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Synthesis method for calix [4] arenes substituted by 2-diphenylphosphine benzoyl and application

A technology based on diphenylphosphine and benzoyl, which is applied in the field of calix[4]arene synthesis, can solve the problems of complex catalyst preparation process, unstable catalyst, and expensive starting materials, and achieve good catalyst stability and good The effect of application value and short steps

Active Publication Date: 2014-06-04
ZHEJIANG UNIV OF TECH
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

Shi Min and others have successfully developed a series of phosphine-containing chiral catalysts, such as catalyst A, which can effectively catalyze the aza-Baylis-Hillman reaction, the reaction time is short, and the yield can reach 90%. However, this type of catalyst is not very stable, After the reaction, more than 90% of A is oxidized to phosphine oxide
In addition, the preparation process of this type of catalyst is complex and the starting materials are expensive (Shi, M.; Chen, L.-H., Chem. Commun., 2003, 1310-1311)

Method used

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  • Synthesis method for calix [4] arenes substituted by 2-diphenylphosphine benzoyl and application
  • Synthesis method for calix [4] arenes substituted by 2-diphenylphosphine benzoyl and application
  • Synthesis method for calix [4] arenes substituted by 2-diphenylphosphine benzoyl and application

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0045] Add p-tert-butylcalix[4]arene (12.96g, 20.00mmol), 2-diphenylphosphinebenzoic acid (9.18g, 30.00mmol), refined toluene 200mL in a 500mL three-necked flask, and add DCC (8.24 g, 40.00mmol), DMAP (0.49g, 4.00mmol), heated to 60°C for reaction, followed by TLC monitoring, and the reaction was complete after 12 hours. Add 160 mL of water, filter with suction, discard the filter cake, extract the filtrate with 200 mL of dichloromethane, wash with saturated brine (200 mL×3), dry over anhydrous sodium sulfate, concentrate under reduced pressure to recover the organic solvent, and the residue is separated by column chromatography. Using a mixture of petroleum ether and ethyl acetate at a volume ratio of 30:1 as the eluent, collect the eluate containing 2-diphenylphosphinebenzoyl-substituted calix[4]arene, and evaporate the solvent to obtain catalyst 2 -Diphenylphosphinebenzoyl-substituted calix[4]arene, white solid, 15.50 g, yield 83%, melting point 156.4-158.2°C. 1 H NMR (400...

Embodiment 2

[0047] Add p-tert-butylcalix[4]arene (12.96g, 20.00mmol), 2-diphenylphosphinebenzoic acid (9.18g, 30.00mmol) and 200mL of refined dichloromethane into a 500mL three-necked flask, and add DCC under nitrogen protection (8.24g, 40.00mmol), DMAP (0.49g, 4.00mmol), heated to 40°C for reaction, followed by TLC monitoring, after 13 hours of complete reaction, the treatment was the same as in Example 1 to obtain 2-diphenylphosphinebenzoyl substituted Calix[4]arene, white solid, 14.07g, yield 75%, melting point 157.3-158.9°C.

Embodiment 3

[0049] Add p-tert-butylcalix[4]arene (12.96g, 20.00mmol), 2-diphenylphosphinebenzoic acid (18.36g, 60.00mmol) and 200mL of refined toluene into a 500mL three-necked flask, and add DCC (8.24 g, 40.00mmol), DMAP (0.49g, 4.00mmol), heated to 80°C for reaction, followed by TLC monitoring, and the reaction was complete after 11 hours. Post-treatment was the same as in Example 1 to obtain 2-diphenylphosphinebenzoyl-substituted calix[4]arene, a white solid, 14.60 g, yield 78%, melting point 155.1-156.2°C.

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Abstract

The invention discloses a synthesis method for calix [4] arenes substituted by 2-diphenylphosphine benzoyl as shown in drawings and discloses the application of calix [4] arenas serving as a catalyst in aza-Baylis-Hillman reaction for effectively preparing aza-Baylis-Hillman reaction affixture. The invention has the advantages of simple preparation technique for catalyst, low catalyst consumption, rapid reaction speed, gentle reaction conditions, etc.

Description

(1) Technical field [0001] The invention relates to a synthesis method of calix[4]arene substituted by 2-diphenylphosphinebenzoyl and its application as a catalyst for aza-Baylis-Hillman reaction. (2) Background technology [0002] The aza-Baylis-Hillman reaction is an organic amine or organophosphine catalyzed carbon-carbon bond formation reaction with atom economy and selectivity (including chemoselectivity, regioselectivity, stereoselectivity) (Declerck, D.; Martinez , J., Lamty, F., Chem. Rev., 2009, 109, 1-48). From the point of view of the reaction itself, all the reaction raw materials have entered the reaction product, and its atom utilization rate is as high as 100%, which is in line with the development direction of green chemistry and has been widely concerned by people. The aza-Baylis-Hillman reaction products, also known as aza-Baylis-Hillman adducts, have various biological activities, such as anti-HIV, anti-cancer, anti-cell proliferation, antithrombotic, hyp...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): C07F9/50B01J31/04C07B37/02C07C311/17C07C311/16C07C303/40C07D213/50C07D333/22C07D307/52
Inventor 钟为慧沈妍彦苏为科唐谦
Owner ZHEJIANG UNIV OF TECH
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