyl aldehyde ethyl phosphate (10g, 59.7mmol) prepared in example 2 at 10 deg.C, heating to 30 deg.C after dropping, reacting for 2 hr, adding 45g 30% industrial hydrochloric acid, heating and refluxing for 1 hr, cooling, introducing ammonia, filtering to obtain ammonium chloride, adding methanolCrystallization yielded 11.6g of white glufosinate-ammonium aminonitrile as a solid with 97% content and 99.2% yield.
Example 4
A reaction flask was charged with 27% aqueous ammonium cyanide solution (containing 5.26g of ammonium cyanide, 119.4mmol), 6.45g of ammonium chloride (containing 119.4mmol) and 20g of 20% aqueous ammonia (containing NH) prepared in example 13239mmol) was added dropwise at 10 ℃ to the ethyl methyl propionaldehyde phosphate (10g, 59.7mmol) obtained in example 2, after the addition was completed, the temperature was raised to 30 ℃ for reaction for 2 hours, 80g of 30% industrial hydrochloric acid was added, the temperature was raised and the mixture was refluxed for 1 hour, the temperature was lowered and cooled, ammonia was introduced, ammonium chloride was filtered out, and methanol was added to crystallize 10.9g of white glufosinate-ammonium aminonitrile solid with a content of 97% and a yield of 93.2%.
Example 5
A reaction flask was charged with 27% aqueous ammonium cyanide solution (containing 5.26g of ammonium cyanide, 119.4mmol), 6.45g of ammonium chloride (containing 119.4mmol) and 20g of 20% aqueous ammonia (containing NH) prepared in example 13239mmol) was added dropwise at 10 ℃ to the ethyl methyl propionaldehyde phosphate prepared in example 2 (10g, 59.7mmol), after the addition was completed, the temperature was raised to 20 ℃ for reaction for 2 hours, 80g of 30% industrial hydrochloric acid was added, the temperature was raised and the mixture was refluxed for 1 hour, the temperature was lowered and cooled, ammonia was introduced, ammonium chloride was filtered out, methanol was added to crystallize 11.5g of white glufosinate-ammonium aminonitrile solid, the content was 97%, and the yield was 98.3%.
Comparative example 1
A reaction flask was charged with 27% aqueous ammonium cyanide solution (containing 5.26g of ammonium cyanide, 119.4mmol), 3.25g of ammonium chloride (59.7 mmol) and 20g of 20% aqueous ammonia (containing NH) prepared in example 13239mmol) was added dropwise to 10 ℃ the ethyl methyl malonyl phosphate (10g, 59.7mmol) obtained in example 2, after the addition was completed, the temperature was raised to 20 ℃ for reaction for 2 hours, 80g of 30% industrial hydrochloric acid was added, the mixture was heated under reflux for 1 hour, the temperature was lowered, cooling was performed, ammonia was introduced, ammonium chloride was filtered off, methanol was added to crystallize 8.4g of white glufosinate-ammonium aminonitrile solid with a content of 97% and a yield of 71.8%.
Comparative example 2
A reaction flask was charged with 30% aqueous sodium cyanide solution (19.5g, 119.4mmol), ammonium chloride (6.45g, 119.4mmol) and 20g of 20% aqueous ammonia (NH therein)3239mmol) was added dropwise at 10 ℃ to the ethyl methyl propionaldehyde phosphate prepared in example 2 (10g, 59.7mmol), after the addition was completed, the temperature was raised to 20 ℃ for reaction for 2 hours, 80g of 30% industrial hydrochloric acid was added, the temperature was raised and the mixture was refluxed for 1 hour, the temperature was lowered and cooled, ammonia was introduced, ammonium chloride was filtered out, methanol was added to crystallize to obtain 9.6g of white glufosinate ammonium aminonitrile solid, the content was 97%, and the yield was 82.1%.
Comparative example 3
A reaction flask was charged with 30% aqueous sodium cyanide solution (19.5g, 119.4mmol), ammonium chloride (6.45g, 119.4mmol) and 18g of 20% aqueous ammonia (NH therein)3215mmol) was added dropwise at 10 ℃ to the ethyl methyl malonyl phosphate prepared in example 2 (10g, 59.7mmol), after the addition was completed, the temperature was raised to 20 ℃ for reaction for 2 hours, 80g of 30% industrial hydrochloric acid was added, the mixture was heated under reflux for 1 hour, the temperature was lowered and cooled, ammonia was introduced, ammonium chloride was filtered off, and methanol was added to crystallize 10.2g of white glufosinate-ammonium aminonitrile solid with a content of 97% and a yield of 87.2%.
The above embodiments are merely illustrative of the technical concept and features of the present invention, and the purpose thereof is to enable those skilled in the art to understand the content of the present invention and implement the invention, and not to limit the scope of the invention, and all equivalent changes or modifications made according to the spirit of the present invention should be covered by the scope of the present invention.
