CN103524336A - Preparation method of 2-(4-pentyloxybenzoyl) benzoic acid with high secondary-tertiary ratio - Google Patents
Preparation method of 2-(4-pentyloxybenzoyl) benzoic acid with high secondary-tertiary ratio Download PDFInfo
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- CN103524336A CN103524336A CN201310425229.5A CN201310425229A CN103524336A CN 103524336 A CN103524336 A CN 103524336A CN 201310425229 A CN201310425229 A CN 201310425229A CN 103524336 A CN103524336 A CN 103524336A
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- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/083—Preparation of carboxylic acids or their salts, halides or anhydrides from carboxylic acid anhydrides
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Abstract
The invention discloses a preparation method of 2-(4-pentyloxybenzoyl) benzoic acid (ABB acid) with high secondary-tertiary ratio. The preparation method of 2-(4-pentyloxybenzoyl) benzoic acid comprises the following steps: in presence of a certain amount of Friedel-Crafts reaction catalyst, mixing phthalic anhydride with a solvent, and dropwise adding a certain amount of tertiary pentyl benzene into the mixture for carrying out a reaction when the temperature ranges from -10 DEG C to 30 DEG C and the pressure is below 50mmHg (absolute pressure); after the reaction is finished, treating reaction mixture to obtain a white solid, namely the product 2-(4-pentyloxybenzoyl) benzoic acid with high secondary-tertiary ratio. The preparation method of 2-(4-pentyloxybenzoyl) benzoic acid has the advantages that yield is 85%, secondary-tertiary ratio is 7, and purity is 98%; the secondary-tertiary ratio of the 2-(4-pentyloxybenzoyl) benzoic acid product is high, and the problem that a downstream product of the 2-(4-pentyloxybenzoyl) benzoic acid is poor in solubility in a specific solution is solved.
Description
Technical field
The invention belongs to the production process of fine chemical product, relate to that to take tert.-amylbenzene and Tetra hydro Phthalic anhydride be the synthetic 2-(4-amylbenzene formyl of raw material) inhibition of isomerization reaction in phenylformic acid process.This method is simple to operate, without adding any acid binding agent, successful.
Background technology
2-(4-amylbenzene formyl) phenylformic acid is white solid powder, is the intermediate by Tetra hydro Phthalic anhydride and the synthetic 2-amyl anthraquinone of tert.-amylbenzene, is important fine chemical material.2-amyl anthraquinone is mainly used in the synthetic catalyzer of hydrogen peroxide.Because the 2-amyl anthraquinone of the high Shuzhong ratio solubleness in synthetic hydrogen-peroxide working solution is large, the high efficient substitute that makes it become 2-ethyl-anthraquinone of hydrogenation efficiency.Along with the fast development of the increase of hydrogen peroxide demand, particularly paper industry, make the 2-amyl anthraquinone of high Shuzhong ratio become quite potential fine chemicals.
Pertinent literature report, the by product HCl producing in the synthetic ABB acid of catalysis Tetra hydro Phthalic anhydride and tert.-amylbenzene process can catalysis tert.-amylbenzene generation isomerization reaction generate sec.-amyl sec-pentyl secondary amyl benzene, and then forms 2-(4-sec.-amyl sec-pentyl secondary amyl benzoyl) phenylformic acid.Therefore the committed step of preparing the ABB acid of high Shuzhong ratio is to find a kind of suitable method, removes in time the by product HCl of acylation reaction, and then inhibition tert.-amylbenzene changes the object of the ABB acid that reaches the high Shuzhong ratio of preparation to sec.-amyl sec-pentyl secondary amyl benzene.
US(4895984) and US(4853481) introduced and adopted the method for acid binding agent trapping HCl to suppress the generation of isomerization reaction in reaction process.This method need to add novel substance, has increased separation costs; And operational condition is loaded down with trivial details, affect yield.
US(4087458) introduced by reducing pressure to 50-250mmHg, and then reduced the impact of HCl on product Shuzhong ratio.The yield of this method is 90%, and Shuzhong ratio is 2.52.
