CN101475447B - Method for synthesizing 2,4,6-pseudocuminol - Google Patents
Method for synthesizing 2,4,6-pseudocuminol Download PDFInfo
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- CN101475447B CN101475447B CN 200810010030 CN200810010030A CN101475447B CN 101475447 B CN101475447 B CN 101475447B CN 200810010030 CN200810010030 CN 200810010030 CN 200810010030 A CN200810010030 A CN 200810010030A CN 101475447 B CN101475447 B CN 101475447B
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- molecular sieve
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- trimethylbenzene
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- hydrogen peroxide
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Abstract
The invention discloses a method for synthesizing 2,4,6-trimethylphenol. The method comprises the following steps that: A) a molecular sieve is taken as a catalyst, and an aqueous solution of halogenated acetic acid containing mesitylene and hydrogen peroxide at a volume concentration of 30 percent react under the action of the molecular sieve, are heated and refluxed; B) a product of a step A) is cooled to room temperature and added with water; C) a solvent is adopted for extraction, separation and washing, and then is recovered; and D) reduced-pressure distillation is carried out, so a final product is obtained, wherein the amount ratio in percentage by mass of the molecular sieve to the mesitylene is 1:0.1-1, and the molar ratio of the mesitylene to the halogenated acetic acid to the hydrogen peroxide at a volume concentration of 30 percent is 1:1-8:1-20. The method has the advantages of simple operation, good selectivity, high yield and suitability for scale production.
Description
Technical field
The invention belongs to the synthetic method field of fine chemicals, relate in particular to a kind of preparation method of 2.
Background technology
2 is a kind of important organic chemical industry's intermediate, is mainly used in medicine, agricultural chemicals, industry such as dyestuff. as pharmaceutically being used for the synthetic (JP58-41835JP60-185738 of vitamin-E; JP62-277336; EP0159240; US4560801), being used for synthesizing of the former medicine of highy potent herbicide CH-2000 (WO 9202512) etc. on agricultural chemicals, is the important high added value chemical of a class.
In nearest document, be oxidation hydroxylation reagent (Kol, M. with the fluorine; Rozen, S.J.Org.Chem., 1993,58,1593) obtain the 2 of 45% yield.
In recent years, the single step reaction that directly benzene hydroxylation is prepared phenol has attracted various countries investigators' extensive concern.This is one and relates to the direct activation c h bond and make the reaction of hydro carbons functionalization, directly hydroxyl is introduced aromatic ring by the activation c h bond, thereby is generated corresponding oxy-compound, and this is one of the most scabrous problem in the synthetic chemistry.Capture this difficulty, selection of catalysts and preparation are the most key factors.
In addition, in the method for the phenol by directly hydroxylating benzene that oneself has, more representational catalyzer has: molecular sieve, heteropolyacid, molysite (FeCl2, FeCl3) loads on the silica gel, and precious metal (Pd, Ir, Pt) loads on Al203, (US:5672777 such as sepiolite; 5808167; 5110995; 5874646; 4683217; 4758419; 5912391; EP43562; 158976), use these catalyzer the direct catalytic hydroxylation of benzene can both be generated phenol under certain conditions, the yield of phenol is between 2%～25%, the selectivity of phenol is between 60%～95%, but the making difficulty that these catalyzer have equally, the cost height, what have at all can not recycling, the catalytic reaction condition harshness that has etc.
Summary of the invention
The present invention is intended to overcome the deficiencies in the prior art part and provides a kind of easy and simple to handle, and selectivity is good, and the yield height is suitable for the synthetic method of the 2 of large-scale production.
For achieving the above object, the present invention is achieved in that
The synthetic method of 2, it comprises the steps:
A) with the molecular sieve be catalyzer, the halogenated acetic acids aqueous solution that will contain sym-trimethylbenzene under the effect of molecular sieve is 30% hydrogen peroxide effect with volumetric concentration, carries out heating reflux reaction;
B) with steps A) products therefrom is cooled to room temperature and adds entry;
C) adopt solvent extraction to separate, solvent is reclaimed in washing;
D) underpressure distillation gets final product.
As a kind of preferred version, the type of molecular sieve of the present invention can be selected 3A or 4A type.
In addition, the consumption of molecular sieve of the present invention is by percentage to the quality: sym-trimethylbenzene: molecular sieve=1: 0.1～1, be preferably 1: 0.2～and 0.5.
The heating reflux reaction time of the present invention is 4～24 hours.
As another kind of preferred version, sym-trimethylbenzene of the present invention, halogenated acetic acids and volumetric concentration are that the mol ratio of 30% hydrogen peroxide is followed successively by: 1: 1～8: 1～20, be preferably 1: 2～6: 5～and 12.
As the third preferred version, halogenated acetic acids of the present invention is monochloracetic acid, dichloro-acetate, three chloro acetate or trifluoroacetic acids.
Halogenated acetic acids of the present invention is also selected two or more the mixture in monochloracetic acid, dichloro-acetate, three chloro acetate or the trifluoroacetic acid component.
