CN102976885B - To the synthetic method of tertiary butyl chlorobenzene - Google Patents
To the synthetic method of tertiary butyl chlorobenzene Download PDFInfo
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- CN102976885B CN102976885B CN201210565174.3A CN201210565174A CN102976885B CN 102976885 B CN102976885 B CN 102976885B CN 201210565174 A CN201210565174 A CN 201210565174A CN 102976885 B CN102976885 B CN 102976885B
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Abstract
The present invention relates to a kind of synthetic method to tertiary butyl chlorobenzene.With chlorobenzene and tert-butyl chloride for raw material, at complex acid HAlCl
4catalysis under reaction obtained.The present invention is to the synthetic method of tertiary butyl chlorobenzene, design ingenious, the hydrogenchloride of raw material and generation can be made full use of, both the recycling and administration of hydrogen chloride gas had been avoided, also a saving raw materials cost, raw material tert-butyl chloride product can be obtained in addition, achieve waste gas utilization and the value of environmental protection at one stroke, reach maximizing the benefits.
Description
Technical field
The present invention relates to a kind of synthetic method to tertiary butyl chlorobenzene.
Background technology
At present, the domestic synthesis document not yet reported tertiary butyl chlorobenzene.Foreign literature report has following methods: 4-bromo chlorobenzene and Grignard reagent or n-Butyl Lithium Reactive Synthesis are to tertiary butyl chlorobenzene, but this method requires harshness to reaction conditions.Report that more is tert.-butylbenzene method in addition, but this method easily obtains the isomers o-tert-butyl chlorobenzene of target product to tertiary fourth chlorobenzene, not easily carries out separating-purifying.
Summary of the invention
The object of the present invention is to provide a kind of new synthetic method to tertiary butyl chlorobenzene.
The technical solution used in the present invention is as follows:
To the synthetic method of tertiary butyl chlorobenzene, with chlorobenzene and tert-butyl chloride for raw material, at complex acid HAlCl
4catalysis under reaction obtained.
In building-up process, the hydrogenchloride trimethyl carbinol of by-product absorbs and prepares tert-butyl chloride.
Complex acid HAlCl
4saturated and obtain through hydrogenchloride by aluminum trichloride (anhydrous).
Aluminum trichloride (anhydrous) consumption is the 1-5% of chlorobenzene quality.
Produce complex acid HAlCl
4do not absorb hydrogen chloride gas completely and prepare tert-butyl chloride with trimethyl carbinol absorption yet.
When the reaction of producing tertiary butyl chlorobenzene is carried out, the hydrogenchloride part of by-product is for the synthesis of complex acid HAlCl
4.
Trimethyl carbinol absorbing hydrogen chloride adopts two-stage tandem to absorb.
The overall thought of the present invention is: in the process of synthesis to tertiary butyl chlorobenzene, need to use complex acid HAlCl
4carry out catalysis, this complex acid can be saturated and obtain through hydrogenchloride by aluminum trichloride (anhydrous).Hydrogenchloride is produced by sodium-chlor and strong sulfuric acid response.But because process during aluminum chloride absorbing hydrogen chloride is slow, theoretical absorption amount is about about 4% of hydrogen chloride gas intake, a large amount of hydrogenchloride of will having more than needed herein; Add that synthesis also has a large amount of hydrogen chloride by-products to during tertiary butyl chlorobenzene, if these hydrogenchloride process, need at substantial financial resource and material resource.Therefore, whole reaction is designed cleverly, the hydrogenchloride of by-product is utilized, be used for producing complex acid catalyzer HAlCl on the one hand
4, only initial a part of hydrogenchloride is produced by sodium-chlor and strong sulfuric acid response, and more than needed then absorbs with the trimethyl carbinol, obtains for the synthesis of one of the raw material to tertiary butyl chlorobenzene tert-butyl chloride.Whole technique environment-protecting clean, pollution-free, and achieve self-produced personal, save cost, reach maximizing the benefits.From synthetic route itself, also can the acquisition of high yield to tertiary butyl chlorobenzene.
The concrete synthetic route of the present invention is as follows:
1, complex acid catalyzer HAlCl
4synthesis:
The hydrogen chloride gas that sodium-chlor and strong sulfuric acid response produce absorbs via aluminum trichloride (anhydrous), obtains complex acid HAlCl
4.