CN (101921189) has introduced a kind of method with the synthetic ABB acid of ionic liquid.Yield 98%, purity 98%.But the Shuzhong ratio of the not mentioned product of this method, and the cost of ionic liquid is high, returnability does not make the industrialization of ionic liquid method synthesis method fail to popularize.
Summary of the invention
Technical problem to be solved by this invention is: proposed a kind of method of ABB acid of the high Shuzhong ratio of preparation without interpolation acid binding agent, simple possible, solved the bad problem of its derived product solvability in particular solution.
A kind of benzoic preparation method of 2-amyl-benzoyl of high Shuzhong ratio, it is characterized in that under a certain amount of friedel-crafts reaction catalyzer existence condition, by tert.-amylbenzene and solvent, in temperature, be-10-30 ℃ that absolute pressure is under 1-50mmHg, a certain amount of tert.-amylbenzene to be added drop-wise in said mixture and to be reacted; After reaction finishes, reaction mixture obtains white solid through aftertreatment, is the 2-amyl-benzoyl phenylformic acid of high Shuzhong ratio;
Preferably, absolute pressure is 1-20mmHg, and temperature of reaction is 0-15 ℃, Tetra hydro Phthalic anhydride: tert.-amylbenzene: the mol ratio of catalyzer is 1:0.9-1.3:2.0-2.6, more preferably: 1:1-1.2:2.2-2.4.
Preferably, organic solvent is chlorobenzene, orthodichlorobenzene, tetracol phenixin, 1,2-ethylene dichloride.
Preferably, wherein catalyzer is aluminum trichloride (anhydrous), FERRIC CHLORIDE ANHYDROUS, ethylaluminum dichloride, zinc chloride.
Preferably, high Shuzhong is than being greater than 7 for mol ratio.
" Shuzhong ratio " of the present invention is 2-(4-tert.-amylbenzene formyl in product) phenylformic acid and 2-(4-sec.-amyl sec-pentyl secondary amyl benzoyl) benzoic molar ratio.
The beneficial effect that the present invention obtains is: without adding additional material, simple to operate, yield is high, constant product quality.The transformation efficiency of reactant Tetra hydro Phthalic anhydride can reach more than 85%, and the benzoic Shuzhong ratio of product 2-(4-amyl-benzoyl) can reach more than 7, and purity is more than 98%.
Embodiment
Example 1
7.4g Tetra hydro Phthalic anhydride and 30ml orthodichlorobenzene are added in 250ml there-necked flask, and stirring and control temperature is 20 ℃.Several times 17.8g aluminum trichloride (anhydrous) is added to above-mentioned there-necked flask.Pressure-controlling is at 3.8mmHg.With constant pressure funnel, 8.14g tert.-amylbenzene is added in above-mentioned there-necked flask subsequently, dripping duration is 5 hours, drip the reaction of end relief and react again 1h, pouring reaction mixture into appropriate massfraction is that in 10% dilute sulphuric acid, hydrolysis, hot water wash obtain white emulsion liquid, add appropriate cold normal hexane, separate out white solid, suction filtration, washing, the dry product that to obtain.Yield 84.4%, Shuzhong is than 7.2.
Example 2
7.4g Tetra hydro Phthalic anhydride and 30ml orthodichlorobenzene are added in 250ml there-necked flask, and stirring and control temperature is 5 ℃.Several times 16.4g FERRIC CHLORIDE ANHYDROUS is added to above-mentioned there-necked flask.Pressure-controlling is at 1.52mmHg.With constant pressure funnel, 8.88g tert.-amylbenzene is added in above-mentioned there-necked flask subsequently, dripping duration is 2 hours, drip the reaction of end relief and react again 1h, pouring reaction mixture into appropriate massfraction is that in 10% dilute sulphuric acid, hydrolysis, hot water wash obtain white emulsion liquid, add appropriate cold normal hexane, separate out white solid, suction filtration, washing, the dry product that to obtain.Yield 85.2%, Shuzhong is than 7.3.