The sym-trimethylbenzene of the present invention to be easy to get, halogenated acetic acids and hydrogen peroxide are reaction raw materials, have shortened the reaction times by the katalysis of molecular sieve, have improved the transformation efficiency of target product-2, are suitable for large-scale production.
Compared with prior art, the invention has the advantages that:
1) under the katalysis of molecular sieve, with the sym-trimethylbenzene that is easy to get, halogenated acetic acids, hydrogen peroxide is a reaction raw materials, has prepared 2;
2) reaction process is a homogeneous reaction, and it is mild that reaction is carried out, and is easy to control;
3) compare with existing method, good selectivity of target products, the yield height is suitable for large-scale production.
The invention will be further described below in conjunction with embodiment.Protection scope of the present invention will not only be confined to the statement of following content.
Embodiment
The present invention is the aqueous solution of sym-trimethylbenzene and halogenated acetic acids, under the catalysis of molecular sieve with 30% hydrogen peroxide effect, behind the heating reflux reaction certain hour, be cooled to room temperature, add entry, separate through solvent extraction, washing, reclaim solvent, the residuum underpressure distillation obtains 2,4, the 6-pseudocuminol, wherein the type of molecular sieve is 3A or 4A type, and consumption (mass percent) is a sym-trimethylbenzene: molecular sieve=1: 0.1～1, be preferably 1: 0.2～and 0.5.The mol ratio of each component of reactant is a sym-trimethylbenzene: halogenated acetic acids: 30% hydrogen peroxide=1: 1～8: 1～20, be preferably 1: 2～6: 5～and 12.The heating reflux reaction time is 4～24 hours, is preferably 6～15 hours.
Embodiment 1
In three mouthfuls of reaction flasks of 250ml, with molecular sieve (3A, 5.0 restrain) join and contain sym-trimethylbenzene (24.0 grams, 0.2 in trifluoroacetic acid mole) (68.4 grams, 0.6 mole) and water (20 milliliters) solution, drip 30% hydrogen peroxide (113.3 grams under the room temperature, 1.0 mole), refluxed then 9 hours, and be cooled to room temperature, add entry (50ml), through benzene (3 * 30ml) extraction separation, wash with water, reclaim solvent, the residuum underpressure distillation, collect 100-105 ℃/20mmHg cut, obtain colorless oil 25.0 grams, yield is 92%, places after fixing.Fusing point: 71-73 ℃.
Product is 99.4% through gas Chromatographic Determination purity.
Embodiment 2
In three mouthfuls of reaction flasks of 250ml, with molecular sieve (3A, 5.0 restrain) join and contain sym-trimethylbenzene (24.0 grams, 0.2 in trichoroacetic acid(TCA) mole) (101.7 grams, 0.6 mole) and water (20 milliliters) solution, drip 30% hydrogen peroxide (113.3 grams under the room temperature, 1.0 mole), refluxed then 9 hours, and be cooled to room temperature, add entry (50ml), through benzene (3 * 30ml) extraction separation, wash with water, reclaim solvent, the residuum underpressure distillation, collect 100-105 ℃/20mmHg cut, obtain colorless oil 23.7 grams, yield is 87%, places after fixing.Fusing point: 71-73 ℃.
Product is 99.2% through gas Chromatographic Determination purity.
Embodiment 3
In three mouthfuls of reaction flasks of 250ml, with molecular sieve (3A, 5.0 restrain) join and contain sym-trimethylbenzene (24.0 grams, 0.2 in dichloro acetic acid mole) (77.4 grams, 0.6 mole) and water (20 milliliters) solution, drip 30% hydrogen peroxide (113.3 grams under the room temperature, 1.0 mole), refluxed then 10 hours, and be cooled to room temperature, add entry (50ml), through benzene (3 * 30ml) extraction separation, wash with water, reclaim solvent, the residuum underpressure distillation, collect 100-105 ℃/20mmHg cut, obtain colorless oil 21.5 grams, yield is 79%, places after fixing.Fusing point: 71-73 ℃.
Product is 99.2% through gas Chromatographic Determination purity.
Embodiment 4
In three mouthfuls of reaction flasks of 250ml, with molecular sieve (3A, 5.0 restrain) join and contain sym-trimethylbenzene (24.0 grams, 0.2 in Mono Chloro Acetic Acid mole) (56.7 grams, 0.6 mole) and water (20 milliliters) solution, drip 30% hydrogen peroxide (113.3 grams under the room temperature, 1.0 mole), refluxed 12 hours, and be cooled to room temperature, add entry (50ml), through benzene (3 * 30ml) extraction separation, wash with water, reclaim solvent, the residuum underpressure distillation, collect 100-105 ℃/20mmHg cut, obtain colorless oil 18.6 grams, yield is 68%, places after fixing.Fusing point: 71-73 ℃.
Product is 99.3% through gas Chromatographic Determination purity.