2, to the synthesis of tertiary butyl chlorobenzene:
To containing complex acid catalyzer HAlCl
4chlorobenzene system in drip tert-butyl chloride, this reaction process realizes generation to tertiary butyl chlorobenzene, continues to produce chlorination chlorine body simultaneously.
3, hydride hydrogen tail gas is absorbed for the synthesis of tert-butyl chloride
The hydrogen chloride gas trimethyl carbinol produced in hydrogen chloride gas more than needed in the building-up process of catalyzer and the building-up process to tertiary butyl chlorobenzene is absorbed.
The present invention, relative to prior art, has following advantage:
The invention discloses a kind of synthetic method to tertiary butyl chlorobenzene, design ingenious, the hydrogenchloride of raw material and generation can be made full use of, namely the recycling and administration of hydrogen chloride gas is avoided, also a saving raw materials cost, raw material tert-butyl chloride product can be obtained in addition, achieve waste gas utilization and the value of environmental protection at one stroke, reach maximizing the benefits.
Accompanying drawing explanation
Fig. 1,2 is respectively the collection of illustrative plates to tertiary butyl chlorobenzene standard substance and product of the present invention of gas Chromatographic Determination under the same terms.
Embodiment
With specific embodiment, technical scheme of the present invention is described below, but protection scope of the present invention is not limited thereto:
Embodiment 1
To the synthetic method of tertiary butyl chlorobenzene, step is as follows:
In No. 1 reactor, add 11.6g sodium-chlor, in constant pressure funnel, add the 12ml vitriol oil.The slow dropping vitriol oil also heats (slowly heat up, outlet temperature is between 90-100 DEG C), produces hydrogen chloride gas.
2, respectively add aluminum chloride 1.2g, chlorobenzene 29.3g in No. 3 reactors, stir, in its constant pressure funnel, respectively add tert-butyl chloride 18.5g, by 2, No. 3 reactor series connection.The hydrogen chloride gas that No. 1 reactor produces is passed into No. 2 reactors, then starts the tert-butyl chloride slowly dripping No. 2, within 1 hour, dropwise, then stirring at normal temperature 3 hours.React complete after, in No. 2 reactors, add 20ml distilled water and 5ml concentrated hydrochloric acid agitator treating, leave standstill after separate upper strata oily liquids.Then dry, filter, obtain tertiary butyl chlorobenzene crude product 38.8g (GC is 78.19%).After being disposed, add chlorobenzene and aluminum chloride, with for subsequent use to No. 2 reactors.
No. 2 reactors, once starting to drip tert-butyl chloride, just have hydrogen chloride gas to produce, and the hydrogenchloride now produced passes into No. 3 reactors, absorb synthesis complex acid catalyzer HAlCl through aluminum chloride
4, slowly drip the tert-butyl chloride of No. 3 reactors, within about 1 hour, dropwise, then stirring at normal temperature 3 hours, post-processing operation is with No. 2.The hydrogen chloride gas that No. 3 reactors produce and absorb incomplete hydrogenchloride and continue absorptions by No. 4 and No. 5 reactors.Each reactor is provided with two interfaces.Gas phase tracing detection to 2 reactor reacts completely, and when adding virgin material, No. 3 reactors react completely not yet, now No. 3 reactor pneumatic outlets are accessed No. 2 reactors, namely No. 2 reactors produce hydrogen chloride gas once reaction, then hydrogen chloride gas are passed into No. 4 and No. 5 reactors, circulate successively.Finally obtaining No. 3 reactors is 81.36% to tertiary butyl chlorobenzene crude product 38.1g(GC).
4, trimethyl carbinol 45g is respectively added in No. 5 reactors.No. 3 reactors absorb incomplete hydrogen chloride gas and enter No. 4 reactors, are absorbed by the trimethyl carbinol, normal-temperature reaction synthesis tert-butyl chloride.Do not absorb completely hydrogen chloride gas by No. 5 reactor double absorptions.GC tracks to and reacts completely.Separatory, obtains supernatant liquid, and lower floor is concentrated hydrochloric acid solution, can be used for washing 2, No. 3 reactor gained crude products.
Collect 2, No. 3 reactors to the underpressure distillation of tertiary butyl chlorobenzene crude product, obtain finished product 54.66g, almost boil without high.Yield is about 81.03%, and through gas chromatographic detection, purity is 99.28%.Fig. 1,2 is respectively the collection of illustrative plates to tertiary butyl chlorobenzene standard substance and product of the present invention of gas Chromatographic Determination under the same terms.
