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Preparation method of 1,4-diaryl-1,3-butadiyne

A diaryl and diacetylene technology, applied in the preparation of amino compounds, organic compounds, organic chemical methods, etc., can solve the problems of high toxicity of catalysts and ligands, and achieve low cost, easy industrialization, and mild reaction conditions Effect

Inactive Publication Date: 2011-01-19
TONGJI UNIV
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  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

[0009] The people such as Regis take β, β-dibromostyrene as raw material, take nickel acetate as catalyst, in the presence of sodium hydride and dipyridine as ligand, prepare 1,4-diphenyl-1,3-butadiyne, But the toxicity of catalyst and ligand in this method is bigger (Regis, V.Tetrahedron Lett.1986, 27, 3517)

Method used

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  • Preparation method of 1,4-diaryl-1,3-butadiyne
  • Preparation method of 1,4-diaryl-1,3-butadiyne

Examples

Experimental program
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Effect test

Embodiment 1

[0027] Embodiment 1: the synthesis of 1,4-bis(4-methoxyphenyl)-1,3-butadiyne

[0028]

[0029] Add 3 mL of dimethyl sulfoxide, 2-(4-methoxyphenyl)-1,1-dibromoethylene (146 mg, 0.5 mmol), DBU (115 mg, 0.75 mmol), cuprous iodide to a 60 mL sealed tube (4.75mg, 0.025mmol), stirred and reacted at 80°C for 8 hours. After the reaction, add 3mL of distilled water to the reaction solution, extract with ethyl acetate, wash the organic layer with saturated brine, dry over anhydrous sodium sulfate, remove the solvent by distillation under reduced pressure to obtain the crude product, and the crude product is subjected to column chromatography (acetic acid Ethyl ester / petroleum ether=1 / 30~1 / 5) separation to obtain 38 mg of light yellow solid 1,4-bis(4-methoxyphenyl)-1,3-butadiyne with a yield of 57%. The characterization data are as follows: 1 H NMR (500MHz, CDCl 3 ): δ=3.82(6H, s), 6.85(4H, d, J=9.0Hz), 7.46(4H, d, J=9.0Hz).

Embodiment 2

[0030] Example 2: Synthesis of 1,4-bis(4-methoxyphenyl)-1,3-butadiyne

[0031]

[0032] Add 3 mL of dimethyl sulfoxide, 2-(4-methoxyphenyl)-1,1-dibromoethylene (146 mg, 0.5 mmol), DBU (230 mg, 1.5 mmol), cuprous iodide to a 60 mL sealed tube (19mg, 0.1mmol), stirred and reacted at 80°C for 8 hours. After the reaction, add 3mL of distilled water to the reaction solution, extract with ethyl acetate, wash the organic layer with saturated brine, dry over anhydrous sodium sulfate, and remove the solvent by distillation under reduced pressure to obtain the crude product. The crude product is subjected to column chromatography (acetic acid Ethyl ester / petroleum ether=1 / 30~1 / 5) separation to obtain 59 mg of light yellow solid 1,4-bis(4-methoxyphenyl)-1,3-butadiyne with a yield of 89%. The characterization data are as follows: 1 H NMR (500MHz, CDCl 3 ): δ=3.82(6H, s), 6.85(4H, d, J=9.0Hz), 7.46(4H, d, J=9.0Hz).

Embodiment 3

[0033] Example 3: Synthesis of 1,4-bis(4-methylphenyl)-1,3-butadiyne

[0034]

[0035] Add 3 mL of dimethyl sulfoxide, 2-(4-methylphenyl)-1,1-dibromoethylene (138 mg, 0.5 mmol), DBU (230 mg, 1.5 mmol), cuprous iodide ( 19mg, 0.1mmol), stirred and reacted at 80°C for 8 hours. After the reaction, add 3mL of distilled water to the reaction solution, extract with ethyl acetate, wash the organic layer with saturated brine, dry over anhydrous sodium sulfate, and remove the solvent by distillation under reduced pressure to obtain the crude product. The crude product is subjected to column chromatography (acetic acid Ethyl ester / petroleum ether=1 / 30~1 / 5) separation to obtain 46 mg of white solid with a yield of 81%.

[0036] The characterization data are as follows: 1 H NMR (500MHz, CDCl 3 ): δ=2.35(6H, s), 7.13(4H, d, J=8.0Hz), 7.41(4H, d, J=8.0Hz).

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Abstract

The invention belongs to the technical field of organic synthesis midbody, medicine, pesticide and liquid crystal materials, in particular to a preparation method of 1,4-diaryl-1,3-butadiyne. In the invention, the easily obtained beta, beta-dibromo arylethylene is served as a raw material, under the catalytic action of cuprous iodide, no ligand is added to the raw material and the 1,4-diaryl-1,3-butadiyne compound is efficiently synthesized in dimethylsulfoxide solvent in the presence of 1,8-dual nitrogen heterocyclic ring hendecene. The 1,4-diaryl-1,3-butadiyne synthesized by the invention can be served as the synthesis midbody of the medicine, the pesticide and the liquid crystal. Compared with the existing synthesis method of noble metal palladium, the method of the invention has the characteristics of easily obtained raw materials, low cost, simple operation, and mild reaction conditions, is easy to be industrialized, and has wide application prospect.

Description

technical field [0001] The invention belongs to the fields of organic synthesis intermediates, medicines, pesticides and liquid crystal materials, and specifically relates to a preparation method of 1,4-diaryl-1,3-butadiyne. Background technique [0002] 1,3-Butadiyne compounds are a very important class of organic compounds, they are widely used in the fields of organic synthesis intermediates, medicine, pesticides and liquid crystal materials. As an important conjugated linker in organic synthesis, 1,3-butadiyne compound is known as a universal module for building molecules, which can be used in the synthesis of macromolecular compounds such as annulene, and can also be used in the synthesis of metal organic compounds and porphyrins Derivatives, etc. (Li, C. Langmuir 2007, 23, 6754). 1,3-Butadiyne compounds are also natural products, structural units of antifungal drugs (Shi Shun, A.L.K. Angew. Chem. Int. Ed. 2006, 45, 1034). Because of its natural photosensitivity, 1,3-...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07B37/00C07C15/50C07C1/30C07C41/30C07C43/215C07C209/74C07C211/50C07D317/50
Inventor 匡春香金辉李世鹏
Owner TONGJI UNIV
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