CN102786547B - Process for synthesizing glyphosine - Google Patents
Process for synthesizing glyphosine Download PDFInfo
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- CN102786547B CN102786547B CN201210312557.XA CN201210312557A CN102786547B CN 102786547 B CN102786547 B CN 102786547B CN 201210312557 A CN201210312557 A CN 201210312557A CN 102786547 B CN102786547 B CN 102786547B
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- 0 *CP(CNCP(*)(O*)=O)CO Chemical compound *CP(CNCP(*)(O*)=O)CO 0.000 description 3
- WOAWYKPABZNBBV-UHFFFAOYSA-N OCN(CC(O)=O)CO Chemical compound OCN(CC(O)=O)CO WOAWYKPABZNBBV-UHFFFAOYSA-N 0.000 description 1
Abstract
The invention relates to the field of chemical synthesis and discloses a process for synthesizing glyphosine. The process comprises the steps of Step 1, subjecting glycine and formaldehyde to an oxidation reaction to generate a compound represented as formula I; Step 2, subjecting the compound represented as formula I and a compound represented as formula II to a mannich reaction to generate a compound represented as formula III; and Step 3, subjecting the compound represented as formula III to a hydrolysis reaction on the highly acidic condition to generate the glyphosine. According to the process, by the aid of reactions between the glycine and the formaldehyde and dialkyl phosphate, the glyphosine is obtained through hydrolysis on the acidic condition, the process is high in conversion ratio of the dialkyl phosphate, and the yield and the purity of final products of the glyphosine are improved.
Description
Technical field
The present invention relates to the field of chemical synthesis, be specifically related to a kind ofly synthesize the method increasing sweet phosphine.
Background technology
Increase sweet phosphine, chemistry N by name, two (phosphonomethyl) glycine of N-, it is a kind of organic phosphine acids plant-growth regulator, absorbed by cauline leaf, be mainly used in sugarcane, improve sugared part content wherein and as ripener, beet and watermelon can also be used for as sugar enriching agent and increasing agent, also can promote the separation of cotton leaf.Increase sweet phosphine not only can improve sugar early stage content at harvesting sugarcane, the phase also can make sucrose content maintain higher level after harvesting, also makes reducing sugar and nonsugar decline simultaneously.Increase sweet phosphine to promote sugar industry output, reduce costs, improve plant factor and labour productivity has significant economic benefit.
The sweet phosphine synthetic method of increasing generally adopted at present be phosphorous acid or phosphorus trichloride directly and the one-step synthesis of glycine and formaldehyde reaction.But the yield of this method is not high, is only 60-70%, this reaction system by product is more simultaneously, and the purity of products therefrom after crystallization is about 90%.
Therefore, provide a kind of and can improve yield, development that the sweet phosphine synthetic method of increasing of purity is conducive to agricultural and promote the economic benefit of sugar industry.
Summary of the invention
In view of this, the object of the present invention is to provide and a kind ofly synthesize the method increasing sweet phosphine, make the method for the invention can improve its yield and purity.
For achieving the above object, the invention provides following technical scheme:
Synthesize the method increasing sweet phosphine, comprise the following steps:
Step 1, glycine and formaldehyde carry out oxidizing reaction, compound shown in production I;
Shown in step 2, formula I, shown in compound and formula II, compound carries out class Mannich reaction, compound shown in production III;
Compound shown in step 3, formula III is hydrolyzed reaction in acid condition, generates and increases sweet phosphine;
Wherein, R
1for alkyl, as preferably, R
1for methyl or ethyl.Shown in formula II of the present invention, compound Chinese named is dialkyl phosphite, works as R
1when being preferably methyl or ethyl, it corresponds to dimethylphosphite or diethyl phosphite.
In the oxidizing reaction of step 1, the present invention can select to add concentrated hydrochloric acid and carry out catalysis, also can not add concentrated hydrochloric acid and react, this for resultant without impact.During oxidizing reaction, by formaldehyde, two H that glycine is directly connected with N are oxidized, generate hydroxyl, compound shown in production I, wherein, volatilizees for preventing formaldehyde high temperature, cause raw material glycine reactant incomplete, residual in thick product, affect thick product purity, temperature of reaction is preferably 0-90 DEG C, more preferably 0-25 DEG C, is more preferably 0 DEG C, and the mol ratio of described glycine and formaldehyde is preferably 1:2-2.5, be more preferably 1:2, reaction formula is as follows:
In the class Mannich reaction of step 2, there is condensation reaction in the H in compound shown in the hydroxyl in compound shown in formula I and formula II, compound shown in production III, this reaction is similar to Mannich reaction, therefore being called class Mannich reaction, the temperature of this step reaction is preferably 60-95 DEG C, is more preferably 90 DEG C, shown in described formula I, shown in compound and formula II, the mol ratio of compound is preferably 1:2, and reaction formula is as follows:
Wherein, R
1for alkyl, as preferably, R
1for methyl or ethyl.
