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Amino acid accelerated CuI catalyzed aryl halide and coupling reaction of alkyl sulfonate

A technology of aryl halides and amino acids, which is applied in the field of coupling reaction between aryl halides and hydrocarbyl sulfinates, which can solve problems such as high temperature, environmental pollution, and limited substrate range, and achieve mild reaction conditions and low price , the effect of good application prospects

Inactive Publication Date: 2005-08-10
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

The traditional method has many defects, and many functional groups cannot tolerate severe reaction conditions; while the palladium catalyst has problems such as high price and serious environmental pollution
The copper-catalyzed reactions reported in the literature have problems such as the use of stoichiometric catalysts, high temperature, and limited substrate range.

Method used

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  • Amino acid accelerated CuI catalyzed aryl halide and coupling reaction of alkyl sulfonate
  • Amino acid accelerated CuI catalyzed aryl halide and coupling reaction of alkyl sulfonate
  • Amino acid accelerated CuI catalyzed aryl halide and coupling reaction of alkyl sulfonate

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0019] 1, Preparation of 4-methoxyphenylmethyl sulfone

[0020]

[0021] In a reaction tube, add 234mg p-methoxyiodobenzene (MW=234.04, 1.0mmol), then add 153mg methylsulfinic acid sodium salt (MW=102.09, 1.2mmol, content 80%), 28mg L-proline Sodium salt (MW=137.05, 0.2mmol), 19mg CuI (MW=190.45, 0.1mmol), 2ml DMSO as solvent, under the protection of nitrogen, react in 80 ℃ oil bath for 24 hours, cool, add 4 milliliters of water, every Once extracted with 10 ml of ethyl acetate, repeated three times, the extract was washed with saturated brine, dried over anhydrous sodium sulfate, filtered, the filtrate was distilled under reduced pressure, and separated by a silica gel column (eluent petroleum ether: ethyl acetate=4: 1), to obtain 156 mg of product 4-methoxyphenylmethyl sulfone, yield 84%.

[0022] 1 H NMR (300MHz, CDCl 3 )δ 3.05(s, 3H), 3.90(s, 3H), 7.04(AB, J 1 =7.5Hz,J 2 =2.1Hz, 2H), 7.88 (AB, J 1 =7.5Hz,J 2 =2.1Hz, 2H); EI-MS (m / z) 186 (M + ), 171, 155, 139, 12...

Embodiment 2

[0025] 2, Preparation of 4-methylphenylmethyl sulfone

[0026]

[0027] In a reaction tube, add 218mg p-methyliodobenzene (MW=218.03, 1.0mmol), then add 153mg methylsulfinic acid sodium salt (MW=102.09, 1.2mmol, content 80%), 28mg L-sodium proline Salt (MW=137.05, 0.2mmol), 19mg CuI (MW=190.45, 0.1mmol), 2ml DMSO as solvent, under nitrogen protection, reacted in 80 ℃ oil bath for 24 hours, cooled, added 4 milliliters of water, each time Extracted with 10 ml of ethyl acetate, repeated three times, the extract was washed with saturated brine, dried over anhydrous sodium sulfate, filtered, the filtrate was distilled under reduced pressure, separated by a silica gel column (petroleum ether:ethyl acetate=4:1 ), to obtain 158mg product 4-methylphenylmethyl sulfone, yield 93%.

[0028] 1 H NMR (400MHz, CDCl 3 )δ2.46(s, 3H), 3.04(s, 3H), 7.36(d, J=8.2Hz, 2H), 7.82(d, J=8.2Hz, 2H); EI-MS (m / z) 170 (M + ), 155, 139, 121, 107, 91, 77, 65, 51, 39.

Embodiment 3

[0030] 3. Preparation of 4-hydroxyphenylmethyl sulfone

[0031]

[0032] In a reaction tube, add 220mg p-hydroxyiodobenzene (MW=220.00, 1.0mmol), then add 153mg methylsulfinic acid sodium salt (MW=102.09, 1.2mmol, content 80%), 28mg L-sodium proline Salt (MW=137.05, 0.2mmol), 19mg CuI (MW=190.45, 0.1mmol), 2ml DMSO as solvent, under nitrogen protection, reacted in 80 ℃ oil bath for 24 hours, cooled, added 4 milliliters of water, each time Extracted with 10 ml of ethyl acetate, repeated three times, the extract was washed with saturated brine, dried over anhydrous sodium sulfate, filtered, the filtrate was distilled under reduced pressure, separated by a silica gel column (petroleum ether:ethyl acetate=3:1 ), to obtain 160mg of product 4-hydroxyphenylmethyl sulfone, yield 93%.

[0033] 1 H NMR (400MHz, CDCl 3 )δ3.05 (s, 3H), 6.96 (d, J=8.7Hz, 2H), 7.74 (d, J=8.7Hz, 2H); EI-MS (m / z) 172 (M+ ), 157, 141, 109, 94, 79, 65, 43.

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Abstract

A process for preparing arylsulfone by the coupling reaction between arylhalide and hydroxysulfonite features that the amin acid is used as the reaction promoter and the CuI is used as catalyst for creating gentle reaction conditions.

Description

technical field [0001] The invention relates to a method for carrying out coupling reaction of aryl halide and hydrocarbyl sulfinate under the condition of using amino acid as additive and CuI as catalyst. Through this method, the reaction of preparing aryl sulfone from a series of aryl halides and the reaction of preparing heteroaryl sulfone from heterocyclic aromatic halides containing nitrogen, oxygen and sulfur are realized. Background technique [0002] Aryl sulfone has its special chemical properties and biological activity, and the structure of aryl sulfone can be found in many drugs. As an important class of organic compounds, their synthesis and application have been extensively studied. The more commonly used synthesis methods of aryl sulfones are: oxidation of corresponding aryl sulfides, sulfonation of aromatic hydrocarbons under acid catalysis, reaction of organolithium, organomagnesium compounds and sulfone esters; and palladium catalyzed hydrocarbyl sulfinate...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07C315/04C07C317/14
Inventor 马大为竺伟
Owner SHANGHAI INST OF ORGANIC CHEM CHINESE ACAD OF SCI
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