CN102731261A - Method for preparing 2-tertiary butyl hydroquinone and co-producing hydroquinone - Google Patents
Method for preparing 2-tertiary butyl hydroquinone and co-producing hydroquinone Download PDFInfo
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- CN102731261A CN102731261A CN2012102412609A CN201210241260A CN102731261A CN 102731261 A CN102731261 A CN 102731261A CN 2012102412609 A CN2012102412609 A CN 2012102412609A CN 201210241260 A CN201210241260 A CN 201210241260A CN 102731261 A CN102731261 A CN 102731261A
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- butyl hydroquinone
- organic solvent
- hydroquinone
- tert
- benzene
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Abstract
The invention relates to a method for preparing 2-tertiary butyl hydroquinone and co-producing hydroquinone, which mainly comprises the steps of placing 2,5-ditertiary butyl hydroquinone in an organic solvent in presence of Lewis acid; maintaining for 2-8 hours at 0-150 DEG C; then adding a hydrochloric acid aqueous solution and separating to obtain an organic phase and an aqueous phase; drying the organic phase, filtering and evaporating for removing the used organic solvent to obtain the 2-tertiary butyl hydroquinone; and extracting the aqueous phase to obtain an extract and concentrating the extract to obtain hydroquinone. The method provided by the invention is simple and easy to operate, and the conversion rate of 2,5-ditertiary butyl hydroquinone is more than 95%. The total mole yield of 2-tertiary butyl hydroquinone and hydroquinone is more than 84%, and commercial value is provided. According to he invention, a compact foundation for comprehensively utilizing 2,5-ditertiary butyl hydroquinone in a large scale is laid.
Description
Technical field
The present invention relates to the method for a kind of 2-of preparation Tert. Butyl Hydroquinone and coproduction Resorcinol, specifically, relate to a kind of method for preparing 2-Tert. Butyl Hydroquinone and coproduction Resorcinol by 2,5 di tert butyl hydroquinone.
Background technology
2-Tert. Butyl Hydroquinone (TBHQ) is a widely used edible grease antioxidant, and it is to be made through the Friedel-Crafts alkylated reaction by the Resorcinol (HQ) and the trimethyl carbinol.In this reaction, because the character of reaction itself can generate 2,5 di tert butyl hydroquinone (DTBHQ) inevitably.Because the use face of DTBHQ is narrow and consumption is very limited, causes its tank farm stock constantly to increase.If do not solve the problem of outlet of DTBHQ, with the production that seriously has influence on TBHQ.
At present; Though existing DTBHQ sloughed a tert-butyl group make it be converted into TBHQ; Or slough two tert-butyl groups and make it be converted into HQ, or the method that obtains the mixture of TBHQ and HQ is in the news, and (thin silk fabric portion justice is controlled .2-t-Block チ Le Ha イ De ロ キ ノ Application manufacture method JP 08176044,1996; By bright leather, 2, the research [D] of the synthetic phenol derivatives of 5-di-tert-butyl hydroquinone dealkylation and tert-butyl group occupy-place. Ji'nan University, 2005; With CN 1699318A), but prior art (mainly being to lack commercial value) also not fully up to expectations still has room for improvement.
Summary of the invention
The objective of the invention is to, provide a kind of and prepare the method for 2-Tert. Butyl Hydroquinone (TBHQ) and coproduction Resorcinol (HQ), overcome the defective that exists in the prior art by 2,5 di tert butyl hydroquinone (DTBHQ).
The present invention generally is the reversible principle according to organic chemical reactions; Designed a kind of dealkylation: promptly under the condition that has Lewis acid to exist; DTBHQ is placed the organic solvent that can accept tertiary butyl radical, slough or the part slough the tertiary butyl, make it to be converted into the mixture of TBHQ and HQ; Separate through simple again, obtain TBHQ and HQ respectively.
Of the present invention by 2; 5-di-tert-butyl hydroquinone (DTBHQ) prepares the method for 2-Tert. Butyl Hydroquinone (TBHQ) and coproduction Resorcinol (HQ); Its key step is: under the condition that has Lewis acid to exist, (DTBHQ) places organic solvent with 2,5 di tert butyl hydroquinone; Keep 2 hours～8 hours (preferred 2.5 hours～4.5 hours) at 0 ℃～150 ℃ (preferred 60 ℃～100 ℃) states; Add aqueous hydrochloric acid again and react, get organic phase (oil phase) and water, separating oil/water two phases behind the standing demix with cancellation; The gained oil phase successively through dry, filter and steam after removing used organic solvent 2-Tert. Butyl Hydroquinone (TBHQ), the gained water obtains Resorcinol (HQ) through extraction and after concentrating the gained extraction liquid;
Wherein, said organic solvent is a benzene or by having to the substituted benzene of the substituting group of electronic effect.
Can know that by technique scheme the present invention is simple, and the transformation efficiency of DTBHQ is more than 95%, and the total recovery of TBHQ and HQ possesses commercial value more than 84%.The present invention has established solid basis for mass-producing comprehensive utilization DTBHQ.
