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Method for preparing 1,3-diolefins

A technology of diolefins and dithioketenes, which is applied in the field of preparation of 1,3-dienes, can solve the problems of high consumption of catalysts and oxidants, complex substrate synthesis, and harsh reaction conditions, so as to avoid pre-functionalization and product The effect of high yield and mild synthesis reaction conditions

Inactive Publication Date: 2016-10-19
DALIAN INST OF CHEM PHYSICS CHINESE ACAD OF SCI
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  • Abstract
  • Description
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  • Application Information

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Problems solved by technology

The disadvantage of the above research is that the amount of catalyst and oxidant is generally high, and most of them use copper salt or silver salt as oxidant, the synthesis of the substrate is more complicated, and the reaction conditions are harsher, etc.

Method used

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  • Method for preparing 1,3-diolefins
  • Method for preparing 1,3-diolefins
  • Method for preparing 1,3-diolefins

Examples

Experimental program
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Effect test

Embodiment 1

[0026]

[0027] Into a 10 mL Schlenk reaction tube, sequentially add palladium acetate (11 mg, 0.05 mmol), 2a (72 mg, 0.5 mmol), dimethyl sulfoxide (2 mL) and tert-butyl acrylate 3a (128 mg, 1.0 mmol) with oxygen as the oxidant (The reaction tube is connected to an oxygen balloon). The reaction was stirred at 50 °C for 24 h. After the reaction solution was cooled to room temperature, 20 mL of water was added, diatomaceous earth was used as a filter aid, and the filter cake (3×10 mL) was washed with ethyl acetate, and the organic phase was separated. Dry over anhydrous magnesium sulfate and filter. The volatile components were removed under reduced pressure, and then separated by silica gel column chromatography (eluent: petroleum ether (60-90°C) / ethyl acetate, v / v=5:1) to obtain the target product 1aa (16 mg, yield rate of 12%).

Embodiment 2

[0029] The reaction steps and operations are the same as in Example 1, except that the reaction solvent is a mixed solvent of acetic acid and dimethyl sulfoxide, and the volume ratio of the two is 3:1. The reaction was stopped, and the target product 1aa (29 mg, yield 22%) was obtained after post-processing. It shows that adding acetic acid can slightly increase the reaction yield.

Embodiment 3

[0031] The reaction steps and operations are the same as in Example 1, except that the reaction solvent is a mixed solvent of acetonitrile, acetic acid and dimethyl sulfoxide, and the volume ratio of the three is 6:3:1. The reaction was stopped, and the target product 1aa (95 mg, yield 72%) was obtained after post-processing. It shows that the ternary mixed solvent of acetonitrile, acetic acid and dimethyl sulfoxide is better than the binary mixed solvent of acetic acid and dimethyl sulfoxide.

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Abstract

The invention discloses a method for preparing 1,3-diolefins. In a ternary mixed solvent of 1,4-dioxane, acetic acid and dimethyl sulphoxide, an oxidative cross-coupling reaction is carried out for ketene dithioacetals with alpha-cyano or ester and olefin which are catalyzed by divalent palladium salt in a condition with oxygen or air which is used as an oxidizing agent, in order to generate 1,3-diolefins. Compared with the reported synthetic method of 1,3-diolefins, the method has the advantages of easily available raw materials, simple operation, mild synthetic reaction condition, and high atom economy.

Description

technical field [0001] The present invention relates to a method for preparing 1,3-dienes. The oxidative cross-coupling reaction of dithioketenes, which are easy to prepare, have structural diversity and multiple reaction centers, and alkenes are used to prepare 1,3-dienes. Compared with the existing 1,3-diene synthesis method, the present invention has easy-to-obtain raw materials, simple and convenient operation, mild synthesis reaction conditions, and uses oxygen or air as the oxidant, which is environmentally friendly; and because the pre-functional group of the substrate is avoided It has the characteristics of high atom economy. Background technique [0002] 1,3-Dienes are an important class of organic compounds, which participate in reactions including [4+2] cycloaddition, π-allyl metal chemistry, etc. Therefore, the development of efficient synthetic methods has attracted people's attention. The methods for synthesizing 1,3-dienes by coupling reactions can be divid...

Claims

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Application Information

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IPC IPC(8): C07D339/06C07D339/08C07C323/54C07C319/20
CPCC07C319/20C07C323/54C07D339/06C07D339/08
Inventor 余正坤杨小格
Owner DALIAN INST OF CHEM PHYSICS CHINESE ACAD OF SCI
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