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Synthesis of 4-phenylmethylene-2,6-di-tert-butyl-2,5-cyclohexadien-1-ketone through solvent-free microwave method

A technology of di-tert-butyl and benzylidene, applied in the field of organic synthetic chemistry, can solve the problems of large recrystallization loss, long operation time, and the need for solvents

Pending Publication Date: 2019-04-19
SOUTHWEST UNIVERSITY
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

The operation time of this method is longer, the recrystallization loss is larger, and the distillation temperature is higher (Monatsh Chem, 2014, 145, 1941-1945)
[0004] The above method has a long reaction time and requires a solvent

Method used

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  • Synthesis of 4-phenylmethylene-2,6-di-tert-butyl-2,5-cyclohexadien-1-ketone through solvent-free microwave method
  • Synthesis of 4-phenylmethylene-2,6-di-tert-butyl-2,5-cyclohexadien-1-ketone through solvent-free microwave method

Examples

Experimental program
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Effect test

example 1

[0017] Example 1 Preparation of 4-phenylmethylene-2,6-di-tert-butyl-2,5-cyclohexadien-1-one (A).

[0018] .

[0019] Weigh 2,6-di-tert-butylphenol (0.969 mmol), add benzaldehyde (1.163 mmol) into the reaction flask, raise the temperature to 120°C, add piperidine (0.969 mmol) dropwise, power 300 W, stir at constant temperature, and react for 30 Minutes; maintain temperature and power, add acetic anhydride (0.969 mmol), and stir for 3 minutes. After cooling, add water to the reaction system, extract the mixture with ethyl acetate and separate the layers, dry the organic phase with anhydrous sodium sulfate, and concentrate to obtain the crude product. The resulting crude product is subjected to column chromatography with an eluent whose volume ratio is ethyl acetate:petroleum ether=1:400 to obtain the prepared 4-phenylmethylene-2,6-di-tert-butyl-2,5 -Cyclohexadiene-1-one ( A ) pure product, yield 70.18%. 1 H NMR (400 MHz, CDCl 3 ) δ 7.45 (d, J = 2.2 Hz,1H), 7.37 (d, J =...

example 2

[0020] Example 2 Preparation of 4-(2-methoxyphenylmethylene)-2,6-di-tert-butyl-2,5-cyclohexadien-1-one ( B ).

[0021] .

[0022] Weigh 2,6-di-tert-butylphenol (0.969 mmol), o-methoxybenzaldehyde (1.163 mmol), and piperidine (0.969 mmol) into the reaction flask, heat up to 120°C, power 300 W, and stir at constant temperature. React for 30 minutes; maintain the temperature and power, add acetic anhydride (0.969 mmol), and stir for 3 minutes. After cooling, add water to the reaction system, extract the mixture with ethyl acetate and separate the layers, dry the organic phase with anhydrous sodium sulfate, and concentrate to obtain the crude product. The resulting crude product is subjected to column chromatography with an eluent whose volume ratio is ethyl acetate:petroleum ether=1:250 to obtain the prepared 4-(2-bromophenylmethylene)-2,6-di-tert-butyl The yield of 2,5-cyclohexadien-1-one ( B ) was 74.92%. 1 H NMR (600 MHz, CDCl 3 ) δ 7.46 (d, J =2.1 Hz, 1H), 7.43 - 7.32...

example 3

[0023] Example 3 Preparation of 4-(4-methoxyphenylmethylene)-2,6-di-tert-butyl-2,5-cyclohexadien-1-one (C).

[0024] .

[0025] Weigh 2,6-di-tert-butylphenol (0.969 mmol), add p-methoxybenzaldehyde (1.163 mmol) into the reaction flask, raise the temperature to 120°C, add piperidine (0.969 mmol) dropwise, power 300 W, constant temperature Stir and react for 30 minutes; maintain the temperature and power, add acetic anhydride (0.969 mmol) and stir for 3 minutes. After cooling, add water to the reaction system, extract the mixture with ethyl acetate and separate the layers, dry the organic phase with anhydrous sodium sulfate, and concentrate to obtain the crude product. The resulting crude product is subjected to column chromatography with an eluent whose volume ratio is ethyl acetate:petroleum ether=1:150 to obtain the prepared 4-(4-methoxyphenylmethylene)-2,6-bis tert-butyl-2,5-cyclohexadien-1-one ( C ) pure product, yield 58.33%. 1 H NMR (600 MHz, CDCl 3 ) δ 7.5 -7.6 (d,...

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Abstract

The invention discloses an environment-friendly preparation method of a 4-phenylmethylene-2,6-di-tert-butyl-2,5-cyclohexadien-1-ketone derivative (p-QM). By utilizing the microwave radiation heating method under solvent-free conditions, 2,6-di-tert-butyl phenol and aromatic aldehyde are subjected to the two-step reaction of Mannich condensation and deamination to obtain the 4-benzylidene-2,6-di-tert-butyl-2,5-cyclohexadiene-1-ketone derivative (p-QM). The method has the advantages that the raw materials are cheap and easy to obtain, the atom economy is high, the reaction time is short, environment friendliness is good, dangerous reagents and solvents are not needed, the synthesis steps are simple and convenient and the like, the reaction conditions are mild, the substrate range applicability is good, and the method is simple and safe to operate and suitable for industrial production.

Description

technical field [0001] The invention belongs to the technical field of organic synthesis chemistry and relates to a preparation method of 4-phenylmethylene-2,6-di-tert-butyl-2,5-cyclohexadien-1-one and derivatives thereof. Background technique [0002] Methylene quinone compounds are intermediates in organic synthesis ( Acc. Chem. Res., 2001, 34, 798-807 ), directional alkylating reagents and DNA crosslinking agents ( J. Am. Chem. Soc., 2003 , 125, 1116-1117). The 2,6-di-tert-butyl substituted methylene quinone compound has the basic characteristics of the p-methylene quinone compound, and is a very stable quinone compound. At the same time, this type of compound also has many other simple p-methylene quinone compounds. The properties that methyl quinone compounds do not have can be used as polymerization inhibitors for unsaturated hydrocarbons ( Org. Process Res. Dev., 2012, 16, 65-69 ). [0003] In 2013, M. G. Olah et al. used the Friedel-Crafts reaction to prepare it af...

Claims

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Application Information

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IPC IPC(8): C07C45/51C07C49/697C07C49/653C07C49/753C07D295/096
CPCC07C45/516C07C49/653C07C49/697C07C49/753C07D295/096C07C2601/16
Inventor 刘章琴管晓渝吴传华
Owner SOUTHWEST UNIVERSITY
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