CN102786547A - Process for synthesizing glyphosine - Google Patents
Process for synthesizing glyphosine Download PDFInfo
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- CN102786547A CN102786547A CN201210312557XA CN201210312557A CN102786547A CN 102786547 A CN102786547 A CN 102786547A CN 201210312557X A CN201210312557X A CN 201210312557XA CN 201210312557 A CN201210312557 A CN 201210312557A CN 102786547 A CN102786547 A CN 102786547A
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- sweet phosphine
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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 of synthetic method that increases sweet phosphine.
Background technology
Increase sweet phosphine, chemistry N by name, two (phosphonic acids methyl) glycocoll of N-; It is a kind of organic phosphine acids plant-growth regulator; Absorb by cauline leaf, be mainly used in sugarcane, improve wherein sugar part content and as ripener; Can also be used for beet and watermelon as sugar enriching agent and raising the output agent, also can promote the separation of cotton leaf.Increase sweet phosphine not only can improve sugar early stage at harvesting sugarcane content, also can make sucrose content maintain higher level, reducing sugar and nonsugar are descended in the results later stage.Increasing sweet phosphine promotes, reduces cost, improves plant factor and labour productivity has remarkable economic efficiency sugar industry output.
Generally adopt at present increase sweet phosphine compound method be phosphorous acid or phosphorus trichloride directly and the one-step synthesis of glycocoll and formolite reaction.But the yield of this method is not high, is merely 60-70%, and this reaction system by product is more simultaneously, products therefrom through the purity after the crystallization about 90%.
Therefore, provide a kind of and can improve the economic benefit that the sweet phosphine compound method of increasing of yield, purity helps Agricultural Development and promotes sugar industry.
Summary of the invention
In view of this, the object of the present invention is to provide a kind of synthetic method that increases sweet phosphine, make the method for the invention can improve its yield and purity.
For realizing above-mentioned purpose, the present invention provides following technical scheme:
A kind of synthetic method that increases sweet phosphine may further comprise the steps:
Step 1, glycocoll and formaldehyde carry out oxidizing reaction, compound shown in the production I;
Compound type of carrying out Mannich reaction shown in compound and the formula II shown in step 2, the formula I, compound shown in the production III;
The reaction that under acidic conditions, is hydrolyzed of compound shown in step 3, the formula III generates and increases sweet phosphine;
Wherein, R
1Be alkyl, as preferably, R
1Be methyl or ethyl.The compound Chinese named is a dialkyl phosphite shown in the formula II according to the invention, 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, and this does not have influence for resultant.During oxidizing reaction, make two H that directly link to each other on the glycocoll that oxidation take place, generate hydroxyl, compound shown in the production I with N through formaldehyde; Wherein,, cause the raw material glycine reactant incomplete for preventing the formaldehyde high temperature volatilization, residual in thick product; Influence thick product purity, temperature of reaction is preferably 0-90 ℃, further is preferably 0-25 ℃, more preferably 0 ℃; The mol ratio of said glycocoll and formaldehyde is preferably 1:2-2.5,1:2 more preferably, and reaction formula is following:
In the class Mannich reaction of step 2, condensation reaction, compound shown in the production III take place in the H shown in hydroxyl shown in the formula I in the compound and the formula II in the compound; This reaction is similar with Mannich reaction; So type of being called Mannich reaction, the temperature of this step reaction is preferably 60-95 ℃, more preferably 90 ℃; The mol ratio of compound shown in compound and the formula II is preferably 1:2 shown in the said formula I, and reaction formula is following:
Wherein, R
1Be alkyl, as preferably, R
1Be methyl or ethyl.
In the described hydrolysis reaction of step 3, the phosphide part hydrolysis under strong acidic condition shown in the formula III in the compound replaces R with H
1Generate hydroxyl, the final generation increases sweet phosphine, and said strong acidic condition is preferably realized through adding concentrated hydrochloric acid, also can reach through other inorganic acids commonly used.Reaction formula is following:
Wherein, R
1Be alkyl, as preferably, R
1Be methyl or ethyl.
Utilize the sweet phosphine that increases of the method for the invention preparation; Through detecting; Its yield is between 70-80%; Bullion purity has reached about 90%, and with respect to about 90% purity behind the yield of existing preparation method 60-70% and the recrystallization, the method for the invention is more suitable for being applied to increase in the preparation process of sweet phosphine.
Can know by above technical scheme; The present invention is through glycocoll and formaldehyde and dialkyl phosphite reaction; Obtain increasing sweet phosphine through hydrolysis under acidic conditions then, this method dialkyl phosphite transformation efficiency is high, and the yield and the purity that make final product increase sweet phosphine all are improved.
Embodiment
The invention discloses a kind of synthetic method that increases sweet phosphine, those skilled in the art can use for reference this paper content, suitably improve processing parameter and realize.Special needs to be pointed out is that all similarly replace and change apparent to those skilled in the art, they all are regarded as and are included in the present invention.Compound of the present invention and method are described through preferred embodiment; The related personnel obviously can be in not breaking away from content of the present invention, spirit and scope to compound as herein described with the preparation method changes or suitably change and combination, realize and use technology of the present invention.
Below in conjunction with embodiment, further set forth the present invention.
