CN103058883B - Preparation technology of solid (chlorine methylene) dimethyl ammonium chloride - Google Patents
Preparation technology of solid (chlorine methylene) dimethyl ammonium chloride Download PDFInfo
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- CN103058883B CN103058883B CN201310019494.3A CN201310019494A CN103058883B CN 103058883 B CN103058883 B CN 103058883B CN 201310019494 A CN201310019494 A CN 201310019494A CN 103058883 B CN103058883 B CN 103058883B
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- dimethyl ammonium
- ammonium chloride
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- phthalic anhydride
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C249/00—Preparation of compounds containing nitrogen atoms doubly-bound to a carbon skeleton
- C07C249/02—Preparation of compounds containing nitrogen atoms doubly-bound to a carbon skeleton of compounds containing imino groups
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention belongs to the technical field of preparation of a chemical product, and relates to a preparation technology of solid (chlorine methylene) dimethyl ammonium chloride. The technology comprises the following steps of: carrying out acylating chlorination reaction to raw materials phthalic anhydride and thionyl chloride to obtain o-phthaloyl chloride, reacting o-phthaloyl chloride with N, N-dimethylformamide to obtain (chlorine methylene) dimethyl ammonium chloride and phthalic anhydride, dissolving generated phthalic anhydride in excessive N, N-dimethylformamide, and obtaining solid (chlorine methylene) dimethyl ammonium chloride through solid-liquid separation. According to the preparation technology, sulfur dioxide is discharged through the first step reaction, so that sulfur dioxide is not needed to be forcedly removed in a high vacuum condition, and the reaction condition is mild and is easy to implement. Pollution of sulfur dioxide generated by a one-pot method to environment is avoided, and the problems of high vacuum degree, unstable operation and difficult discharging of a method for forcedly removing sulfur dioxide in the high vacuum are also avoided. The preparation technology has the characteristics of being safe and convenient to operate and easy to implement.
Description
Technical field
The invention belongs to Chemicals preparing technical field, relate to the preparation technology of a kind of solid (chlorine methylene radical) alkyl dimethyl ammonium chloride.
Background technology
Solid (chlorine methylene radical) alkyl dimethyl ammonium chloride is a kind of reagent with powerful reactive behavior, and it can make the hydroxyl in alcohol, enol, phenol and carboxylic acid molecules be replaced by chlorine, and generates corresponding organic chloride; Also aldehyde radical can be introduced in the molecule of some compounds; Carboxylic acid can also be made to become its active ester derivative etc., and tool has been widely used.
In prior art, react obtained (chlorine methylene radical) alkyl dimethyl ammonium chloride by sulfur oxychloride and DMF (DMF), have two kinds of forms: I type is liquid, and activity is lower, II type is solid, active high compared with I type.The conversion reaction of I type and II type is a reversible reaction, and sulfurous gas is bonded in I type, reaction be made to the right to carry out obtaining II type, high vacuum need be adopted SO
2remove.
Reaction equation is as follows:
This method is high to vacuum level requirements, once vacuum tightness reduces, due to the existence of sulfurous gas, II type is rapidly to I type and transforms, and releases heat, causes (chlorine methylene radical) alkyl dimethyl ammonium chloride to produce and decomposes, then produce a large amount of gas and sharply heat release, easily cause explosion hazard; And the easily crystallization on reactor wall of the solid that the method obtains (chlorine methylene radical) alkyl dimethyl ammonium chloride, must adopt and manually solid (chlorine methylene radical) alkyl dimethyl ammonium chloride be scraped, ability discharging, not only reduce production efficiency, too increase the chance that product exposes contact wetting in atmosphere.
Summary of the invention
The object of this invention is to provide the preparation technology of a kind of solid (chlorine methylene radical) alkyl dimethyl ammonium chloride, this technique both avoided sulfurous gas that " one kettle way " produce to the pollution of environment, it also avoid the problem that vacuum tightness is high, operation is unstable, discharging is difficult of high vacuum scrubbing CO_2 method by force.
