Organic base catalyst for synthesizing aryl carboxylate through ester exchange

A technology for synthesizing aryl carboxylic acid esters and organic bases, which is applied in organic compound/hydride/coordination complex catalysts, organic chemistry, physical/chemical process catalysts, etc., and can solve the problems of slow reaction rate, long production operation period, The active center metal ions are easy to lose and other problems, and achieve the effects of short reaction time, good catalyst performance and mild operating conditions

Inactive Publication Date: 2011-04-27
JILIN UNIV
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  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

[0004] In the transesterification method, phenol and dimethyl carbonate transesterification reaction synthesis diphenyl carbonate method researches more, as JP323654, US5426207, DE2528142, patents such as CN1803282 (200610020205.1) have been reported, the raw material dimethyl carbonate used in this method Cheap and easy to obtain, the problem of this process is that methanol and dimethyl carbonate form an azeotrope, which increases the difficulty of separation of raw materials and products; the reaction rate is too slow, and the production operation cycle is too long
In the above-mentioned patents, when dimethyl oxalate is used as a raw material to prep...

Method used

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  • Organic base catalyst for synthesizing aryl carboxylate through ester exchange
  • Organic base catalyst for synthesizing aryl carboxylate through ester exchange
  • Organic base catalyst for synthesizing aryl carboxylate through ester exchange

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Experimental program
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Effect test

Embodiment 1

[0028] The embodiment of the present invention is to investigate under the catalyst catalytic reaction conditions of the present invention, take dimethyl oxalate and phenol as raw materials to prepare methyl phenyl oxalate and diphenyl oxalate as an example, the reaction process is the same as that in the background technology (4)-(6) The reaction steps are the same.

[0029] The specific process is carried out in a 100ml three-necked flask, heated by heat-collecting electromagnetic stirring, equipped with a thermometer to display the temperature of the reaction system. The consumption of technical grade dimethyl oxalate is 17 millimoles, the consumption of analytical pure phenol is 85 millimoles, 0.3 gram Cp ' (CH 2 ) 3 -MCM-41 is a heterogeneous catalyst (containing 0.38 mmoles of alkene in 0.3 g of catalyst), added under normal pressure. Stir and heat up, the reaction temperature is controlled at 180±2°C, and the reaction time is 2 hours. (4)-(6) The reaction equilibrium...

Embodiment 2-5

[0031] With the cyclocene material Cp’(CH) immobilized on Si-MCM-41 2 ) 3 -MCM-41 is a heterogeneous catalyst, and the catalyst consumption is 0.3 grams (containing 0.38 millimoles in 0.3 grams of catalysts), and the reaction time is carried out respectively for 4, 6, 8, and 10 hours. Under the circumstances, carry out transesterification reaction and form embodiment 2-5, examine reaction result.

[0032] Table 1: Cp'(CH 2 ) 3 -Reaction evaluation when MCM-41 is used as catalyst

[0033]

Embodiment 6-10

[0035] With 0.38 mmol Cp'(CH 2 ) 3 -MCM-41 is a homogeneous catalyst, the amount of catalyst is 0.38 mmol, and the reaction time is carried out respectively for 2, 4, 6, 8, and 10 hours. Embodiment 6-10, investigate reaction result.

[0036] Table 2: Cp'(CH 2 ) 3 Si(OEt) 3 Reaction evaluation when used as a catalyst

[0037]

[0038] Comparing Examples 1-5 and 6-10, it can be seen that after the immobilization of the cyclocene is not only conducive to the separation of the reaction material and the catalyst, but also under the condition that the activity of the catalyst is kept little changed, the total selectivity of the catalyst to the main product MPO and DPO Improvement, especially in the selectivity of the final product DPO. In Example 5, when reacting for 10 hours, the yield of diphenyl oxalate reached 41.5%.

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Abstract

The invention relates to an organic base catalyst for synthesizing aryl carboxylate through ester exchange, belonging to the technical field of organic chemistry and catalytic chemistry. In a process of synthesizing aryl carboxylate through ester exchange, phenyl methyl oxalate and phenyloxalate are synthesized by using phenol and dimethyl oxalate as raw materials through ester exchange. The organic base catalyst is an organic compound containing nitrogen, phosphorus and halogen elements and immobilized organic base thereof; and hydroxyl on the surface of an immobilized heterogeneous catalyst is subjected to treatment of silane reagents with different polarities to obtain a catalyst with different surface polarities. The catalyst has good catalysis property, is easy to separate from a reaction system, is mild in ester exchange condition, convenient for continuation, and is suitable for industrialized application, wherein the transfer rate of the dimethyl oxalate can reach above 90 percent and the selectivity of the phenyloxalate can reach above 70 percent.

Description

[0001] The patent application for the present invention is a divisional application. The invention title of the original application is "organic acid-base catalyst for the synthesis of aryl carboxylate by transesterification", the filing date is January 2, 2008, and the application number is 200810050203.6. technical field [0002] The invention belongs to the technical field of organic chemistry and catalytic chemistry, and relates to a class of organic acid-base catalysts for synthesizing monoaryl carboxylate and diaryl carboxylate by transesterification of dialkyl carboxylate and monoaryl hydroxyl compound. Background technique [0003] Diaryl carbonate is an important organic carbonate with low toxicity and no pollution. It can be used to synthesize many important organic compounds and polymer materials. ) reaction, non-phosgene transesterification polycondensation into high-quality polycarbonate, which has high economic value. The synthesis methods of diaryl carbonate ...

Claims

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Application Information

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IPC IPC(8): B01J31/02C07C69/36C07C67/03
Inventor 贾明君赵国明刘燕张文祥刘钢王振旅吴淑杰石景慧
Owner JILIN UNIV
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