1,1-diacetate synthesis catalyzed by sulfonated cage-type mesoporous carbon

A technology for sulfonating cage type and diacetate, which is applied in the field of carbonyl ester compounds, can solve the problems of difficult separation of products, long reaction time, low recovery rate and the like, and achieves high yield, mild reaction conditions, and high reaction short time effect

Inactive Publication Date: 2015-05-20
SHAANXI NORMAL UNIV
View PDF0 Cites 0 Cited by
  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

However, the main disadvantages of the above catalysts are strong acid conditions, long reaction time, low yield and selectivity, difficult product separation, high price, low recycling rate, etc.

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
  • 1,1-diacetate synthesis catalyzed by sulfonated cage-type mesoporous carbon
  • 1,1-diacetate synthesis catalyzed by sulfonated cage-type mesoporous carbon
  • 1,1-diacetate synthesis catalyzed by sulfonated cage-type mesoporous carbon

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0023] Taking the synthesis of 1,1-diacetoxy-1-(2-trifluoromethylphenyl)methane as an example, 1,1-diacetoxy-1-(2-trifluoromethylphenyl)methane The structural formula is:

[0024]

[0025] Its synthesis method is as follows:

[0026] Add 2mmol of 2-trifluoromethylbenzaldehyde, 5mmol of acetic anhydride, and 30mg of sulfonated cage-type mesoporous carbon into a 25mL single-necked bottle, stir and react for 5 minutes at room temperature without solvent, track the reaction until complete by TLC, add ethyl acetate 20-30mL, filter the catalyst, and use saturated NaHCO 3 The solution was washed 3 times, washed 1 time with water, and the organic phase was washed with anhydrous Na 2 SO 4 After drying, the solvent was evaporated under reduced pressure to obtain a crude product. The crude product was separated by column chromatography (the volume ratio of ethyl acetate to petroleum ether as the eluent was 1:8) to obtain a pure product with a yield of 96%, m.p.71-72°C; 1 H NMR (4...

Embodiment 2

[0029] Taking the synthesis of 1,1-diacetoxy-1-(2-bromo-4,5-dimethoxyphenyl)methane as an example, 1,1-diacetoxy-1-(2-bromo-4 ,5-dimethoxyphenyl)methane has the structural formula:

[0030]

[0031] Its synthesis method is as follows:

[0032] Add 2mmol of 2-bromo-4,5-dimethoxybenzaldehyde, 5mmol of acetic anhydride, and 30mg of sulfonated cage-type mesoporous carbon into a 25mL single-necked bottle, stir and react at room temperature for 5 minutes without solvent, and track the reaction to complete, add 20-30 mL of ethyl acetate, filter the catalyst, and use saturated NaHCO 3 The solution was washed 3 times, washed 1 time with water, and the organic phase was washed with anhydrous Na 2 SO 4 After drying, the solvent was evaporated under reduced pressure to obtain a crude product. The crude product was separated by column chromatography (the volume ratio of ethyl acetate to petroleum ether as the eluent was 1:5) to obtain a pure product with a yield of 97%, m.p.84-85°C;...

Embodiment 3

[0034] Taking the synthesis of 1,1-diacetoxy-1-(phenyl)methane as an example, the structural formula of 1,1-diacetoxy-1-(phenyl)methane is:

[0035]

[0036] Its synthesis method is as follows:

[0037] Add 2 mmol of benzaldehyde, 5 mmol of acetic anhydride, and 30 mg of sulfonated cage-type mesoporous carbon into a 25 mL single-necked bottle, stir and react at room temperature for 5 minutes without solvent, and track the reaction until complete with TLC. Add 20-30 mL of ethyl acetate, filter the catalyst, and wash the filtrate with saturated NaHCO 3 The solution was washed 3 times, washed 1 time with water, and the organic phase was washed with anhydrous Na 2 SO 4 After drying, the solvent was evaporated under reduced pressure to obtain a crude product. The crude product was recrystallized with ethanol to obtain a pure product, the yield was: 96%, m.p.65-66 ° C, MS (EI): 238 (M + ),179,153,135,107,92,77,43.

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
specific surface areaaaaaaaaaaa
Login to view more

Abstract

The invention relates to 1,1-diacetate synthesis catalyzed by sulfonated cage-type mesoporous carbon. The method is characterized in that aldehyde and acetic anhydride are placed in a reactor according to a molar ratio of 1:1-3; a sulfonated cage-type mesoporous carbon catalyst is added, wherein 5-20mg of the sulfonated cage-type mesoporous carbon catalyst is added to each mole of aldehyde; the materials are stirred under room temperature until a reaction is sufficiently carried out; ethyl acetate with a volume 20-30 times that of the reaction liquid is added; the catalyst is removed by filtering; a filtrate is washed three times by using a saturated NaHCO3 water solution, and once by using water; an organic phase is dried by using anhydrous Na2SO4; the solvent is removed by reduced-pressure distillation under a pressure of 0.09MPa, such that a crude product is obtained; and re-crystallization or column chromatographic separation is carried out, such that 1,1-diacetate is obtained. Compared with existing 1,1-diacetate synthesizing method, the method provided by the invention has the advantages of short reaction time, high yield, mild reaction condition, recyclable catalyst, and the like. The method can be used for synthesizing 1,1-diacetate.

Description

technical field [0001] The invention belongs to the technical field of carbonyl ester compounds, in particular to 1,1-diacetate. Background technique [0002] 1,1-diacetate belongs to alkaloid ester compounds, which are important intermediates in organic synthesis; through the nucleophilic substitution reaction of 1,1-diacetate obtained from aromatic aldehydes, high-yield Obtain nitrile compounds; 1,1-diacetate derived from allyl aldehyde can be converted into poly A useful compound; 1,1-diacetate is also a precursor for the synthesis of acetoxydienes and a substitute for carbonyl compounds in asymmetric synthesis; more attention has been paid to 1,1-diacetate in recent years It has become an important product for the selective protection of aldehyde groups in organic synthesis. [0003] 1,1-Diacetate is usually produced from carbonyl compounds and acetic anhydride in the presence of an acidic catalyst. Catalysts that have been used so far in this reaction are protic acid...

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
Patent Type & Authority Patents(China)
IPC IPC(8): C07C69/63C07C67/293C07C69/16C07D307/46
CPCY02P20/584
Inventor 李宝林郑彦军卢俊金贾玉才王伟
Owner SHAANXI NORMAL UNIV
Who we serve
  • R&D Engineer
  • R&D Manager
  • IP Professional
Why Eureka
  • Industry Leading Data Capabilities
  • Powerful AI technology
  • Patent DNA Extraction
Social media
Try Eureka
PatSnap group products

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

© 2024 PatSnap. All rights reserved.Legal|Privacy policy|Modern Slavery Act Transparency Statement|Sitemap