CN103012056A - Industrial preparation method of cinnamyl chloride - Google Patents
Industrial preparation method of cinnamyl chloride Download PDFInfo
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- CN103012056A CN103012056A CN 201210569109 CN201210569109A CN103012056A CN 103012056 A CN103012056 A CN 103012056A CN 201210569109 CN201210569109 CN 201210569109 CN 201210569109 A CN201210569109 A CN 201210569109A CN 103012056 A CN103012056 A CN 103012056A
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Abstract
The invention belongs to the field of chemical synthesis, and relates to an industrial method of cinnamyl chloride. A target product cinnamyl chloride is synthesized directly by using thionyl chloride and cinnamyl alcohol as raw materials under a solvent-free condition. Waste gas produced during the reaction process is absorbed by a tail gas absorption apparatus. Compared with a conventional method, the method provided by the invention is simple and practical, has reduced cost and increased yield, is helpful for protecting environment, and is suitable for industrialized production.
Description
Technical field
The invention belongs to the field of chemical synthesis, specifically refer to a kind of industrial production process of cinnamyl chloride.
Background technology
Cinnamyl chloride is a kind of common medicine intermediate, often is used to the calcium antagonist class medicines such as synthetic CN, the sharp qin in hydrochloric acid fluorine osmanthus, also is a kind of spices simultaneously.The method for the synthesis of cinnamyl chloride has following several in the bibliographical information at present: (1) is vinylbenzene, formaldehyde, hydrogenchloride generation chloromethylation under the katalysis of nitric acid, and yield is about 65%.(2) be vinylbenzene under the solvent, trioxymethylene, hydrogenchloride generation chloromethylation at Resorcinol, yield 62.1%.(3) take styryl carbinol, sulfur oxychloride, pyridine as the synthetic cinnamyl chloride of main raw material, productive rate 85.5%.(4) take styryl carbinol, sulfur oxychloride, triethylamine as the synthetic cinnamyl chloride of main raw material, productive rate 87.9%.(5) take styryl carbinol, sulfur oxychloride, liquefied ammonia as the synthetic cinnamyl chloride of main raw material, yield reaches 90.5%.More than these method required equipmenies complicated, last handling process is loaded down with trivial details, needs to add a large amount of organic solvents in the reaction, cost is high, environmental pollution is serious, is unfavorable for very much suitability for industrialized production.
Summary of the invention
The present invention mainly is for the deficiency in the conventional art, the method that provide that a kind of cost is low, simple to operate, environmental protection, industry that yield is high prepares cinnamyl chloride.
In order to realize the foregoing invention purpose, the industrial production process of cinnamyl chloride provided by the present invention, carry out according to following steps:
(1) with in the sulfur oxychloride suction reactor, opens the chilled brine cooling;
(2) drip styryl carbinol, temperature is controlled at below 15 ℃ in the dropping process, opens simultaneously device for absorbing tail gas;
(3) dropwise after, close the chilled brine terminal valve, continue stirring reaction;
(4) reaction is complete, adds saturated Na
2CO
3Or NaHCO
3Aqueous solution neutralization, standing demix is isolated lower floor's crude product, after crude product washs through neutralizing, rectification under vacuum, 105～110 ℃ cut gets light yellow oily liquid under the collection 1600pa, is cinnamyl chloride.
In the aforesaid operations, be cooled to below 15 ℃ in (1);
In the aforesaid operations, the mol ratio of sulfur oxychloride and styryl carbinol is 1.1～1.5:1 in (1);
In the aforesaid operations, device for absorbing tail gas is comprised of vacuum pump and cushion valve in (2), and the water in the vacuum pump adds Na
2CO
3Or NaHCO
3Keep alkalescence;
In the aforesaid operations, churning time is 3～4 hours in (3);
In the aforesaid operations, static layering is 2～3 hours in (4).
Beneficial effect of the present invention:
The present invention is under solvent-free condition, and feeding sequence is to add first sulfur oxychloride, then drips styryl carbinol, has so not only reduced cost, has improved simultaneously the transformation efficiency of styryl carbinol, thereby improves productive rate; Device for absorbing tail gas is comprised of vacuum pump and cushion valve; water in the vacuum pump keeps alkalescence by adding yellow soda ash or sodium bicarbonate; can take the gases such as the hydrogenchloride that produces in the reaction process, sulfurous gas out of rear direct absorption via vacuum pump like this; avoided in the past among the preparation method by adding the method for the organic reagent absorbing waste gas such as triethylamine, pyridine; reduced cost; be conducive to environment protection, be fit to suitability for industrialized production.
