Preparation method of 4-[hydroxy(methyl)phosphoryl]-2-oxobutanoic acid as glufosinate intermediate

A technology of hydroxymethyl phosphoryl and carbonyl butyric acid, which is applied in chemical instruments and methods, compounds of Group 5/15 elements of the periodic table, organic chemistry, etc., to achieve the effects of high yield and easy operation

Active Publication Date: 2016-10-12
ANHUI COSTAR BIOCHEM CO LTD
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  • Summary
  • Abstract
  • Description
  • Claims
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Problems solved by technology

But prepare 4-(hydroxymethylphosphoryl)-2-carbonylbutyric acid by cyclic phosphoric anhydride and do not see relevant patent, bibliographical report

Method used

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  • Preparation method of 4-[hydroxy(methyl)phosphoryl]-2-oxobutanoic acid as glufosinate intermediate
  • Preparation method of 4-[hydroxy(methyl)phosphoryl]-2-oxobutanoic acid as glufosinate intermediate
  • Preparation method of 4-[hydroxy(methyl)phosphoryl]-2-oxobutanoic acid as glufosinate intermediate

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Experimental program
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Effect test

Embodiment 1

[0022] Add cyclic phosphoric anhydride 5.0g (37mmol), methanol 5ml, ether 30ml, tetrabutylammonium bromide 0.25g, sodium methoxide 1.8g (37mmol), diethyl oxalate 5.4g (37mmol), -30 Stir at ℃ for 5h, warm up to room temperature, stir for 24h, filter to obtain 8.1g of white solid, yield 93.5%; take 2-[(2-methyl-2,5-dioxo-1,2-oxophosphorine Pentane)-4-yl]-2-oxoethyl acetate 4.7g (20mmol), add 20ml of water to it, slowly pass in hydrogen chloride gas, heat up to 100°C, react for 16h, rotary evaporate to remove water, vacuum dry After drying, 3.2 g of the product was obtained with a purity of 92%.

[0023] HPLC conditions: stainless steel column 125X 4.6mm, filler SB, particle size 5mm, UV detection wavelength 195nm, injection volume 20u1, column temperature 30°C, flow rate 1.3m1 / 1, eluent: 0.1mol / 1KH 2 P0 4 .

Embodiment 2

[0025] Add cyclic phosphoric anhydride 5.0g (37mmol), methanol 5ml, ether 30ml, benzyltriethylammonium chloride 0.25g, sodium methoxide 1.8g (37mmol), dimethyl oxalate 4.4g (37mmol) into a 100ml three-necked flask, Stir at -30°C for 5h, warm up to room temperature, stir for 24h, and filter to obtain 7.9g of a white solid with a yield of 97.5%; take 2-[(2-methyl-2,5-dioxo-1,2-oxophos Heterocyclopentane)-4-yl]-2-oxomethyl acetate 4.4g (20mmol), add 20ml of water to it, slowly pass in hydrogen chloride gas, heat up to 100°C, react for 16h, spin evaporate to remove water, Vacuum dried to obtain 3.4 g of the product with a purity of 94.4%.

Embodiment 3

[0027] Add cyclic phosphoric anhydride 5.0g (37mmol), methanol 5ml, ether 30ml, tetrabutylammonium chloride 0.5g, sodium methoxide 1.8g (37mmol), diethyl oxalate 5.4g (37mmol), -30 Stir at ℃ for 5h, warm up to room temperature, stir for 24h, and filter to obtain 8.2g of white solid, yield 94.7%; Pentane)-4-yl]-2-oxoethyl acetate 4.7g (20mmol), add 20ml of water to it, slowly pass in hydrogen chloride gas, heat up to 100°C, react for 16h, rotary evaporate to remove water, vacuum dry After drying, 3.4 g of the product was obtained with a yield of 94%.

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Abstract

The invention discloses a preparation method of 4-[hydroxy(methyl)phosphoryl]-2-oxobutanoic acid as a glufosinate intermediate. The method comprises the following steps: 1) proper organic solvent, alkaline substance and phase-transfer catalyst are added to cyclic phosphoric anhydride at the temperature of subzero 30 DEG C, stirred, heated to 25-50 DEG C, subjected to a reaction with diethyl oxalate at the room temperature and stirred, and a product is obtained through direct precipitation and filtration from the solvent; 2) water is added to the product, hydrogen chloride is introduced slowly, the pH is controlled, heating is performed, water is removed through rotary evaporation after the reaction is performed for 16 h, and a final product is obtained through vacuum drying. The method has the advantages that the problems of poor solubility and high probability of precipitation of cyclic phosphoric anhydride at a low temperature as well as high probability of ring opening of anhydride and high probability of decomposition of phosphate groups of cyclic phosphoric anhydride under an alkaline condition due to temperature increasing are solved, and the feasibility for preparing 4-[hydroxy(methyl)phosphoryl]-2-oxobutanoic acid as the glufosinate intermediate from cyclic phosphoric anhydride is realized successfully.

Description

technical field [0001] The invention belongs to the technical field of chemical synthesis, and in particular relates to a preparation method of an intermediate 4-(hydroxymethylphosphoryl)-2-carbonylbutyric acid of the herbicide glufosinate. Background technique [0002] Glufosinate (Glufosinafe) is a high-efficiency, low-toxicity, non-selective herbicide first developed by Hoechest Company, and its trade name is Basta. The synthetic method of glufosinate has multiple, and in the seventies of 20th century, Hoechest reported the method utilizing cyclic phosphoric anhydride to prepare glufosinate, and this method has avoided using methyl diethyl phosphite, directly uses methyl phosphorus dichloride React with acrylic acid to obtain 3-(chloromethylphosphoryl)-propionyl chloride, and then through cyclization to obtain flame retardant 2-methyl-2,5-dioxo-1,2-oxophospholane ( Commonly known as cyclic phosphoric anhydride), and then undergo condensation and decarboxylation to obtain...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07F9/30
CPCC07F9/301
Inventor 谷顺明曾辉夏向荣葛德强张志宏黄成强
Owner ANHUI COSTAR BIOCHEM CO LTD
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