Synthetic method for L-phosphinothricin

A glufosinate-ammonium synthesis reaction technology, applied in the field of pesticide chemical herbicide synthesis, can solve the problems of high price, difficult substrate synthesis, unsuitable for industrial production, etc., and achieve the effect of low cost

Inactive Publication Date: 2015-12-09
XIAN MODERN CHEM RES INST
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  • Abstract
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  • Application Information

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Problems solved by technology

[0006] The substrate synthesis of this method is difficult, the process is cumbersome, the total yield of the four-step reaction is 26.7%, and the catalyst is a noble metal catalyst (Rh-(R,R)-Norphos), which is expensive and not suitable for industrial production

Method used

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  • Synthetic method for L-phosphinothricin
  • Synthetic method for L-phosphinothricin
  • Synthetic method for L-phosphinothricin

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0033] (1)

[0034]

[0035] In a 50mL three-neck flask, add 2.53g (0.01mol) of dibenzylidene glycine methyl ester, 3.26g (0.01mol) of cesium carbonate, 0.52g (0.001mol) of catalyst and 15mL of dichloromethane in sequence, and cool the system down to -20°C , slowly drop into a solution of 1.2g (0.01mol) of methyl vinyl phosphonate in dichloromethane (5mL), react at -20°C, monitor the reaction in the liquid phase until the reaction of dibenzylidene glycine methyl ester is complete, filter, Filtrate desolvation column chromatography (catalyst recovery) to obtain colorless oily liquid (S)-2-diphenylmethylene amino-4-methoxy (methyl) phosphonobutanoic acid methyl ester 2.51g, yield 66.7%, 1 HNMR (500MHz, CDCl 3 ):7.60-7.63(dd,2H,2×Ar-H),7.43-7.45(m,3H,3×Ar-H),7.36-7.39(t,1H,Ar-H),7.30-7.33(t ,2H,2×Ar-H),7.14-7.17(dd,2H,2×Ar-H),3.95-3.96(m,1H,CH),3.63-3.66(dd,3H,OCH 3 ),3.85(s,3H,OCH 3 ),2.04-2.15(m,2H,CH 2 ),1.75-1.86(m,2H,CH 2 ), 1.42-1.46 (d, 3H, J=3.8Hz, CH 3 ). 31 ...

Embodiment 2

[0040] (1)

[0041]

[0042] In a 50mL three-neck flask, add 2.95g (0.01mol) tert-butyl dibenzylidene glycine, 0.56g (0.01mol) potassium hydroxide, 0.488g (0.001mol) catalyst and 15mL toluene in sequence, and cool the system down to -10°C , slowly drop 1.2g (0.01mol) of methyl vinyl phosphonate in toluene (5mL) solution, react at -10°C, monitor the reaction in the liquid phase until the reaction of tert-butyl dibenzylidene glycine is completed, filter, and the filtrate Desolvation column chromatography (catalyst recovery) gave 2.66 g of colorless oily liquid (S)-2-diphenylmethyleneamino-4-methoxy (methyl) phosphonobutanoic acid tert-butyl ester, yield 64.1%, 1 HNMR (500MHz, CDCl 3 ):7.63-7.64(dd,2H,2×Ar-H),7.44-7.45(m,3H,3×Ar-H),7.38-7.41(t,1H,Ar-H),7.31-7.34(t ,2H,2×Ar-H),7.16-7.18(dd,2H,2×Ar-H),3.94-3.96(m,1H,CH),3.67-3.69(dd,3H,OCH 3 ),2.06-2.16(m,2H,CH 2 ),1.74-1.86(m,2H,CH 2 ),1.44-1.46(m,12H,CH 3 ,t-Bu). 31 PNMR (500MHz,D 2 O): 56.6.

[0043] (2)

[0044] ...

Embodiment 3

[0047] (1)

[0048]

[0049] In a 50mL three-necked flask, add 2.95g (0.01mol) tert-butyl dibenzylidene glycine, 0.96g (0.01mol) sodium tert-butoxide, 0.511g (0.001mol) catalyst and 15mL tetrahydrofuran, and cool the system to -10 ℃, slowly drop 1.2g (0.01mol) tetrahydrofuran (5mL) solution of methyl vinyl phosphonate, react at -10 ℃, monitor the reaction in the liquid phase until the reaction of tert-butyl dibenzylidene glycine is completed, filter, The filtrate was desolvated by column chromatography (catalyst recovery) to obtain 2.59 g of colorless oily liquid (S)-2-diphenylmethyleneamino-4-methoxy(methyl)phosphonobutanoic acid tert-butyl ester. The rate is 62.4%.

[0050] (2)

[0051]

[0052] Add 2g (0.0048mol) (S)-2-diphenylmethyleneamino-4-methoxy(methyl)phosphonobutanoic acid tert-butyl ester into 40mL hydrochloric acid solution (6mol / L), the reaction solution Raise the temperature to reflux, monitor the liquid phase until the reaction of the raw materials is ...

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Abstract

The invention discloses a synthetic method for L-phosphinothricin. The synthetic method has a reaction formula as shown in a formula described in the specification. The method comprises the following steps: with a methylvinylphosphonate compound (II) and a benzylideneglycinate compound (III) as raw materials, carrying out an addition reaction so as to obtain an intermediate, i.e., an S-benzylidenephosphonobutyrate compound (IV); then carrying out hydrolysis so as to obtain hydrochloride (V); and carrying out neutralization so as to obtain the L-phosphinothricin (I). The method provided by the invention uses chiral phase transfer catalysis (a cinchonidine chiral quaternary ammonium salt derivative) as a means to construct a chiral center of a phosphinothricin molecular structure, so a chiral herbicide, i.e., the L-phosphinothricin, is obtained.

Description

technical field [0001] The present invention relates to the synthetic technique of pesticide chemical herbicide, specifically, the present invention relates to the synthetic method of L-glufosinate-ammonium of chiral organophosphorus herbicide. Background technique [0002] Glufosinate-ammonium is a high-efficiency, broad-spectrum, low-toxic non-selective herbicide developed by the German Hoechst company, which kills weeds quickly and is safe for crops. Glufosinate-ammonium is currently one of the three largest herbicide production varieties in the world. In 1999, the global sales volume was less than 100 million US dollars. In 2006, it reached 500 million US dollars. It is expected to exceed 1 billion US dollars by 2015. With the rapid development of glufosinate-resistant transgenic crops, the market demand for glufosinate-ammonium will be huge in the future, and the prospect is very broad. [0003] Currently, the commercially available glufosinate-ammonium are all racemat...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07F9/30
Inventor 毛明珍郑晓蕊张媛媛张晓光黄晓瑛何琦文王威魏乐苏天铎王列平林双政宁斌科
Owner XIAN MODERN CHEM RES INST
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