In hydrolysis reaction described in step 3, the phosphide part in compound shown in formula III is hydrolyzed under strongly acidic conditions, replaces R with H
1generate hydroxyl, final generation increases sweet phosphine, and described strong acidic condition realizes preferably by adding concentrated hydrochloric acid, also reaches by other conventional inorganic acids.Reaction formula is as follows:
Wherein, R
1for alkyl, as preferably, R
1for methyl or ethyl.
The sweet phosphine of the increasing utilizing the method for the invention to prepare, after testing, its yield is between 70-80%, crude product purity reaches about 90%, relative to after the yield of existing preparation method 60-70% and recrystallization about 90% purity, the method for the invention is more suitable for being applied in the preparation process increasing sweet phosphine.
From above technical scheme, the present invention is reacted by glycine and formaldehyde and dialkyl phosphite, then obtain increasing sweet phosphine by hydrolysis in acid condition, the method dialkyl phosphite transformation efficiency is high, makes final product increase the yield of sweet phosphine and purity is all improved.
Embodiment
The invention discloses and a kind ofly synthesize the method increasing sweet phosphine, those skilled in the art can use for reference present disclosure, and suitable improving technique parameter realizes.Special needs to be pointed out is, all similar replacements and change apparent to those skilled in the art, they are all deemed to be included in the present invention.Compound of the present invention and method are described by preferred embodiment, related personnel obviously can not depart from content of the present invention, spirit and scope compound as herein described and preparation method are changed or suitably change with combination, realize and apply the technology of the present invention.
Below in conjunction with embodiment, set forth the present invention further.
Embodiment 1: the method for the invention preparation increases sweet phosphine
By glycine 3.75g(0.05mol) be dissolved in 50ml water, the formalin 8.6g(0.1mol that percent by volume is 37% is added) under ice bath, react 3 hours under room temperature, add dimethylphosphite 11g(0.1mol), react 3 hours at 90 DEG C, this reaction solution of concentrating under reduced pressure obtains viscous liquid subsequently, then add concentrated hydrochloric acid 35ml, be warming up to 120 DEG C of back hydrolysis 5 hours, stopped reaction, concentrating under reduced pressure reaction system again, vaccum dewatering obtains sticky mass, gained sticky mass is and increases sweet phosphine, after testing, yield is 79%, purity is 91%.Reaction formula is as follows:
The above-mentioned sticky mass heavy water that takes a morsel dissolves, and carries out magnetic resonance detection, and its structure is consistent with the sweet phosphine structure of increasing, and nuclear magnetic resonance result is as follows:
1H-NMR(D
2O,600MHz)δ:3.45(d,J=12.6Hz,4H),4.17(s,2H);
Embodiment 2: the method for the invention preparation increases sweet phosphine
0.05mol glycine is dissolved in 50ml water, the formalin (amount of substance of formaldehyde is 0.125mol) that percent by volume is 37% is added at 25 DEG C, react 3 hours under room temperature, add 0.1mol diethyl phosphite, react 3 hours at 60 DEG C, this reaction solution of concentrating under reduced pressure obtains viscous liquid subsequently, then add vitriol oil 35ml, be warming up to 120 DEG C of back hydrolysis 5 hours, stopped reaction, concentrating under reduced pressure reaction system again, vaccum dewatering obtains sticky mass, and gained sticky mass is and increases sweet phosphine, after testing, yield is 73%, and purity is 89%.Reaction formula is as follows:
The above-mentioned sticky mass heavy water that takes a morsel dissolves, and carry out magnetic resonance detection, detected result is identical with embodiment 1, and its structure is consistent with the sweet phosphine structure of increasing.
