CN102584893A - Preparation method for glufosinate - Google Patents

Preparation method for glufosinate Download PDF

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CN102584893A
CN102584893A CN2012100258156A CN201210025815A CN102584893A CN 102584893 A CN102584893 A CN 102584893A CN 2012100258156 A CN2012100258156 A CN 2012100258156A CN 201210025815 A CN201210025815 A CN 201210025815A CN 102584893 A CN102584893 A CN 102584893A
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CN102584893B (en
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杜晓华
李以名
徐振元
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Zhejiang University of Technology ZJUT
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Abstract

The invention relates to a new preparation method for herbicide glufosinate. The method comprises the following steps of: performing Bucherer-Bergs cyclization reaction on a methylphosphonate derivative type compound (II), ammonium carbonate and cyanide serving as raw materials to obtain a compound shown by a formula (III); and then hydrolyzing to prepare glufosinate compound shown by a formula (I). According to the preparation method, hemiacetal or acetal is used as a raw material, and the Bucherer-Bergs cyclization reaction is performed to obtain a glycolylurea derivative, so that high yield, easiness for detection and mild condition are guaranteed; and after glycolylurea is cyclihydrolyzed, a product has high purity, and ammonium salt can be removed without multiple recrystallization processes.

Description

A kind of preparation method of careless ammonium phosphine
(1) technical field
The present invention relates to the new preparation process of a kind of weedicide grass ammonium phosphine, particularly with methylphosphonate derivatives quasi-compound and volatile salt and prussiate utilize Bucherer-Bergs react cyclization again hydrolysis prepare the method for careless ammonium phosphine.
(2) technical background
Grass ammonium phosphine (glufosinate) is a kind of efficient, low toxicity, non-selective (natural disposition of going out) organic phosphates weedicide with part systemic action, and its former medicine be white to light yellow crystalline powder, and is soluble in water, is insoluble in organic solvent, and light is stablized; Facile hydrolysis in the aqueous solution of PH=5～9.Its compound method has fermentation method and chemical synthesis.
Compound I I can be made by methyl phosphonous acid diethyl ester and acrolein reaction, and reaction conditions is gentle, and yield is high.(WO?79/00405，CN?1858054A，US6359162)
Figure BDA0000134243520000011
The technology of chemical synthesis comparative maturity is to utilize Strecker reaction (US6359162) to prepare the urea anhydride compound, and hydrolysis obtains careless ammonium phosphine then.
Figure BDA0000134243520000012
This technology is raw material with methyl phosphonous acid diester, and obtains the acetal product behind the acrolein reaction, obtains urea anhydride through reactions such as prussiate, ammonium chlorides again, and hydrolysis obtains careless ammonium phosphine then.This process recovery ratio is stable, mild condition, but the ammonium chloride in the reaction brings three wastes problem bigger, ammonium chloride of sneaking in the product simultaneously and product grass ammonium phosphine separation difficulty, and it is loaded down with trivial details to remove technology, has influenced product gas purity and production cost greatly.Intermediate product cyanamide compound boiling point height does not have obvious uv-absorbing yet in addition, is difficult to follow the tracks of the detection reaction process with gc and liquid chromatography, is unfavorable for that production process carries out intermediate controlled.
Other chemical synthesis process such as high pressure catalysis are synthetic, low temperature directed synthetic, A Buzuofu is synthetic, drop cloth riel-ethyl malonate is synthetic, chirality is synthetic etc., and all there are following one or more shortcomings in method: 1) severe reaction conditions; 2) expensive raw materials; Shortcoming such as 3) reaction yield is low is not suitable for suitability for industrialized production.
(3) summary of the invention
The present invention provides the novel method of synthetic careless ammonium phosphine in view of the shortcoming of Strecker reaction existence.
