Looking for breakthrough ideas for innovation challenges? Try Patsnap Eureka!

2,6-di-tert-butyl-4-(-4-fluorobenzylidene)-2,5-cyclohexadiene-1-one and preparation method thereof

A technology of fluorobenzylidene and di-tert-butylphenol, which is applied in the field of organic compounds and their synthesis, can solve the problems of high operation and equipment requirements, large environmental pollution, high price, etc., so as to improve the conversion rate of raw materials and reduce the The effect of reaction yield and accelerated formation rate

Inactive Publication Date: 2014-10-29
ZHEJIANG UNIV
View PDF4 Cites 6 Cited by
  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0011] The synthesis of QM-ph by methylene oxidation requires the use of a highly toxic solvent, benzene, and an oxidant, potassium ferricyanide, which causes great environmental pollution.
Synthesis of QM-ph by phenyllithium method or Grignard reagent method, the raw materials are phenyllithium and 3,5-di-tert-butyl-4-hydroxybenzaldehyde, the price is more expensive; the reaction needs to be carried out in anhydrous or anhydrous and oxygen-free environment It is carried out under high conditions and has high requirements for operation and equipment, so it is not suitable for industrial production
The currently reported Mannich method has a yield of up to 86.1%. However, after the Mannich base is formed, the Mannich base is deaminated to obtain the final product QM-ph. This process requires the use of xylene, HCl, acetic anhydride, etc. A large amount of chemicals, large emissions, serious pollution
And the amount of secondary amine exceeds the equimolar amount of 2,6-di-tert-butylphenol, which will lead to an increase in cost

Method used

the structure of the environmentally friendly knitted fabric provided by the present invention; figure 2 Flow chart of the yarn wrapping machine for environmentally friendly knitted fabrics and storage devices; image 3 Is the parameter map of the yarn covering machine
View more

Image

Smart Image Click on the blue labels to locate them in the text.
Viewing Examples
Smart Image
  • 2,6-di-tert-butyl-4-(-4-fluorobenzylidene)-2,5-cyclohexadiene-1-one and preparation method thereof
  • 2,6-di-tert-butyl-4-(-4-fluorobenzylidene)-2,5-cyclohexadiene-1-one and preparation method thereof
  • 2,6-di-tert-butyl-4-(-4-fluorobenzylidene)-2,5-cyclohexadiene-1-one and preparation method thereof

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0048] Example 1, a preparation of 2,6-di-tert-butyl-4-(-4-fluorobenzylidene)-2,5-cyclohexadien-1-one (QM-ph-p-F) method, follow the steps below:

[0049] A. Preparation of Mannich bases

[0050] Add 41.2g (0.2mol) of 2,6-di-tert-butylphenol and 34.8g (0.28mol) of p-fluorobenzaldehyde into a 250mL three-necked flask with a condensing water separator and a stirrer, stir and heat to a small amount of reflux (about 145°C), after reflux for 20 minutes, keep warm and slowly add 20mL (0.2mol) of piperidine dropwise, and drop it in 3 hours. During the reaction process, the generated water will be evaporated. Monitored by GC.

[0051] B. Mannich base removal of secondary amines

[0052] Transfer the above reaction solution into a 250mL single-necked flask, carry out vacuum distillation under the pressure of 150mmHg, heat the flask with an oil bath, set the oil temperature to 120°C, and continue the distillation for about 3 hours. After the kettle liquid is cooled, a reddish-brown s...

Embodiment 2

[0056] Example 2, a preparation of 2,6-di-tert-butyl-4-(-4-fluorobenzylidene)-2,5-cyclohexadien-1-one (QM-ph-p-F) method, follow the steps below:

[0057] A. Preparation of Mannich bases

[0058] Add 41.2g (0.2mol) of 2,6-di-tert-butylphenol and 34.8g (0.28mol) of p-fluorobenzaldehyde into a 250mL three-necked flask with a condensing water separator and a stirrer, stir and heat to a small amount of reflux (about 145°C), after reflux for 20 minutes, keep warm and slowly drop into about 60.8mL of 33wt% dimethylamine aqueous solution (containing dimethylamine 0.4mol), drop it in 3 hours, steam the water generated during the reaction, continue to keep warm after dropping The reaction was refluxed for 3 hours, the reaction was stopped, and GC was used to monitor during the reaction.

