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A method for synthesizing 2-amido-4-(o-alkylphosphonyl)-2-butenoic acid and esters thereof

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

Active Publication Date: 2019-07-02
NANJING TECH UNIV
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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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  • A method for synthesizing 2-amido-4-(o-alkylphosphonyl)-2-butenoic acid and esters thereof
  • A method for synthesizing 2-amido-4-(o-alkylphosphonyl)-2-butenoic acid and esters thereof
  • A method for synthesizing 2-amido-4-(o-alkylphosphonyl)-2-butenoic acid and esters thereof

Examples

Experimental program
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Effect test

Embodiment 1

[0043] Embodiment 1: the preparation of 2-(O-methylphosphono) acetaldehyde diethyl acetal (compound V)

[0044] Diethyl methylphosphonite (compound VII) (54.0 g, 0.5 mol) and bromoacetaldehyde diethyl acetal (98.5 g, 0.5 mol) were added to a 250 mL round bottom flask. Heating, reflux reaction at 120°C for 2h (reaction monitored by GC), cooling to room temperature, the reaction solution was distilled under reduced pressure, and 120°C fraction (Compound V) 84.2g was collected under 15mmHg pressure, yield 80.2%.

Embodiment 2

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

[0046] In a 500 mL round bottom flask were added diethyl methylphosphonite (compound VII) (68.0 g, 0.5 mol), bromoacetaldehyde diethyl acetal (98.5 g, 0.5 mol) and toluene (200 ml). Heated, reflux reaction at 110°C for 4h (reaction monitored by GC), cooled to room temperature, the reaction solution was distilled under reduced pressure, and 101.9g of the 120°C fraction (compound V) was collected under a pressure of 15mmHg, with a yield of 91.0%. 1 H NMR (400MHz, CDCl 3 , δppm): 1.22 (td, J 1 =6.8Hz,J 2 =3.2Hz, 6H), 1.33(t, J=6.8Hz, 3H), 1.53(d, J=14.4Hz, 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] In a 500 mL round bottom flask, add O, O-diisopropylmethylphosphonite (compound VII) (82.0 g, 0.5 mol), bromoacetaldehyde diethyl acetal (98.5 g, 0.5 mol) and acetonitrile (200ml). Heated and refluxed at 80°C for 24h (reaction monitored by GC), cooled to room temperature, the reaction liquid was distilled under reduced pressure, and 86.0 g of fraction (compound V) at 122°C was collected under 15 mmHg pressure, with a yield of 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 field of chemistry. It specifically relates to a method for synthesizing 2-amido-4-(O-alkylphosphono)-2-butenoic acid and esters thereof. Background technique [0002] Glufosinate ammonium (glufosinate, C 5 h 15 N 2 o 4 P) is a high-efficiency broad-spectrum non-selective herbicide developed by Hurst, and its main component is 2-amino-4-(hydroxymethylphosphonyl) butyric acid (phosphinothricin, C 5 h 12 NO 4 P). Glufosinate-ammonium is a racemic mixture of two configurations of DL, and only the L-form (L-phosphinothricin) has been reported to have herbicidal activity. In recent years, many methods of biological or chemical synthesis of L-glufosinate have been developed one after another. Biological method such as Bartsch has reported the method (US06936444) that 2-carbonyl-4-(hydroxymethylphosphono) butanoic acid utilizes transamination to produce L-glufosinate, and Lothar has r...

Claims

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Application Information

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Patent Type & Authority Patents(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 TECH UNIV
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