The technical scheme that the present invention adopts is:
The method of the careless ammonium phosphine compound shown in a kind of preparation formula (I); Described method comprises the steps: that (1) is raw material with the methylphosphonate derivatives quasi-compound shown in the formula (II) and volatile salt and prussiate MCN, with alcohol, and water; Perhaps water is solvent with the mixed solution of alcohol, ether or ketone; Under the nitrogen protection condition, under 0～100 ℃, carry out the Bucherer-Bergs ring-closure reaction, make the compound shown in the formula (III); The mol ratio of said prussiate and methyl-phosphorous acid ester derivative is 1.0～5.0: 1, and the mol ratio of said volatile salt and methyl-phosphorous acid ester derivative is 1.0～10.0: 1; Reaction process can be followed the tracks of the feedstock conversion situation with gas phase, follows the tracks of product generation situation with liquid phase and judges reaction end; Said ring-closure reaction also can have phase-transfer catalyst in the presence of carry out;
Figure BDA0000134243520000031
In its Chinese style (II), the formula (III), R 1, R 2, R 3Independent separately be the acyl group of H, C1-C8, without replacing or through substituted C1～C8 alkyl, without replacement or through substituted benzyl or phenyl, described independently is halogen, nitro, alkylsulfonyl or cyanic acid through substituted C1～C8 alkyl or the substituting group in substituted benzyl or phenyl separately; M among the described prussiate MCN is Na, K or H.Described halogen is F -, Cl -, Br -, I -
(2) compound and the alkali heating reflux reaction 20～30h in water shown in the formula (III) that step (1) is made; It is 5～6 that reaction finishes back adding acid for adjusting pH; Filter; (refilter after perhaps revolving the steaming precipitation earlier, also can add methanol extraction earlier before filtering) regulated pH=12 with ammoniacal liquor after filtrating was revolved and steamed precipitation, concentrated back adding recrystallizing methanol and got the careless ammonium phosphine compound shown in the formula (I); Said alkali is Ba (OH) 2, NaOH, KOH or Ca (OH) 2, the feed intake ratio of molar weight of the compound shown in said alkali and the formula (III) is preferably 0.2～3: 1;
Figure BDA0000134243520000032
R among the present invention 1, R 2, R 3Independently be preferably the alkyl of C1～C8 or the acyl group of C1～C8 separately.
Preferred R 1Be the alkyl of C1～C4, R 2Be the alkyl of C1～C4 or the acyl group of C1～C4, R 3Acyl group for C1～C4.
Described alcohol is methyl alcohol, ethanol, propyl alcohol, Virahol or butanols; Described ether is ether, butyl ether or THF; Described ketone is acetone or butanone.
The preferred described solvent of the present invention is that described solvent is the mixed solution of water and alcohol, ether or ketone, and wherein the volume ratio of alcohol, ether or ketone and water is recommended as 0.2～4.0: 1, be preferably 1: 1.
The methylphosphonate derivatives quasi-compound of prussiate of the present invention and formula (II) the amount of substance ratio that feeds intake is preferably 1.0～2.0: 1; More preferably ratio is 1.2: 1; The methylphosphonate derivatives quasi-compound of described volatile salt and formula (II) the amount of substance ratio that feeds intake is preferably 2.0～5.0, and more preferably ratio is 2.5: 1.
The temperature of reaction is preferably 70 ℃ in this bright step (1).
The reaction times of step (1) is 1～48 hour, and the preferred reaction time is 3 hours.Obtain pure article after can treated (reaction finishes afterreaction liquid and concentrates through precipitation, adds ethanol again and filters desalination) after step (1) reaction finishes and carry out next step reaction, also can be not treated, directly carry out step (2) and obtain finished product.
Alkali is preferably Ba (OH) described in the step (2) 2, said Ba (OH) 2Be preferably 2: 1 with the feed intake ratio of molar weight of the compound shown in the formula (III).
Acid is HCl, H described in the step (2) 2SO 4, HNO 3Or H 3PO 4, H most preferably 2SO 4
Beneficial effect of the present invention is mainly reflected in: the present invention is a raw material with semi-acetal or acetal, obtains hydantoin deriv through Bucherer-Bergs reaction cyclization, high, the easy detection of yield, mild condition; Glycolylurea cyclizing hydrolysis after product purity is high, need not repeatedly recrystallization and removes ammonium salt.
(4) embodiment:
Following specific embodiments of the invention describes, but protection scope of the present invention is not limited to these embodiment.