The preparation technology of solid of the present invention (chlorine methylene radical) alkyl dimethyl ammonium chloride, first raw material phthalic anhydride and sulfur oxychloride are carried out acyl chloride reaction to obtain phthalyl chloride, phthalyl chloride again with N, dinethylformamide is obtained by reacting (chlorine methylene radical) alkyl dimethyl ammonium chloride and phthalic anhydride, the phthalic anhydride generated is dissolved in excessive N, in dinethylformamide, obtain solid (chlorine methylene radical) alkyl dimethyl ammonium chloride through solid-liquid separation.
The present invention carries out in two steps:
(1) synthesis of phthalyl chloride:
Raw material phthalic anhydride and sulfur oxychloride are carried out acyl chloride reaction and obtains phthalyl chloride and sulfurous gas, technique is carried out routinely; The SO produced in production process
2through reclaiming the production can overlapped for sulfur oxychloride, realize recycling economy.
(2) synthesis of solid (chlorine methylene radical) alkyl dimethyl ammonium chloride:
The phthalyl chloride that the first step is obtained and N, dinethylformamide is obtained by reacting (chlorine methylene radical) alkyl dimethyl ammonium chloride and phthalic anhydride, the phthalic anhydride generated is dissolved in excessive DMF, and solid (chlorine methylene radical) alkyl dimethyl ammonium chloride obtains through solid-liquid separation.
Described phthalyl chloride and DMF temperature of reaction are 0-60 DEG C.
The consumption of described DMF is 1.5-5 times of raw material phthalic anhydride quality, and the consumption of DMF is excessive relative to phthalic anhydride.Reason is that phthalic anhydride is at N, solubleness in dinethylformamide is very large, use excessive N, the phthalic anhydride (namely as the phthalic anhydride that reactant drops into) that step (2) can generate by dinethylformamide all dissolves, and (chlorine methylene radical) alkyl dimethyl ammonium chloride is almost insoluble in the DMF solution of phthalic anhydride, in solid state, thus carry out solid-liquid separation, solid (chlorine methylene radical) alkyl dimethyl ammonium chloride can be obtained.
The present invention is realized by stepwise reaction, and the first step is the synthesis of phthalyl chloride, and first by sulfur dioxide removal, second step generates solid (chlorine methylene radical) alkyl dimethyl ammonium chloride, reclaims phthalic anhydride simultaneously.By stepwise reaction, both obtained solid (chlorine methylene radical) alkyl dimethyl ammonium chloride, again the phthalic anhydride used as raw material had been regenerated.Solid (chlorine methylene radical) alkyl dimethyl ammonium chloride can be obtained smoothly by the instrumentality of stepwise reaction and phthalic anhydride.
Mass percentage >=85.0% of obtained solid (chlorine methylene radical) alkyl dimethyl ammonium chloride.
Reaction equation of the present invention is as follows:
The present invention has following beneficial effect:
Reacted by the first step in the present invention and first sulfurous gas is released, thus do not need scrubbing CO_2 by force in high vacuum conditions, make reaction conditions gentle, easy to implement.The sulfurous gas that the present invention both avoided " one kettle way " produces is to the pollution of environment, it also avoid the problem that vacuum tightness is high, operation is unstable, discharging is difficult of high vacuum scrubbing CO_2 method by force, the present invention has operational safety, convenience, feature easy to implement.
Embodiment
Below in conjunction with embodiment, the present invention is described further:
Embodiment 1
In 1000ml reaction flask, add phthalic anhydride 60g, slowly drip sulfur oxychloride 300ml, dropwise, temperature reaction is to emission-free generation, and normal pressure steams excess thionyl chloride, and decompression steams phthalyl chloride.
