Application of diphenylphosphine methyl-substituted calix [4] arene

A technology of diphenylphosphinomethyl and aromatic hydrocarbons, applied in organic compound/hydride/coordination complex catalysts, sulfonamide preparation, organic chemistry, etc., to achieve high catalytic activity, reduce phosphorus pollution, and good stability Effect

Active Publication Date: 2012-07-25
ZHEJIANG UNIV OF TECH
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0007]Calixarene is a "novel" macrocyclic compound with a unique hole structure. Diphenylphosphinomethyl-substituted calix[4]arene has been used as a ligand to interact with Metal complexation to treat nuclear industry waste (Emil T., Supramol. Chem., 2007, 19(7), 447~457) or for molecular recognition, etc. , there is no report on the use of diphenylphosphinomethyl-substituted calix[4]arenes as organocatalysts

Method used

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  • Application of diphenylphosphine methyl-substituted calix [4] arene
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  • Application of diphenylphosphine methyl-substituted calix [4] arene

Examples

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Effect test

Embodiment 1

[0035] In a 100 mL three-necked bottle, add N -Benzylidene-4-methylbenzenesulfonimide 12.95 g (50 mmol), methyl vinyl ketone 7.00 g (100 mmol), catalyst diphenylphosphinomethyl-substituted calix[4]arene 4.23 g (5 mmol), 26 g of dichloromethane, stirred at 20°C for 58 h, TLC tracking showed that the reaction of the raw materials was complete. Add 120 g of dichloromethane, wash with saturated brine (30 mL×2), dry the organic phase over anhydrous sodium sulfate and concentrate in vacuo, add 10 g of cold methanol, a solid precipitates, filter to obtain the catalyst, and weigh after drying to obtain 3.47 g, the recovery rate was 82%; after the filtrate was concentrated, it was separated by column chromatography, using petroleum ether / ethyl acetate=4:1 (v / v) as the eluent, and detected by TLC. The eluent of the product, the eluent is distilled to remove the eluent to obtain the aza-Baylis-Hillman adduct 4-methyl- N -(2-Methylene-3-oxo-1-phenylbutyl)benzenesulfonamide, white solid,...

Embodiment 2

[0037] In a 100 mL three-necked bottle, add N -Benzylidene-4-methylbenzenesulfonimide 12.95 g (50 mmol), methyl vinyl ketone 4.20 g (60 mmol), catalyst diphenylphosphinomethyl-substituted calix[4]arene 0.42 g (0.5 mmol), 38 g of ethanol, stirred at 40 °C for 43 h, TLC tracking showed that the reaction of the raw materials was complete. Add 26 g of ethyl acetate for extraction, wash with saturated brine (30 mL×2), dry the organic phase over anhydrous sodium sulfate and concentrate in vacuo, add 1.68 g of cold methanol, a solid precipitates, filter to obtain the catalyst, dry and weigh 0.37 g was obtained, and the recovery rate was 89%; the filtrate was concentrated and separated by column chromatography, using petroleum ether / ethyl acetate=4:1 (v / v) as the eluent, detected by TLC, and collected the aza-Baylis-Hillman plus The eluent of the product, the eluent is distilled to remove the eluent to obtain the aza-Baylis-Hillman adduct 4-methyl- N -(2-Methylene-3-oxo-1-phenylbuty...

Embodiment 3

[0039] In a 100 mL three-necked bottle, add N -Benzylidene-4-methylbenzenesulfonimide 12.95 g (50 mmol), methyl vinyl ketone 10.50 g (150 mmol), catalyst diphenylphosphinomethyl-substituted calix[4]arene 21.17 g (25 mmol), 48 g of ethyl acetate, stirred at 15°C for 50 h, and TLC tracking showed that the reaction of the raw materials was complete. Add 130 g of diethyl ether for extraction, wash with saturated brine (30 mL×2), dry the organic phase with anhydrous sodium sulfate and concentrate in vacuo, add 21.17 g of cold methanol, a solid precipitates, filter to obtain the catalyst, and weigh after drying to obtain 15.88 g, the recovery rate was 75%; the filtrate was concentrated and separated by column chromatography, using petroleum ether / ethyl acetate = 4:1 (v / v) as the eluent, and detected by TLC, the collection contained aza-Baylis-Hillman The eluent of the product, the eluent is distilled to remove the eluent to obtain the aza-Baylis-Hillman adduct 4-methyl- N -(2-Meth...

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Abstract

The invention discloses an application of diphenylphosphine methyl-substituted calix [4] arene serving as a catalyst for aza-Baylis-Hillman reaction and an application method by which an aza-Baylis-Hillman affixture with high yield can be prepared. The method is characterized in that the reaction condition is wild, the catalyst dosage is less, the catalyst recovery and reuse are easy and the like, thereby having greater implementation value and social and economic benefits.

Description

technical field [0001] The invention relates to a calix[4]arene substituted with diphenylphosphinemethyl, which can be used as a catalyst in the aza-Baylis-Hillman reaction and can be recovered and used mechanically. Background technique [0002] The Baylis-Hillman reaction, first reported in a patent by Baylis and Hillman in 1972 (Baylis, A. B.; Hillman, M. E. D. Ger. Offen ., 1972, 2, 155, 113). This reaction is to activate the reaction of olefins with aldehydes, ketones, etc. under the action of catalysts (such as tertiary amines, phosphines), and obtain a product with multiple functional groups. The reaction conditions are mild, the raw materials are cheap and readily available, and it is atom-economical. Theoretically, the Baylis-Hillman reaction has good application prospects both in laboratory synthesis research and in the chemical industry (Basavaiah, D.; Raoand, P. D.; Hyma, R. S. Tetrahedron , 1996, 52 , 8001-8062; Basavaiah, D.; Rao, A. J.; Satyanarayana, T.,...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): B01J31/02C07C303/36C07C311/17C07C311/16C07C311/19
Inventor 钟为慧郑叶敏施湘君沈妍彦苏为科
Owner ZHEJIANG UNIV OF TECH
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