CN101462948A - Method for producing methyl benzoie acid by catalytic oxidation of dimethylbenzene - Google Patents
Method for producing methyl benzoie acid by catalytic oxidation of dimethylbenzene Download PDFInfo
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- CN101462948A CN101462948A CNA2007101590307A CN200710159030A CN101462948A CN 101462948 A CN101462948 A CN 101462948A CN A2007101590307 A CNA2007101590307 A CN A2007101590307A CN 200710159030 A CN200710159030 A CN 200710159030A CN 101462948 A CN101462948 A CN 101462948A
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Abstract
The invention relates to a new method for preparing methyl benzoic acid by catalytic oxidation of dimethylbenzene; under the action of a bi-component nonmetal catalysis system which is composed of an imine compound with a dextr-form structure and a quinines compound, air or oxygen is utilized as oxygen supply for efficiently catalyzing and oxidizing the dimethylbenzene to prepare the methyl benzoic acid under a certain condition. The imine compound comprises a monoamine with a formyl imine structure, a diamine organic compound and substitutive derivatives thereof; the quinines compound comprises organic compounds of benzoquinones, naphthaquinones and anthraquinones, and the like and the substitutive derivatives thereof. In the method, no catalyst is used for preparing the methyl benzoic acid, the reaction condition is mild and the target products have high selectivity.
Description
Technical field
The present invention relates to the novel method that a kind of efficiently catalyzing and oxidizing dimethylbenzene prepares p-methylbenzoic acid, the i.e. a kind of nonmetal composite catalyst system of forming by two kinds of organism, specifically, be by quinones or under the oxygen condition, can generate the diphenols organism of quinones and to have
The nonmetal catalyst system of the two-pack that the imine compound of structure is formed has been worked in coordination with the effect of catalyzer, is oxygen source with air or oxygen, and under certain condition, efficiently catalyzing and oxidizing dimethylbenzene prepares tolyl acid.
Background technology
Tolyl acid comprises o-toluic acid, m-methyl benzoic acid and p-methylbenzoic acid, and they are important organic synthesis intermediate and industrial chemicals, is widely used in agricultural chemicals, spices, dyestuff, chlorobutylene initiator and other fine chemicals.Its preparation method mainly contains toluene oxidation carbonylation, dimethylbenzene nitric acid oxidation method, dimethylbenzene air oxidation process etc.
With the liquid phase oxidation of nitric acid as oxidant, purpose product selectivity and yield are low, and etching problem is serious, and development is subjected to serious restriction; And the toluene oxidation carbonylation is reaction raw materials with toluene, must use precious metals such as palladium to be catalyzer, and product yield is lower.
Dimethylbenzene is cheap and easy to get, and oxygen is a kind of cleaning resource.Therefore be oxygen source with the air/oxygen, the synthetic p-methylbenzoic acid of the direct catalyzed oxidation of dimethylbenzene is a kind of low cost and eco-friendly synthetic method.But the used catalyzer of this method mostly is the metallic compound that contains Cr, Co etc. at present, and efficient is lower.And the atmospheric oxidation method of dimethylbenzene, generally with the Co/Mn/Br catalyst system at 175～225 ℃, 1.5～3.0Mpa carries out oxidation, product is a terephthalic acid, contains a spot of p-methylbenzoic acid by product.Ishii etc. have developed the catalyst system of Co/NHPI, can be implemented in the oxidation of the dimethylbenzene under the normal temperature condition, primary product is a p-methylbenzoic acid, but used a large amount of NHPI in the reaction process, use the acetate of about 20 times of volumes simultaneously, product p-methylbenzoic acid product is dissolved in the solution fully, separates more complicated from reaction system, but exist reaction heat to reclaim, a series of problems such as the solvent loss amount is big.
Summary of the invention
The objective of the invention is to develop the novel method that a kind of high efficiency selected catalyzed oxidation dimethylbenzene prepares p-methylbenzoic acid, the i.e. nonmetal composite catalyst of forming by organism, utilize air or oxygen for oxygen source under certain condition efficiently catalyzing and oxidizing dimethylbenzene prepare tolyl acid.