By the 100gN measured, dinethylformamide is put in the reaction flask of 500ml, fills high pure nitrogen protection; open and stir, in reaction flask, drip phthalyl chloride, regulating rate of addition to control temperature of reaction is 55-60 DEG C; dropwise; in 55-60 DEG C of insulated and stirred 0.5h, be discharged to strainer, High Purity Nitrogen is protected; filter; filter cake is with DMF washing extremely without phthalic anhydride, and blowing is packed.Solid (chlorine methylene radical) the alkyl dimethyl ammonium chloride quality obtained is 47.88g, and mass percentage is 86.22%.
Embodiment 2
In 1000ml reaction flask, add phthalic anhydride 60g, slowly drip sulfur oxychloride 300ml, dropwise, temperature reaction is to emission-free generation, and normal pressure steams excess thionyl chloride, and decompression steams phthalyl chloride.
By the 150gN measured, dinethylformamide is put in the reaction flask of 500ml, fills high pure nitrogen protection; open and stir, in reaction flask, drip phthalyl chloride, regulating rate of addition to control temperature of reaction is 45-50 DEG C; dropwise; in 40-45 DEG C of insulated and stirred 0.5h, be discharged to strainer, High Purity Nitrogen is protected; filter; filter cake is with DMF washing extremely without phthalic anhydride, and blowing is packed.Solid (chlorine methylene radical) the alkyl dimethyl ammonium chloride quality obtained is 46.21g, and mass percentage is 87.15%.
Embodiment 3
In 1000ml reaction flask, add phthalic anhydride 60g, slowly drip sulfur oxychloride 300ml, dropwise, temperature reaction is to emission-free generation, and normal pressure steams excess thionyl chloride, and decompression steams phthalyl chloride.
The 180g DMF measured is put in the reaction flask of 500ml, fills high pure nitrogen protection; open and stir, in reaction flask, drip phthalyl chloride, regulating rate of addition to control temperature of reaction is 30-35 DEG C; dropwise; in 30-35 DEG C of insulated and stirred 0.5h, be discharged to strainer, High Purity Nitrogen is protected; filter; filter cake is with DMF washing extremely without phthalic anhydride, and blowing is packed.Solid (chlorine methylene radical) the alkyl dimethyl ammonium chloride quality obtained is 47.21g, and mass percentage is 85.22%.
Embodiment 4
In 1000ml reaction flask, add phthalic anhydride 60g, slowly drip sulfur oxychloride 300ml, dropwise, temperature reaction is to emission-free generation, and normal pressure steams excess thionyl chloride, and decompression steams phthalyl chloride.
The 240g DMF measured is put in the reaction flask of 500ml, fills high pure nitrogen protection; open and stir, in reaction flask, drip phthalyl chloride, regulating rate of addition to control temperature of reaction is 20-25 DEG C; dropwise; in 20-25 DEG C of insulated and stirred 0.5h, be discharged to strainer, High Purity Nitrogen is protected; filter; filter cake is with DMF washing extremely without phthalic anhydride, and blowing is packed.Solid (chlorine methylene radical) the alkyl dimethyl ammonium chloride quality obtained is 47.98g, and mass percentage is 86.36%.
Embodiment 5
In 1000ml reaction flask, add phthalic anhydride 60g, slowly drip sulfur oxychloride 300ml, dropwise, temperature reaction is to emission-free generation, and normal pressure steams excess thionyl chloride, and decompression steams phthalyl chloride.
The 300g DMF measured is put in the reaction flask of 500ml, fills high pure nitrogen protection; open and stir, in reaction flask, drip phthalyl chloride, regulating rate of addition to control temperature of reaction is 0-10 DEG C; dropwise; in 0-10 DEG C of insulated and stirred 0.5h, be discharged to strainer, High Purity Nitrogen is protected; filter; filter cake is with DMF washing extremely without phthalic anhydride, and blowing is packed.Solid (chlorine methylene radical) the alkyl dimethyl ammonium chloride quality obtained is 45.29g, and mass percentage is 87.55%.
