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Synthetic method for silthiopham

A technology of silthiofacillin and synthetic method, which is applied in the field of organic synthesis, can solve the problems of many by-products, cumbersome synthesis process, environmental pollution, etc., and achieve the effect of simple route, cheap and easy-to-obtain raw materials, and high yield

Active Publication Date: 2015-12-02
HANGZHOU NORMAL UNIVERSITY
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  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

[0004] In order to solve the problem that the synthesis process of silthiocarb is relatively cumbersome, there are many by-products in the production process, and the serious pollution to the environment, the present invention proposes a method for synthesizing silthiocarb. The raw materials used in the method are cheap and easy The route is simple, the yield is higher, and the use of tert-butyl nitrous acid ( t -BuONO) and thionyl chloride and other reagents that seriously pollute the environment

Method used

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  • Synthetic method for silthiopham
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  • Synthetic method for silthiopham

Examples

Experimental program
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Effect test

Embodiment 1

[0027] (1) The method for preparing methyl trimethylsilyl propiolate is:

[0028] Under nitrogen protection, trimethylsilylacetylene (4.0mL, 28.6mmol) was added to dry THF (20mL), cooled to -78°C, and n-butyllithium (18.0mL, 28.6mmol) was slowly added to the system , and stirred at this temperature for 30 minutes, then warmed to room temperature, and added methyl chloroformate (2.4 mL, 31.4 mmol), followed by stirring the reaction for 2.5 hours. The reaction mixture was poured into ammonium chloride solution to quench the reaction, and extracted with diethyl ether, the organic phase was washed with water and brine and dried with anhydrous sodium sulfate, the solvent (tetrahydrofuran and diethyl ether) was removed in vacuo, and the obtained crude product was purified by column chromatography ( 5%EtOAc / PE), to obtain yellow oil product methyl trimethylsilylpropiolate 4.2g, yield 95.0%;

[0029] (2) Preparation N -Allyl-3-(trimethylsilyl)propynamide

[0030] Under nitrogen pro...

Embodiment 2

[0036] (1) Preparation of ethyl trimethylsilyl propiolate

[0037] Under nitrogen protection, trimethylsilylacetylene (5.6mL, 40mmol) was added to dry THF, cooled to -65°C, tert-butyllithium (32.62mL, 52.0mmol) was slowly added to the system, and at this temperature It was stirred for 30 minutes, then warmed to room temperature, and ethyl chloroformate (6.48 g, 60 mmol) was added, followed by stirring for 2.5 hours. The reaction mixture was poured into ammonium chloride solution to quench the reaction, and extracted with diethyl ether. The organic phase was washed with water and brine and dried over anhydrous sodium sulfate. The solvent was removed in vacuo, and the obtained crude product was purified by column chromatography (5% EtOAc / PE) to obtain 6.34 g of methyl trimethylsilylpropiolate as a yellow oil product, with a yield of 93.0%.

[0038] (2) Preparation N -Allyl-3-(trimethylsilyl)propynamide

[0039] Under nitrogen protection, 30% mol catalyst tetraisopropyl titana...

Embodiment 3

[0044] (1) Preparation of methyl trimethylsilyl propiolate

[0045] Under nitrogen protection, trimethylsilylacetylene (4.0mL, 28.6mmol) was added to dry THF (20mL), cooled to -50°C, methyllithium (26.86mL, 60mmol) was slowly added to the system, and in Stir at this temperature for 30 minutes, then warm to room temperature, and add methyl chloroformate (2.03 mL, 37.2 mmol), then stir the reaction for 2.5 hours. The reaction mixture was poured into ammonium chloride solution to quench the reaction, and extracted with diethyl ether. The organic phase was washed with water and brine and dried over anhydrous sodium sulfate. The solvent was removed in vacuo, and the obtained crude product was purified by column chromatography (5% EtOAc / PE) to obtain 4.1 g of methyl trimethylsilylpropiolate as a yellow oil product, with a yield of 93.0%.

[0046] (2) Preparation N -Allyl-3-(trimethylsilyl)propynamide

[0047] Under the protection of nitrogen, the catalyst zirconium tetra-tert-but...

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Abstract

The invention provides a synthetic method for silthiopham, which belongs to the technical field of organic synthesis. The objective of the invention is to overcome the problems of complicated synthesis process, a great number of byproducts and severe environmental pollution of conventional synthetic methods for silthiopham. The synthetic method provided by the invention comprises the following steps: (1) with trimethylsilylacetylene as a raw material, under the protection of inert gas, reacting trimethylsilylacetylene with methyl chloroformate under the action of organic base so as to obtain methyl (trimethylsilyl)propiolate; (2) reacting methyl (trimethylsilyl)propiolate with allyl amine in a solvent under the action of a catalyst so as to obtain N-allyl-3-(trimethylsilyl)propiolamide; and (3) subjecting N-allyl-3-(trimethylsilyl)propiolamide with 3-mercapto-2-butanone to a heating reflux reaction under the action of an alkali catalyst and carrying out dehydration so as to obtain the final product silthiopham. The method has the advantages of usage of cheap and easily available raw materials, simple route, high yield and no usage of reagents severely polluting the environment, e.g., t-butyl nitrous acid and thionyl chloride.

Description

technical field [0001] The invention belongs to the technical field of organic synthesis, in particular to a pesticide silthiocarb (N-allyl-4,5-dimethyl-2-(trimethylsilyl)thiophene-3-carboxamide) efficient synthesis process. Background technique [0002] Wheat take-all (Gaeumammomycesgramini) is one of the devastating diseases of wheat. Silthiopham (Silthiopham) is a seed treatment agent with special effects on wheat take-all caused by wheat take-all, which was officially launched by Monsanto in 1999. . However, currently known methods for synthesizing silthiocarb have the disadvantages of many reaction steps and involving the use of various highly toxic substances, low overall yield, and high cost. Therefore, it is urgent to develop an efficient and low-cost method for the synthesis of silthiocarb. [0003] U.S. Patent No. 5,486,621 reported the total synthesis of silthiocarb for the first time. They used 2-butanone, ethyl cyanoacetate and sulfur to react in one step to ...

Claims

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Application Information

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IPC IPC(8): C07F7/10
Inventor 郑战江王丁徐利文徐征杨科芳蒋剑雄
Owner HANGZHOU NORMAL UNIVERSITY
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