CN101591224A - A kind of method for preparing the 2-tertiary butyl-4-methylphenol - Google Patents
A kind of method for preparing the 2-tertiary butyl-4-methylphenol Download PDFInfo
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- CN101591224A CN101591224A CNA2009100535833A CN200910053583A CN101591224A CN 101591224 A CN101591224 A CN 101591224A CN A2009100535833 A CNA2009100535833 A CN A2009100535833A CN 200910053583 A CN200910053583 A CN 200910053583A CN 101591224 A CN101591224 A CN 101591224A
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- methylphenol
- tertiary butyl
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Abstract
The invention discloses the method for a kind of 2-of preparation tertiary butyl-4-methylphenol, this method comprises two steps: at first be Preparation of catalysts: with imidazoles, 1,4-dibromobutane, 1,4-butane sultone, sulfuric acid, sodium hydroxide etc. are catalyzer for feedstock production multi-sulfonic ionic liquid; Next prepares the 2-tertiary butyl-4-methylphenol: with the ionic liquid that makes is catalyzer, and under the condition that hexanaphthene exists, the p-cresol and the trimethyl carbinol carry out alkylated reaction, obtain the 2-tertiary butyl-4-methylphenol.Method of the present invention has environmental friendliness, the transformation efficiency height, and selectivity is good, and temperature of reaction is low, and catalyzer is easily separated, reclaim and advantage such as use again.
Description
Technical field
The present invention relates to the synthetic method of a kind of 2-tertiary butyl-4-methylphenol, belong to the fine chemical product synthesis technical field.
Background technology
The 2-tertiary butyl-4-methylphenol claims the o-tert-butyl p-cresol again, popular name 2, and 4-phenol is a kind of organic intermediate, occupies critical role in the organic synthesis field.Be widely used in the production of tensio-active agent, antioxidant and UV light absorber.With it mainly produce 2246, the high-grade phenol antioxidant of 2246-S and photostabilizer UV-326 etc.Compare with BHT (antioxidant 264), high-grade phenols not only toxicity is low, pollution-free, and to oxygen, the material surface be full of cracks aging and that daylight causes that heat causes has protective benefits; Sulfuration and plasticity number to rubber all do not have influence; Latex is not had the destabilization effect, in water, easily disperse, easy to use; Detrimentally affect in the time of in natural gum, reducing over cure.At present, because 2, the shortage of 4-phenol, thus limited with 2, and 4-phenol is the production of the phenol antioxidant such as 2246-S of raw material.
The 2-tertiary butyl-4-methylphenol is mainly synthetic by the Friedel-Crafts tertiary butyl reaction by p-cresol, and the synthetic method of having reported has trimethyl carbinol method, iso-butylene method, methyl tertiary butyl ether method etc.Though the iso-butylene low price, utilization ratio is low, the transportation difficulty, is unfavorable for the production of short run fine chemical product.Shortcomings such as there is expensive raw material price in methyl tertiary butyl ether, and reactive behavior is low, and by-product carbinol toxicity is big.Trimethyl carbinol method is because raw material sources are abundant, and reaction conditions is gentle and be subjected to extensive concern.
People such as G.D.Yadav reported with mesoporous molecular sieve carried SO in 1999
4 2-/ ZrO
2As catalyzer, carried out the alkylating research (Green Chemistry, 1999,269 ~ 274) of p-methyl phenol and methyl tertiary butyl ether, peak rate of conversion has only 49%.People such as Biju M.Devassy have delivered and have been entitled as " Alkylation of p-cresol with tert-butanol catalyzed by heteropolyacid supported on zirconia catalyst " paper (Journal of MolecularCatalysis: A:Chemical, 2003,125 ~ 130), reported loaded by heteropoly acid ZrO
2Be catalyzer, maximum conversion rate is 61%, but to the selectivity 81.4% of the 2-tertiary butyl-4-methylphenol, catalyst deactivation is fast.Therefore, need the suitable new catalytic material of exploitation to realize the preparation 2-tertiary butyl-4-methylphenol of high yield.
Summary of the invention
The object of the present invention is to provide a kind of eco-friendly, method that heterogeneous catalysis prepares the 2-tertiary butyl-4-methylphenol, is that catalyzer solves the existing problem of background technology with the multi-sulfonic ionic liquid.
The object of the present invention is achieved like this:
A kind of method for preparing the 2-tertiary butyl-4-methylphenol, this method with heterogeneous multi-sulfonic ionic liquid as catalyzer, the trimethyl carbinol as alkylating reagent, specifically may further comprise the steps:
The first step Preparation of catalysts
Imidazoles, sodium hydroxide and DMSO (dimethyl sulfoxide (DMSO)) (analytical pure) solution is mixed, 60～70 ℃ are stirred 2～6h down, with 1, the 4-dibromobutane is added drop-wise in the mixing solutions, continues to stir 2～4h, reaction finishes, reaction solution is poured in the big water gaging, left standstill 6～12h, suction filtration, vacuum-drying 2～4h obtains polyazin; With polyazin and 1, the 4-butane sultone at room temperature stirs 3～5d, with the ethyl acetate washing, obtains inner salt; The gained inner salt is carried out acidifying 6～8h with sulfuric acid (analytical pure), and making the multi-sulfonic ionic liquid is catalyzer; Imidazoles and 1 wherein, the mol ratio of 4-dibromobutane is 1.8～2.5: 1; The mol ratio of imidazoles and sodium hydroxide is 1～1.5: 1; The consumption of DMSO is 150～250ml/mol imidazoles; The consumption of water is 2500ml～5000ml/mol imidazoles; 1, the mol ratio of 4-butane sultone and polyazin is 2～5: 1; The mol ratio of sulfuric acid and inner salt is 2～4: 1.