Embodiment 1: the method for the invention preparation increases sweet phosphine
Glycocoll 3.75g (0.05mol) is dissolved in the 50ml water, and the adding percent by volume is 37% formalin 8.6g (0.1mol) under ice bath, and reaction is 3 hours under the room temperature; Add dimethylphosphite 11g (0.1mol), 90 ℃ were reacted 3 hours down, and this reaction solution of concentrating under reduced pressure obtains viscous liquid subsequently; Then add concentrated hydrochloric acid 35ml, be warming up to 120 ℃ of back hydrolysis 5 hours, stopped reaction; Concentrating under reduced pressure reaction system once more, vaccum dewatering gets thick material, and the thick material of gained is and increases sweet phosphine; Through detecting, yield is 79%, and purity is 91%.Reaction formula is following:
The above-mentioned thick material that takes a morsel dissolves with heavy water, carries out magnetic resonance detection, and its structure is with to increase sweet phosphine structure consistent, and nuclear magnetic resonance result is following:
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
The 0.05mol glycocoll is dissolved in the 50ml water, and the adding percent by volume is 37% formalin (amount of substance of formaldehyde is 0.125mol) under 25 ℃, and reaction is 3 hours under the room temperature; Add the 0.1mol diethyl phosphite, 60 ℃ were reacted 3 hours down, and this reaction solution of concentrating under reduced pressure obtains viscous liquid subsequently; Then add vitriol oil 35ml, be warming up to 120 ℃ of back hydrolysis 5 hours, stopped reaction; Concentrating under reduced pressure reaction system once more, vaccum dewatering gets thick material, and the thick material of gained is and increases sweet phosphine; Through detecting, yield is 73%, and purity is 89%.Reaction formula is following:
The above-mentioned thick material that takes a morsel dissolves with heavy water, carries out magnetic resonance detection, and detected result is identical with embodiment 1, and its structure is with to increase sweet phosphine structure consistent.
Embodiment 3: the method for the invention preparation increases sweet phosphine
Glycocoll 3.75g (0.05mol) is dissolved in the 50ml water, and the adding percent by volume is 37% formalin 8.6g (0.1mol) and concentrated hydrochloric acid 1g (0.01mol) under 90 ℃, and reaction is 3 hours under the room temperature; Add dimethylphosphite 11g (0.1mol), 95 ℃ were reacted 3 hours down, and this reaction solution of concentrating under reduced pressure obtains viscous liquid subsequently; Then add concentrated hydrochloric acid 35ml, be warming up to 120 ℃ of back hydrolysis 5 hours, stopped reaction; Concentrating under reduced pressure reaction system once more, vaccum dewatering gets thick material, and the thick material of gained is and increases sweet phosphine; Through detecting, yield is 76%, and purity is 90%.Reaction formula is following:
The above-mentioned thick material that takes a morsel dissolves with heavy water, carries out magnetic resonance detection, and detected result is identical with embodiment 1, and its structure is with to increase sweet phosphine structure consistent.
The above only is a preferred implementation of the present invention; Should be pointed out that for those skilled in the art, under the prerequisite that does not break away from the principle of the invention; Can also make some improvement and retouching, these improvement and retouching also should be regarded as protection scope of the present invention.
Claims (10)
1. a synthetic method that increases sweet phosphine is characterized in that, may further comprise the steps:
Step 1, glycocoll and formaldehyde carry out oxidizing reaction, compound shown in the production I;
Compound type of carrying out Mannich reaction shown in compound and the formula II shown in step 2, the formula I, compound shown in the production III;
The reaction that under strong acidic condition, is hydrolyzed of compound shown in step 3, the formula III generates and increases sweet phosphine;
Wherein, R
1Be alkyl.
2. according to the said method of claim 1, it is characterized in that said R
1Be methyl or ethyl.
3. according to the said method of claim 1, it is characterized in that step 1 also is included in when carrying out oxidizing reaction and adds concentrated hydrochloric acid and carry out catalytic step.
4. according to the said method of claim 1, it is characterized in that the mol ratio of said glycocoll and formaldehyde is 1:2-2.5.
5. according to the said method of claim 1, it is characterized in that the temperature of said oxidizing reaction is 0-90 ℃.
6. according to the said method of claim 5, it is characterized in that the temperature of said oxidizing reaction is 0-25 ℃.
7. according to the said method of claim 1, it is characterized in that the mol ratio of compound shown in compound and the formula II is 1:2 shown in the said formula I.
8. according to the said method of claim 1, it is characterized in that the temperature of said type of Mannich reaction is 60-95 ℃.
9. said according to Claim 8 method is characterized in that, the temperature of said type of Mannich reaction is 90 ℃.
10. according to the said method of claim 1, it is characterized in that said strong acidic condition is realized through adding concentrated hydrochloric acid.
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| 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 true CN102786547A (en) | 2012-11-21 |
| CN102786547B CN102786547B (en) | 2015-05-20 |
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| CN201210312557.XA Active CN102786547B (en) | 2012-08-29 | 2012-08-29 | Process for synthesizing glyphosine |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110463717A (en) * | 2019-09-02 | 2019-11-19 | 中国农业科学院棉花研究所 | Cotton defoliation ripening composition and cotton defoliation ripening agent |
| CN112279995A (en) * | 2020-11-09 | 2021-01-29 | 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 (3)
| 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 |
| US20040225147A1 (en) * | 1997-05-05 | 2004-11-11 | Monsanto Company | Method for preparing formylphosphonic acid |
| 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 |
-
2012
- 2012-08-29 CN CN201210312557.XA patent/CN102786547B/en active Active
Patent Citations (3)
| 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 |
| US20040225147A1 (en) * | 1997-05-05 | 2004-11-11 | Monsanto Company | Method for preparing formylphosphonic acid |
| 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 |
|---|
| 朱如麟: "Manich反应及其应用", 《赣南师范学院学报》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110463717A (en) * | 2019-09-02 | 2019-11-19 | 中国农业科学院棉花研究所 | Cotton defoliation ripening composition and cotton defoliation ripening agent |
| CN112279995A (en) * | 2020-11-09 | 2021-01-29 | 山东省海洋化工科学研究院 | Intrinsic flame-retardant waterborne polyurethane and preparation method thereof |
| 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 |
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| CN102786547B (en) | 2015-05-20 |
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