By the about 10ml 5% sodium bicarbonate aqueous solution washing of 4, No. 5 reactor gained supernatant liquids, separatory, dry, obtain 53.28g tert-butyl chloride (GC is 99.36%), do not need to purify.
Above-described embodiment is the preferred embodiment of the present invention, but embodiments of the present invention are not restricted to the described embodiments, and the change that other any the present invention of not deviating from does all should be equivalent substitute mode, is included within protection scope of the present invention.
Claims (1)
1. the synthetic method of pair tertiary butyl chlorobenzene, it is characterized in that, step is as follows:
(I), in No. 1 reactor add 11.6g sodium-chlor, add the 12ml vitriol oil in constant pressure funnel, drip the vitriol oil and the heating that slowly heats up, outlet temperature, between 90-100 DEG C, produces hydrogen chloride gas;
(II), respectively add aluminum chloride 1.2g, chlorobenzene 29.3g in 2, No. 3 reactors, stir, in its constant pressure funnel, respectively add tert-butyl chloride 18.5g, by 2, No. 3 reactors series connection; The hydrogen chloride gas that No. 1 reactor produces is passed into No. 2 reactors, then starts the tert-butyl chloride slowly dripping No. 2, within 1 hour, dropwise, then stirring at normal temperature 3 hours; React complete after, in No. 2 reactors, add 20ml distilled water and 5ml concentrated hydrochloric acid agitator treating, leave standstill after separate upper strata oily liquids; Then dry, filter, obtain tertiary butyl chlorobenzene crude product 38.8g, GC is 78.19%; After being disposed, add chlorobenzene and aluminum chloride, with for subsequent use to No. 2 reactors;
(III), No. 2 reactors once starting to drip tert-butyl chloride, just have hydrogen chloride gas to produce, the hydrogenchloride now produced passes into No. 3 reactors, absorbs synthesis complex acid catalyzer HAlCl through aluminum chloride
4, slowly drip the tert-butyl chloride of No. 3 reactors, within 1 hour, dropwise, then stirring at normal temperature 3 hours, post-processing operation is with No. 2; The hydrogen chloride gas that No. 3 reactors produce and absorb incomplete hydrogenchloride and continue absorptions by No. 4 and No. 5 reactors; Each reactor is provided with two interfaces, gas phase tracing detection to 2 reactor reacts completely, when adding virgin material, No. 3 reactors react completely not yet, now No. 3 reactor pneumatic outlets are accessed No. 2 reactors, and namely No. 2 reactors produce hydrogen chloride gas once reaction, again hydrogen chloride gas is passed into No. 4 and No. 5 reactors, circulate successively, finally obtain No. 3 reactors to tertiary butyl chlorobenzene crude product 38.1g, GC is 81.36%;
(IV), respectively add trimethyl carbinol 45g in 4, No. 5 reactors, No. 3 reactors absorb incomplete hydrogen chloride gas and enter No. 4 reactors, are absorbed by the trimethyl carbinol, normal-temperature reaction synthesis tert-butyl chloride; Do not absorb completely that hydrogen chloride gas is by No. 5 reactor double absorptions, GC tracks to and reacts completely; Separatory, obtains supernatant liquid, and lower floor is concentrated hydrochloric acid solution, is used for washing 2, No. 3 reactor gained crude products;
(V), collect 2, No. 3 reactors to the underpressure distillation of tertiary butyl chlorobenzene crude product, obtain finished product 54.66g, almost boil without high, yield is 81.03%, and through gas chromatographic detection, purity is 99.28%
;by the 10ml 5% sodium bicarbonate aqueous solution washing of 4, No. 5 reactor gained supernatant liquids, separatory, dry, obtain 53.28g tert-butyl chloride, GC is 99.36%.
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Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1603293A (en) * | 2004-08-02 | 2005-04-06 | 常州市牛塘化工厂 | Process for preparing 4-tert-butoxy-chlorobenzene |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1603293A (en) * | 2004-08-02 | 2005-04-06 | 常州市牛塘化工厂 | Process for preparing 4-tert-butoxy-chlorobenzene |
Non-Patent Citations (1)
| Title |
|---|
| 醚型拟除虫菊酯的合成研究I.氯醚菊酯的合成;顾可权等;《应用化学》;19881231;第5卷(第1期);第71-73页 * |
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