The preparation of the second step 2-tertiary butyl-4-methylphenol
The multi-sulfonic ionic liquid that makes with the first step is a catalyzer, and under the condition that 50～80 ℃, hexanaphthene exist, the p-methyl phenol and the trimethyl carbinol carry out alkylated reaction, make the 2-tertiary butyl-4-methylphenol at normal pressure, temperature; Wherein: the mol ratio of the trimethyl carbinol and p-methyl phenol is 1～3: 1; Catalyst levels is 0.4～0.75mol/mol p-methyl phenol; The hexanaphthene consumption is 1.44～4.32g/g p-methyl phenol.
The present invention is a catalyzer with the multi-sulfonic ionic liquid in the preparation 2-tertiary butyl-4-methylphenol process, and after reaction finished, ionic liquid washed ionic liquid 3 times with hexanaphthene, and vacuum-drying 1h is promptly reusable then.
The present invention has environmental friendliness, the transformation efficiency height, and selectivity is good, and temperature of reaction is low, and catalyzer is easily separated, reclaims and advantage such as to use again.
Embodiment
Embodiment 1
The first step Preparation of catalysts
6.819g imidazoles, 4.137gNaOH and 20mlDMSO are stirred 2h down at 60 ℃, drip 6ml1, the 4-dibromobutane continues to stir 2h down at 60 ℃; Reacted reaction solution has been poured in the 500ml water, left standstill 8h, suction filtration, vacuum-drying 2h obtains polyazin; With polyazin and 1, the 4-butane sultone at room temperature stirs 3d, with the ethyl acetate washing, obtains inner salt; The gained inner salt is carried out acidifying 7h with sulfuric acid, make the multi-sulfonic ionic liquid.
The preparation of the second step 2-tertiary butyl-4-methylphenol
Be furnished with in the there-necked flask of magnetic stirring apparatus, reflux exchanger, dropping funnel, normal pressure, under 70 ℃, add 5mmol p-methyl phenol, the 5mmol trimethyl carbinol and 0.5mol/1mol multi-sulfonic ionic-liquid catalyst, band aqua hexanaphthene is 3ml, reacts 7h down at 70 ℃, makes product: the 2-tertiary butyl-4-methylphenol, timing sampling in the reaction process carries out the qualitative and GC quantitative analysis of GC-MS.The transformation efficiency of p-methyl phenol is 85%, and the selectivity of the 2-tertiary butyl-4-methylphenol is 95%.
Example 2～4
Except for the following differences, all the other are identical with embodiment 1, and the trimethyl carbinol is in the ratio consumption of table 1.
Table 1
Embodiment 5～8
Except for the following differences, all the other are identical with embodiment 1, and catalyst levels is pressed table 2.
Table 2
Embodiment 9～11
Except for the following differences, all the other are identical with embodiment 1, and temperature of reaction is pressed table 3.
Table 3
Embodiment 12～13
Except for the following differences, all the other are identical with embodiment 1, and the consumption of band aqua hexanaphthene is pressed table 4.
Table 4
Embodiment 14～18
Except for the following differences, all the other are identical with embodiment 1, and catalyzer is reused number of times result's influence is seen Table 5.
Table 5
Comparative example 19～20
Under the condition of embodiment 1, use 30%TPA/ZrO
2Be catalyzer, all the other are identical with embodiment 1, make comparisons for the multi-sulfonic ionic liquid with catalyzer, see table 6 for details.
