Synthesizing method for preparing trisubstituted olefin by decarboxylation reaction

A technology of decarboxylation reaction and synthesis method, which is applied in the preparation of carbon-based compounds, chemical instruments and methods, and the preparation of organic compounds, etc., to achieve the effects of high regio and stereoselectivity, wide sources, and mild reaction conditions

Active Publication Date: 2018-10-16
CHUZHOU UNIV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

However, decarboxylation and hydrogen-alkylation of aryl-alkylacetylenes to prepare single-configuration trisubstituted alkenes have not been reported by researchers.

Method used

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  • Synthesizing method for preparing trisubstituted olefin by decarboxylation reaction
  • Synthesizing method for preparing trisubstituted olefin by decarboxylation reaction
  • Synthesizing method for preparing trisubstituted olefin by decarboxylation reaction

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Experimental program
Comparison scheme
Effect test

Embodiment 1

[0043] Embodiment 1, the reaction formula of this embodiment is as follows:

[0044]

[0045] (1) Under air, nickel(II) diethylene glycol dimethyl ether complex (12mol%), 4,4'-di-tert-butyl-2,2'-bipyridine (15mol%), ring Hexyl carboxylate (1eq), calcium acetate (3eq) was added to a sealed reaction tube with a branched tube containing magnetons, and the reaction tube was pumped three times with argon. Under the protection of argon, add 1mL N,N-dimethylacetamide to the reaction tube, stir at room temperature for 5 minutes, then add phenylpropyne (2.5eq) and (Me 2 SiH) 2 O (180 μL) was added to the reaction solution, the stopper was tightly plugged, and placed in an oil bath at 40° C. and stirred for 4 hours.

[0046] (2) Add ethyl acetate to the material obtained in step (1) and mix thoroughly, filter out the solid residue with a short silica gel column, and keep the organic phase.

[0047] (3) Spin dry the solvent in the organic phase obtained in step (2) to obtain a crud...

Embodiment 2

[0049] The reaction formula of this embodiment is as follows:

[0050]

[0051] (1) Under air, nickel(II) diethylene glycol dimethyl ether complex (12mol%), 4,4'-di-tert-butyl-2,2'-bipyridine (15mol%), four Hydropyranocarboxylate (1eq) and calcium acetate (3eq) were added to a branched, sealed reaction tube containing magnetons, and the reaction tube was purged with argon three times. Under the protection of argon, add 1mL N,N-dimethylacetamide to the reaction tube, stir at room temperature for 5 minutes, then add phenylpropyne (2.5eq) and (Me 2 SiH) 2 O (180 μL) was added to the reaction solution, the stopper was tightly plugged, and placed in an oil bath at 40° C. and stirred for 4 hours.

[0052] (2) Add ethyl acetate to the material obtained in step (1) and mix thoroughly, filter out the solid residue with a short silica gel column, and keep the organic phase.

[0053] (3) Spin dry the solvent in the organic phase obtained in step (2) to obtain a crude product, and t...

Embodiment 3

[0055] The reaction formula of this embodiment is as follows:

[0056]

[0057] (1) Under air, nickel(II) diethylene glycol dimethyl ether complex (12mol%), 4,4'-di-tert-butyl-2,2'-bipyridine (15mol%), ring Hexenyl formate (1 eq) and calcium acetate (3 eq) were added to a sealed reaction tube with a branched tube containing magnets, and the reaction tube was purged with argon three times. Under the protection of argon, add 1mL N,N-dimethylacetamide to the reaction tube, stir at room temperature for 5 minutes, then add phenylpropyne (2.5eq) and (Me 2 SiH) 2 O (180 μL) was added to the reaction solution, the stopper was tightly plugged, and placed in an oil bath at 40° C. and stirred for 4 hours.

[0058] (2) Add ethyl acetate to the material obtained in step (1) and mix thoroughly, filter out the solid residue with a short silica gel column, and keep the organic phase.

[0059] (3) Spin dry the solvent in the organic phase obtained in step (2) to obtain a crude product, a...

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Abstract

The invention provides a synthesizing method for preparing trisubstituted olefin by decarboxylation reaction. The synthesizing method is characterized in that alkyl carboxylic ester and aryl-alkyl acetylene are used as the raw materials, and generate reaction in a solvent according to the following reaction formula under the functions of a nickel catalyst, a ligand, alkaline and silane, so as to obtain a trisubstituted olefin compound with single configuration. The synthesizing method has the advantage that the alkyl carboxylic ester and the aryl-alkyl acetylene are used as the reaction primers, so as to overcome the limitation that only alkyl halide and alkyl sulfonic ester are used in the existing method for preparing the trisubstituted olefin by the alkyne hydrogen alkylation reaction.The trisubstituted olefin synthesized by the synthesizing method has the advantages that the area selectivity and stereo activity are very high the trisubstituted olefin with single configuration canbe completely obtained, and the problem of separating in mixed olefin products is solved; meanwhile, the material adding type of the reaction system is simple, the metal reagent sensitive to the waterand air is not used, and more convenience is realized in actual use; the source of the alkyl carboxylic ester is wide, and the synthesizing is simple.

Description

technical field [0001] The invention relates to the technical field of compound substance preparation, in particular to a synthesis method for preparing trisubstituted olefins by decarboxylation reaction. Background technique [0002] Substituted olefins are an important class of compounds in organic chemistry and widely exist in materials, petrochemical and pharmaceutical industries. The synthesis method of substituted alkenes has always been the focus of people's attention. The traditional synthesis methods include reduction reaction, Wittig reaction and Julia olefination reaction. These reactions generally have disadvantages such as harsh reaction conditions, high reaction temperature, and the need to use a relatively strong base in the reaction system. The most important point is that the reaction selectivity for the synthesis of substituted olefins with cis / trans isomers is not high, and the products are difficult to separate. [0003] In recent years, chemical synthes...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07C1/32C07C13/28C07D309/04C07C45/69C07C49/683C07D211/16C07D211/96C07J9/00
CPCC07C1/323C07C45/69C07C49/683C07D211/16C07D211/96C07D309/04C07J9/00C07C2601/14C07C2601/16C07C13/28
Inventor 陆晓雨洪美岚
Owner CHUZHOU UNIV
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