Example 3
By 7.4g Tetra hydro Phthalic anhydride and 35ml1,2-ethylene dichloride adds in 250ml there-necked flask, and stirring and control temperature is 20 ℃.Several times the anhydrous tri-chlorination zinc of 15g is added to above-mentioned there-necked flask.Pressure-controlling is at 7.6mmHg.With constant pressure funnel, 9.62g tert.-amylbenzene is added in above-mentioned there-necked flask subsequently, dripping duration is 3 hours, drip the reaction of end relief and react again 1h, pouring reaction mixture into appropriate massfraction is that in 10% dilute sulphuric acid, hydrolysis, hot water wash obtain white emulsion liquid, add appropriate cold normal hexane, separate out white solid, suction filtration, washing, the dry product that to obtain.Yield 86.6%, Shuzhong is than 7.7.
Example 4
7.4g Tetra hydro Phthalic anhydride and 40ml tetracol phenixin are added in 250ml there-necked flask, and stirring and control temperature is 0 ℃.Several times 13.6g ethylaluminum dichloride is added to above-mentioned there-necked flask.Pressure-controlling is at 3.8mmHg.With constant pressure funnel, 7.4g tert.-amylbenzene is added in above-mentioned there-necked flask subsequently, dripping duration is 4 hours, drip the reaction of end relief and react again 1h, pouring reaction mixture into appropriate massfraction is that in 10% dilute sulphuric acid, hydrolysis, hot water wash obtain white emulsion liquid, add appropriate cold normal hexane, separate out white solid, suction filtration, washing, the dry product that to obtain.Yield 87.5%, Shuzhong is than 7.1.
Example 5
7.4g Tetra hydro Phthalic anhydride and 40ml orthodichlorobenzene are added in 250ml there-necked flask, and stirring and control temperature is 10 ℃.Several times 16.4g aluminum trichloride (anhydrous) is added to above-mentioned there-necked flask.Pressure-controlling is at 1.52mmHg.With constant pressure funnel, 8.88g tert.-amylbenzene is added in above-mentioned there-necked flask subsequently, dripping duration is 2 hours, drip the reaction of end relief and react again 1h, pouring reaction mixture into appropriate massfraction is that in 10% dilute sulphuric acid, hydrolysis, hot water wash obtain white emulsion liquid, add appropriate cold normal hexane, separate out white solid, suction filtration, washing, the dry product that to obtain.Yield 85.7%, Shuzhong is than 7.3.
Example 6
7.4g Tetra hydro Phthalic anhydride and 50ml orthodichlorobenzene are added in 250ml there-necked flask, and stirring and control temperature is 15 ℃.Several times 15g aluminum trichloride (anhydrous) is added to above-mentioned there-necked flask.Pressure-controlling is at 7.6mmHg.With constant pressure funnel, 6.66g tert.-amylbenzene is added in above-mentioned there-necked flask subsequently, dripping duration is 3 hours, drip the reaction of end relief and react again 1h, pouring reaction mixture into appropriate massfraction is that in 10% dilute sulphuric acid, hydrolysis, hot water wash obtain white emulsion liquid, add appropriate cold normal hexane, separate out white solid, suction filtration, washing, the dry product that to obtain.Yield 86.3%, Shuzhong is than 7.6.
Claims (8)
1. the benzoic preparation method of 2-amyl-benzoyl of one kind high Shuzhong ratio; it is characterized in that: under a certain amount of friedel-crafts reaction catalyzer existence condition; by tert.-amylbenzene and solvent; in temperature, be-10-30 ℃; absolute pressure is under 1-50mmHg, a certain amount of tert.-amylbenzene to be added drop-wise in said mixture and to be reacted; after reaction finishes, reaction mixture obtains white solid through aftertreatment, is the 2-amyl-benzoyl phenylformic acid of high Shuzhong ratio.