Table 6
Claims (1)
1, a kind of method for preparing the 2-tertiary butyl-4-methylphenol is characterized in that this method comprises following concrete steps:
The first step Preparation of catalysts
Imidazoles, sodium hydroxide and DMSO solution are mixed, and 60～70 ℃ are stirred 2～6h down, and with 1, the 4-dibromobutane is added drop-wise in the mixing solutions, continue to stir 2～4h, reaction finishes, and reaction solution is poured in the big water gaging, leaves standstill 6～12h, suction filtration, vacuum-drying 2～4h obtains polyazin; With polyazin and 1, the 4-butane sultone at room temperature stirs 3～5d, with the ethyl acetate washing, obtains inner salt; The gained inner salt is carried out acidifying 6～8h with sulfuric acid, and making the multi-sulfonic ionic liquid is catalyzer; Imidazoles and 1 wherein, the mol ratio of 4-dibromobutane is 1.8～2.5: 1; The mol ratio of imidazoles and sodium hydroxide is 1～1.5: 1; The consumption of DMSO is 150～250ml/mol imidazoles; The consumption of water is 2500ml～5000ml/mol imidazoles; 1, the mol ratio of 4-butane sultone and polyazin is 2～5: 1; The mol ratio of sulfuric acid and inner salt is 2～4: 1;
The preparation of the second step 2-tertiary butyl-4-methylphenol
The multi-sulfonic ionic liquid that makes with the first step is a catalyzer, and under the condition that 50～80 ℃, hexanaphthene exist, the p-methyl phenol and the trimethyl carbinol carry out alkylated reaction, make the 2-tertiary butyl-4-methylphenol at normal pressure, temperature; Wherein: the mol ratio of the trimethyl carbinol and p-methyl phenol is 1～3: 1; Catalyst levels is 0.4～0.75mol/mol p-methyl phenol; The hexanaphthene consumption is 1.44～4.32g/g p-methyl phenol.
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102019202A (en) * | 2010-09-30 | 2011-04-20 | 南京工业大学 | Sulfonic acid dual-core ion liquid catalyst and method using same for synthesizing polydiethylene glycol sebacate |
| CN103249703A (en) * | 2010-12-10 | 2013-08-14 | 雪佛龙奥伦耐有限责任公司 | Skewed and middle attached linear chain alkylphenol and method of making the same |
| CN103992208A (en) * | 2014-05-30 | 2014-08-20 | 湖南利洁科技有限公司 | Method for synthesizing 2-tertiary butyl-p-cresol through catalysis of modified Y zeolite |
| CN106631707A (en) * | 2016-11-16 | 2017-05-10 | 广东希必达新材料科技有限公司 | Method for preparing p-cresol dicyclopentadiene butylation product |
| CN108929200A (en) * | 2018-08-31 | 2018-12-04 | 荆州市天翼精细化工开发有限公司 | A kind of preparation method of tert-butylhydroquinone |
| CN111167516A (en) * | 2020-02-21 | 2020-05-19 | 浙江大学 | Porous carbon supported monomolecular heteropoly acid catalyst and preparation method and application thereof |
| CN112225643A (en) * | 2020-11-16 | 2021-01-15 | 安徽时联特种溶剂股份有限公司 | Method for performing cresol alkylation reaction in microreactor by using acidic ionic liquid |
| CN113087598A (en) * | 2021-04-20 | 2021-07-09 | 宿州学院 | Method for preparing 2-tert-butyl-p-cresol by using eutectic solvent catalysis |
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2009
- 2009-06-23 CN CNA2009100535833A patent/CN101591224A/en active Pending
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102019202A (en) * | 2010-09-30 | 2011-04-20 | 南京工业大学 | Sulfonic acid dual-core ion liquid catalyst and method using same for synthesizing polydiethylene glycol sebacate |
| CN102019202B (en) * | 2010-09-30 | 2013-02-06 | 南京工业大学 | Sulfonic acid dual-core ion liquid catalyst and method using same for synthesizing polydiethylene glycol sebacate |
| CN103249703A (en) * | 2010-12-10 | 2013-08-14 | 雪佛龙奥伦耐有限责任公司 | Skewed and middle attached linear chain alkylphenol and method of making the same |
| JP2013544885A (en) * | 2010-12-10 | 2013-12-19 | シェブロン・オロナイト・カンパニー・エルエルシー | Tilted and center-bound linear alkylphenols and methods of making |
| CN103992208A (en) * | 2014-05-30 | 2014-08-20 | 湖南利洁科技有限公司 | Method for synthesizing 2-tertiary butyl-p-cresol through catalysis of modified Y zeolite |
| CN103992208B (en) * | 2014-05-30 | 2016-04-13 | 湖南利洁科技有限公司 | A kind of Y zeolite of modification catalyzes and synthesizes the method for 2-t-butyl-p-cresol |
| CN106631707A (en) * | 2016-11-16 | 2017-05-10 | 广东希必达新材料科技有限公司 | Method for preparing p-cresol dicyclopentadiene butylation product |
| CN108929200A (en) * | 2018-08-31 | 2018-12-04 | 荆州市天翼精细化工开发有限公司 | A kind of preparation method of tert-butylhydroquinone |
| CN111167516A (en) * | 2020-02-21 | 2020-05-19 | 浙江大学 | Porous carbon supported monomolecular heteropoly acid catalyst and preparation method and application thereof |
| CN112225643A (en) * | 2020-11-16 | 2021-01-15 | 安徽时联特种溶剂股份有限公司 | Method for performing cresol alkylation reaction in microreactor by using acidic ionic liquid |
| CN113087598A (en) * | 2021-04-20 | 2021-07-09 | 宿州学院 | Method for preparing 2-tert-butyl-p-cresol by using eutectic solvent catalysis |
| CN113087598B (en) * | 2021-04-20 | 2023-04-11 | 宿州学院 | Method for preparing 2-tert-butyl-p-cresol by using eutectic solvent catalysis |
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