Embodiment 3: the method for the invention preparation increases sweet phosphine
By glycine 3.75g(0.05mol) be dissolved in 50ml water, the formalin 8.6g(0.1mol that percent by volume is 37% is added at 90 DEG C) and concentrated hydrochloric acid 1g(0.01mol), react 3 hours under room temperature, add dimethylphosphite 11g(0.1mol), react 3 hours at 95 DEG C, this reaction solution of concentrating under reduced pressure obtains viscous liquid subsequently, then add concentrated hydrochloric acid 35ml, be warming up to 120 DEG C of back hydrolysis 5 hours, stopped reaction, concentrating under reduced pressure reaction system again, vaccum dewatering obtains sticky mass, gained sticky mass is and increases sweet phosphine, after testing, yield is 76%, purity is 90%.Reaction formula is as follows:
The above-mentioned sticky mass heavy water that takes a morsel dissolves, and carry out magnetic resonance detection, detected result is identical with embodiment 1, and its structure is consistent with the sweet phosphine structure of increasing.
The above is only the preferred embodiment of the present invention; it should be pointed out that for those skilled in the art, under the premise without departing from the principles of the invention; can also make some improvements and modifications, these improvements and modifications also should be considered as protection scope of the present invention.
Claims (10)
1. synthesize the method increasing sweet phosphine, it is characterized in that, comprise the following steps:
Step 1, glycine and formaldehyde carry out oxidizing reaction, compound shown in production I;
Shown in step 2, formula I, compound and dialkyl phosphite carry out class Mannich reaction, compound shown in production III;
Compound shown in step 3, formula III is hydrolyzed reaction under strongly acidic conditions, generates and increases sweet phosphine;
Wherein, R
1for alkyl.
2. method according to claim 1, it is characterized in that, described dialkyl phosphite is dimethylphosphite or diethyl phosphite.
3. method according to claim 1, is characterized in that, step 1 is also included in and adds concentrated hydrochloric acid when carrying out oxidizing reaction and carry out catalytic step.
4. method according to claim 1, it is characterized in that, the mol ratio of described glycine and formaldehyde is 1:2-2.5.
5. method according to claim 1, it is characterized in that, the temperature of described oxidizing reaction is 0-90 DEG C.
6. method according to claim 5, it is characterized in that, the temperature of described oxidizing reaction is 0-25 DEG C.
7. method according to claim 1, it is characterized in that, shown in described formula I, the mol ratio of compound and dialkyl phosphite is 1:2.
8. method according to claim 1, it is characterized in that, the temperature of described class Mannich reaction is 60-95 DEG C.
9. method according to claim 8, it is characterized in that, the temperature of described class Mannich reaction is 90 DEG C.
10. method according to claim 1, is characterized in that, described strong acidic condition realizes by adding concentrated hydrochloric acid.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210312557.XA CN102786547B (en) | 2012-08-29 | 2012-08-29 | Process for synthesizing glyphosine |
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|---|---|---|---|
| CN201210312557.XA CN102786547B (en) | 2012-08-29 | 2012-08-29 | Process for synthesizing glyphosine |
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| CN102786547A CN102786547A (en) | 2012-11-21 |
| CN102786547B true CN102786547B (en) | 2015-05-20 |
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| CN110463717B (en) * | 2019-09-02 | 2020-10-23 | 中国农业科学院棉花研究所 | Cotton defoliation ripening composition and cotton defoliation ripening agent |
| CN112279995B (en) * | 2020-11-09 | 2022-03-15 | 山东省海洋化工科学研究院 | Intrinsic flame-retardant waterborne polyurethane and preparation method thereof |
| CN113024599A (en) * | 2021-03-11 | 2021-06-25 | 廊坊师范学院 | Preparation process of glycine dimethylidene phosphonic acid |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5041628A (en) * | 1989-06-15 | 1991-08-20 | Finchimica S.P.A. | Method for the preparation of N-phosphonomethyl glycine |
| CN101591352A (en) * | 2008-05-28 | 2009-12-02 | 北京紫光英力化工技术有限公司 | Novel process for preparing glyphosate by glycin method |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6054608A (en) * | 1997-05-05 | 2000-04-25 | Monsanto Company | Method for preparing formylphosphonic acid |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5041628A (en) * | 1989-06-15 | 1991-08-20 | Finchimica S.P.A. | Method for the preparation of N-phosphonomethyl glycine |
| CN101591352A (en) * | 2008-05-28 | 2009-12-02 | 北京紫光英力化工技术有限公司 | Novel process for preparing glyphosate by glycin method |
Non-Patent Citations (1)
| Title |
|---|
| Manich反应及其应用;朱如麟;《赣南师范学院学报》;19841231;第27—34页 * |
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