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

Synthetic method of 1, 2-diol dicarboxylic ester

A technology of carboxylic acid and compound, applied in the field of preparation of 1,2-diol dicarboxylate

Inactive Publication Date: 2015-06-10
CHANGSHA UNIVERSITY OF SCIENCE AND TECHNOLOGY
View PDF3 Cites 0 Cited by
  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

However, the synthesis of unsymmetrical diesters is still a great challenge

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
  • Synthetic method of 1, 2-diol dicarboxylic ester
  • Synthetic method of 1, 2-diol dicarboxylic ester
  • Synthetic method of 1, 2-diol dicarboxylic ester

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0013] Embodiment 1, use 2,3-dichloro-5,6-dicyano-1,4-benzoquinone to promote cyclic acetal and carboxylic acid to synthesize diester and detect the influence of different solvents on the esterification reaction (expressed in formula Show I-1 compound as an example).

[0014] 2,3-dichloro-5,6-dicyano-1,4-p-benzoquinone (1.2 mmol), benzoic acid (1 mmol), different reaction solvents (2 mL) (nitromethane, acetonitrile, Ethyl acetate, chloroform, 1,2-dichloroethane, dichloromethane, benzene) and benzaldehyde ethylene acetal (2 mmol) were added into the sealed tube, and placed directly at 80°C for 10 hours. Add saturated aqueous sodium bicarbonate solution to the reaction solution, extract with ethyl acetate, separate the esterification product by silica gel column chromatography, and calculate the separation yield as shown in Table 1, wherein, the yield of the target product ester in dichloromethane is obtained The highest value, 90%, sets the best solvent as dichloromethane.

...

Embodiment 2

[0018] Embodiment 2, the influence of reaction temperature on the dehydrogenation coupling reaction of the present invention.

[0019] Except for different reaction temperatures (100°C, 80°C, 60°C, 40°C), other reaction conditions were the same as in Example 1, and the influence of reaction temperature on the coupling reaction yield was detected. After the reaction, the measurement results of the separation yield of the target ester are shown in Table 2, which shows that there is an optimum value for the yield of the coupling reaction with the change of the reaction temperature, and the optimum reaction temperature is set at 80°C.

[0020] Reaction temperature (°C) 100 80 60 40 Separation yield (%) 89 90 78 57

Embodiment 3

[0021] Example 3, the effect of the ratio of cyclic acetal to carboxylic acid on the dehydrogenation coupling reaction of the present invention.

[0022] Except the molar ratio of cyclic acetal and carboxylic acid is different (1:1, 2:1, 3:1, 4:1, 10; 1), other reaction conditions are the same as in Example 1, and the detection of cyclic acetal and carboxylic acid Effect of molar ratio of acid on yield of coupling reaction. After the reaction finishes, the separation yield measurement result of target ester is as shown in table 3, shows that along with the change of the molar ratio of cyclic acetal and carboxylic acid, there is an optimal value in the yield of coupling reaction, and cyclic acetal and The optimal molar ratio of carboxylic acid is 2:1.

[0023] Cyclic acetal / carboxylic acid ratio (mol / mol) 1 2 3 4 10 Separation yield (%) 68 90 90 90 85

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

No PUM Login to View More

Abstract

The invention discloses a synthetic method of 1, 2-diol dicarboxylic ester. The method comprises the following step: by taking 2,3-dichloro-5, 6-dicyan-1,4-benzoquinone as a dehydrogenation agent, carrying out reaction on cycloacetal and carboxylic acid in a dried organic solvent for 6-48 hours at 20-140 DEG C to obtain 1, 2-diol dicarboxylic ester, wherein the molar ratio of cycloacetal to carboxylic acid is (1-10): 1 and the molar ratio of the dehydrogenation agent to carboxylic acid is (1-10): 1. The method overcomes the defects that in the prior art, a strong acid or an expensive coupling agent is required, monoester needs to be pre-prepared when asymmetrical dicarboxylic ester is synthesized, and 1,2-diol in the process is excessive in amount and the like. The synthetic method has the advantages that 1) by taking 2,3-dichloro-5,6-dicyan-1,4-benzoquinone as the dehydrogenation agent, non-metal coupling is realized, and heavy metal ions are prevented from being left in a product; 2) the reaction product is easy to separate and the dehydrogenation agent is easy to regenerate; 3) the process is simple, the cost is low, the product is good in specificity and environmental-friendly; and 4) the conversion efficiency is high. The synthetic method disclosed by the invention plays an important role in industrial production of 1, 2-diol dicarboxylic ester.

Description

technical field [0001] The present invention relates to a kind of preparation method of 1,2-diol dicarboxylate, specifically, relate to a kind of cyclic acetal and carboxylic acid in dehydrogenation reagent 2,3-dichloro-5,6-dicyano - A method for preparing 1,2-diol dicarboxylate through dehydrogenation coupling reaction under the action of 1,4-benzoquinone. Background technique [0002] Carboxylate is an important class of chemical raw materials. It has a wide range of uses and can be used as spices, solvents, plasticizers and intermediates in organic synthesis. It also has important use values ​​in coatings, medicine and other industries. Traditional preparation methods of esters usually require strong acid catalysts, expensive dehydration reagents, and easily produce by-products in the process. With the rapid development of C-H functionalization technology, the direct oxidative esterification of carboxylic acids by hydrocarbon compounds via C-H bond activation has been de...

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): C07C67/24C07C69/78C07C69/92C07C205/57C07C201/12C07D307/68
Inventor 李江胜付东梅薛媛李志伟李道林达玉栋刘东华黄鹏
Owner CHANGSHA UNIVERSITY OF SCIENCE AND TECHNOLOGY
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