For achieving the above object, the technical solution used in the present invention is:
A kind of method of producing methyl benzoie acid by catalytic oxidation of dimethylbenzene is by having
The imines type organic of structure, with quinones or under the oxygen condition, can generate the effect that the nonmetal catalyst system of two-pack that the diphenols organism of quinones formed has been worked in coordination with catalyzer, be combined into nonmetal composite catalyst system, utilize air or oxygen for oxygen source catalyzed oxidation dimethylbenzene, prepare corresponding tolyl acid.
Imine compound, R
1, R
2Be respectively hydrogen atom, alkyl, aryl or cycloalkyl etc., R
1, R
2Perhaps can constitute two keys, aromatic ring, cycloaliphatic ring.X can be Sauerstoffatom, hydroxyl or ester group.R
1Or R
2On can be connected with the amine that one or two N replaces, the amine that described one or two N replaces can be by two keys, aromatic ring, cycloaliphatic ring and R
1, R
2Common formation.Imine compound directly is added in the reaction solution in reaction.
Described quinones and under the oxygen condition, can generate the organic compound of quinones; Wherein, quinones comprises benzoquinones class, naphthoquinones class and anthraquinone class organic compound; The organic compound that can generate quinones under the oxygen condition is meant diphenols compounds such as dihydroxy-benzene class, naphthalenediol class and oxanthranol class.
Described imines type organic, quinones can be not contain substituent parent compound, also can be to contain one or more substituent derivative; Described substituting group comprises-R ,-OH ,-NH
2,-OR ,-COOH ,-COOR ,-F ,-Cl ,-Br ,-CN etc.; Substituent position can be various possible positions.
The reaction pressure scope 0.1-10.0MPa of producing methyl benzoie acid by catalytic oxidation of dimethylbenzene, pressure range commonly used is 0.1-5.0MPa, and preferable reaction pressure is 0.5-2MPa, and best reaction pressure is 1MPa; Temperature range 25-160 ℃, preferable temperature of reaction is 80-140 ℃, and best temperature of reaction is 100-120 ℃.
Prepare in the reaction of p-methylbenzoic acid at catalyzed oxidation dimethylbenzene, the mass concentration scope of described nonmetal composite catalyst system can 0.1-20%; When usage quantity was high, oxidation effectiveness was better, but can increase cost, and therefore, preferable concentration is 0.5-15%, and best concentration is 1-10%.
In the described nonmetal composite catalyst system, the mass ratio of the quinones of use and N-hydroxyphthalimide can be 0.01-10, and preferable mass ratio is 0.05-5, and best mass ratio is 0.1-1.
The inventive method is the containing metal compound not, can be under mild reaction conditions, respectively at adjacent,, three kinds of dimethylbenzene are realized that selective catalytic oxidations generate corresponding methylbenzyl alcohol, tolyl aldehyde, tolyl acid, wherein tolyl acid is a primary product.
The present invention has following advantage: the reaction conditions gentleness, do not use metallic compound, and the reaction conversion ratio height, target product selectivity is good.
Embodiment
Below by embodiment method provided by the invention is described in detail, but do not limit the present invention in any form.
Embodiment 1: normal pressure has under the solvent condition, the o-Xylol atmospheric oxidation
In 250 milliliters there-necked flask, drop into 25 milliliters of o-Xylols, 75 milliliters of acetonitriles, 1.6 gram N-hydroxyphthalimides and 1.0 gram 2-ethyls-9, the 10-anthraquinone; Stir heat temperature raising to 80 ° C down, with the airway in the insertion reaction liquid, continuous bubbling air, air flow quantity is 50 ml/min, tail gas is discharged from serpentine condenser, reacts 15 hours, forms with the gas chromatograph assay products.The result is, the transformation efficiency of o-Xylol is 75%, and the selectivity of o-toluic acid is 63%, o-methyl-benzene formaldehyde 28%, o-methyl-benzene methyl alcohol 6%.