Embodiment
Further set forth the present invention below in conjunction with specific embodiment.Following examples only are for to further specific descriptions of the present invention, rather than are used for the restriction to the claimed scope of the present invention.
Embodiment 1
Before reinforced, check carefully whether each pipeline valve of reactor can normally use, whether tail gas absorbs valve tube unimpeded, reactor oven dry, cooling.With load weighted sulfur oxychloride 98kg suction reactor, chilled brine is cooled to below 15 ℃; With 100kg styryl carbinol suction header tank, begin to drip, the still temperature remains on below 15 ℃ in the dropping process, opens simultaneously device for absorbing tail gas, and the water in the vacuum pump adds Na
2CO
3Or NaHCO
3Keep alkalescence; After styryl carbinol dropwises, close the chilled brine terminal valve, continue to stir stopped reaction after 3 hours; Add saturated Na
2CO
3Or NaHCO
3The aqueous solution is transferred PH to 7, and standing demix 2 hours is isolated again neutralization washing behind lower floor's crude product, and 105～110 ℃ cut is collected under the 1600pa in rectifying, gets finished product, product purity 97.02%, yield 91.5%.
Embodiment 2
Before reinforced, check carefully whether each pipeline valve of reactor can normally use, whether tail gas absorbs valve tube unimpeded, reactor oven dry, cooling.With load weighted sulfur oxychloride 133kg suction reactor, chilled brine is cooled to below 15 ℃; With 100kg styryl carbinol suction header tank, begin to drip, the still temperature remains on below 15 ℃ in the dropping process, opens simultaneously device for absorbing tail gas, and the water in the vacuum pump adds Na
2CO
3Or NaHCO
3Keep alkalescence; After styryl carbinol dropwises, close the chilled brine terminal valve, continue to stir stopped reaction after 4 hours; Add saturated Na
2CO
3Or NaHCO
3The aqueous solution is transferred PH to 7, and standing demix 3 hours is isolated again neutralization washing behind lower floor's crude product, and 105～110 ℃ cut is collected under the 1600pa in rectifying, gets finished product, product purity 97.8%, yield 91.1%.
Comparative Examples 1
In the flask of 1000mL, drop into the mixing solutions of styryl carbinol 128. 5mL, chloroform 250mL, ice-water bath is cooled to below 10 ℃ under magnetic agitation, begin to drip the sulfur oxychloride of 68mL (1.2mol) and pass into liquefied ammonia, whole dropping process remains on below 25 ℃ ice-water bath again.Dropwise under the rear ice-water bath and stir the regular hour, until pasty substance all disappears on the bottle wall.Leave standstill branch vibration layer, the organic layer anhydrous sodium sulfate drying filters.Filtrate is reclaimed solvent C HCl under normal pressure
31.3kPa/95 ~ 100 ℃ cut is collected in rear rectification under vacuum, can get colourless transparent liquid cinnamyl chloride 138.2g, and yield can reach 90.5%.
Can find out that from Comparative Examples 1 its productive rate reaches 90.5%, but need to add solvent chloroform in the reaction process, and need to reclaim that need simultaneously to pass into liquefied ammonia and be used as acid binding agent except the waste gas that produces in the dereaction, complex process is unfavorable for suitability for industrialized production.
Comparative Examples 2
With styryl carbinol 26.8g(0.2mol) be dissolved in the 10ml chloroform, under magnetic agitation, in 1.5h, drip thionyl chloride 28.6g(0.24mol), the mixing solutions of pyridine 21ml and chloroform 20ml, and with the ice-water bath cooling, react again 2h, remove chloroform, pyridine, 104-108 ℃ of cut under the 1600pa collected in underpressure distillation, get colourless transparent liquid 26.1g, yield 85.5%.
Can find out that from Comparative Examples 2 the method prepares in the process of cinnamyl chloride and needs to add the sour gas that produces in the pyridine absorption reaction, complex process, and environment had pollution, be unfavorable for suitability for industrialized production.
Comparative Examples 3
In two mouthfuls of bottles of 150ml, add the 80ml dry ether, 30ml triethylamine and 40.0g styryl carbinol, temperature control drip the 22.5ml thionyl chloride in 30-35 ℃ under strong stirring, add the about 1h of rear continuation stirring reaction, leave standstill 6h, filter anhydrous sodium sulfate drying, underpressure distillation behind the normal pressure recovery ether, collect 108-110 ℃/1088.8pa cut, get the 40.5g transparent liquid, yield 87.9%.
Can be found out that by Comparative Examples 3 this experiment adds triethylamine and removes the waste gas that produces in the experimentation, ether needs fully dry and needs to reclaim, and preparation process is complicated, is unfavorable for suitability for industrialized production.
