CN110590836B - Synthetic method of glufosinate-ammonium intermediate - Google Patents
Synthetic method of glufosinate-ammonium intermediate Download PDFInfo
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- CN110590836B CN110590836B CN201910939838.XA CN201910939838A CN110590836B CN 110590836 B CN110590836 B CN 110590836B CN 201910939838 A CN201910939838 A CN 201910939838A CN 110590836 B CN110590836 B CN 110590836B
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- ammonium
- glufosinate
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- ethyl phosphate
- ammonium chloride
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- 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
Abstract
The invention relates to a synthesis method of glufosinate-ammonium intermediate, which is used for synthesizing methyl propionaldehyde ethyl phosphate and NH 4 CN reacts in the presence of ammonium chloride and ammonia water to prepare the ammonium oxalateThe phosphine intermediate glufosinate-amino nitrile. 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, no report is made on the synthesis of cyanamide as an intermediate of glufosinate-ammonium by using ammonium cyanide as a cyaniding reagent.
Disclosure of Invention
The invention aims to provide a synthetic method of a glufosinate intermediate with a cheap cyaniding reagent.
In order to solve the technical problems, the invention adopts the following technical scheme:
a synthetic method of a glufosinate-ammonium intermediate, which leads methyl propionaldehyde ethyl phosphate and NH 4 CN 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 NH 4 The 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 mol ratio of the methylpropionaldehyde ethyl phosphate to the 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 cyanamide.
Preferably, said NH 4 CN 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 NH 4 The preparation method of the CN comprises the following steps: mixing NaCN and ammonium bicarbonate in water, stirring at 10-20 ℃ for reaction to form sodium bicarbonate precipitate, and filtering to obtain NH 4 And (3) CN aqueous solution.
Preferably, the preparation method of the methyl propionaldehyde ethyl phosphate comprises the following steps: diethyl methylphosphite and acrolein are subjected to Michael reaction in the presence of ethanol and then hydrolyzed under acidic conditions to generate the ethyl methyl propionaldehyde 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 NH 4 And 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 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 68g of diethyl methylphosphite (0.5 mol) into a reaction bottle in sequence, dropwise adding acrolein (28g of 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 carrying out reduced pressure distillation after the reaction is finished to obtain the residue 3- (methylethoxy) phosphoryl acetal diethanol. 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) 3 119.4mmol), dropping 10 ℃ the methyl propionaldehyde ethyl phosphate (10g, 59.7mmol) prepared in example 2, heating to 30 ℃ after dropping, reacting for 2 hours, adding 45g of 30% industrial hydrochloric acid, heating and refluxing for 1 hour, cooling, introducing ammonia, filtering out ammonium chloride, adding methanol to crystallize to obtain 11.6g of white glufosinate-ammonium aminonitrile solid with the content of 97% and the yield of 99.2%.
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 1 3 239mmol), adding dropwise the methyl propyl aldehyde ethyl phosphate (10g, 59.7mmol) prepared in example 2 at 10 ℃, heating to 30 ℃ after the dropwise addition, reacting for 2 hours, adding 80g of 30% industrial hydrochloric acid, heating and refluxing for 1 hour, cooling, introducing ammonia, filtering out ammonium chloride, adding methanol to crystallize to obtain 10.9g of white glufosinate-ammonium aminonitrile solid with the content of 97% and the 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 1 3 Is 239mmol) of the compound, 10g of the ethyl methyl propionaldehyde phosphate (59.7 mmol) prepared in the example 2 is added dropwise at 10 ℃, after the dropwise addition, the temperature is raised to 20 ℃ for reaction for 2 hours, 80g of 30% industrial hydrochloric acid is added, the temperature is raised and the reflux is carried out for 1 hour, the temperature is reduced and the reaction is cooled, ammonia is introduced, ammonium chloride is filtered out, methanol is added for crystallization, 11.5g of white glufosinate-ammonium aminonitrile solid is obtained, the content is 97%, and the yield is 98.3%.
Comparative example 1
Into a reaction flask were charged 27% aqueous ammonium cyanide solution (containing 5.26g, 119.4mmol of ammonium cyanide) prepared in example 1, ammonium chloride (3.25g, 59.7mmol) and 20g of 20% aqueous ammonia (containing NH) 3 239mmol), adding dropwise the methyl propyl aldehyde ethyl phosphate (10g, 59.7mmol) prepared in example 2 at 10 ℃, heating to 20 ℃ after the dropwise addition, reacting for 2 hours, adding 80g of 30% industrial hydrochloric acid, heating and refluxing for 1 hour, cooling, introducing ammonia, filtering out ammonium chloride, adding methanol to crystallize to obtain 8.4g of white glufosinate-ammonium cyanamide solid with the content of 97% and the 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) 3 239mmol), adding dropwise the methyl propyl aldehyde ethyl phosphate (10g, 59.7mmol) prepared in example 2 at 10 ℃, heating to 20 ℃ after the dropwise addition, reacting for 2 hours, adding 80g of 30% industrial hydrochloric acid, heating and refluxing for 1 hour, cooling, introducing ammonia, filtering out ammonium chloride, adding methanol to crystallize to obtain 9.6g of white glufosinate-ammonium aminonitrile solid with the content of 97% and the yield of 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-among them) 3 215mmol) was added dropwise at 10 ℃ the methyl propionaldehyde ethyl phosphate (10g, 59.7mmol) obtained in example 2, after the end of the dropwise addition, 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 reflux was carried out for 1 hour, the temperature was lowered and the reaction was cooled, ammonia was introduced, ammonium chloride was filtered, 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 (6)
1. A synthetic method of a glufosinate-ammonium intermediate is characterized by comprising the following steps: preparation of NH 4 CN, mixing NaCN and ammonium bicarbonate in water, stirring and reacting at 10-20 ℃ to form sodium bicarbonate precipitate, and then filtering to obtain NH 4 CN aqueous solution; reacting methylpropionaldehyde ethyl phosphate with the NH 4 CN reacts in the presence of ammonium chloride and ammonia water to prepare a glufosinate-ammonium intermediate, wherein the feeding molar ratio of the methyl propyl aldehyde ethyl phosphate to the ammonium chloride is 1: 1.5-2.5, and the NH is 4 CN is fed in the form of an ammonium cyanide aqueous solution, wherein the mass content of ammonium cyanide in the ammonium cyanide aqueous solution is 20-35%, and the methyl propyl aldehyde ethyl phosphate and the NH are 4 The charging molar ratio of CN is 1: 1.5-2.5.
2. A synthesis method of a glufosinate intermediate according to claim 1, characterized in that: the reaction temperature is 15-30 ℃.
3. The method for synthesizing 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.
4. The method for synthesizing a glufosinate intermediate according to claim 1, characterized in that: the preparation method of the methyl propionaldehyde ethyl phosphate comprises the following steps: diethyl methylphosphite and acrolein are subjected to Michael reaction in the presence of ethanol and then hydrolyzed under acidic conditions to generate the ethyl methyl propionaldehyde phosphate.
5. The method of synthesizing a glufosinate intermediate according to claim 4, characterized in that: the feeding molar ratio of the diethyl methylphosphite to the acrolein is 1: 1-1.2.
6. The method for synthesizing a glufosinate intermediate according to claim 4, 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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| CN111659330B (en) * | 2020-04-23 | 2021-05-07 | 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 |
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 |
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| 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 |
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