Embodiment 2: dimethylbenzene oxygen oxidation in the middle of the autoclave pressure
In 70 milliliters autoclave pressure, drop into 10 milliliters of m-xylenes, 30 milliliters of acetonitriles, 0.6 gram N-acetoxyl group phthalic imidine and 0.3 grams 1,4-diamino-2,3-two chloro-9,10-anthraquinone; The envelope still stirs down heat temperature raising when temperature in the kettle is 100 ℃, and aerating oxygen oxygen to the still is pressed and reached 1MPa, react 6 hours, with gas chromatograph assay products composition.The result is, the transformation efficiency of m-xylene is 59%, and the selectivity of m-methyl benzoic acid is 71%, a tolyl aldehyde 20%, a methylbenzyl alcohol 6%.
Embodiment 3: p-Xylol dioxygen oxidation in the autoclave pressure
By embodiment 2 identical methods p-Xylol is carried out catalyzed oxidation, the different quinoness that only is to use, reaction result sees Table 1.
Table 1: various quinones or diphenols compound are used for the reaction result of p xylene oxidation
| The numbering number | Quinones or diphenols compounds | Transformation efficiency (%) | P-methylbenzoic acid selectivity (%) | P-tolyl aldehyde selectivity (%) | To methylbenzyl alcohol selectivity (%) |
| 1 | 2,3-dimethoxy para benzoquinone | 40 | 25 | 55 | 16 |
| 2 | Resorcinol | 38 | 27 | 54 | 17 |
| 3 | 1, the 4-naphthoquinones | 50 | 45 | 40 | 13 |
| 5 | 1,4-naphthoquinones-2-carboxylate methyl ester | 53 | 50 | 38 | 11 |
| 6 | 1, the 4-dihydroxy naphthlene | 21 | 18 | 63 | 17 |
| 7 | 9, the 10-anthraquinone | 47 | 35 | 50 | 12 |
| 9 | 2-fluoro-9, the 10-anthraquinone | 15 | 4 | 65 | 19 |
| 11 | 1,4-diamino-2,3-two chloro-9,10-anthraquinone | 59 | 71 | 20 | 6 |
| 12 | 1,4-diamino-2,3-dicyano-9,10-anthraquinone | 55 | 69 | 23 | 7 |
Embodiment 4 o-Xylol dioxygen oxidations
In 500 milliliters autoclave pressure, drop into 300 milliliters of o-Xylols, 7.2 gram N, equal pyromellitic dimide of N '-dihydroxyl and 3.7 grams 1,4-diamino-2,3-two chloro-9,10-anthraquinone; The envelope still stirs down heat temperature raising when temperature in the kettle is 90 ℃, and aerating oxygen oxygen to the still is pressed and reached 0.8MPa, react 6 hours, with gas chromatograph assay products composition.The result is, the transformation efficiency of o-Xylol is 65%, and the selectivity of o-toluic acid is 74%, o-methyl-benzene formaldehyde 18%, o-methyl-benzene methyl alcohol 5%.
Embodiment 5 m-xylene dioxygen oxidations
In 500 milliliters autoclave pressure, drop into 300 milliliters of m-xylenes, 7.2 gram N-benzyl acyloxy phthalic imidines and 40 milligrams 1,4-diamino-2,3-two chloro-9,10-anthraquinone; The envelope still stirs down heat temperature raising when temperature in the kettle is 100 ℃, and aerating oxygen oxygen to the still is pressed and reached 1.0MPa, react 20 hours, with gas chromatograph assay products composition.The result is, the transformation efficiency of m-xylene is 93%, and the selectivity of m-methyl benzoic acid is 90%, a tolyl aldehyde 5%, a methylbenzyl alcohol 2%.
