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Preparation method of 2,3,5-trimethyl hydroquinone diester

A technology of trimethylhydroquinone diester and carboxymethyl, which is applied in the field of preparation of 2,3,5-trimethylhydroquinone diester by rearrangement of oxoisophorone, which can solve the reaction conversion rate Only 38%, cumbersome catalyst preparation process, unsatisfactory product selectivity and other problems, to achieve the effect of catalytic efficiency and specificity, green environmental protection and three wastes, and inhibit the migration of hydroxyl groups

Active Publication Date: 2019-07-05
WANHUA CHEM GRP CO LTD
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

[0006] In CN1886361A, a novel method for preparing 2,3,5-trimethylhydroquinone diester is disclosed, which uses trivalent indium salts (such as indium trichloride and indium trifluoromethanesulfonate) as catalysts Catalytic KIP reacts with acid anhydride to prepare 2,3,5-trimethylhydroquinone diester, although the corresponding yield can reach 90%, but the catalyst used in this method is expensive and easy to pollute the environment
[0007] In CN101607896A, report uses ionic liquid as catalyst, catalyzes KIP and acid anhydride reaction to prepare 2,3,5-trimethylhydroquinone diester, and ionic liquid consumption is few, and separation is simple, but reaction conversion ratio has only 38%, and selectivity is 93%, lower one-way yield
[0008] To sum up, in the existing technology for preparing 2,3,5-trimethylhydroquinone diester, corrosive acids are used, which require high equipment, or the catalyst preparation process is cumbersome (such as ionic liquid) and corrosive High stability, or low conversion rate, unsatisfactory product selectivity and other defects

Method used

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  • Preparation method of 2,3,5-trimethyl hydroquinone diester

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0043] 10g of carboxymethyl-β-cyclodextrin and 80mL of polyallylamine solution (molecular weight 5000, concentration 20wt%, viscosity 13mpa·s) were fully stirred and reacted for 8h in a constant temperature shaker at 60℃. After the reaction was completed Washed with deionized water for 3 times, and then dried under vacuum to obtain polyallylamine modified carboxymethyl-β-cyclodextrin (PAA-CM-β-CD), IR: 1656.01cm- 1 (Secondary amide C=O), 1556.99cm- 1 (Secondary amide NH bond).

[0044] Weigh 5g PAA-CM-β-CD, 10g SO 4 2- / ZrO 2 The solid acid and 100g ethanol were placed in a 250ml three-necked flask, mechanically stirred at 20°C for 5h, filtered with suction, and the filter cake was vacuum dried to obtain a modified cyclodextrin-supported solid acid catalyst (denoted as catalyst a), IR: 1656.01cm- 1 (Secondary amide C=O), 1556.99cm- 1 (Secondary amide NH bond), 1586.08cm- 1 (NH 2 + ).

Embodiment 2

[0046] Mix 20g of carboxymethyl-β-cyclodextrin and 160mL of polyallylamine solution (molecular weight 5000, concentration 20wt%, viscosity 13mpa·s) in a constant temperature shaker at 60°C for 8 hours. After the reaction, Washed with deionized water for 3 times, and then dried under vacuum to obtain polyallylamine modified carboxymethyl-β-cyclodextrin (PAA-CM-β-CD), IR: 1656.06cm- 1 (Secondary amide C=O), 1556.96cm- 1 (Secondary amide NH bond).

[0047] Weigh 20g PAA-CM-β-CD, 10g SO 4 2- / ZrO 2 The solid acid and 200g ethanol were placed in a 500ml three-necked flask, mechanically stirred at 40°C for 1h, filtered with suction, and the filter cake was vacuum dried to obtain a modified cyclodextrin-supported solid acid catalyst (denoted as catalyst b), IR: 1656.01cm- 1 (Secondary amide C=O), 1556.99cm- 1 (Secondary amide NH bond), 1586.18cm- 1 (NH 2 + ).

Embodiment 3

[0049] 10g of carboxymethyl-β-cyclodextrin and 80mL of polyallylamine solution (molecular weight 5000, concentration 20wt%, viscosity 13mpa·s) were fully stirred and reacted for 8h in a constant temperature shaker at 60℃. After the reaction was completed Wash 3 times with deionized water, and then vacuum dry to obtain polyallylamine modified carboxymethyl-β-cyclodextrin (PAA-CM-β-CD) IR: 1655.91cm- 1 (Secondary amide C=O), 1556.92cm- 1 (Secondary amide NH bond).

[0050] Weigh 5g PAA-CM-β-CD, 10g SO 4 2- / ZrO 2 Solid acid and 100g ethanol were placed in a 250ml three-necked flask, mechanically stirred at 30°C for 2h, filtered with suction, and the filter cake was vacuum dried to obtain a modified cyclodextrin-supported solid acid catalyst (denoted as catalyst c), IR: 1656.02cm- 1 (Secondary amide C=O), 1556.98cm- 1 (Secondary amide NH bond), 1586.12cm- 1 (NH 2 + ).

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Abstract

The invention discloses a preparation method of 2,3,5-trimethyl hydroquinone diester. According to the preparation method, oxo-isophorone and acetic anhydride carry out rearrangement and acylation under the catalytic action of a modified cyclodextrin supported solid acid to prepare 2,3,5-trimethyl hydroquinone diester. The solid acid is loaded on poly(allyl amine) modified methyl-beta-cyclodextrin; the reaction conditions are mild, the oxo-isophorone conversion rate and the product selectivity are high, the catalyst can be repeatedly used, and the shortages of a conventional preparation technology such as bad selectivity, severe equipment corrosion, complicated operation, and the like, are overcome.

Description

Technical field [0001] The present invention relates to the field of organic synthesis, in particular to a rearrangement reaction, and more specifically to a preparation method for preparing 2,3,5-trimethylhydroquinone diester by oxoisophorone rearrangement. Background technique [0002] 2,3,5-Trimethylhydroquinone diester is an important intermediate for the preparation of vitamin E, which can directly react with isophytoalcohol to form vitamin E acetate. [0003] For a long time, 3,5,5-trimethyl-cyclohex-2-ene-1,4-dione (oxoisophorone, KIP) is converted into 2,3,5-trimethylhydroquinone There are many known methods for diesters. [0004] In DE2149159, oxoisophorone and acetic anhydride are used to prepare 2,3,5-trimethylhydroquinone diester under the catalysis of protic acid or Lewis acid. The disadvantage of this method is that a large amount of acid (sulfuric acid) , Nitric acid, hydrochloric acid, etc.), and the reaction yield is low (66%). In addition, US5955628, CN1420859A, ...

Claims

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Application Information

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IPC IPC(8): C07C67/00C07C69/157B01J31/06B01J31/26
CPCB01J31/065B01J31/26C07C67/00C07C69/157
Inventor 刘英瑞曹善健张涛吕英东宋明焱郭劲资李莉宋军伟孙犀璨杨宗龙程晓波刘齐兴
Owner WANHUA CHEM GRP CO LTD
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