The preparation of embodiment 1:5-(2-(methyl ethoxy phosphono) ethyl) glycolylurea
Figure BDA0000134243520000051
In the 500ml there-necked flask, add (3-acetoxy-3-oxyethyl group) propyl group methyl phosphinicacid ethyl ester 25.2g (0.1mol) successively; NaCN 5.9g (0.12mol); 100ml ethanol; Feed nitrogen, drip the 100ml aqueous solution that contains 21.0g (0.25mol) volatile salt behind the stirring at room 15min, be warmed up to 70 ℃ of reaction 3h.80 ℃ of condition underspins steam precipitation except that desolvating and volatile salt, get thick product 5-(2-(methyl ethoxy phosphono) ethyl) glycolylurea 24.5g, content 87.2%, yield 91.3% behind adding 100mL dissolve with ethanol, filtration, the precipitation. 1H?NMR(500MHz，DMSO)：δ：1.203-1.233(m，3H)；δ：1.409(d，J＝13.8Hz，3H)δ：1.653-1.888(m，4H)；δ：3.901-3.962(m，2H)；δ：4.081(t，J＝5.6Hz，1H)δ：7.988(s，1H)；δ：10.681(s，1H)。
The preparation of embodiment 2:5-(2-(methyl ethoxy phosphono) ethyl) glycolylurea
In the 500ml there-necked flask, add (3-acetoxy-3-oxyethyl group) propyl group methyl phosphinicacid ethyl ester 25.2g (0.1mol) successively; NaCN 5.9g (0.12mol); 100ml ethanol; Feed nitrogen, drip the 100ml aqueous solution that contains 21.0g (0.25mol) volatile salt behind the stirring at room 15min, be warmed up to 70 ℃ of reaction 1.5h.80 ℃ of condition underspins steam precipitation except that desolvating and volatile salt, get thick product 5-(2-(methyl ethoxy phosphono) ethyl) glycolylurea 23.5g, content 79.1%, yield 79.4% behind adding 100mL dissolve with ethanol, filtration, the precipitation.
The preparation of embodiment 3:5-(2-(methyl ethoxy phosphono) ethyl) glycolylurea
In the 500ml there-necked flask, add (3-acetoxy-3-oxyethyl group) propyl group methyl phosphinicacid ethyl ester 25.2g (0.1mol) successively; NaCN 5.9g (0.12mol); 100ml ethanol; Feed nitrogen, drip the 100ml aqueous solution that contains 21.0g (0.25mol) volatile salt behind the stirring at room 15min, be warmed up to 40 ℃ of reaction 3h.80 ℃ of condition underspins steam precipitation except that desolvating and volatile salt, get thick product 5-(2-(methyl ethoxy phosphono) ethyl) glycolylurea 11.5g, content 76.2%, yield 37.4% behind adding 100mL dissolve with ethanol, filtration, the precipitation.
The preparation of embodiment 4:5-(2-(methyl ethoxy phosphono) ethyl) glycolylurea
In the 500ml there-necked flask, add (3-acetoxy-3-oxyethyl group) propyl group methyl phosphinicacid ethyl ester 25.2g (0.1mol) successively; NaCN 5.9g (0.12mol); 100ml water; Feed nitrogen, drip the 100ml aqueous solution that contains 21.0g (0.25mol) volatile salt behind the stirring at room 15min, be warmed up to 70 ℃ of reaction 3h.80 ℃ of condition underspins steam precipitation except that desolvating and volatile salt, get thick product 5-(2-(methyl ethoxy phosphono) ethyl) glycolylurea 16.5g, content 85.1%, yield 60.0% behind adding 100mL dissolve with ethanol, filtration, the precipitation.
The preparation of embodiment 5:5-(2-(methyl ethoxy phosphono) ethyl) glycolylurea
In the 500ml there-necked flask, add (3-acetoxy-3-oxyethyl group) propyl group methyl phosphinicacid ethyl ester 25.2g (0.1mol) successively; NaCN 5.9g (0.12mol); 100 THFs; Feed nitrogen, drip the 100ml aqueous solution that contains 21.0g (0.25mol) volatile salt behind the stirring at room 15min, be warmed up to 70 ℃ of reaction 3h.80 ℃ of condition underspins steam precipitation except that desolvating and volatile salt, get thick product 5-(2-(methyl ethoxy phosphono) ethyl) glycolylurea 23.5g, content 87.1%, yield 87.5% behind adding 100mL dissolve with ethanol, filtration, the precipitation.
