CN105175214A - Method of preparing 5-tertiary butyl trimethylbenzene from ionic liquid catalyst - Google Patents
Method of preparing 5-tertiary butyl trimethylbenzene from ionic liquid catalyst Download PDFInfo
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- CN105175214A CN105175214A CN201510574799.XA CN201510574799A CN105175214A CN 105175214 A CN105175214 A CN 105175214A CN 201510574799 A CN201510574799 A CN 201510574799A CN 105175214 A CN105175214 A CN 105175214A
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- ionic liquid
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- trimethylbenzene
- hemimellitene
- 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
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- Y02P20/584—Recycling of catalysts
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Abstract
The invention provides a method of preparing 5-tertiary butyl trimethylbenzene from an ionic liquid catalyst. Trimethylbenzene and tert-butylchloride are taken as reactants and quaternary ammonium salt ionic liquid [Et3NHCl][AlCl3] as the catalyst, and the reaction temperature is 0 to 20 DEG C, and the reaction time is 3h to 6 h, and the molar ratio of the tert-butylchloride to the trimethylbenzene is 1:1 to 4:1, and the mass ratio of the ionic liquid to the trimethylbenzene is 0.05:1 to 0.2:1, and the molar ratio of the negative ion [AlCl3] to the positive ion [Et3NHCl] of the ionic liquid is 1.5:1 to 2.5:1. After a reaction is ended, the ionic liquid catalyst can be recycled after directly subjected to layering, therefore the energy consumption of an after-treatment process is reduced, and the overall operating cost is reduced; under the optimized reaction conditions, the reaction percent conversion can reach 100 percent, and the selectivity reaches 95 percent. The catalyst used by the method is simple in preparation process and easy to get raw materials.
Description
Technical field
The present invention relates to a kind of method that ionic-liquid catalyst prepares 5-tertiary butyl hemimellitene, belong to the technical field of organic chemical reactions method.
Background technology
In recent years, due to natural musk limited source, can not satisfy the demands far away, therefore all replace with the synthetic musk of synthesis.Nitro musk due to molecular structure simple, raw material is easy to get, low price, becomes applied range, rising synthetic musk.
Musk tibetene (having another name called musk tibetene), be then a kind of exploitation artificial synthetic nitro-musks comparatively early, chemical name is the 5-tertiary butyl-1,2,3 trimethylbenzene-4,6-dinitrobenzene, and molecular formula is C
13h
18n
2o
4, white or Light yellow crystals, fusing point 135.5 ~ 136.5 DEG C, water insoluble, be slightly soluble in ethanol.Have the fragrance of sweet and soft natural musk, lasting is strong lastingly, meets light and stablizes nondiscoloration, is the important source material manufacturing highclass perfumes, essence.
In recent years, the building-up process of many scholars to nitro musk is studied.At first, the musk tibetene of reported in literature is all take m-xylene as raw material, through the series of steps manufacture such as tert-butylation, chloromethylation, reduction reaction and nitration reaction, neutralization &washing, separation and purification.But there is flow process complexity in this technique, product yield is low, the shortcoming that production cost is high.For above-mentioned technique Problems existing, the operational path that it is Material synthesis musk tibetene that a lot of scholar proposes with mixed C9 arenes or hemimellitene, as document " with C9 BTX aromatics for Material synthesis musk tibetene ", " research of mixed C9 arenes synthesis musk tibetene novel process ", " exploring musk tibetene synthesis and refining technique " and patent CN103601642A " a kind of synthetic method of musk tibetene ", patent CN1488621A " with the method for C9 BTX aromatics for Material synthesis musk tibetene ".In above-mentioned document and patent, are all two step synthesis musk tibetenes: first carry out alkylated reaction by raw material and synthesize the intermediate 5-tertiary butyl and connect Three methyl Benzene, then connect Three methyl Benzene by the 5-tertiary butyl and carry out nitration reaction and obtain musk tibetene.
Can find out thus, the 5-tertiary butyl connects the important chemical intermediate that Three methyl Benzene is synthesis musk tibetene.In addition, 5-tertiary butyl Three methyl Benzene also obtains highly purified hemimellitene by dealkylation.Therefore, also more to the scholar of its research in recent years.Document " Synthesis of 5-tert-butyl-1,2,3-trimethylbenzene by One Step ", " preparation of the high purity 5-tertiary butyl-1，2，3-trimethylbenzene ", " preparation of 5-tertiary butyl hemimellitene " are all studied in detail its preparation process.
Below be no matter that its catalyzer selected is aluminum chloride to the research of musk tibetene building-up process or the research 5-tertiary butyl being connected to Three methyl Benzene building-up process.Make catalyzer with aluminum chloride, although reaction can be made to carry out smoothly, exist the not reproducible utilization of catalyzer, reaction product aftertreatment trouble and produce a large amount of waste liquid, to shortcomings such as equipment corrosion are serious.
