CN102976885A - Synthesis method of 4-tert-butyl-1-chlorobenzene - Google Patents
Synthesis method of 4-tert-butyl-1-chlorobenzene Download PDFInfo
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- CN102976885A CN102976885A CN2012105651743A CN201210565174A CN102976885A CN 102976885 A CN102976885 A CN 102976885A CN 2012105651743 A CN2012105651743 A CN 2012105651743A CN 201210565174 A CN201210565174 A CN 201210565174A CN 102976885 A CN102976885 A CN 102976885A
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- chlorobenzene
- tertiary butyl
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- hydrogen chloride
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Abstract
The invention relates to a synthesis method of 4-tert-butyl-1-chlorobenzene. The synthesis method is characterized by taking chlorobenzene and chloro-2-methylpropane as raw materials to react under catalysis of complex acid HAlCl4 to prepare 4-tert-butyl-1-chlorobenzene. The synthesis method has the advantages that the synthesis method is ingenious in design, can take full advantages of the raw materials and the generated hydrogen chloride, avoids recovery treatment of hydrogen chloride, saves the raw material costs, can also obtain the raw material chloro-2-methylpropane product, achieves tail gas utilization and environmental value at one stroke and achieves benefit maximization.
Description
Technical field
The present invention relates to a kind of synthetic method to tertiary butyl chlorobenzene.
Background technology
At present, the domestic synthetic document of not yet reporting tertiary butyl chlorobenzene.The foreign literature report has following methods: 4-bromo chlorobenzene and Grignard reagent or n-Butyl Lithium reaction are synthetic to tertiary butyl chlorobenzene, but this method requires harshness to reaction conditions.Reporting in addition more is the tert.-butylbenzene method, but this method obtains target product easily to the isomers o-tert-butyl chlorobenzene of uncle's fourth chlorobenzene, is difficult for carrying 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, take chlorobenzene and tert-butyl chloride as raw material, at complex acid HAlCl
4Catalysis under react and make.
The hydrogenchloride of by-product absorbs the preparation tert-butyl chloride with the trimethyl carbinol in the building-up process.
Complex acid HAlCl
4Saturated and get through hydrogenchloride by aluminum trichloride (anhydrous).
The aluminum trichloride (anhydrous) consumption is the 1-5% of chlorobenzene quality.
Produce complex acid HAlCl
4Not absorbing completely, hydrogen chloride gas also absorbs the preparation tert-butyl chloride with the trimethyl carbinol.
When the reaction of producing tertiary butyl chlorobenzene was carried out, the hydrogenchloride of by-product part was 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 synthetic process to tertiary butyl chlorobenzene, need to use complex acid HAlCl
4Come catalysis, this complex acid can be saturated and get through hydrogenchloride by aluminum trichloride (anhydrous).Hydrogenchloride is produced by sodium-chlor and strong sulfuric acid response.But process is slow during owing to the aluminum chloride absorbing hydrogen chloride, and theoretical absorbed dose is about about 4% of hydrogen chloride gas intake, a large amount of hydrogenchloride of herein will having more than needed; Add when synthesizing tertiary butyl chlorobenzene also to have a large amount of hydrogen chloride by-products, if these hydrogenchloride are processed, need to expend a large amount of financial resource and material resource.Therefore, whole reaction is designed cleverly, the hydrogenchloride of by-product is utilized, be used for producing on the one hand complex acid catalyzer HAlCl
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 to one of the raw material of tertiary butyl chlorobenzene tert-butyl chloride.Whole technique environment-protecting clean, pollution-free, and realized self-produced using by oneself, and saved cost, reached maximizing the benefits.From synthetic route itself, acquisition that also can high yield is to tertiary butyl chlorobenzene.
The concrete synthetic route of the present invention is as follows:
1, complex acid catalyzer HAlCl
4Synthetic:
The hydrogen chloride gas that sodium-chlor and strong sulfuric acid response produce absorbs via aluminum trichloride (anhydrous), obtains complex acid HAlCl
4
2, synthesizing tertiary butyl chlorobenzene:
To containing complex acid catalyzer HAlCl
4The chlorobenzene system in drip tert-butyl chloride, this reaction process realizes the generation to tertiary butyl chlorobenzene, continues simultaneously to produce the chlorination chlorine body.
3, absorb hydride hydrogen tail gas for the synthesis of tert-butyl chloride
The hydrogen chloride gas body and function trimethyl carbinol that produces 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 has following advantage with respect to prior art:
The invention discloses a kind of synthetic method to tertiary butyl chlorobenzene, design ingenious, can take full advantage of the hydrogenchloride of raw material and generation, namely avoided the recycling and administration of hydrogen chloride gas, also saved raw materials cost, can obtain in addition raw material tert-butyl chloride product, realize waste gas utilization and the value of environmental protection at one stroke, reach maximizing the benefits.
Description of drawings
Fig. 1,2 is respectively under the same terms gas Chromatographic Determination to the collection of illustrative plates of tertiary butyl chlorobenzene standard substance and product of the present invention.
Embodiment
Below with specific embodiment technical scheme of the present invention is described, but protection scope of the present invention is not limited to this:
Embodiment 1
To the synthetic method of tertiary butyl chlorobenzene, step is as follows:
In No. 1 reactor, add 11.6g sodium-chlor, add the 12ml vitriol oil in the constant pressure funnel.Slowly drip the vitriol oil and heating (slowly heat up, outlet temperature is between 90-100 ℃), produce hydrogen chloride gas.