Comparative Examples 4
With hydrochloric acid 1300ml(36%) be added among the trioxymethylene 93g, in stirring the lower 3g of adding Resorcinol, behind dissolve complete, add again vinylbenzene 320g, slowly be warming up to 80 ℃ of reaction 7h, tell organic phase, wash with saturated sodium bicarbonate solution, washing, anhydrous sodium sulfate drying, 105-110 ℃/1.6kpa is collected in underpressure distillation, get colourless transparent liquid 22.91g, yield 62.1%.
Can find out that from Comparative Examples 2 the cinnamyl chloride yield is very low, is not suitable for suitability for industrialized production.
In sum; preparation method of the present invention compares with Comparative Examples, and its step is to add first sulfur oxychloride, drips styryl carbinol again; whole reaction process does not need to add solvent; the waste gas that produces in the experimentation is taken out of through vacuum pump, is then absorbed the method simple possible by the basic solution in the pump; not only reduced cost; improve productive rate, and be conducive to environment protection, be fit to suitability for industrialized production.
Claims (6)
1. the industrial production process of a cinnamyl chloride is characterized in that, may further comprise the steps:
(1) with in the sulfur oxychloride suction reactor, opens the chilled brine cooling;
(2) drip styryl carbinol, temperature is controlled at below 15 ℃ in the dropping process, opens simultaneously device for absorbing tail gas;
(3) dropwise after, close the chilled brine terminal valve, continue stirring reaction;
(4) reaction is complete, adds saturated Na
2CO
3Or NaHCO
3Aqueous solution neutralization, standing demix is isolated lower floor's crude product, after crude product washs through neutralizing, rectification under vacuum, 105～110 ℃ cut gets light yellow oily liquid under the collection 1600pa, is cinnamyl chloride.
2. the industrial production process of described a kind of cinnamyl chloride according to claim 1 is characterized in that: be cooled to below 15 ℃ in (1).
3. the industrial production process of described a kind of cinnamyl chloride according to claim 1, it is characterized in that: the sulfur oxychloride in (1) and the mol ratio of styryl carbinol are 1.1～1.5:1.
4. the industrial production process of described a kind of cinnamyl chloride according to claim 1, it is characterized in that: the device for absorbing tail gas in (2) is comprised of vacuum pump and surge tank, and the water in the vacuum pump adds Na
2CO
3Or NaHCO
3Keep alkalescence.
5. the industrial production process of described a kind of cinnamyl chloride according to claim 1, it is characterized in that: stirring reaction time is 3～4 hours in (3).
6. the industrial production process of described a kind of cinnamyl chloride according to claim 1, it is characterized in that: the standing demix time in (4) is 2～3 hours.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201210569109 CN103012056A (en) | 2012-12-25 | 2012-12-25 | Industrial preparation method of cinnamyl chloride |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201210569109 CN103012056A (en) | 2012-12-25 | 2012-12-25 | Industrial preparation method of cinnamyl chloride |
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|---|---|
| CN103012056A true CN103012056A (en) | 2013-04-03 |
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ID=47961224
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|---|---|---|---|
| CN 201210569109 Pending CN103012056A (en) | 2012-12-25 | 2012-12-25 | Industrial preparation method of cinnamyl chloride |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108164423A (en) * | 2017-12-27 | 2018-06-15 | 福建金山准点制药有限公司 | A kind of preparation method of naftifine hydrochloride |
-
2012
- 2012-12-25 CN CN 201210569109 patent/CN103012056A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108164423A (en) * | 2017-12-27 | 2018-06-15 | 福建金山准点制药有限公司 | A kind of preparation method of naftifine hydrochloride |
| CN108164423B (en) * | 2017-12-27 | 2021-07-13 | 福建金山准点制药有限公司 | Preparation method of naftifine hydrochloride |
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| PB01 | Publication | ||
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| CB02 | Change of applicant information |
Address after: 430064 B, Jia Jia Hotel, 496 Zhongshan Road, Wuchang District, Hubei, Wuhan, China Applicant after: HUBEI YUANCHENG PHARMACEUTICAL CO., LTD. Address before: 430064 B, Jia Jia Hotel, 496 Zhongshan Road, Wuchang District, Hubei, Wuhan, China Applicant before: Hubei Yuancheng Pharmaceutical Co., Ltd. |
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Free format text: CORRECT: APPLICANT; FROM: HUBEI YUANCHENG PHARMACEUTICAL CO., LTD. TO: HUBEI YUANCHENG SAICHUANG TECHNOLOGY CO., LTD. |
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| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
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Application publication date: 20130403 |