Embodiment 5
In three mouthfuls of reaction flasks of 250ml, with molecular sieve (4A, 5.0 restrain) join and contain sym-trimethylbenzene (24.0 grams, 0.2 in trifluoroacetic acid mole) (68.4 grams, 0.6 mole) and water (20 milliliters) solution, drip 30% hydrogen peroxide (113.3 grams under the room temperature, 1.0 mole), refluxed then 10 hours, and be cooled to room temperature, add entry (50ml), through benzene (3 * 30ml) extraction separation, wash with water, reclaim solvent, the residuum underpressure distillation, collect 100-105 ℃/20mmHg cut, obtain colorless oil 23.0 grams, yield is 86%, places after fixing.Fusing point: 71-73 ℃.
Product is 99.4% through gas Chromatographic Determination purity.
Embodiment 6
According to the experimentation of the foregoing description 1, change more type and the consumption and the reaction times of molecular sieve, other reaction conditionss and proportioning raw materials are constant, and the experimental result tabulation that obtains is summarized as follows:
Table one: there be the synthetic of 2 in molecular sieve
| Sequence number | Molecular sieve type | Molecular sieve consumption gram/gram | Reaction times/hour | Yield % |
| 1 | 3A | 0.1 | 12 | 84 |
| 2 | 3A | 0.2 | 9 | 92 |
| 3 | 3A | 0.3 | 7 | 87 |
| 4 | 3A | 0.4 | 7 | 86 |
| 5 | 4A | 0.1 | 14 | 80 |
| 6 | 4A | 0.2 | 10 | 86 |
| 7 | 4A | 0.3 | 8 | 82 |
Comparative example (not adding molecular sieve)
In three mouthfuls of reaction flasks of 250ml, to containing sym-trimethylbenzene (24.0 grams, 0.2 (68.4 grams of trifluoroacetic acid mole), 0.6 the mole) and water (20 milliliters) solution in, under room temperature, drip 30% hydrogen peroxide (113.3 grams, 1.0 moles), refluxed 18 hours, be cooled to room temperature, add entry (50ml), (3 * 30ml) extraction separation wash with water through benzene, reclaim solvent, 100-105 ℃/20mmHg cut is collected in the residuum underpressure distillation, obtains colorless oil 21.2 grams, yield is 78%, places after fixing.Fusing point: 71-73 ℃.
Claims (8)
1.2,4, the synthetic method of 6-pseudocuminol is characterized in that, comprises the steps:
A) with the molecular sieve be catalyzer, the halogenated acetic acids aqueous solution that will contain sym-trimethylbenzene under the effect of molecular sieve is 30% hydrogen peroxide effect with volumetric concentration, carries out heating reflux reaction; Described molecular sieve is 3A or 4A type;
B) with steps A) products therefrom is cooled to room temperature and adds entry;
C) adopt solvent extraction to separate, solvent is reclaimed in washing;
D) underpressure distillation gets final product.
2. the synthetic method of 2 according to claim 1, it is characterized in that: the consumption of described molecular sieve is by percentage to the quality: sym-trimethylbenzene: molecular sieve=1: 0.1～1.
3. the synthetic method of 2 according to claim 2, it is characterized in that: the described heating reflux reaction time is 4～24 hours.
4. the synthetic method of 2 according to claim 1, it is characterized in that: described sym-trimethylbenzene, halogenated acetic acids and volumetric concentration are that the mol ratio of 30% hydrogen peroxide is followed successively by: 1: 1～8: 1～20.
5. the synthetic method of 2 according to claim 4, it is characterized in that: described halogenated acetic acids is monochloracetic acid, dichloro-acetate, three chloro acetate or trifluoroacetic acids.
6. the synthetic method of 2 according to claim 4 is characterized in that: described halogenated acetic acids is two or more the mixture in monochloracetic acid, dichloro-acetate, three chloro acetate or the trifluoroacetic acid component.
7. the synthetic method of 2 according to claim 2, it is characterized in that: the consumption of described molecular sieve is by percentage to the quality: sym-trimethylbenzene: molecular sieve=1: 0.2～0.5.
8. the synthetic method of 2 according to claim 4, it is characterized in that: described sym-trimethylbenzene, halogenated acetic acids and volumetric concentration are that the mol ratio of 30% hydrogen peroxide is followed successively by: 1: 2～6: 5～12.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200810010030 CN101475447B (en) | 2008-01-04 | 2008-01-04 | Method for synthesizing 2,4,6-pseudocuminol |
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| CN 200810010030 CN101475447B (en) | 2008-01-04 | 2008-01-04 | Method for synthesizing 2,4,6-pseudocuminol |
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| CN101475447A CN101475447A (en) | 2009-07-08 |
| CN101475447B true CN101475447B (en) | 2011-11-16 |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102974354B (en) * | 2012-11-26 | 2014-08-13 | 东南大学 | Catalyst for synthesizing 2,3,6-trimethylphenol and preparation method thereof |
| CN113083339B (en) * | 2021-04-15 | 2022-11-08 | 万华化学(四川)有限公司 | Catalyst for preparing vitamin E and preparation method and application thereof |
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Non-Patent Citations (1)
| Title |
|---|
| Berryinne Chou，et，al..Cu-substituted molecular sieves as liquid phase oxidation catalysts.《Microporous and mesoporous materials》.2001,第48卷309-317. * |
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