CN101311155B - Process for preparing chloro-pivalyl chloride - Google Patents
Process for preparing chloro-pivalyl chloride Download PDFInfo
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- CN101311155B CN101311155B CN2007101076915A CN200710107691A CN101311155B CN 101311155 B CN101311155 B CN 101311155B CN 2007101076915 A CN2007101076915 A CN 2007101076915A CN 200710107691 A CN200710107691 A CN 200710107691A CN 101311155 B CN101311155 B CN 101311155B
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Abstract
The invention relates to a preparation method for chloro-pivaloyl chloride, in particular to a method that pivalic acid is taken as starting material to synthesize pivaloyl chloride by phosphorus trichloride acyl chlorination; then, gas-phase photocatalysis chlorination is carried out on the pivaloyl chloride by adopting reactive rectification technique; finally the chloro-pivaloyl chloride is prepared by vacuum rectification. The method of the invention can effectively inhibit the generation of multi chlorine substitutes and has simple production technique, safe operation, no pollution, low production cost and high production quality.
Description
Invention field
The present invention relates to a kind of method for preparing Chloropivaloyl chloride, specifically, this method is starting raw material with the trimethylacetic acid, through the phosphorus trichloride chloride, synthetic pivaloyl chloride, with reaction rectification technique pivaloyl chloride is carried out gas-phase photocatalysis chlorine again, and then carry out rectification under vacuum and prepare Chloropivaloyl chloride.The invention still further relates to the method for preparing pivaloyl chloride.
Background technology
Chloropivaloyl chloride (claims 3-chloro-2 again; 2-dimethyl propylene acyl chlorides) be that a kind of important acylating reagent becomes cyclization reagent with isoxazolone; be widely used in the organic synthesis industry, at present main as medicine intermediate, pesticide intermediate, and as the synthesis material of rubber accelerator and sensitive photographic material.
The synthetic precursor pivaloyl chloride (claiming trimethyl-acetyl chloride again) that adopts in the operational path of the present invention is crucial acylating reagent equally, and it has purposes widely in synthetic various medicine (antiviral agent, antiphlogistic) and Pesticidal products.It also can be as the initiator of synthetic polymer.
Finished product Chloropivaloyl chloride of the present invention, single with regard to it as with regard to the pesticide intermediate ten thousand, for example be new and effective weedicide clomazone synthetic intermediate.In recent years, along with popularizing of chemical weed control technology, chemical herbicide has obtained the welcome and the understanding of vast farmers.But, be unfavorable for applying of this product because the synthetic used Chloropivaloyl chloride raw materials cost height of clomazone causes the high situation of clomazone weedicide production cost.
With regard to the synthetic precursor pivaloyl chloride of the present invention, it is mainly as medicine intermediate, in the preparation of many amidess and phenol lipid drug as main raw material; Be used for medicine production such as azanol penicillin G and cephalo azanol benzyl, Kefzol, two pivaloyl suprarenal gland at present, also be used to produce the peresters class initiator of polyvinyl chloride and sensitive photographic material etc.Therefore, enforcement of the present invention can also provide the pivaloyl chloride of super quality and competitive price simultaneously, reduces relevant industry cost, has important society and economic benefit equally.
The synthetic method of Chloropivaloyl chloride has had many reports.Now industrial manufacture process adopts for example following three kinds of methods: one is that the starting raw material height is pressed into trimethylacetic acid with iso-butylene and carbon monoxide, and with it with chlorination reaction, the pivaloyl chloride of generation adopts chlorine catalytic chlorination generation Chloropivaloyl chloride.Its two, be the synthetic trimethylacetic acid of starting raw material with tertiary butyl chloride and formic acid, and will it and chlorination reaction, the pivaloyl chloride of generation adopts chlorine catalytic chlorination generation Chloropivaloyl chloride.Its three, having in the presence of catalyzer such as aluminum chloride or the iron trichloride, be starting raw material with tertiary butyl chloride and carbon monoxide, tertiary butyl chloride is carried out carbonylation, produce pivaloyl chloride, carry out chlorination reaction then, generate Chloropivaloyl chloride (referring to, US4770821 for example; US5312982; FR2623496A; CN1227836A; J.AM.CHEM.SOC.54, PP3438-41; TETRAHEDRONLETT. (1998), 29 (36), 4569-72; Speciality Petrochemicals, 1997 (1), PP15-18).