Claims (1)
1. a preparation technology for solid (chlorine methylene radical) alkyl dimethyl ammonium chloride, is characterized in that: comprise the following steps:
In 1000ml reaction flask, add phthalic anhydride 60g, slowly drip sulfur oxychloride 300ml, dropwise, temperature reaction is to emission-free generation, and normal pressure steams excess thionyl chloride, and decompression steams phthalyl chloride;
By the 300g N measured; dinethylformamide is put in the reaction flask of 500ml; fill high pure nitrogen protection; open and stir; phthalyl chloride is dripped in reaction flask; regulating rate of addition to control temperature of reaction is 0-10 DEG C, dropwises, in 0-10 DEG C of insulated and stirred 0.5h; be discharged to strainer; High Purity Nitrogen is protected, and filters, filter cake N; dinethylformamide washing is extremely without phthalic anhydride; blowing is packed, and solid (chlorine methylene radical) the alkyl dimethyl ammonium chloride quality obtained is 45.29g, and mass percentage is 87.55%.
Priority Applications (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310019494.3A CN103058883B (en) | 2013-01-18 | 2013-01-18 | Preparation technology of solid (chlorine methylene) dimethyl ammonium chloride |
| KR1020157021168A KR20150096530A (en) | 2013-01-18 | 2013-03-05 | Process for preparing solid (chlorine methylene) dimethyl ammonium chloride |
| PCT/CN2013/000225 WO2014110696A1 (en) | 2013-01-18 | 2013-03-05 | Process for preparing solid (chlorine methylene) dimethyl ammonium chloride |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310019494.3A CN103058883B (en) | 2013-01-18 | 2013-01-18 | Preparation technology of solid (chlorine methylene) dimethyl ammonium chloride |
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| Publication Number | Publication Date |
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| CN103058883A CN103058883A (en) | 2013-04-24 |
| CN103058883B true CN103058883B (en) | 2015-01-21 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN201310019494.3A Active CN103058883B (en) | 2013-01-18 | 2013-01-18 | Preparation technology of solid (chlorine methylene) dimethyl ammonium chloride |
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| KR (1) | KR20150096530A (en) |
| CN (1) | CN103058883B (en) |
| WO (1) | WO2014110696A1 (en) |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2006056436A1 (en) * | 2004-11-26 | 2006-06-01 | Basf Aktiengesellschaft | Method for the production of phthalic dichloride |
| WO2007017891A2 (en) * | 2005-05-04 | 2007-02-15 | Pharmed Medicare Private Limited | Generation of phosphorus oxychloride as by-product from phosphorus pentachloride and dmf and its use for chlorination reaction by converting into vilsmeier-haack reagent. |
| CN101560146A (en) * | 2009-04-08 | 2009-10-21 | 淄博达隆制药科技有限公司 | Preparation method of paraphthaloyl chloride with high purity |
| EP2325158A1 (en) * | 2008-07-29 | 2011-05-25 | Iharanikkei Chemical Industry Co., Ltd. | Process for production of phthaloyl dichloride compounds, catalyst to be used therein, and process for preparation of same |
| JP2012136502A (en) * | 2010-12-10 | 2012-07-19 | Ihara Nikkei Kagaku Kogyo Kk | Method for producing imidoyl chloride compound, and method for producing various compounds by using the same |
| CN102675146A (en) * | 2012-05-22 | 2012-09-19 | 山东凯盛新材料股份有限公司 | Method for preparing novel solid chlorating agent (chloromethylene) dimethyl ammonium chloride |
-
2013
- 2013-01-18 CN CN201310019494.3A patent/CN103058883B/en active Active
