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Coupling reaction of end group alkine and aryl halide

A technology for aryl halide and coupling reaction, which is applied in the field of coupling reaction of terminal alkyne and aryl halide, can solve the problems of expensive palladium catalyst, environmental pollution and serious problems, and achieves mild reaction conditions and good application. Prospect, cheap effect

Inactive Publication Date: 2005-07-06
SHANGHAI INST OF ORGANIC CHEM CHINESE ACAD OF SCI
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

However, due to the relatively expensive palladium catalyst and serious environmental pollution, in the past few years, some relatively mild methods that use Cu as a catalyst and react by adding ligands have been greatly developed.

Method used

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  • Coupling reaction of end group alkine and aryl halide
  • Coupling reaction of end group alkine and aryl halide
  • Coupling reaction of end group alkine and aryl halide

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0025] 1. Preparation of 1-methoxy-4-phenylethynylbenzene

[0026]

[0027] In a reaction tube, add 122mg phenylacetylene (MW=102.14, 1.2mmol), then add 234mg p-methoxyiodobenzene (MW=234.04, 1mmol), 414mg K 2 CO 3 (MW=138.21, 3mmol), 42mg N, N-dimethylglycine hydrochloride (MW=139.58, 0.3mmol), 19mg CuI (MW=190.446, 0.1mmol), 2ml DMF and 0.05ml water are as solvent, in Under argon protection, react in an oil bath at 100°C for 24 hours, cool, add 2 ml of water, extract with 4 ml of ethyl acetate each time, repeat three times, wash the extract with saturated brine, dry over anhydrous sodium sulfate, and filter. The filtrate was distilled under reduced pressure and separated through a silica gel column (petroleum ether as the eluent) to obtain 175 mg of the product 1-methoxy-4-phenylethynyl-benzene with a yield of 84%.

[0028] 1 H NMR (CDCl 3 , 300MHz) δ 3.81(s, 3H), 6.87(d, J=8.4Hz, 2H), 7.31-7.53(m, 7H); MS m / z 208(M + ).

Embodiment 2

[0030] 2. 4-Phenylethynylbenzoic acid

[0031]

[0032] In a reaction tube, add 122mg phenylacetylene (MW=102.14, 1.2mmol), then add 248mg p-iodobenzoic acid (MW=248.02, 1mmol), 414mg K 2 CO 3 (MW=138.21, 3mmol), 42mgN, N-dimethylglycine hydrochloride (MW=139.58, 0.3mmol), 19mg CuI (MW=190.446, 0.1mmol), 2ml DMF and 0.05ml water are as solvent, in argon Under air protection, react in an oil bath at 100°C for 24 hours, cool, add 2 ml of water, wash with 2N hydrochloric acid until PH = 2, extract with 4 ml of ethyl acetate each time, repeat three times, and wash the extract with saturated saline. After drying over sodium sulfate, filter, the filtrate was distilled under reduced pressure, and separated through a silica gel column (petroleum ether: ethyl acetate = 1:1 as the eluent) to obtain 153 mg of the product 4-phenylethynylbenzoic acid, with a yield of 69%.

[0033] 1 H NMR (CD 3 COCD 3 , 300MHz) δ7.45(t, J=3.3Hz, 2H), 7.59-7.62(m, 1H), 7.68(d, J=8.1Hz, 1H), 7.80(d, ...

Embodiment 3

[0035] 3. Preparation of 1-methoxy-2-phenylethynyl-benzene

[0036]

[0037] In a reaction tube, add 122mg phenylacetylene (MW=102.14, 1.2mmol), then add 234mg o-methoxy iodobenzene (MW=234.04, 1mmol), 414mg K 2 CO 3(MW=138.21, 3mmol), 42mg N, N-dimethylglycine hydrochloride (MW=139.58, 0.3mmol), 19mg CuI (MW=190.446, 0.1mmol), 2ml DMF and 0.05ml water are as solvent, in Under argon protection, react in an oil bath at 100°C for 24 hours, cool, add 2 ml of water, extract with 4 ml of ethyl acetate each time, repeat three times, wash the extract with saturated brine, dry over anhydrous sodium sulfate, and filter. The filtrate was distilled under reduced pressure and separated through a silica gel column (petroleum ether as the eluent) to obtain 172 mg of the product 1-methoxy-2-phenylethynyl-benzene with a yield of 82%.

[0038] 1 H NMR (CDCl 3 , 300MHz) δ3.91(s, 3H), 6.89-6.97(m, 2H), 7.25-7.36(m, 4H), 7.49-7.58(m, 3H); MS m / z 208(M + ).

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Abstract

The present invention relates to a method for the coupling reaction of terminal alkynes and aryl halides. The invention provides a coupling reaction method, that is, amino acid is used as an additive and CuI is used as a catalyst, so that the coupling reaction of terminal alkynes and aryl halides can be carried out under relatively mild conditions. The invention also provides some new coupling reaction products. The reactions involved in the present invention can be represented by the following general reaction formula. The catalyst and ligand used in the present invention are cheap, easy to get, and stable in the air. Compared with the same type of reaction reported in the literature, the average temperature of the reaction is reduced by about 20 ° C, and the reaction conditions are very mild. Good application prospects.

Description

technical field [0001] This invention relates to a process for the coupling reaction of terminal alkynes and aryl halides. Coupling reactions of a series of aryl halides and terminal alkynes have been realized by this method. Background technique [0002] Acetylene derivatives are widely used in organic synthesis, and their synthetic methods have received extensive attention in recent years. More commonly used is the Sonogashira reaction (Sonogashira, K.; Tohda, Y.; Hagihara, N. Tetrahedron Letter. 1975, 50, 4467.), using copper and palladium to co-catalyze terminal alkynes and aryl halides and alkenes Coupling reactions of halides. However, due to the relatively expensive palladium catalyst and serious environmental pollution, in the past few years, some relatively mild methods that use Cu as a catalyst and react by adding ligands have been greatly developed. ((a) Miura, M.J.Org.Chem.1993, 58, 4716-4721; (b) Gujadhur, R.K,; Bates, C.G.; Venkataraman, D.Org.Lett.2001, 3, ...

Claims

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Application Information

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IPC IPC(8): C07B37/00C07B41/00C07C2/00C07C15/48C07C41/30C07C43/243C07C43/247C07C45/61C07C47/232C07C47/24C07C47/277C07C59/64C07C201/12C07C205/11
Inventor 马大为刘烽
Owner SHANGHAI INST OF ORGANIC CHEM CHINESE ACAD OF SCI
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