Claims (12)
1. A synthetic method of a glufosinate-ammonium intermediate is characterized by comprising the following steps: reacting methylpropionaldehyde ethyl phosphate and NH4CN reacts in the presence of ammonium chloride and ammonia water to prepare glufosinate-ammonium aminonitrile as a glufosinate-ammonium intermediate.
2. A synthesis method of a glufosinate intermediate according to claim 1, characterized in that: the methyl propyl aldehyde ethyl phosphate and the NH4The feeding molar ratio of CN is 1: 1-6.
3. A synthesis method of a glufosinate intermediate according to claim 1, characterized in that: the reaction temperature is 15-30 ℃.
4. A synthesis method of a glufosinate intermediate according to claim 1, characterized in that: the feeding molar ratio of the methyl propyl aldehyde ethyl phosphate to the ammonium chloride is 1: 1-6.
5. The method of synthesizing a glufosinate intermediate according to claim 4, characterized in that: the feeding molar ratio of the methyl propyl aldehyde ethyl phosphate to the ammonium chloride is 1: 1.5-3.
6. A synthesis method of a glufosinate intermediate according to claim 1, characterized in that: the feeding molar ratio of the methyl propyl aldehyde ethyl phosphate to the ammonia in the ammonia water is 1: 1-6.
7. A synthesis method of a glufosinate intermediate according to claim 1, characterized in that: after the reaction is finished, adding hydrochloric acid into the reaction solution, heating up and refluxing, then cooling down, introducing ammonia gas, filtering out ammonium chloride, adding methanol and recrystallizing to obtain the glufosinate-ammonium aminonitrile.
8. A synthesis method of a glufosinate intermediate according to claim 1, characterized in that: the NH4CN is fed in the form of an ammonium cyanide aqueous solution, wherein the mass content of the ammonium cyanide in the ammonium cyanide aqueous solution is 20-35%.
9. A synthesis method of a glufosinate intermediate according to claim 1 or 8, characterized in that: the NH4The preparation method of CN comprises the following steps: mixing NaCN and ammonium bicarbonate in water, stirring and reacting at 10-20 ℃ to form sodium bicarbonate precipitate, and filtering to obtain NH4And (3) CN aqueous solution.
10. A synthesis method of a glufosinate intermediate according to claim 1, characterized in that: the preparation method of the methyl propionaldehyde ethyl phosphate comprises the following steps: the methyl diethyl phosphite and acrolein are subjected to Michael reaction in the presence of ethanol, and then are hydrolyzed under acidic conditions to generate the methyl propionaldehyde ethyl phosphate.
11. A synthesis method of a glufosinate intermediate according to claim 10, characterized in that: the feeding molar ratio of the diethyl methylphosphite to the acrolein is 1: 1-1.2.
12. A synthesis method of a glufosinate intermediate according to claim 10, characterized in that: the feeding temperature of the reaction is controlled to be 10-20 ℃, and the reaction temperature is controlled to be 20-50 ℃.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113087008A (en) * | 2021-03-31 | 2021-07-09 | 神华准能资源综合开发有限公司 | Preparation method of gallium chloride |
| WO2021212910A1 (en) * | 2020-04-23 | 2021-10-28 | 河北威远生物化工有限公司 | Process and equipment for continuously producing glufosinate-ammonium |
| CN114163472A (en) * | 2021-11-27 | 2022-03-11 | 永农生物科学有限公司 | Method for synthesizing alpha-aminonitrile under alcohol solvent, and synthesis method and product of glufosinate-ammonium |
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| CN1267305A (en) * | 1997-08-20 | 2000-09-20 | 赫彻斯特-舍林农业发展有限公司 | Method for producing glufosinates and intermediate products for same |
| CN105037060A (en) * | 2015-07-08 | 2015-11-11 | 河北威远生化农药有限公司 | Clean synthesis process of alpha-amino acid compounds |
| CN109879910A (en) * | 2018-10-22 | 2019-06-14 | 江苏长青农化股份有限公司 | A kind of preparation method of glufosinate-ammonium intermediate |
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- 2019-09-30 CN CN201910939838.XA patent/CN110590836B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1267305A (en) * | 1997-08-20 | 2000-09-20 | 赫彻斯特-舍林农业发展有限公司 | Method for producing glufosinates and intermediate products for same |
| CN105037060A (en) * | 2015-07-08 | 2015-11-11 | 河北威远生化农药有限公司 | Clean synthesis process of alpha-amino acid compounds |
| CN109879910A (en) * | 2018-10-22 | 2019-06-14 | 江苏长青农化股份有限公司 | A kind of preparation method of glufosinate-ammonium intermediate |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2021212910A1 (en) * | 2020-04-23 | 2021-10-28 | 河北威远生物化工有限公司 | Process and equipment for continuously producing glufosinate-ammonium |
| CN113087008A (en) * | 2021-03-31 | 2021-07-09 | 神华准能资源综合开发有限公司 | Preparation method of gallium chloride |
| CN114163472A (en) * | 2021-11-27 | 2022-03-11 | 永农生物科学有限公司 | Method for synthesizing alpha-aminonitrile under alcohol solvent, and synthesis method and product of glufosinate-ammonium |
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