Only reach 98% with above-mentioned preparation method's product purity, but also contain the impurity of higher amount such as each, and energy consumption is big especially greater than pivaloyl chloride more than 0.5% and dichloro-pivaloyl chloride.Other producers all do not have breakthrough the Chloropivaloyl chloride unstable product quality of being produced, cost height to this both at home and abroad.
For overcoming the defective of aforesaid method, people are seeking a kind of operational path of even more ideal synthetic Chloropivaloyl chloride always.In the last few years, bibliographical information about this respect for example has, disclosing with special valeral and chlorine among the US5872290 is the operational path of starting raw material, this operational path adopt chlorine with special valeral catalyst-free, initiator and have or the condition of unglazed photograph under chlorination generate pivaloyl chloride, carry out chlorination reaction subsequently, produce Chloropivaloyl chloride; It is the operational path of starting raw material that CN1272104A discloses with lactone and chlorizating agent, and it is in the presence of catalyzer such as carbamide compound, prepares Chloropivaloyl chloride by corresponding lactone and chlorination reaction; CN1227836A discloses following method: PIVALIC ACID CRUDE (25) and benzenyl trichloride catalyzed reaction generate pivaloyl chloride, carry out chlorination reaction then, produce Chloropivaloyl chloride.Aforesaid method though avoid or part is avoided the existing technical disadvantages of industrial manufacture process, because of the price of raw material or be subjected to the restriction of processing condition, is not the ideal industrialized preparing process.
The present inventor is by intensive research, and the present invention selects for use trimethylacetic acid as starting raw material, and selects suitable chlorizating agent and reaction conditions, synthesizes Chloropivaloyl chloride, can overcome defective of the prior art.It is cheap and easy to get that this operational path has raw material trimethylacetic acid, phosphorus trichloride and the chlorine average price of employing, the processing condition gentleness, easy and simple to handle, reaction is easy to control, good stability, by product is few, many advantages such as yield height, and also facility investment is few, technology is little to the equipment corrosion degree, therefore three-waste free discharge, is very suitable for suitability for industrialized production.
Summary of the invention
The purpose of this invention is to provide a kind of with trimethylacetic acid (2, the 2-neopentanoic acid) be starting raw material, through the phosphorus trichloride chloride, synthetic pivaloyl chloride, and then with reaction rectification technique pivaloyl chloride is carried out gas-phase photocatalysis chlorine again, carry out the method that rectification under vacuum prepares Chloropivaloyl chloride.
Operational path of the present invention is with trimethylacetic acid, and the reaction of chlorination reagent phosphorus trichloride under little negative pressure, adopts reaction rectification technique to carry out the chlorination of gas phase light the products therefrom pivaloyl chloride afterwards, makes product through rectifying again.Unreacted raw material is recycled behind rectifying and product separation.
Fig. 1 is a Chloropivaloyl chloride synthetic process flow sheet.
Fig. 2 is Chloropivaloyl chloride synthesizer figure.
The method that the present invention prepares Chloropivaloyl chloride adopts following synthetic route:
(1) trimethylacetic acid makes pivaloyl chloride through the phosphorus trichloride chlorination, and its reaction formula is as follows:
(CH
3)
2CCOOH+PCl
3→(CH
3)
3CCOCl+H
3PO
3
(2) adopt reaction rectification technique, carry out the gas phase light chlorination of pivaloyl chloride, make Chloropivaloyl chloride, its reaction equation is as follows:
(CH
3)
3CCOCl+Cl
2→ClCH
2(CH
3)
2CCOCl+HCl
In specific embodiment, for example to prepare the method for Chloropivaloyl chloride as follows in the present invention:
The mol ratio of trimethylacetic acid and phosphorus trichloride is 1:0.33-0.43 in reactions steps (1).In the pivaloyl chloride reactor, add trimethylacetic acid under the normal temperature earlier, add phosphorus trichloride again, mix, slowly be warming up to 45-70 ℃, react about 2h, separate supernatant liquid, carry out rectifying, collect 104-105 ℃ cut, promptly get the elaboration pivaloyl chloride.