The preparation of embodiment 6:5-(2-(methyl isobutoxy phosphono) ethyl) glycolylurea
In the 500mL there-necked flask, add (3 successively; 3 '-diacetoxy) propyl group methyl phospho acid isobutylate 29.4g (0.1mol); NaCN 5.9g (0.12mol), 100mL ethanol feeds nitrogen; Drip the 100mL aqueous solution that contains 21.0g (0.25mol) volatile salt behind the stirring at room 15min, be warmed up to 70 ℃ of reaction 3h.80 ℃ of condition underspins steam precipitation except that desolvating and volatile salt, get thick product 5-(2-(methyl-isobutyl phosphono) ethyl) glycolylurea 26.8g, content 89.9%, yield 92.0% behind adding 100mL dissolve with ethanol, filtration, the precipitation.δ：0.813(d，J＝7Hz，6H)；δ：1.413(d，J＝13.6Hz，3H)δ：1.521-2.080(m，5H)；δ：3.956-4.017(m，2H)；δ：4.291(t，J＝5.8Hz，1H)δ：7.977(s，1H)；δ：10.673(s，1H)。
Embodiment 7:
In the 250mL there-necked flask, add 5-(2-(methyl ethoxy phosphono) ethyl) glycolylurea 13.4g (content 87.2%) that embodiment 1 makes (0.05mol), water 150mL, Ba (OH) 28H 2O31.5g (0.1mol), reflux 30h, adding sulfuric acid (20%, w/w) regulate pH to 6; Filter, filtrating revolve steam add behind the precipitation ammoniacal liquor (25%, w/w) regulate pH to 12; Add methyl alcohol 30mL recrystallization and get careless ammonium phosphine solid 9.7g, purity 98.1%, yield 96.0%. 1H?NMR(500MHz，，D 2O)δ：1.256(d，J＝13.5Hz，3H)；1.598(m，2H)；2.072(m，2H)；3.791(t，J＝6Hz，1H)； 31PNMR(500MHz，D 2O)δ：41.99。
Embodiment 8:
In the 250mL there-necked flask, add 5-(2-(methyl ethoxy phosphono) ethyl) glycolylurea 13.4g (content 87.2%) that embodiment 1 makes (0.05mol), water 150mL, NaOH4.0g (0.1mol), reflux 30h.Add sulfuric acid (20%) and regulate pH to 6, revolve to steam and add dissolve with methanol behind the precipitation and filter, filtrating is regulated pH to 12 with ammoniacal liquor (25%), concentrates back adding methyl alcohol 30mL recrystallization and gets careless ammonium phosphine solid 9.6g, purity 96.2%, yield 93.3%.
Embodiment 9:
In the 250mL there-necked flask, add 5-(2-(methyl isobutoxy phosphono) ethyl) glycolylurea 14.6g (content 89.9%) that embodiment 5 makes (0.05mol), water 150mL, Ba (OH) 28H 2O 31.5g (0.1mol), reflux 30h.Adding sulfuric acid (20%) is regulated pH to 6, filters, and filtrating adds ammoniacal liquor (25%) adjusting pH to 12 after revolving and steaming precipitation, adds methyl alcohol 30mL recrystallization and gets careless ammonium phosphine solid 9.7g, purity 96.6%, yield 95%.
Embodiment 10 (this example is one kettle way embodiment):
In the 500ml there-necked flask, add (3-acetoxy-3-oxyethyl group) propyl group methyl phosphinicacid ethyl ester 25.2g (0.1mol) successively; NaCN 5.9g (0.12mol); 100ml ethanol feeds nitrogen, drips the 100ml aqueous solution that contains 21.0g (0.25mol) volatile salt behind the stirring at room 15min; Be warmed up to 70 ℃ of reaction 3h and stop, adding Ba (OH) 28H 2O 31.5g (0.1mol), reflux 30h, adding sulfuric acid (20%) is regulated pH to 6, filters, and filtrating adds ammoniacal liquor (25%) adjusting pH to 12 after revolving and steaming precipitation, adds methyl alcohol 30mL recrystallization and gets careless ammonium phosphine solid 8.8g, purity 97.0%, yield 86.2%.