How to optimize the synthetic reaction process that the 5-tertiary butyl connects this intermediate of Three methyl Benzene, to raising enterprise overall economic benefit, social benefit and Environmental Effect Yidu are very important.
Novel as one, the environmentally friendly catalyzer of ionic liquid, has the advantages such as steam forces down, fusing point is low, solvability is good, easily separated, non-corrosiveness; Meanwhile, by selecting the kind of zwitterion, can regulate and control the physics and chemistry character of ionic liquid, therefore, ionic liquid is subject to investigation and application widely, is widely used in the chemical processes such as separation, alkylation, acylations and isomerization.The current kind about ionic liquid and involved field also get more and more.Patent CN102757344A, CN1405140, CN101172949A have all reported the reaction carried out using ionic liquid as catalyzer, also have all carried out setting forth explanation to the advantage of ionic liquid.
Although the application of Many researchers to building-up process and ionic liquid that the 5-tertiary butyl connects Three methyl Benzene is studied, there is no the method connecting Three methyl Benzene with ionic liquid as the catalyst preparing 5-tertiary butyl.
Summary of the invention
The present invention is intended to find a kind of new catalyst and proposes a kind of novel method, utilizes ionic liquid as catalyzer, optimizes the building-up process that the 5-tertiary butyl connects Three methyl Benzene.
Technical scheme of the present invention is as follows:
The invention provides a kind of method preparing 5-tertiary butyl hemimellitene with ionic liquid, the method overcome existing when taking aluminum chloride as catalyzer, reaction conversion ratio and reaction yield low, the problem of aftertreatment trouble and catalyzer reusing difference.
The invention provides a kind of method utilizing ionic-liquid catalyst to prepare 5-tertiary butyl hemimellitene, it is characterized in that using hemimellitene and tert-butyl chloride as reactant, with ion liquid of quaternaries [Et
3nHCl] [AlCl
3] as catalyzer, temperature of reaction is 0 ~ 20 DEG C, the reaction times is 3h ~ 6h, and the mol ratio of tert-butyl chloride and hemimellitene is 1:1 ~ 4:1, and the mass ratio of ionic liquid and hemimellitene is 0.05:1 ~ 0.2:1, the negatively charged ion [AlCl of ionic liquid
3] and positively charged ion [Et
3nHCl] mol ratio be 1.5:1 ~ 2.5:1.
The invention provides a kind of method that ionic-liquid catalyst prepares 5-tertiary butyl hemimellitene, using hemimellitene and tert-butyl chloride as reactant, using ion liquid of quaternaries as catalyzer; After reaction terminates, ionic liquid and reaction product layering, after adopting physical method for separation, can utilize by direct circulation.Under the reaction conditions optimized, reaction conversion ratio can reach 100%, and selectivity reaches 95%.
The method overcome with aluminum chloride that catalyzer not reproducible utilization when being catalyzer, reaction yield are low, aftertreatment trouble and the pollution to environment and the etching problem to equipment.The method has the features such as Production Flow Chart is short, product yield is high, running cost is low, has obvious social benefit, environmental benefit and economic benefit.
Embodiment
Do a step below by embodiment to the present invention to describe, be conducive to understanding the present invention better, but the invention is not restricted to following examples.
The invention provides a kind of method preparing 5-tertiary butyl hemimellitene with hemimellitene and tert-butyl chloride, it is characterized in that using hemimellitene and tert-butyl chloride as reactant, with ion liquid of quaternaries [Et
3nHCl] [AlCl
3] as catalyzer, temperature of reaction is 0 ~ 20 DEG C, the reaction times is 3h ~ 6h, and the mol ratio of tert-butyl chloride and hemimellitene is 1:1 ~ 4:1, and the mass ratio of ionic liquid and hemimellitene is 0.05:1 ~ 0.2:1, the negatively charged ion [AlCl of ionic liquid
3] and positively charged ion [Et
3nHCl] mol ratio be 1.5:1 ~ 2.5:1.
Embodiment 1
By 2.07g ionic liquid triethylamine hydrochloride-aluminum chloride (negatively charged ion [AlCl of ionic liquid
3] and positively charged ion [Et
3nHCl] mol ratio be 2.5:1), (mol ratio of tert-butyl chloride and hemimellitene is 1:1 for 7.98g tert-butyl chloride, 10.37g hemimellitene, the mass ratio of ionic liquid and hemimellitene is 0.2:1), add the reactor being connected to super constant temperature trough, ethanol is as circulatory mediator, and simultaneous reactions device is inserted with thermometer and carries out accurate temperature controlling.Reaction conditions: temperature of reaction is 0 DEG C, the reaction times is 6hr.After reaction terminates, ionic liquid layering directly reuses, and upper strata alkylide directly carries out quantitatively, qualitative analysis.With this understanding, reaction conversion ratio can reach 99.5%, and reaction preference can reach 93.32%.