In reactions steps (2), earlier a certain amount of pivaloyl chloride is added in the tower still of Chloropivaloyl chloride synthesizer (see figure 2), reflux slowly feeds chlorine to stable.The control pivaloyl chloride: the mol ratio=6:1-20:1 of chlorine is preferably 10:1-15:1.105 ℃-150 ℃ of the temperature of reaction in light chlorination district are preferably 120 ℃-140 ℃.When tower still temperature rose to 145-150 ℃, beginning fed pivaloyl chloride and continuous extraction reaction solution continuously.Reaction solution goes to distillation system, carries out rectification under vacuum and obtains Chloropivaloyl chloride finished product more than 99.5%.
By product of the present invention in addition can fully utilize.There is phosphorous acid to produce in the reactions steps (1), has hydrogenchloride to produce in the reactions steps (2).Phosphorous acid can be sold, and also can produce sodium phosphite; The hydrogenchloride water absorbs, and can be used as hydrochloric acid and sells.Therefore the invention belongs to a kind of clean synthesis process, belong to the developing direction that the world today pays attention to environmental protection.
This shows that the present invention prepares that the raw material trimethylacetic acid, phosphorus trichloride and the chlorine that adopt in the operational path of Chloropivaloyl chloride are all inexpensive to be easy to get, and processing condition are relatively gentleer, easy and simple to handle, be easy to control, safe and reliable, by product is few, the yield height, and facility investment is few, and technology is little to the equipment corrosion degree, three-waste free discharge, therefore, be fit to very much suitability for industrialized production.
Because to have technology simple, easy to operate for production technology of the present invention, be convenient to control, and quality is good and stablize, yield is high, greatly reduces production cost, for the scale production of pivaloyl chloride and Chloropivaloyl chloride provides assurance.
Adopt operational path of the present invention, product purity can reach more than 99.5%, the constant product quality of Chloropivaloyl chloride, and cost is low.Adopting the product of explained hereafter of the present invention is all to have competitiveness in the international market on price or aspect quality.
Embodiment
Industrial implementation example: the example of producing the Chloropivaloyl chloride of 1 ton of 99.5% above content.
1, in reactions steps (1), (claim trimethyl-acetyl chloride again, structural formula is (CH to the pivaloyl chloride of output
3)
3CCOCl) molecular formula is C
5H
9ClO, molecular weight are 120.5)
Raw materials used (1) trimethylacetic acid, content〉98% (2) phosphorus trichloride, content 98%
At 2m
3Reactor in drop into 937kg trimethylacetic acid and 405kg phosphorus trichloride.Under agitation slowly heated up 2 hours, and rose to 55 ℃, continue insulated and stirred after 2 hours, the standing separation upper strata stillness of night, 104-105 ℃ cut is collected in rectifying, gets elaboration pivaloyl chloride 1050kg, content 99.5%, and yield is more than 92%.
2, in reactions steps (2), output finished product 3-chloro-2,2-dimethyl propylene acyl chlorides (claims Chloropivaloyl chloride again, structural formula ClCH
2(CH
3)
2CCOCl, molecular formula is C
5H
8Cl
2O, molecular weight are 155).
Raw materials used (1) trimethyl-acetyl chloride (pivaloyl chloride), content〉98%, (2) chlorine
In reactions steps (2), the pivaloyl chloride with 810kg adds in the tower still of Chloropivaloyl chloride synthesizer (see figure 2) earlier, and reflux slowly feeds chlorine to stable.Control pivaloyl chloride: the mol ratio=15:1 of chlorine.130 ℃ of the temperature of reaction in light chlorination district.When tower still temperature rose to 145 ℃, beginning fed pivaloyl chloride and continuous extraction reaction solution continuously.Reaction solution goes to distillation system, carries out rectification under vacuum and obtains Chloropivaloyl chloride finished product 1000kg more than 99.5%.Content 99.5%, yield is more than 90%.