Claims (10)

1. method for preparing the careless ammonium phosphine compound shown in the formula (I), described method comprises the steps:
(1) be raw material with the methylphosphonate derivatives quasi-compound shown in the formula (II) and volatile salt and prussiate MCN; With alcohol; Water, perhaps water is solvent with the mixed solution of alcohol, ether or ketone, under the nitrogen protection condition; Under 0～100 ℃, carry out the Bucherer-Bergs ring-closure reaction, make the compound shown in the formula (III); The mol ratio of said prussiate and methyl-phosphorous acid ester derivative is 1.0～5.0: 1, and the mol ratio of said volatile salt and methyl-phosphorous acid ester derivative is 1.0～10.0: 1;
Figure FDA0000134243510000011
In its Chinese style (II), the formula (III), R 1, R 2, R 3Independent separately be the acyl group of H, C1～C8, without replacing or through substituted C1～C8 alkyl, without replacement or through substituted benzyl or phenyl, described independently is halogen, nitro, alkylsulfonyl or cyanic acid through substituted C1～C8 alkyl or the substituting group in substituted benzyl or phenyl separately; M among the described prussiate MCN is Na, K or H;
(2) compound and the alkali heating reflux reaction 20～30h in water shown in the formula (III) that step (1) is made; It is 5～6 that reaction finishes back adding acid for adjusting pH; Filter, filtrating is regulated pH=12 with ammoniacal liquor after revolving and steaming precipitation, adds recrystallizing methanol after concentrating and gets the careless ammonium phosphine compound shown in the formula (I); Said alkali is Ba (OH) 2, NaOH, KOH or Ca (OH) 2
Figure FDA0000134243510000012
2. the method for claim 1 is characterized in that R 1, R 2, R 3Independent separately is the alkyl of C1～C8 or the acyl group of C1～C8.
3. method as claimed in claim 2 is characterized in that R 1Be the alkyl of C1～C4, R 2Be the alkyl of C1～C4 or the acyl group of C1～C4, R 3Acyl group for C1～C4.
4. the method for claim 1, it is characterized in that: described alcohol is methyl alcohol, ethanol, propyl alcohol, Virahol or butanols; Described ether is ether, butyl ether or THF; Described ketone is acetone or butanone.
5. method as claimed in claim 4 is characterized in that described solvent is the mixed solution of water and alcohol, ether or ketone, and wherein the volume ratio of alcohol, ether or ketone and water is 0.2～4.0: 1.
6. the method for claim 1; The methylphosphonate derivatives quasi-compound that it is characterized in that prussiate and formula (II) the amount of substance ratio that feeds intake is 1.0～2.0: 1, and the methylphosphonate derivatives quasi-compound of described volatile salt and formula (II) the amount of substance ratio that feeds intake is 2.0～5.0: 1.
7. the method for claim 1 is characterized in that the temperature of ring-closure reaction in the described step (1) is 70 ℃.
8. the method for claim 1, the reaction times that it is characterized in that step (1) is 1～48 hour.
