Synthetic method of p-tert-butylbenzaldehyde

A technology of p-tert-butyltoluene and p-tert-butyl, which is applied in the field of highly selective synthesis of p-tert-butylbenzaldehyde by catalytic oxidation of p-tert-butyltoluene, which can solve the problems of expensive template agent, complex process and low conversion rate , to achieve the effect of avoiding deep oxidation, good selectivity and high conversion rate

Inactive Publication Date: 2019-04-12
CHANGZHOU UNIV
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  • Abstract
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Problems solved by technology

In the Chinese patent documents whose patent numbers are respectively CN 101440028 A and CN102989499 A, there have been reports about the synthesis of p-tert-butylbenzaldehyde by oxidation of p-tert-butyltoluene. X, SBA-15, MCM-41, the result is that the selectivity of the product is about 45%, and the by-product is more p-tert-butylbenzoic acid, and the template agent in the production process is more expensive, such as SBA-15 and other carriers. and time-consuming
[0004] In the patent No. CN 1944368 A Chinese patent literature, it is reported that using methyl p-tert-butylbenzoate as raw material, in MnO / r-Al 2 o 3 , ZnO / r-Al 2 o 3 Under catalysis, the method of hydrogenation under normal pressure and high temperature is used to prepare p-tert-butylbenzaldehyde. The process is complicated, including the oxidation of aromatic hydrocarbons to carboxylic acids, and then esterification and hydrogenation to synthesize aromatic aldehydes. The reaction temperature is above 400°C , the yield is also lower
Among the many methods adopted in this field at present, there are problems of low conversion rate and low selectivity.

Method used

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Examples

Experimental program
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Effect test

Embodiment 1

[0024] The preparation of 15%Ni / NaY: Adopt equal volume impregnation method, can know that the specific pore volume of NaY molecular sieve is 0.36ml / g by BET detection, then when the required active component content (calculated as oxide) is 15%, can Knowing that the required impregnating solution concentration is 0.5mol / L, it is deduced that Ni(NO 3 ) 2 ·6H 2 O 7.25g. 7.25g Ni(NO 3 ) 2 ·6H 2 Dissolve O in 50 mL of deionized water to obtain impregnating solution No. 1, add 5 g of NaY molecular sieves to magnetically stir for 3 h, let stand for 12 h to age overnight, filter with suction, dry at 80°C for 12 h, and roast at 450°C for 4 h to obtain 15% Ni / NaY catalyst .

[0025] Oxidation reaction: Add 6mL p-tert-butyltoluene and 18mL acetonitrile (1:3 volume ratio) into a 25mL three-necked flask, heat in an oil bath at 70°C, condense and reflux, and magnetically stir at 200r / min. When the temperature reaches 70°C, add 0.2g15%Ni / NaY and 0.1gN-hydroxyphthalimide (mass ratio ...

Embodiment 2

[0027] The preparation of 25%Ni / NaY: adopt equal volume impregnation method, can know that the specific pore volume of NaY molecular sieve is 0.36ml / g by BET detection, then when the required active component content (calculated as oxide) is 25%, can Knowing that the required impregnating solution concentration is 1.0mol / L, it is deduced that Ni(NO 3 ) 2 ·6H 2 O 14.50g. 14.50g Ni(NO 3 ) 2 ·6H 2 Dissolve O in 50mL of deionized water to obtain impregnating solution No. 2, add 5g NaY molecular sieve to magnetically stir for 3h, let stand for 12h to age overnight, filter with suction, dry at 80°C for 12h, and roast at 450°C for 4h to obtain 25% Ni / NaY catalyst .

[0028] Oxidation reaction: Add 6mL p-tert-butyltoluene and 18mL acetonitrile (1:3 volume ratio) into a 25mL three-necked flask, heat in an oil bath at 70°C, condense and reflux, and magnetically stir at 200r / min. When the temperature reaches 70°C, add 0.2g 25% Ni / NaY and 0.1g N-hydroxyphthalimide (mass ratio is 2:...

Embodiment 3

[0030] The preparation of 35%Ni / NaY: adopt equal volume impregnation method, can know that the specific pore volume of NaY molecular sieve is 0.36ml / g by BET detection, then when the required active component content (calculated as oxide) is 35%, can Knowing that the required impregnation solution concentration is 1.5mol / L, it is deduced that Ni(NO 3 ) 2 ·6H 2 O 21.75g. 21.75g ​​Ni(NO 3 ) 2 ·6H 2 O was dissolved in 50mL of deionized water to obtain impregnation solution No. 3, and 5g NaY molecular sieve was added to magnetically stir for 3h, left to stand for 12h to age overnight, filtered with suction, dried at 80°C for 12h, and calcined at 450°C for 4h to obtain 35% Ni / NaY catalyst .

[0031] Oxidation reaction: Add 6mL p-tert-butyltoluene and 18mL acetonitrile (1:3 volume ratio) into a 25mL three-necked flask, heat in an oil bath at 70°C, condense and reflux, and magnetically stir at 200r / min. When the temperature reaches 70°C, add 0.2g35%Ni / NaY and 0.1gN-hydroxyphth...

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Abstract

The invention provides a synthetic method of p-tert-butylbenzaldehyde. A liquid-phase oxidation method is used, p-tert-butyltoluene as a raw material, oxygen as an oxidizing agent, N-hydroxyl phthalimide as an initiator and acetonitrile as a solvent are used under the action of a catalyst for reacting for 7 hours at the temperature of 70 DEG c under the magnetic stirring rotating speed of 200r/minso as to obtain the p-tert-butylbenzaldehyde. The selected catalyst is a Ni-loaded microporous molecular sieve, and preparation raw materials comprise a nickel salt, a molecular sieve and deionized water; the microporous molecular sieve is used as a carrier for loading of an active component by an impregnation method to prepare the catalyst containing the active component nickel, the catalyst hasrelatively high selectivity and activity, the conversion rate of the raw material in the reaction for preparing the p-tert-butylbenzaldehyde by the liquid-phase oxidation reaches 30.6%, the selectivity of the target product reaches 77.2%. Compared with other catalysts in the prior art, the catalyst has the advantages that the selectivity is obviously improved.

Description

technical field [0001] The invention relates to a method for synthesizing p-tert-butylbenzaldehyde with high selectivity by catalytic oxidation of p-tert-butyltoluene under normal pressure conditions and preparation of a catalyst thereof. Background technique [0002] 4-tert-Butylbenzaldehyde is an important intermediate and is widely used in pharmaceuticals, dyes and other chemicals, especially in the synthesis of lilial, which is in great demand. [0003] The synthesis method of p-tert-butylbenzaldehyde is divided into oxidation method and hydrogenation method, wherein the oxidation method is divided into chemical oxidation method, air oxidation method and electrochemical oxidation method, etc. At present, the main method for preparing p-tert-butylbenzaldehyde is method of oxidation. In the Chinese patent documents whose patent numbers are respectively CN 101440028 A and CN102989499 A, there have been reports about the synthesis of p-tert-butylbenzaldehyde by oxidation of...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07C45/36C07C47/542B01J29/14
CPCB01J29/146B01J2229/18C07C45/36C07C47/542
Inventor 马江权殷倩沈婷婷孔泳左士祥高晓新姚超
Owner CHANGZHOU UNIV
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