Embodiment 6 p-Xylol dioxygen oxidations
In 500 milliliters autoclave pressure, drop into 300 milliliters of p-Xylol, 7.2 gram N-maloyl imines and 4 milligrams 9, the 10-dihydroxy-anthracene; The envelope still stirs down heat temperature raising when temperature in the kettle is 60 ℃, and aerating oxygen oxygen to the still is pressed and reached 1.5MPa, react 24 hours, with gas chromatograph assay products composition.The result is, the transformation efficiency of p-Xylol is 40%, and the selectivity of p-methylbenzoic acid is 36%, and the selectivity of p-methylbenzoic acid is 72%, and p-tolyl aldehyde 19% is to methylbenzyl alcohol 6%.
Embodiment 7 o-Xylol dioxygen oxidations
In 500 milliliters autoclave pressure, drop into 300 milliliters of o-Xylols, 7.2 gram N-hydroxyls-3,4,5,6-tetrachloro-phthalic imidine and 4 milligram 9,10-dihydroxy-anthracene; The envelope still stirs down heat temperature raising when temperature in the kettle is 60 ℃, and aerating oxygen oxygen to the still is pressed and reached 1.0MPa, react 18 hours, with gas chromatograph assay products composition.The result is that the transformation efficiency of o-Xylol is 77%, the selectivity 83% of o-toluic acid, o-methyl-benzene formaldehyde 9%, o-methyl-benzene methyl alcohol 6%.
Embodiment 8 m-xylene dioxygen oxidations
In 500 milliliters autoclave pressure, drop into 300 milliliters of m-xylenes, 7.2 gram N-hydroxyls-3,4,5,6-tetrabromo-phthalic imidine and 4 milligram 1,4-diamino-2,3-dicyano-9,10-anthraquinone; The envelope still stirs down heat temperature raising when temperature in the kettle is 120 ℃, and aerating oxygen oxygen to the still is pressed and reached 1.2MPa, react 12 hours, with gas chromatograph assay products composition.The result is that the transformation efficiency of m-xylene is 95%, the selectivity 96% of m-methyl benzoic acid, a tolyl aldehyde 2%, a methylbenzyl alcohol 1%.
Embodiment 9 p-Xylol dioxygen oxidations
In 500 milliliters autoclave pressure, drop into 300 milliliters of p-Xylol, 7.2 gram N-hydroxyl-3-fluoro-phthalic imidines and 2.0 gram 1-amino-2-bromo-4-hydroxyls-9, the 10-anthraquinone; The envelope still stirs down heat temperature raising when temperature in the kettle is 100 ℃, and aerating oxygen oxygen to the still is pressed and reached 1.5MPa, react 12 hours, with gas chromatograph assay products composition.The result is, the transformation efficiency of p-Xylol ketone is 84%, the selectivity 90% of p-methylbenzoic acid, and p-tolyl aldehyde 7% is to methylbenzyl alcohol 1%.
Embodiment 10 p-Xylol dioxygen oxidations
In 500 milliliters autoclave pressure, drop into 300 milliliters of p-Xylol, 7.2 gram N-hydroxy-4-methyl-phthalic imidines and 2.0 gram 1-amino-2-bromo-4-hydroxyls-9, the 10-anthraquinone; The envelope still stirs down heat temperature raising when temperature in the kettle is 70 ℃, and aerating oxygen oxygen to the still is pressed and reached 0.5MPa, react 12 hours, with gas chromatograph assay products composition.The result is, the transformation efficiency of p-Xylol ketone is 67%, the selectivity 85% of p-methylbenzoic acid, and p-tolyl aldehyde 7% is to methylbenzyl alcohol 5%.
Claims (10)
1. the method for a producing methyl benzoie acid by catalytic oxidation of dimethylbenzene is characterized in that: have
Under the nonmetal catalyst system effect of the two-pack that the imine compound of structure and quinones are formed, air or oxygen direct oxidation dimethylbenzene prepares corresponding tolyl acid;
R wherein
1, R
2Be respectively hydrogen atom, alkyl, aryl or cycloalkyl; X can be Sauerstoffatom, hydroxyl or acyloxy.
2. according to the described method of claim 1, it is characterized in that: described R
1, R
2Be respectively hydrogen atom, alkyl, aryl or cycloalkyl, R
1, R
2Between constitute two keys, aromatic ring or cycloaliphatic ring; Imine compound directly is added in the reaction solution in reaction.