Embodiment
The used Lewis acid of the present invention is to be used for the anti-Lewis acid of Friedel-Crafts alkylation, like (but being not limited to): FeCl
3, AlCl
3Or ZnCl
2Deng.
In optimal technical scheme of the present invention, the consumption of Lewis acid is 0.6 times～1.2 times of 2,5 di tert butyl hydroquinone (DTBHQ) molar weight;
In another optimal technical scheme of the present invention, said organic solvent is: benzene, or by C
1～C
4Straight or branched alkyl or hydroxyl etc. have to the substituted benzene of the substituting group of electronic effect; Preferred organic solvent is: benzene or by methyl substituted benzene; Best organic solvent is: benzene, toluene or YLENE;
In another optimal technical scheme of the present invention, the consumption of said organic solvent is 10 times～50 times of 2,5 di tert butyl hydroquinone (DTBHQ) molar weight, more preferably 15 times～25 times.
In sum, of the present inventionly prepare the method for TBHQ and coproduction HQ by DTBHQ, its key step is: at benzene, in toluene or the YLENE, add Lewis acid (like FeCl
3, AlCl
3Or ZnCl
2Deng), make its dissolving or be dispersed in wherein, add DTBHQ again; After treating that it dissolves fully, heat temperature raising kept 2.5 hours～4.5 hours at 60 ℃～100 ℃ states; In reaction system, add diluted hydrochloric acid aqueous solution again, get oily, water two phases, separating oil/water two phases; The gained oil phase successively through dry, filter and steam and remove used benzene, behind toluene or the YLENE TBHQ, the gained water extract successively (extraction agent is an ETHYLE ACETATE), and concentrate the gained extraction liquid after obtain HQ.
Below through instance the present invention is elaborated, but the example of being lifted does not limit protection scope of the present invention.Although the present invention is specified, and quoted some specific exampless as proof, for a person skilled in the art, only otherwise leave the spirit and scope of the present invention, it is obvious doing various variations and correction.
Embodiment 1
In 500ml there-necked flask (device has mechanical stirring, spherical condensation tube and TM), add 300ml toluene (industrial goods, 99%, China petroleum Chemicals Co., Ltd. Town Hai Lian Hua branched Corporation) and the anhydrous AlCl of 15g
3(industrial goods, 98%, the inferior favour chemical industry in Zhangjagang City ltd) is heated to 80 ℃ under stirring, and works as AlCl
3After being dispersed in the toluene, add 2,5 di tert butyl hydroquinone (industrial goods, 97.9% of 30g (0.135mol); Occasion chemical industry ltd is praised in Shanghai), maintain the temperature at 90 ℃ of reaction 3.5h, stop heating, make reaction solution naturally cool to envrionment temperature under stirring; Be poured in the 300ml water (containing 10ml 15%HCl), standing demix, organic phase (toluene layer) adopts anhydrous magnesium sulfate drying, filters; Filtrate decompression distillation obtains toluene (200mL), resistates is placed in 5 ℃～10 ℃ the environment to cool off, and filters; Filter cake is the 2-Tert. Butyl Hydroquinone, fusing point 125-128 ℃, and the recyclable p-tert-butyltoluene of filtrate water vapor distillation (30ml).Water layer is used ethyl acetate extraction, and extraction liquid can get Resorcinol, fusing point through concentrating: 168-170 ℃.The molar yield 85% of 2-Tert. Butyl Hydroquinone and Resorcinol sum.
Embodiment 2
In 500ml there-necked flask (device has mechanical stirring, spherical condensation tube and TM), add 330ml YLENE and the anhydrous AlCl of 13g
3, be heated to 80 ℃ under stirring, work as AlCl
3After being dispersed in the toluene, add 2,5 di tert butyl hydroquinone (industrial goods, 97.9% of 30g (0.135mol); Occasion chemical industry ltd is praised in Shanghai), maintain the temperature at 90 ℃ of reaction 3h, stop heating, make reaction solution be cooled to envrionment temperature under stirring; Reaction solution is poured in the 330ml water (containing 10ml 15%HCl), standing demix, organic phase (YLENE layer) adopts anhydrous magnesium sulfate drying, filters; The filtrate decompression distillation obtains YLENE (200mL), and resistates is placed on 5 ℃～10 ℃ coolings, filters; Filter cake is the 2-Tert. Butyl Hydroquinone, fusing point 125-128 ℃, and the recyclable tertiary butyl YLENE of filtrate water vapor distillation (33ml).Water layer is used ethyl acetate extraction, and extraction liquid can get Resorcinol, fusing point through concentrating: 168-170 ℃.Total molar yield of 2-Tert. Butyl Hydroquinone and Resorcinol reaches 84%.