2. the benzoic preparation method of 2-amyl-benzoyl of high Shuzhong ratio according to claim 1, is characterized in that: absolute pressure is 1-20mmHg.
3. the benzoic preparation method of 2-amyl-benzoyl of high Shuzhong ratio according to claim 1, is characterized in that: temperature of reaction is 0-15 ℃.
4. the benzoic preparation method of 2-amyl-benzoyl of high Shuzhong ratio according to claim 1, is characterized in that: Tetra hydro Phthalic anhydride: tert.-amylbenzene: the mol ratio of catalyzer is 1:0.9-1.3:2.0-2.6.
5. the benzoic preparation method of 2-amyl-benzoyl of high Shuzhong ratio according to claim 1, is characterized in that: Tetra hydro Phthalic anhydride: tert.-amylbenzene: the mol ratio of catalyzer is 1:1-1.2:2.2-2.4.
6. the benzoic preparation method of 2-amyl-benzoyl of high Shuzhong ratio according to claim 1, is characterized in that: organic solvent is chlorobenzene, orthodichlorobenzene, tetracol phenixin, 1,2-ethylene dichloride.
7. the benzoic preparation method of 2-amyl-benzoyl of high Shuzhong ratio according to claim 1, is characterized in that: catalyzer is aluminum trichloride (anhydrous), FERRIC CHLORIDE ANHYDROUS, ethylaluminum dichloride, zinc chloride.
8. the benzoic preparation method of 2-amyl-benzoyl of high Shuzhong ratio according to claim 1, is characterized in that: the high Shuzhong in the 2-amyl-benzoyl phenylformic acid of high Shuzhong ratio is than being greater than 7 for mol ratio.
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Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
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CN104262131A (en) * | 2014-08-26 | 2015-01-07 | 湖州吉昌化学有限公司 | Production method of 2-(4'-tertpentylbenzoyl)benzoic acid |
CN109320414A (en) * | 2018-11-16 | 2019-02-12 | 中触媒新材料股份有限公司 | A kind of preparation method of 2- (4- amyl benzoyl) benzoic acid |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4895984A (en) * | 1986-06-06 | 1990-01-23 | Basf Aktiengesellschaft | Acylation of aromatics |
US5136089A (en) * | 1990-04-12 | 1992-08-04 | Basf Aktiengesellschaft | Acylation of alkyl aromatic hydrocarbons |
JP2010105942A (en) * | 2008-10-29 | 2010-05-13 | Yamamoto Chem Inc | Anthraquinone composition and method for producing the same |
CN101921189A (en) * | 2010-08-27 | 2010-12-22 | 黎明化工研究院 | Preparation method of 2-(4'-amyl-benzoyl) benzoic acid |
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2013
- 2013-09-18 CN CN201310425229.5A patent/CN103524336A/en active Pending
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4895984A (en) * | 1986-06-06 | 1990-01-23 | Basf Aktiengesellschaft | Acylation of aromatics |
US5136089A (en) * | 1990-04-12 | 1992-08-04 | Basf Aktiengesellschaft | Acylation of alkyl aromatic hydrocarbons |
JP2010105942A (en) * | 2008-10-29 | 2010-05-13 | Yamamoto Chem Inc | Anthraquinone composition and method for producing the same |
CN101921189A (en) * | 2010-08-27 | 2010-12-22 | 黎明化工研究院 | Preparation method of 2-(4'-amyl-benzoyl) benzoic acid |
Non-Patent Citations (1)
Title |
---|
于海涛等: "2-戊基蒽醌的合成研究", 《精细化工》 * |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN104262131A (en) * | 2014-08-26 | 2015-01-07 | 湖州吉昌化学有限公司 | Production method of 2-(4'-tertpentylbenzoyl)benzoic acid |
CN109320414A (en) * | 2018-11-16 | 2019-02-12 | 中触媒新材料股份有限公司 | A kind of preparation method of 2- (4- amyl benzoyl) benzoic acid |
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