Embodiment 2
By 1.037g ionic liquid triethylamine hydrochloride-aluminum chloride (negatively charged ion [AlCl of ionic liquid
3] and positively charged ion [Et
3nHCl] mol ratio be 2:1), (mol ratio of tert-butyl chloride and hemimellitene is 2:1 for 15.97g tert-butyl chloride, 10.37g hemimellitene, the mass ratio of ionic liquid and hemimellitene is 0.1:1), add the reactor being connected to super constant temperature trough, ethanol is as circulatory mediator, and simultaneous reactions device is inserted with thermometer and carries out accurate temperature controlling.Reaction conditions: temperature of reaction 10 DEG C, reaction times 5hr.After reaction terminates, ionic liquid layering directly reuses, and upper strata alkylide directly carries out quantitatively, qualitative analysis.With this understanding, reaction conversion ratio can reach 100%, and reaction preference can reach 95%.
Embodiment 3
By 0.52g ionic liquid triethylamine hydrochloride-aluminum chloride (negatively charged ion [AlCl of ionic liquid
3] and positively charged ion [Et
3nHCl] mol ratio be 1.5:1), (mol ratio of tert-butyl chloride and hemimellitene is 4:1 for 31.94g tert-butyl chloride, 10.37g hemimellitene, the mass ratio of ionic liquid and hemimellitene is 0.05:1), add the reactor being connected to super constant temperature trough, ethanol is as circulatory mediator, and simultaneous reactions device is inserted with thermometer and carries out accurate temperature controlling.Reaction conditions: temperature of reaction 20 DEG C, reaction times 3hr.After reaction terminates, ionic liquid layering directly reuses, and upper strata alkylide directly carries out quantitatively, qualitative analysis.With this understanding, reaction conversion ratio can reach 99%, and reaction preference can reach 93.5%.
The invention provides a kind of ionic-liquid catalyst and prepare the method that the 5-tertiary butyl connects Three methyl Benzene, the method overcome with aluminum chloride that catalyzer not reproducible utilization when being catalyzer, reaction yield are low, post-reaction treatment trouble and the pollution to environment and the etching problem to equipment.The method has the features such as Production Flow Chart is short, product yield is high, running cost is low, has obvious social benefit, environmental benefit and economic benefit.
Claims (1)
1. utilize ionic-liquid catalyst to prepare a method for 5-tertiary butyl hemimellitene, it is characterized in that using hemimellitene and tert-butyl chloride as reactant, with ion liquid of quaternaries [Et
3nHCl] [AlCl
3] as catalyzer, temperature of reaction is 0 ~ 20 DEG C, the reaction times is 3h ~ 6h, and the mol ratio of tert-butyl chloride and hemimellitene is 1:1 ~ 4:1, and the mass ratio of ionic liquid and hemimellitene is 0.05:1 ~ 0.2:1, the negatively charged ion [AlCl of ionic liquid
3] and positively charged ion [Et
3nHCl] mol ratio be 1.5:1 ~ 2.5:1.
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| CN201510574799.XA CN105175214A (en) | 2015-09-09 | 2015-09-09 | Method of preparing 5-tertiary butyl trimethylbenzene from ionic liquid catalyst |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108794038A (en) * | 2018-06-06 | 2018-11-13 | 苏州宏久航空防热材料科技有限公司 | A kind of preparation method of the inexpensive carbon fiber reinforced carbon matrix composite material based on in-situ polymerization |
| CN109400434A (en) * | 2018-10-31 | 2019-03-01 | 濮阳市欧亚化工科技有限公司 | A method of 5- tert-butyl meta-xylene is prepared using tubular reactor |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1824632A (en) * | 2006-01-26 | 2006-08-30 | 彭光辉 | Manufacturing method of alkyl benzene solvent and its application |
-
2015
- 2015-09-09 CN CN201510574799.XA patent/CN105175214A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1824632A (en) * | 2006-01-26 | 2006-08-30 | 彭光辉 | Manufacturing method of alkyl benzene solvent and its application |
Non-Patent Citations (1)
| Title |
|---|
| 陈晗等: "盐酸三乙胺-三氯化铝离子液体催化甲苯与氯代叔丁烷烷基化反应", 《高等化学工程学报》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108794038A (en) * | 2018-06-06 | 2018-11-13 | 苏州宏久航空防热材料科技有限公司 | A kind of preparation method of the inexpensive carbon fiber reinforced carbon matrix composite material based on in-situ polymerization |
| CN108794038B (en) * | 2018-06-06 | 2021-08-03 | 苏州宏久航空防热材料科技有限公司 | Preparation method of low-cost carbon fiber reinforced carbon-based composite material based on in-situ polymerization |
| CN109400434A (en) * | 2018-10-31 | 2019-03-01 | 濮阳市欧亚化工科技有限公司 | A method of 5- tert-butyl meta-xylene is prepared using tubular reactor |
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Application publication date: 20151223 |
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