- 2013-03-05 KR KR1020157021168A patent/KR20150096530A/en not_active Application Discontinuation
- 2013-03-05 WO PCT/CN2013/000225 patent/WO2014110696A1/en active Application Filing
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2006056436A1 (en) * | 2004-11-26 | 2006-06-01 | Basf Aktiengesellschaft | Method for the production of phthalic dichloride |
| WO2007017891A2 (en) * | 2005-05-04 | 2007-02-15 | Pharmed Medicare Private Limited | Generation of phosphorus oxychloride as by-product from phosphorus pentachloride and dmf and its use for chlorination reaction by converting into vilsmeier-haack reagent. |
| EP2325158A1 (en) * | 2008-07-29 | 2011-05-25 | Iharanikkei Chemical Industry Co., Ltd. | Process for production of phthaloyl dichloride compounds, catalyst to be used therein, and process for preparation of same |
| CN101560146A (en) * | 2009-04-08 | 2009-10-21 | 淄博达隆制药科技有限公司 | Preparation method of paraphthaloyl chloride with high purity |
| JP2012136502A (en) * | 2010-12-10 | 2012-07-19 | Ihara Nikkei Kagaku Kogyo Kk | Method for producing imidoyl chloride compound, and method for producing various compounds by using the same |
| CN102675146A (en) * | 2012-05-22 | 2012-09-19 | 山东凯盛新材料股份有限公司 | Method for preparing novel solid chlorating agent (chloromethylene) dimethyl ammonium chloride |
Non-Patent Citations (4)
| Title |
|---|
| New preparation method for Vilsmeier reagent and related imidoyl chlorides;Yoshikazu Kimura等;《Tetrahedron Letters》;20111230;第53卷(第9期);第1116-1118页 * |
| Phthalyl Chloride;L. P. Kyrides;《J. Am. Chem. Soc.》;19370101;第59卷;第206-208页 * |
| Studies on the Vilsmeier-Haack Reaction. Ⅱ. Characteration of Thionyl Chloride-Dimethylformamide Complexes;Kiyomi Kikugawa等;《Chem. Pharm. Bull.》;19711231;第19卷(第12期);第2629-2630页 * |
| 邻、间、对苯二甲酰氯的合成工艺;魏文珑等;《山西化工》;20090228;第29卷(第1期);第20页右栏第1段-第21页左栏第5段 * |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2014110696A1 (en) | 2014-07-24 |
| CN103058883A (en) | 2013-04-24 |
| KR20150096530A (en) | 2015-08-24 |
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Address after: Zichuan District of Zibo City, 255190 double Yang Shandong city in Zibo Province Applicant after: SHANDONG KAISHENG NEW MATERIALS CO., LTD. Address before: Zichuan District of Zibo City, 255190 double Yang Shandong city in Zibo Province Applicant before: Shandong Kaisheng New Materials Co.,Ltd. |
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Inventor after: Zhang Shanmin Inventor after: Li Yunlong Inventor after: Wang Jiarong Inventor after: Xue Juqiang Inventor after: Yang Deyao Inventor after: Sun Fengchun Inventor after: Li Wenjuan Inventor after: Jia Yuanchao Inventor after: Zhang Qingxin Inventor after: Wang Ronghai Inventor before: Zhang Zhenxia Inventor before: Zhang Shanmin Inventor before: Wang Jiarong Inventor before: Xue Juqiang Inventor before: Yang Deyao Inventor before: Sun Fengchun Inventor before: Li Wenjuan Inventor before: Jia Yuanchao Inventor before: Zhang Qingxin |
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Free format text: CORRECT: INVENTOR; FROM: ZHANG ZHENXIA ZHANG SHANMIN WANG JIARONG XUE JUQIANG YANG DEYAO SUN FENGCHUN LI WENJUAN JIA YUANCHAO ZHANG QINGXIN TO: ZHANG SHANMIN WANG JIARONG XUE JUQIANG YANG DEYAO SUN FENGCHUN LI WENJUAN JIA YUANCHAO ZHANG QINGXIN WANG RONGHAI LI YUNLONG |
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Address after: Double Yang Zichuan District 255190 Shandong city of Zibo Province Patentee after: Shandong Kaisheng New Materials Co.,Ltd. Address before: Double Yang Zichuan District 255190 Shandong city of Zibo Province Patentee before: SHANDONG KAISHENG NEW MATERIALS CO., LTD. |