9. the method for claim 1 is characterized in that alkali described in the step (2) is Ba (OH) 2
10. the method for claim 1 is characterized in that acid described in the step (2) is HCl, H 2SO 4, HNO 3Or H 3PO 4
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Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103288874A (en) * 2013-05-15 2013-09-11 山东省农药研究所 Preparation method of glufosinate-ammonium and derivatives thereof
CN103396440A (en) * 2013-08-23 2013-11-20 重庆紫光化工股份有限公司 Preparation method of glufosinate-ammonium
CN103880786A (en) * 2014-03-18 2014-06-25 南京师范大学 Method for recovering useful constituents in mixed waste solvent during glufosinate ammonium production process
CN103965241A (en) * 2014-05-06 2014-08-06 西安近代化学研究所 Preparation method of glufosinate-ammonium
CN109776605A (en) * 2019-01-17 2019-05-21 浙江工业大学 A kind of synthetic method of glufosinate-ammonium
CN111574389A (en) * 2020-05-14 2020-08-25 河北威远生物化工有限公司 Process for preparing cis-isomers of 1-amino-4-substituted cyclohexyl carboxylic acids and salts thereof
CN111659330A (en) * 2020-04-23 2020-09-15 河北威远生物化工有限公司 Process and equipment for continuously producing glufosinate-ammonium
CN112574116A (en) * 2019-09-29 2021-03-30 利尔化学股份有限公司 Method for preparing glufosinate intermediate and analogue
CN112574118A (en) * 2019-09-29 2021-03-30 利尔化学股份有限公司 Process for preparing glufosinate-hydantoin intermediates and analogues
CN114585631A (en) * 2020-01-13 2022-06-03 利尔化学股份有限公司 Process for preparing L-glufosinate intermediates
WO2022217816A1 (en) * 2021-04-13 2022-10-20 河北威远生物化工有限公司 Method for synthesizing glufosinate
WO2022217817A1 (en) * 2021-04-13 2022-10-20 河北威远生物化工有限公司 Preparation method for glufosinate

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CN103288874A (en) * 2013-05-15 2013-09-11 山东省农药研究所 Preparation method of glufosinate-ammonium and derivatives thereof
CN103288874B (en) * 2013-05-15 2015-05-20 山东省农药科学研究院 Preparation method of glufosinate-ammonium and derivatives thereof
CN103396440B (en) * 2013-08-23 2016-03-16 重庆紫光化工股份有限公司 A kind of preparation method of careless ammonium phosphine
CN103396440A (en) * 2013-08-23 2013-11-20 重庆紫光化工股份有限公司 Preparation method of glufosinate-ammonium
CN103880786A (en) * 2014-03-18 2014-06-25 南京师范大学 Method for recovering useful constituents in mixed waste solvent during glufosinate ammonium production process
CN103880786B (en) * 2014-03-18 2015-11-18 南京师范大学 A kind of method reclaiming useful component in careless ammonium phosphine production process mixing solvent slop
CN103965241A (en) * 2014-05-06 2014-08-06 西安近代化学研究所 Preparation method of glufosinate-ammonium
CN103965241B (en) * 2014-05-06 2017-01-11 西安近代化学研究所 Preparation method of glufosinate-ammonium
CN109776605A (en) * 2019-01-17 2019-05-21 浙江工业大学 A kind of synthetic method of glufosinate-ammonium
CN109776605B (en) * 2019-01-17 2021-08-03 浙江工业大学 Synthesis method of glufosinate-ammonium
CN112574118B (en) * 2019-09-29 2023-10-31 利尔化学股份有限公司 Process for preparing glufosinate-hydantoin intermediates and analogues
CN112574116A (en) * 2019-09-29 2021-03-30 利尔化学股份有限公司 Method for preparing glufosinate intermediate and analogue
CN112574118A (en) * 2019-09-29 2021-03-30 利尔化学股份有限公司 Process for preparing glufosinate-hydantoin intermediates and analogues
CN114585631A (en) * 2020-01-13 2022-06-03 利尔化学股份有限公司 Process for preparing L-glufosinate intermediates
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
CN111659330A (en) * 2020-04-23 2020-09-15 河北威远生物化工有限公司 Process and equipment for continuously producing glufosinate-ammonium
CN111574389B (en) * 2020-05-14 2023-08-18 河北威远生物化工有限公司 Process for preparing cis-isomer of 1-amino-4-substituted cyclohexylcarboxylic acid and salts thereof
CN111574389A (en) * 2020-05-14 2020-08-25 河北威远生物化工有限公司 Process for preparing cis-isomers of 1-amino-4-substituted cyclohexyl carboxylic acids and salts thereof
WO2022217816A1 (en) * 2021-04-13 2022-10-20 河北威远生物化工有限公司 Method for synthesizing glufosinate
WO2022217817A1 (en) * 2021-04-13 2022-10-20 河北威远生物化工有限公司 Preparation method for glufosinate

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