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Method for preparing alkenyl cyanide compounds

A compound, the technology of alkenyl cyanide, applied in the field of preparation of alkenyl cyanide compounds, can solve the problems of low efficiency and yield, harsh reaction conditions, and narrow scope of substrate application

Active Publication Date: 2019-09-24
SHANGHAI INST OF ORGANIC CHEMISTRY - CHINESE ACAD OF SCI
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0019] The technical problem to be solved by this invention is to overcome in the preparation method of alkenyl cyanide in the prior art, usually use hypertoxic hydrocyanic acid as cyanogen source, and usually use expensive catalyst, substrate applicable range is narrow, harsh reaction conditions, The disadvantages of poor stereo and regioselectivity and low efficiency and yield, thus providing a method for the preparation of alkenyl cyanide compounds

Method used

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  • Method for preparing alkenyl cyanide compounds
  • Method for preparing alkenyl cyanide compounds
  • Method for preparing alkenyl cyanide compounds

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0098] Example 1 compound (1a)

[0099]

[0100] In a glove box filled with nitrogen atmosphere, Ni(acac) was sequentially added to the 8.0mL reaction flask 2 (0.025mmol, 6.4mg), Mn (0.1mmol, 5.5mg), Zn(CN) 2 (0.4mmol, 47.0mg), p-methylphenylacetylene (0.5mmol, 58.1mg) and acetonitrile (2.5mL), then the reaction flask was tightly capped and removed from the glove box and water (0.5mL) was added with a syringe, and the Seal the lid of the reaction bottle completely and place it in an oil bath preheated to 25°C for reaction. Stop the reaction after 24 hours. After the reaction liquid is cooled to room temperature, add 10% ammonia water to quench, extract with ethyl acetate, wash with water, Wash with saturated sodium chloride solution, dry over anhydrous sodium sulfate, filter, concentrate, and directly purify by silica gel column chromatography, eluent: petroleum ether to petroleum ether / ethyl acetate = 100:1 gradient elution, the product is a yellow oily liquid 59.1mg, yi...

Embodiment 2

[0101] Example 2 Compound (1a)

[0102] In the embodiment 2-6 of the present invention, the technical scheme is basically the same as that of the embodiment 1, and the only difference is that the ligand is different.

[0103]

[0104] Using the scheme of Example 1, bipyridine was used as the ligand, purified by silica gel column chromatography, eluent: gradient elution from petroleum ether to petroleum ether / ethyl acetate=100:1, the yield was 82%, 1 H NMR purity greater than 98%. 1 H NMR (400MHz, CDCl 3 ): δ2.37(s,3H),6.02(s,1H),6.27(s,1H),7.21(d,J=8.0Hz,2H),7.48(d,J=8.0Hz,2H). 13 C NMR (100MHz, CDCl 3 ): δ21.14, 117.79, 122.63, 125.49, 126.82, 129.45, 129.57, 140.04. HRMS (EI) calculated value C 10 h 9 N[M] + :143.0735, the measured value is 143.0734.

Embodiment 3

[0105] Example 3 Compound (1a)

[0106]

[0107] Using the protocol of Example 1, 4,4'-di-tert-butyl-2,2'-bipyridine is used as a ligand, purified by silica gel column chromatography, eluent: petroleum ether to petroleum ether / ethyl acetate=100:1 Gradient elution, yield 74%, 1 H NMR purity greater than 98%. 1 H NMR (400MHz, CDCl 3 ): δ2.37(s,3H),6.02(s,1H),6.27(s,1H),7.21(d,J=8.0Hz,2H),7.48(d,J=8.0Hz,2H). 13 C NMR (100MHz, CDCl 3 ): δ21.14, 117.79, 122.63, 125.49, 126.82, 129.45, 129.57, 140.04. HRMS (EI) calculated value C 10 h 9 N[M] + :143.0735, the measured value is 143.0734.

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Abstract

The invention discloses a method for preparing alkenyl cyanide compounds represented by formula II. Alkynes represented by formula I and a cyanation reagent are subjected to a reduction reaction represented by a formula shown in the description in an organic solvent under the protection of a gas at 20-100 DEG C under the action of a nickel catalyst, a reducing agent and H2O to prepare the alkenyl cyanide compounds represented by formula II. The preparation method of the invention, which adopts the cheap nickel as the catalytic system, has the advantages of simplicity in operation, mild reaction conditions, good compatibility of functional groups, wide application range of the substrate, high reaction efficiency and high yield, so the method has high application and promotion values.

Description

technical field [0001] The invention belongs to the field of organic chemistry, and in particular relates to a preparation method of alkenyl cyanide compounds. Background technique [0002] The cyano group is an important functional group in organic synthesis, which can undergo a variety of chemical conversion reactions, such as carboxylic acids, aldehydes, ketones, esters, amides, amines, tetrazoles and other nitrogen heterocyclic compounds. In addition, due to the strong polarity, strong electron-withdrawing properties and good metabolic stability of the cyano group, the cyano group has become a very important functional group in the research of medicinal chemistry and material chemistry; therefore, the research on the cyano functionalization of organic molecules The reaction, especially the catalyzed cyanation reaction is undoubtedly a very important and challenging topic in synthetic organic chemistry. [0003] The hydrogen-cyanation reaction of transition metal catalyz...

Claims

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Application Information

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IPC IPC(8): C07C253/12C07C255/33C07C255/34C07C255/35C07C255/41C07D213/57C07C255/07C07C255/09C07C255/10C07C255/15C07C255/36C07C255/31C07C255/42C07D209/08C07C255/40C07D295/155C07J41/00C07F7/08
CPCC07C253/12C07C255/33C07C255/34C07C255/35C07C255/41C07D213/57C07C255/07C07C255/09C07C255/10C07C255/15C07C255/36C07C255/31C07C255/42C07D209/08C07C255/40C07D295/155C07J41/0094C07F7/083C07C2601/14C07F7/081
Inventor 刘元红张兴杰
Owner SHANGHAI INST OF ORGANIC CHEMISTRY - CHINESE ACAD OF SCI
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