Claims (3)
1. method for preparing Chloropivaloyl chloride, this method comprises the steps:
(1) trimethylacetic acid makes pivaloyl chloride through the phosphorus trichloride chlorination, and its reaction formula is as follows:
(CH
3)
3CCOOH+PCl
3→(CH
3)
3CCOCl+H
3PO
3
Add phosphorus trichloride under the normal temperature in trimethylacetic acid, slowly be warming up to 45 ℃-70 ℃ then and keep about 2 hours of reaction, the mol ratio of trimethylacetic acid and phosphorus trichloride is 1: 0.33-0.43, separate supernatant liquid, carry out rectifying, collect 104-105 ℃ cut, get the elaboration pivaloyl chloride;
(2) pivaloyl chloride is carried out the chlorination of gas phase light, make Chloropivaloyl chloride, its reaction equation is as follows:
(CH
3)
3CCOCl+C1
2→C1CH
2(CH
3)
2CCOCl+HCl
Pivaloyl chloride is added in the tower still of Chloropivaloyl chloride synthesizer, reflux slowly feeds C1 to stable
2Gas, the mol ratio of control pivaloyl chloride and chlorine is 6: 1-20: 1, react in optical chlorinating reaction district in the Chloropivaloyl chloride synthesizer, the temperature of reaction in light chlorination district is 105 ℃-150 ℃, when tower still temperature rises to 145-150 ℃, beginning feeds pivaloyl chloride and continuous extraction reaction solution continuously, and reaction solution goes to distillation system.
2. according to the process of claim 1 wherein:
In the described step (2), the temperature of reaction in light chlorination district is 120 ℃-140 ℃, the mol ratio 10 of pivaloyl chloride and chlorine: 1-15: 1; Pivaloyl chloride and chlorine enter the photochmeical reaction district of Chloropivaloyl chloride synthesizer continuously, and the Chloropivaloyl chloride crude product leaves the rectification zone of Chloropivaloyl chloride synthesizer continuously, and the Chloropivaloyl chloride content in crude product is controlled at 70-80%.
3. according to the method for claim 1 or 2, wherein
Go to distillation system from the Chloropivaloyl chloride crude product of described step (2) preparation, carry out rectification under vacuum, get the Chloropivaloyl chloride more than 99.5%.
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| CN107721841A (en) * | 2017-11-11 | 2018-02-23 | 山东民基化工有限公司 | A kind of method that pivalic acid is reclaimed in the distillation residual liquid from pivaloyl chloride |
| CN108341744B (en) * | 2018-05-17 | 2023-11-28 | 山东民基新材料科技有限公司 | Method and device for preparing chloro pivaloyl chloride |
| CN109438223B (en) * | 2018-12-03 | 2021-04-16 | 山东民基新材料科技有限公司 | Method and equipment for continuously preparing pivaloyl chloride |
| CN109336759A (en) * | 2018-12-03 | 2019-02-15 | 山东民基化工有限公司 | Continuously prepare the method and device thereof of chloro-pivalyl chloride |
| CN110818558B (en) * | 2019-12-17 | 2023-09-08 | 山东民基新材料科技有限公司 | Method and device for continuously preparing chloro-pivaloyl chloride by utilizing micro-channel |
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| CN1491932A (en) * | 2002-10-24 | 2004-04-28 | 建湖建农农药化工有限公司 | Process for preparing chloro pivaloyl chloride |
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| CN1491932A (en) * | 2002-10-24 | 2004-04-28 | 建湖建农农药化工有限公司 | Process for preparing chloro pivaloyl chloride |
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Owner name: JIANGSU JIANNONG PLANT PROTECTION CO., LTD. Free format text: FORMER OWNER: JIANGSU JIANNONG AGROCHEMICAL CO., LTD. Effective date: 20130702 |
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Effective date of registration: 20130702 Address after: 224700, Jiangsu Binhai Economic Development Zone, coastal industrial park, Huang Hai Road Patentee after: JIANGSU JIANNONG PLANT PROTECTION CO., LTD. Address before: Five road 224700 in Jianhu County of Jiangsu Province Economic Development Zone weft Patentee before: Jiangsu Jiannong Agrochemical Co., Ltd. |