2, respectively add aluminum chloride 1.2g in No. 3 reactors, chlorobenzene 29.3g stirs, and respectively adds tert-butyl chloride 18.5g in its constant pressure funnel, with 2, No. 3 reactor series connection.The hydrogen chloride gas of No. 1 reactor generation is passed into reactor No. 2, then begin slowly to drip No. 2 tert-butyl chloride, dropwised in 1 hour, then stirring at normal temperature is 3 hours.React complete after, in No. 2 reactors, add 20ml distilled water and 5ml concentrated hydrochloric acid agitator treating, tell the upper strata oily liquids after leaving standstill.Then dry, filter, get to tertiary butyl chlorobenzene crude product 38.8g (GC is 78.19%).After being disposed, add chlorobenzene and aluminum chloride to No. 2 reactors, with for subsequent use.
No. 2 reactors just have hydrogen chloride gas to produce once beginning to drip tert-butyl chloride, and the hydrogenchloride that produce this moment passes into reactor No. 3, absorb synthetic complex acid catalyzer HAlCl through aluminum chloride
4, slowly drip the tert-butyl chloride of No. 3 reactors, dropwised in about 1 hour, then stirring at normal temperature is 3 hours, and post-processing operation is with No. 2.The hydrogen chloride gas that No. 3 reactors produce and absorb incomplete hydrogenchloride and continue absorption by No. 4 and No. 5 reactors.Each reactor is provided with two interfaces.Gas phase is followed the tracks of detection to No. 2 reactors and is reacted completely, and when adding virgin material, No. 3 reactor does not react completely yet, this moment is with No. 2 reactors of No. 3 reactor pneumatic outlet accesses, No. 2 reactor namely produces hydrogen chloride gas once reaction, hydrogen chloride gas is passed into No. 4 and No. 5 reactors, successively circulation again.Getting No. 3 reactors at last is 81.36% to tertiary butyl chlorobenzene crude product 38.1g(GC).
4, respectively add trimethyl carbinol 45g in No. 5 reactors.No. 3 reactors absorb incomplete hydrogen chloride gas and enter reactor No. 4, are absorbed by the trimethyl carbinol, and normal-temperature reaction is synthesized tert-butyl chloride.Do not absorb completely hydrogen chloride gas by No. 5 reactor double absorptions.GC tracks to and reacts completely.Separatory gets supernatant liquid, and lower floor is concentrated hydrochloric acid solution, can be used for washing reactor gained crude product 2, No. 3.
Collect 2, No. 3 reactors to the underpressure distillation of tertiary butyl chlorobenzene crude product, get finished product 54.66g, almost boil without height.Yield is about 81.03%, and through gas chromatographic detection, purity is 99.28%.Fig. 1,2 is respectively under the same terms gas Chromatographic Determination to the collection of illustrative plates of tertiary butyl chlorobenzene standard substance and product of the present invention.
4, No. 5 reactor gained supernatant liquids are washed with about 10ml 5% sodium bicarbonate aqueous solution, separatory, drying gets 53.28g tert-butyl chloride (GC is 99.36%), need not 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 the substitute mode of equivalence, is included within protection scope of the present invention.
Claims (7)
1. to the synthetic method of tertiary butyl chlorobenzene, it is characterized in that, take chlorobenzene and tert-butyl chloride as raw material, at complex acid HAlCl
4Catalysis under react and make.
2. the synthetic method to tertiary butyl chlorobenzene as claimed in claim 1 is characterized in that, the hydrogenchloride of by-product absorbs the preparation tert-butyl chloride with the trimethyl carbinol in the building-up process.
3. the synthetic method to tertiary butyl chlorobenzene as claimed in claim 1 or 2 is characterized in that, complex acid HAlCl
4Saturated and get through hydrogenchloride by aluminum trichloride (anhydrous).
4. the synthetic method to tertiary butyl chlorobenzene as claimed in claim 3 is characterized in that, produces complex acid HAlCl
4Not absorbing completely, hydrogen chloride gas also absorbs the preparation tert-butyl chloride with the trimethyl carbinol.
5. the synthetic method to tertiary butyl chlorobenzene as claimed in claim 3 is characterized in that, the aluminum trichloride (anhydrous) consumption is the 1-5% of chlorobenzene quality.
6. such as claim 2 or 4 described synthetic methods to tertiary butyl chlorobenzene, it is characterized in that when the reaction of producing tertiary butyl chlorobenzene was carried out, the hydrogenchloride of by-product part was for the synthesis of complex acid HAlCl
4
7. such as claim 2 or 4 described synthetic methods to tertiary butyl chlorobenzene, it is characterized in that trimethyl carbinol absorbing hydrogen chloride adopts two-stage tandem to absorb.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210565174.3A CN102976885B (en) | 2012-12-24 | 2012-12-24 | To the synthetic method of tertiary butyl chlorobenzene |
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| CN201210565174.3A CN102976885B (en) | 2012-12-24 | 2012-12-24 | To the synthetic method of tertiary butyl chlorobenzene |
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| CN102976885A true CN102976885A (en) | 2013-03-20 |
| CN102976885B CN102976885B (en) | 2015-10-21 |
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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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Patent 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 |
Non-Patent Citations (1)
| Title |
|---|
| 顾可权等: "醚型拟除虫菊酯的合成研究I.氯醚菊酯的合成", 《应用化学》 * |
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Effective date of registration: 20210412 Address after: 472123 No.01, west side of Guanda Road, Guanyintang town industrial cluster, Shanzhou District, Sanmenxia City, Henan Province Patentee after: Sanmenxia Aoke Technology Co.,Ltd. Address before: 472123 Shanxian industrial cluster, Sanmenxia City, Henan Province (Guanyintang) Patentee before: SANMENXIA AOKE CHEMICAL INDUSTRY Co.,Ltd. |