Method for synthesizing diaryl ether by using amino acid as additive

A synthesis method and a technology for diaryl ethers, which are applied in the field of Ullmann diaryl ether synthesis, can solve the problems of expensive palladium reagents and difficult reactions, and achieve the effects of easy products, low prices and good application prospects.

Inactive Publication Date: 2003-12-24
SHANGHAI INST OF ORGANIC CHEMISTRY - CHINESE ACAD OF SCI
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

However, there are still many limitations in the use of palladium catalysts, such as many substrates co

Method used

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Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0015] Preparation of 4-methoxyphenylphenyl ether

[0016] In a reaction tube, add 468mg p-methoxyiodobenzene (MW=234.04, 2.0mmol), then add 282mg phenol (MW=94.11, 3mmol), 1.3g Cs 2 CO 3 (MW=325.82, 4mmol), 21mg N, N-dimethylglycine (MW=139.58, 0.15mmol), 8mg CuI (MW=190.446, 0.04mmo), 4ml Dioxane as solvent, under nitrogen protection, at 90°C React in an oil bath for 22 hours, cool, add 5 ml of water, extract with 10 ml of ethyl acetate each time, repeat four times, wash the extract with saturated brine, dry over anhydrous sodium sulfate, filter, and distill the filtrate under reduced pressure, pass through silica gel Column separation (petroleum ether:ethyl acetate=30:1 as the eluent) yielded 350 mg of product with a yield of 87%. 1 H NMR (CDCl 3 , 300 MHz) δ3.80(s, 3H), 6.87-7.00(m, 7H), 7.29(m, 1H); MS m / z 200(M + ), 185, 169, 129, 123, 95, 77, 63, 51, 50, 41.

Embodiment 2

[0018] 3,5-Dimethylphenylphenyl ether

[0019] In a reaction tube, add 464mg 3,5-dimethyliodobenzene (MW=232.01, 2.0mmol), then add 282mg phenol (MW=94.11, 3mmol), 1.3g Cs 2 CO 3 (MW=325.82, 4mmol), 21mg N, N-dimethylglycine (MW=139.58, 0.15mmol), 8mg CuI (MW=190.446, 0.04mmo), 4ml Dioxane as solvent, under nitrogen protection, at 90°C React in an oil bath for 16 hours, cool, add 5 ml of water, extract with 10 ml of ethyl acetate each time, repeat four times, wash the extract with saturated brine, dry over anhydrous sodium sulfate, filter, distill the filtrate under reduced pressure, and pass through silica gel Column separation (petroleum ether:ethyl acetate=30:1 as the eluent) yielded 383 mg of product with a yield of 97%.

[0020] 1 H NMR (CDCl 3 , 300MHz) δ2.28(s, 6H), 6.64(s, 2H), 6.73(s, 1H), 7.01(m, 3H), 7.32(m, 2H); MS m / z 198(M + ), 183, 169, 155, 129, 115, 105, 98, 91, 77, 65, 51, 41.

Embodiment 3

[0022] Preparation of m-nitrophenylphenyl ether

[0023] In a reaction tube, add 498mg m-nitroiodobenzene (MW=249.01, 2.0mmol), then add 282mg phenol (MW=94.11, 3mmol), 1.3g Cs 2 CO 3 (MW = 325.82, 4mmol), 21mg N, N-dimethylglycine (MW = 139.58, 0.15mmol), 8mg CuI (MW = 190.446, 0.04mmol), 4ml Dioxane as a solvent, under nitrogen protection, at 90 ℃ oil React in a bath for 16 hours, cool, add 5 ml of water, extract with 10 ml of ethyl acetate each time, repeat four times, wash the extract with saturated brine, dry over anhydrous sodium sulfate, filter, and distill the filtrate under reduced pressure, pass through a silica gel column After separation (petroleum ether:ethyl acetate=30:1 as eluent), 3422 mg of product was obtained with a yield of 98%.

[0024] 1 H NMR (CDCl3 , 300MHz) δ7.07(m, 2H), 7.22(m, 1H), 7.32(m, 1H), 7.40-7.53(m, 3H), 7.80(t, J=2.1Hz, 1H); MS m / z 215(M + ), 198, 168, 141, 128, 115, 102, 92, 77, 63, 51.

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Abstract

A process using amino acids as additive for synthesizing biarylether features use of amino acid as additive and Cu salt as catalyst. The said amino acid may be the monosubstituted (or bisubstituted)-on-nitrogen alpha-amino acid or beta-amino acid. Its advantages are very gentle reaction, condition and high output rate.

Description

technical field [0001] The invention relates to a method for synthesizing Ullmann's diaryl ether under the condition of using amino acid as additive and copper salt as catalyst. Through this method, a series of diaryl ether compounds have been synthesized. Background technique [0002] Ullmann's diaryl ether synthesis reaction (Ullmann, F.ber Dtsch.Chem.Ges.1904,37,853.) has a long history of development both academically and industrially (Lindley, J.Tetrahedron 1984,40 , 1433). However, the application of this reaction is greatly limited because the reaction requires high temperature conditions, a large amount of copper reagent is required, and the yield is low. Palladium catalysts have been used in recent years ((a) Torraca, K.E.; Huang, X.; Parrish, C.A.; Buchwald, S.L.J. Am. Chem. Soc. 2002, 123, 10770; (b) Aranyos, A.; Old, D.W ; Kiyomori, A.; Wolfe, J.P; Sadighi, J.P.; Buchwald, S.L.J. Am. Chem. Soc. 1999, 121, 4369; .Am.Chem.Soc.1999,121,3224), the condition that ...

Claims

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Application Information

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IPC IPC(8): C07C41/01C07C43/257C07C43/263C07C43/29C07C45/61C07C49/84C07C201/12C07C205/38C07C253/30C07C255/54
Inventor 马大为蔡倩
Owner SHANGHAI INST OF ORGANIC CHEMISTRY - CHINESE ACAD OF SCI
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