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Method for synthesizing pesticide intermediate 2-amido-4-(O-alkylmethylphosphonyl)-2-butenoic acid and its ester

A technology of alkylmethylphosphono, synthesis method, applied in the field of chemistry

Active Publication Date: 2017-12-05
NANJING UNIV OF TECH
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

And this reaction is used for the synthesis of glufosinate-ammonium and there is no report at present

Method used

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  • Method for synthesizing pesticide intermediate 2-amido-4-(O-alkylmethylphosphonyl)-2-butenoic acid and its ester
  • Method for synthesizing pesticide intermediate 2-amido-4-(O-alkylmethylphosphonyl)-2-butenoic acid and its ester
  • Method for synthesizing pesticide intermediate 2-amido-4-(O-alkylmethylphosphonyl)-2-butenoic acid and its ester

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0043] Example 1: Preparation of 2-(O-methylmethylphosphono)acetaldehyde diethyl acetal (compound V)

[0044] A 250 mL round bottom flask was charged with diethyl methyl phosphonite (compound VII) (54.0 g, 0.5 mol) and bromoacetaldehyde diethyl acetal (98.5 g, 0.5 mol). Heating, refluxing reaction at 120°C for 2h (GC monitoring reaction), cooling to room temperature, distilling the reaction solution under reduced pressure, collecting 120°C fraction (Compound V) 84.2g under 15mmHg pressure, yield 80.2%.

Embodiment 2

[0045] Example 2: Preparation of 2-(O-ethylmethylphosphono)acetaldehyde diethyl acetal (compound V)

[0046] A 500 mL round bottom flask was charged with diethyl methylphosphonite (compound VII) (68.0 g, 0.5 mol), bromoacetaldehyde diethyl acetal (98.5 g, 0.5 mol) and toluene (200 ml). Heating, refluxing reaction at 110°C for 4h (GC monitoring reaction), cooling to room temperature, distilling the reaction solution under reduced pressure, collecting 120°C fraction (compound V) 101.9g under 15mmHg pressure, yield 91.0%, 1 H NMR(400MHz, CDCl 3 ,Δppm): 1.22(td, J 1 =6.8Hz, J 2 = 3.2 Hz, 6H), 1.33 (t, J = 6.8 Hz, 3H), 1.53 (d, J = 14.4 Hz, 3H), 2.16 (pd, J 1 =15.8Hz, J 2 =5.2Hz, 2H), 3.62 (m, 4H), 4.06 (m, 2H), 4.88 (dd, J 1 =11.4Hz, J 2 =5.2Hz, 1H), 31 P NMR(162MHz, CDCl 3 , Δppm): 51.06.

Embodiment 3

[0047] Example 3: Preparation of 2-(O-isopropylmethylphosphono)acetaldehyde diethyl acetal (compound V)

[0048] Add O, O-diisopropyl methylphosphonite (Compound VII) (82.0g, 0.5mol), bromoacetaldehyde diethyl acetal (98.5g, 0.5mol) and acetonitrile into a 500mL round bottom flask (200ml). Heating, refluxing reaction at 80°C for 24h (GC monitoring reaction), cooling to room temperature, distilling the reaction solution under reduced pressure, collecting 122°C fraction (compound V) 86.0g under 15mmHg pressure, yield 72.3%.

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Abstract

The invention belongs to the technical field of pesticide intermediates for synthesizing herbicides and particularly relates to a method for synthesizing a pesticide intermediate 2-amido-4-(O-alkylmethylphosphonyl)-2-butenoic acid and its ester. The method comprises that a compound VII and a compound VI undergo an Arbuzov reaction to produce a compound V, the compound V is hydrolyzed through an acid to produce a compound IV, the compound IV and a compound III undergo a reaction under action of a condensation reagent and a catalyst to produce a compound II and the compound II is hydrolyzed into a compound I. Compared with the existing synthesis route, the method has simple processes, high atom economy and high stereoselectivity, is environmentally friendly, realizes a low cost and has an industrial prospect. In the formula, R1 represents C1-4 alkyl; R2 and R3 represent CnH2n+1 and n is 1, 2, 3 or 4, or R2 or R3 represents -CmH2m- and m is 2 or 3; R4 represents C1-4 alkyl or C6-10 aryl; R5 represents hydrogen or C1-4 alkyl; and X represents chlorine or bromine.

Description

Technical field [0001] The invention belongs to the synthesis of organic compounds in the chemical field. Specifically, it relates to a method for synthesizing 2-amido-4-(O-alkylmethylphosphono)-2-butenoic acid and its esters. Background technique [0002] Glufosinate (Glufosinate, C 5 H 15 N 2 O 4 P) is an efficient and broad-spectrum non-selective herbicide developed by Hearst Company. Its main component is 2-amino-4-(hydroxymethylphosphono) butyric acid (phosphinothricin, C 5 H 12 NO 4 P). Glufosinate-ammonium is a racemic mixture of two DL configurations, and only L-phosphinothricin has herbicidal activity reported in the literature. In recent years, many biological or chemical methods of synthesizing L-phosphinothricin have been developed. Biological methods such as Bartsch reported the use of 2-carbonyl-4-(hydroxymethylphosphono) butyric acid to produce L-phosphinothricin (US06936444) through transamination. Lothar reported the use of L-amidase selective hydrolysis (R, S...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07F9/32
CPCC07F9/3217C07F9/3264
Inventor 朱红军马时涵席洋何广科刘睿宋广亮
Owner NANJING UNIV OF TECH
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