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Method for realizing phase-transfer catalysis beta-dicarbonyl compound alkylation reaction by microchannel reactor

A dicarbonyl compound and microchannel reactor technology, which is applied in the preparation of organic compounds, chemical instruments and methods, chemical/physical/physical chemical reactors, etc., can solve the problems of difficult recovery and prolonged reaction time, and shorten the reaction time Effects of time, efficient recovery, stable scale-up and safe production process

Pending Publication Date: 2022-05-27
XIAN MODERN CHEM RES INST
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  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

[0003] In the actual scale-up process, phase transfer catalysis is used to realize the alkylation reaction of β-dicarbonyl compounds, which is limited by the mass transfer efficiency between the two phases, resulting in prolonged reaction time
Small molecule phase transfer catalysts are usually dissolved in one of the phases (organic or aqueous), making recovery difficult

Method used

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  • Method for realizing phase-transfer catalysis beta-dicarbonyl compound alkylation reaction by microchannel reactor
  • Method for realizing phase-transfer catalysis beta-dicarbonyl compound alkylation reaction by microchannel reactor
  • Method for realizing phase-transfer catalysis beta-dicarbonyl compound alkylation reaction by microchannel reactor

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Experimental program
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Effect test

Embodiment 1

[0044]

[0045] Add 10g SBA-15 (mesoporous molecular sieve), 5g tetrabutylammonium bromide (TBAB, quaternary ammonium salt) and 50mL toluene into a 100mL reaction flask, heat under reflux for 24h, remove toluene by vacuum distillation, and vacuum dry to obtain SBA-15-supported tetrabutylammonium bromide phase transfer catalyst 14.9 g (50% TBAB / SBA-15).

[0046] Disperse 0.310 g (1 mmol) 1-indanone-2-carboxylate adamantyl ester (A-1), 0.257 g (1.5 mmol) benzyl bromide (B-1), 0.03 g 50% TBAB / SBA-15 in 20 mL of toluene , an organic phase was obtained. A 1% KOH solution was prepared to obtain the aqueous phase. The flow rate of the organic phase was 5mL / min, and the flow rate of the aqueous phase was 5mL / min and passed into the microchannel reactor to carry out the alkylation reaction, the reaction temperature was 80°C, and the residence time was 30min to obtain 0.368g product (C-1, yield 92%). ). The reaction solution was filtered and washed with water to obtain a recovered...

Embodiment 7

[0055]

[0056] 10 g of chloromethylated polystyrene resin (PS, belonging to polystyrene resin), 1.2 g of tributylamine (Bu), 100 mL of dichloroethane and 50 mL of ethanol were added to a 250 mL reaction flask, and heated under reflux for 24 h. Filter and dry to obtain 11g PS grafted quaternary ammonium salt phase transfer catalyst (10%Bu / PS)

[0057] Disperse 0.345g (1mmol) of 5-chloro-1-indanone-2-carboxylate adamantate (A-2), 0.370g (2mmol) of m-methyl benzyl bromide (B-2), 0.069g of 10% Bu / PS In 20 mL of xylene, the organic phase was obtained. Formulated with 1% Na 2 CO 3 The solution gave an aqueous phase. The flow rate of the organic phase was 5mL / min, and the flow rate of the aqueous phase was 0.5mL / min and passed into the microchannel reactor to carry out the alkylation reaction. The reaction temperature was 60° C. and the residence time was 40min to obtain 0.386g of product (C-2, yield 86 %).

Embodiment 8

[0059]

[0060] Add 2g chloromethylated polystyrene resin (PS, belongs to polystyrene resin), 2.1g tetramethylpropylenediamine, 6g bromopropyltributylphosphonium bromide, and 100mL DMF into a 250mL reaction flask, and heat Reflux for 12h. Filter and dry to obtain 6.08 g of PS-grafted quaternary phosphonium salt phase transfer catalyst (300% P / PS).

[0061] 0.324g (1mmol) 4-methyl-1-indanone-2-carboxylate adamantyl ester (A-3), 0.717g (3mmol) p-trifluoromethyl benzyl bromide (B-3), 0.0648g 300%P / PS was dispersed in 20 mL of mesitylene to obtain an organic phase. Formulated 20% K 2 HPO 4 The solution gave an aqueous phase. The flow rate of the organic phase was 5mL / min, and the flow rate of the aqueous phase was 2.5mL / min and passed into the microchannel reactor to carry out the alkylation reaction, the reaction temperature was 100°C, and the residence time was 10min to obtain 0.429g product (C-3, yield 89 %).

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Abstract

The invention belongs to the technical field of organic synthesis, and provides a method for realizing phase-transfer catalysis of an alkylation reaction of a beta-dicarbonyl compound by using a microchannel reactor. According to the method, the phase-transfer catalysis beta-dicarbonyl compound alkylation reaction is realized in the microchannel reactor by using the supported phase-transfer catalyst, the reaction temperature is 20-100 DEG C, the retention time is 10-120 minutes, and the highest product yield is more than 95%. According to the method, the supported phase transfer catalyst is easy to recover while the dosage of the catalyst is reduced and the reaction rate is increased, so that the reaction cost is reduced. Meanwhile, a liquid-liquid two-phase phase transfer reaction is realized in the micro-channel reactor, so that the reaction time is greatly shortened, continuous synthesis is realized, and the method has the advantages of large-scale production and low cost.

Description

technical field [0001] The invention belongs to the technical field of organic synthesis, and in particular relates to a method for realizing a phase transfer catalyzed β-dicarbonyl compound alkylation reaction in a microchannel reactor. Background technique [0002] Alpha-alkylated-beta-dicarbonyl compounds are key structures for many drugs. Compounds such as tricyclic pyrazolopyrimidines, methylvitamin D derivatives, and star anise sesquiterpene natural products contain such structures. Patent CN101460448A introduces a method for asymmetric alkylation of carbonyl groups, which is mainly aimed at the stereoselective preparation of the antidepressant ideprom. Patents CN107519828A and CN107523328A introduce a novel microchannel reactor alkylation method and device, which are mainly aimed at the alkylation reaction of isobutane and olefin under acid catalysis to obtain alkylated oil. Patent CN110872232A introduces a method for realizing asymmetric α-difluoromethylation of β-...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07C67/343C07C69/757B01J19/00
CPCC07C67/343B01J19/0093C07C69/757Y02P20/584
Inventor 唐晓飞张瑶廉鹏朱军臣张圣龙王锡杰王栋嵘陈松
Owner XIAN MODERN CHEM RES INST
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