Claims (9)
1. method for preparing 2-Tert. Butyl Hydroquinone and coproduction Resorcinol; Its key step is: under the condition that has Lewis acid to exist; 2,5 di tert butyl hydroquinone is placed organic solvent, kept 2 hours～8 hours at 0 ℃～150 ℃ states; Add aqueous hydrochloric acid again; Separating obtained organic phase and water, gained organic phase successively through dry, filter, and steam after removing used organic solvent the 2-Tert. Butyl Hydroquinone, the gained water extracts successively, and concentrate the gained extraction liquid after obtain Resorcinol;
Wherein, said organic solvent is a benzene or by having to the substituted benzene of the substituting group of electronic effect.
2. the method for claim 1 is characterized in that, wherein 2,5 di tert butyl hydroquinone is placed organic solvent, keeps 2.5 hours～4.5 hours at 60 ℃～100 ℃ states.
3. according to claim 1 or claim 2 method is characterized in that wherein said organic solvent is: benzene, or by C1～C4 straight or branched alkyl or the substituted benzene of hydroxyl.
4. method as claimed in claim 3 is characterized in that, wherein said organic solvent is: benzene or by methyl substituted benzene.
5. method as claimed in claim 4 is characterized in that, wherein said organic solvent is: benzene, toluene or YLENE.
6. like claim 3 or 5 described methods, it is characterized in that the consumption of wherein said organic solvent is 10 times～50 times of 2,5 di tert butyl hydroquinone molar weight.
7. method as claimed in claim 6 is characterized in that, the consumption of wherein said organic solvent is 15 times～25 times of 2,5 di tert butyl hydroquinone molar weight.
8. method as claimed in claim 7 is characterized in that, wherein used Lewis acid is: FeCl3, AlCl3 or ZnCl2.
9. method as claimed in claim 8 is characterized in that, the consumption that wherein Lewis is sour is 0.6 times～1.2 times of 2,5 di tert butyl hydroquinone molar weight.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2012102412609A CN102731261A (en) | 2012-07-12 | 2012-07-12 | Method for preparing 2-tertiary butyl hydroquinone and co-producing hydroquinone |
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|---|---|---|---|
| CN2012102412609A CN102731261A (en) | 2012-07-12 | 2012-07-12 | Method for preparing 2-tertiary butyl hydroquinone and co-producing hydroquinone |
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1359290A (en) * | 1971-08-12 | 1974-07-10 | Kodak Ltd | Preparation of t-butylhydroquinone |
| DE10020272A1 (en) * | 1999-04-26 | 2000-12-14 | Sumitomo Chemical Co | P,p'-biphenol preparation comprises debutylating a 4,4'-biphenol compound with at least one tert.-butyl group in the presence of or treating with sulfuric or (hypo)phosphorous acid |
| JP2004224736A (en) * | 2003-01-23 | 2004-08-12 | Honshu Chem Ind Co Ltd | Method for producing 4,4'-biphenol |
| JP3570760B2 (en) * | 1994-12-26 | 2004-09-29 | 本州化学工業株式会社 | Method for producing 2-t-butylhydroquinone |
| CN1699318A (en) * | 2005-05-13 | 2005-11-23 | 广东省食品工业研究所 | Improved process for preparing edible grease antioxidant 2-tert-butyl hydroquinone |
| CN102516033A (en) * | 2011-10-26 | 2012-06-27 | 广东省食品工业研究所 | Method for preparing hydroquinone by taking 2,5-ditertiary butyl hydroquinone as raw material |
-
2012
- 2012-07-12 CN CN2012102412609A patent/CN102731261A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1359290A (en) * | 1971-08-12 | 1974-07-10 | Kodak Ltd | Preparation of t-butylhydroquinone |
| JP3570760B2 (en) * | 1994-12-26 | 2004-09-29 | 本州化学工業株式会社 | Method for producing 2-t-butylhydroquinone |
| DE10020272A1 (en) * | 1999-04-26 | 2000-12-14 | Sumitomo Chemical Co | P,p'-biphenol preparation comprises debutylating a 4,4'-biphenol compound with at least one tert.-butyl group in the presence of or treating with sulfuric or (hypo)phosphorous acid |
| JP2004224736A (en) * | 2003-01-23 | 2004-08-12 | Honshu Chem Ind Co Ltd | Method for producing 4,4'-biphenol |
| CN1699318A (en) * | 2005-05-13 | 2005-11-23 | 广东省食品工业研究所 | Improved process for preparing edible grease antioxidant 2-tert-butyl hydroquinone |
| CN102516033A (en) * | 2011-10-26 | 2012-06-27 | 广东省食品工业研究所 | Method for preparing hydroquinone by taking 2,5-ditertiary butyl hydroquinone as raw material |
Non-Patent Citations (2)
| Title |
|---|
| 孙诗澄等: "取代苯酚的脱叔丁基反应", 《有机化学》 * |
| 由明革: "2,5-二叔丁基对苯二酚脱烷基化及叔丁基占位合成酚类衍生物的研究", 《中国优秀硕士学位论文全文数据库工程科技I辑》 * |
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Application publication date: 20121017 |