3. according to the described method of claim 1, it is characterized in that: R
1Or R
2On can be connected with the amine that one or two N replaces, the amine that described one or two N replaces can be by two keys, aromatic ring, cycloaliphatic ring and R
1, R
2Common formation.
4. according to the described method of claim 1, it is characterized in that: described quinones is benzoquinones class, naphthoquinones class or anthraquinone class organic compound.
5. according to the described method of claim 1, it is characterized in that: described quinones is for generating the diphenols compound of quinone structure under the oxygen condition.
6. according to the described method of claim 5, it is characterized in that: described diphenols compound is dihydroxy-benzene class, naphthalenediol class or oxanthranol compounds.
7. according to the described method of claim 5, it is characterized in that: described quinones is for containing substituent parent compound, or contains one or more substituent naphthoquinone derivatives; Described substituting group is-R ,-OH ,-NH
2,-OR ,-COOH ,-COOR ,-F ,-Cl ,-Br or-CN.
8. according to the described method of claim 1, it is characterized in that: the reaction pressure scope 0.1-10.0MPa of producing methyl benzoie acid by catalytic oxidation of dimethylbenzene, temperature range 25-160 ℃.
9. according to the described method of claim 1, it is characterized in that: prepare in the reaction of p-methylbenzoic acid at the catalyzed oxidation p-Xylol, the mass concentration scope of described nonmetal composite catalyst system can 0.1-20%.
10. according to the described method of claim 1, it is characterized in that: the mass ratio of quinones and imine compound can be 0.01-10.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2012056851A (en) * | 2010-09-04 | 2012-03-22 | Nagoya Industrial Science Research Inst | Method for producing aromatic carboxylic acid compound |
| CN107011152A (en) * | 2016-01-27 | 2017-08-04 | 中国石化扬子石油化工有限公司 | The method that Selectivity for paraxylene catalysis oxidation prepares p-methylbenzoic acid |
| CN109678723A (en) * | 2018-12-03 | 2019-04-26 | 浙江工业大学 | A kind of preparation method of substituted benzoyl acids compound |
| CN114249675A (en) * | 2020-09-22 | 2022-03-29 | 北京颖泰嘉和生物科技股份有限公司 | Preparation method of 2-nitro-4-methylsulfonylbenzoic acid |
| CN115215739A (en) * | 2022-02-25 | 2022-10-21 | 上海应用技术大学 | Method for preparing p-toluic acid by oxidizing p-xylene through synergistic catalytic system |
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2007
- 2007-12-19 CN CNA2007101590307A patent/CN101462948A/en active Pending
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2012056851A (en) * | 2010-09-04 | 2012-03-22 | Nagoya Industrial Science Research Inst | Method for producing aromatic carboxylic acid compound |
| CN107011152A (en) * | 2016-01-27 | 2017-08-04 | 中国石化扬子石油化工有限公司 | The method that Selectivity for paraxylene catalysis oxidation prepares p-methylbenzoic acid |
| CN109678723A (en) * | 2018-12-03 | 2019-04-26 | 浙江工业大学 | A kind of preparation method of substituted benzoyl acids compound |
| CN109678723B (en) * | 2018-12-03 | 2021-12-10 | 浙江工业大学 | Preparation method of substituted benzoic acid compound |
| CN114249675A (en) * | 2020-09-22 | 2022-03-29 | 北京颖泰嘉和生物科技股份有限公司 | Preparation method of 2-nitro-4-methylsulfonylbenzoic acid |
| CN114249675B (en) * | 2020-09-22 | 2023-11-21 | 北京颖泰嘉和生物科技股份有限公司 | Preparation method of 2-nitro-4-methylsulfonyl benzoic acid |
| CN115215739A (en) * | 2022-02-25 | 2022-10-21 | 上海应用技术大学 | Method for preparing p-toluic acid by oxidizing p-xylene through synergistic catalytic system |
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Application publication date: 20090624 |