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Method for preparing, separating and purifying biphenyl derivative through catalytic coupling

A technology of derivatives and biphenyl, which is applied in the field of synthetic chemistry, catalytic coupling preparation and separation and purification of biphenyl derivatives, can solve the problems affecting the reaction process and difficult to reduce, and achieve the effect of simple method of purification

Active Publication Date: 2021-10-08
HARBIN INST OF TECH AT WEIHAI
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

Otherwise it is difficult to reduce the preparation cost of 3,4-BPDA
[0005] By-product ZnCl in traditional nickel-catalyzed coupling systems 2 , is easily adsorbed on the surface of active zinc powder, thereby affecting the reaction process, which is also the excessive use of the existing patent method (up to 4 times the theoretical amount)

Method used

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  • Method for preparing, separating and purifying biphenyl derivative through catalytic coupling
  • Method for preparing, separating and purifying biphenyl derivative through catalytic coupling
  • Method for preparing, separating and purifying biphenyl derivative through catalytic coupling

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0028] Take a 500mL three-neck flask, put dimethyl 4-chlorophthalate (22.8g, 0.1moL), N-phenyl-3-chlorophthalimide (25.7g, 0.1moL), zinc powder (6.5g, 0.1moL), anhydrous NiCl 2 (255mg, 2mmoL) and triphenylphosphine (0.5g, 2mmoL), mixed in a nitrogen atmosphere, added 145mL of anhydrous DMAc, 50 ℃ ultrasonically assisted stirring reaction for 4 hours, filtered the insoluble matter, and the obtained filtrate was decompressed in a round bottom flask 125 mL of the solvent DMAc was recovered to obtain a viscous solid.

[0029] 1) Add 150g of ethanol to the system and reflux for 30 minutes, filter out the insoluble matter N-phenyl-N'-phenyl-2,2',3,3'-biphenylbisimine (collectively: 3,3 '-biphenylbisimine), dried at 100°C for 10 hours to obtain 10 g of 3,3'-biphenylbisimine, added 24 g of 20% aqueous sodium hydroxide solution to a 200 mL reaction flask, heated to reflux for 24 hours, filtered off Insoluble matter, cooled, adjusted pH=1 with concentrated hydrochloric acid, cooled to...

Embodiment 2

[0033]Take a 500mL three-neck flask, put dimethyl 4-chlorophthalate (22.8g, 0.1moL), N-methyl-3-chlorophthalimide (9.8g, 0.05moL), zinc powder (5.2g, 0.08moL), anhydrous NiCl 2 (255mg, 2mmoL) and triphenylphosphine (3.5g, 14mmoL), mixed in a nitrogen atmosphere, added 160mL of anhydrous DMAc, 500w ultrasonic assisted 100 ℃ stirring reaction for 1 hour, filtered the insoluble matter, and the obtained filtrate was reduced in a round bottom flask 140 mL of solvent DMAc was recovered under pressure.

[0034] 1) Add 100g of ethanol to the system and reflux for 30 minutes, all of which are dissolved, and no 2,2',3,3'-biphenylbisimine is formed. All the mixture in the system is a mixture of 4,4'-biphenyl tetramethyl ester and N-methyl-34'-biphenylimine dimethyl ester, distilled off to recover ethanol, and add 20% hydroxide to the phase system at the same time Sodium aqueous solution 64g, heated to reflux for 12 hours, filtered off insoluble matter, cooled, and adjusted to pH=1 with...

Embodiment 3

[0036] Take a 500mL three-neck flask, put dimethyl 4-chlorophthalate (22.8g, 0.1moL), N-methyl-3-chlorophthalimide (19.5g, 0.1moL), zinc powder (13g, 0.2moL), anhydrous NiCl 2 (510mg, 4mmoL) and 2,2-bipyridine (2.18g, 14mmoL), mixed in a nitrogen atmosphere, then added 140mL of anhydrous NMP, 400w ultrasonic assisted stirring reaction at 90 ° C for 2 hours, filtered the insoluble matter, and the obtained filtrate was in the round bottom The solvent NMP 120mL was recovered under reduced pressure in the flask to obtain a viscous solid.

[0037] 1) Add 120 g of ethanol to the obtained viscous solid, reflux for 30 minutes, filter out the insoluble matter while hot to obtain N-methyl-N'-methyl-2,2',3,3'-biphenylbisimine ( Collectively: 3,3'-biphenylbisimine) 7.5g, alcohol mother liquor for later use. Add 20g of 20% sodium hydroxide aqueous solution to 3,3'-biphenylbisimine, heat and reflux for 24 hours, filter off insoluble matter, cool, adjust pH=1 with concentrated hydrochloric...

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Abstract

The invention discloses a method for preparing, separating and purifying a biphenyl derivative through catalytic coupling, which mainly comprises the following steps: by taking a nickel salt catalyst and zinc as a reducing agent, in an aprotic solvent system, adopting a mixture of 3-halogenated phthalimide and 4-halogenated biphenyl dimethyl dicarboxylate as a raw material, and carrying out cross coupling under ultrasonic-assisted catalysis to generate 3,4'-biphenyl dianhydride and also generate 3,3'- and 4,4'-biphenyl derivatives. According to the method, the three generated biphenyl derivatives are separated according to different solubilities, 3,4'-, 3,3'- and 4,4'-biphenyl derivatives are obtained respectively, and three pure biphenyl dianhydride isomers are obtained respectively after the three biphenyl derivatives are hydrolyzed and dehydrated.

Description

technical field [0001] The invention relates to a method for preparing, separating and purifying biphenyl derivatives through catalytic coupling, which belongs to the category of synthetic chemistry. Background technique [0002] Biphenyltetra-acid dianhydride, referred to as BPDA, is one of the iconic dianhydride monomers for synthetic polyimide materials, and is expensive. At present, the industrial preparation of biphenyltetracarboxylic dianhydride is mainly prepared by noble metal palladium catalyzed coupling. Related research reports such as patents JP7352749, US5243067, CN201310049837, etc., are expensive, but have the asymmetry required for low-viscosity processing characteristics. Biphenyldianhydride 3,4'-BPDA is more than 10 times the price of conventional product 4,4'-BPDA. The application market of benzene-type polyimide materials is greatly limited, so it is of great significance to develop an inexpensive catalytic coupling reaction system to prepare biphenyl di...

Claims

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Application Information

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IPC IPC(8): C07D307/89
CPCC07D307/89
Inventor 高昌录孙秀花
Owner HARBIN INST OF TECH AT WEIHAI
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