[0059] B. Mannich base removal of secondary amines

[0060] Transfer the above reaction solution into a 250mL single-necked flask, carry out vacuum distillation under the pressure of 150mmHg, heat ...

the structure of the environmentally friendly knitted fabric provided by the present invention; figure 2 Flow chart of the yarn wrapping machine for environmentally friendly knitted fabrics and storage devices; image 3 Is the parameter map of the yarn covering machine
Login to View More

PUM

PropertyMeasurementUnit
Melting pointaaaaaaaaaa
Login to View More

Abstract

The invention discloses 2,6-di-tert-butyl-4-(-4-fluorobenzylidene)-2,5-cyclohexadiene-1-one. A preparation method of 2,6-di-tert-butyl-4-(-4-fluorobenzylidene)-2,5-cyclohexadiene-1-one comprises the following steps: 1) preparing mannich base, namely heating 2,6-di-tert-butylphenol and p-fluorobenzaldehyde to reflux temperature of 100-160 DEG C, and then dropwise adding secondary amine under heat preservation, so that 2,6-di-tert-butylphenol and p-fluorobenzaldehyde are subjected to reflux reaction in a solvent-free condition under the catalytic action of the secondary amine; 2) removing the secondary amine from the mannich base, namely carrying out reduced pressure distillation on reaction liquid obtained in the step 1), thereby removing the secondary amine from the mannich base to obtain a crude product; 3) recrystallizing the crude product, namely carrying out recrystallization on the crude product obtained in the step 2) by adopting a hot-melt cold-precipitation method, so as to obtain 2,6-di-tert-butyl-4-(-4-fluorobenzylidene)-2,5-cyclohexadiene-1-one.

Description

technical field [0001] The present invention relates to an organic compound and its synthesis method, in particular to 2,6-di-tert-butyl-4-(-4-fluorobenzylidene)-2,5-cyclohexadien-1-one (QM-ph-p-F) and its preparation method. Background technique [0002] 2,6-Di-tert-butyl-4-(-4-fluorobenzylidene)-2,5-cyclohexadien-1-one (QM-ph-p-F), whose molecular formula is C 21 h 25 OF, whose chemical formula is shown in formula S-1, is a p-methylene quinone compound. [0003] [0004] At present, there is no literature report about the substance and its synthesis method. By consulting the literature, we found that the methods for its analogue 2,6-di-tert-butyl-4-benzylidene-2,5-cyclohexadien-1-one (QM-ph) mainly include the following: [0005] 1), methylene oxidation method: Mueller E. et al. reported a method of using 2,6-di-tert-butylphenol and benzyl alcohol as raw materials, first adding dehydration and then oxidation to prepare QM-ph, such as formula S -2 shown; [0006] 2...

Claims

the structure of the environmentally friendly knitted fabric provided by the present invention; figure 2 Flow chart of the yarn wrapping machine for environmentally friendly knitted fabrics and storage devices; image 3 Is the parameter map of the yarn covering machine
Login to View More

Application Information

Patent Timeline
no application Login to View More
IPC IPC(8): C07C49/697C07C45/65
CPCC07C45/65C07C213/02C07C2601/16C07D295/096C07C49/697C07C215/50
Inventor 陈新志王铃贾银霞钱超
Owner ZHEJIANG UNIV
Who we serve
  • R&D Engineer
  • R&D Manager
  • IP Professional
Why Patsnap Eureka
  • Industry Leading Data Capabilities
  • Powerful AI technology
  • Patent DNA Extraction
Social media
Patsnap Eureka Blog
Learn More
PatSnap group products

Browse by: Latest US Patents, China's latest patents, Technical Efficacy Thesaurus, Application Domain, Technology Topic, Popular Technical Reports.

© 2024 PatSnap. All rights reserved.Legal|Privacy policy|Modern Slavery Act Transparency Statement|Sitemap|About US| Contact US: help@patsnap.com