CN1304353C - Process for preparing chloro pivaloyl chloride - Google Patents
Process for preparing chloro pivaloyl chloride Download PDFInfo
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- CN1304353C CN1304353C CNB021465908A CN02146590A CN1304353C CN 1304353 C CN1304353 C CN 1304353C CN B021465908 A CNB021465908 A CN B021465908A CN 02146590 A CN02146590 A CN 02146590A CN 1304353 C CN1304353 C CN 1304353C
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Abstract
The present invention relates to a method for preparing chloropivaloyl chloride, particularly to a method that isobutanol or tertiary butyl alcohol and formic acid are used as initial raw materials to synthesize pivaloyl chloride; the pivaloyl chloride is chlorinated to generate chloropivaloyl chloride. A production technological technique adopted by the present invention has the advantage that the technology is simple; the production temperature and the pressure are low, which is easy to operate and convenient to control; the quality is good and stable, the yield is high, and thus, the production cost is greatly reduced; the technique guarantees the scale production of the chloropivaloyl chloride.
Description
Technical Field
The invention relates to a method for preparing chloro pivaloyl chloride, in particular to a method for synthesizing the pivaloyl chloride by using isobutanol or tert-butanol and formic acid as starting materials and chloridizing the pivaloyl chloride to generate the chloro pivaloyl chloride.
Background
Chloro pivaloyl chloride (also known as 3-chloro-2, 2-dimethylpropionyl chloride) is an important acylation reagent and isoxazolone cyclization reagent, is widely used in the organic synthesis industry, is mainly used as a medical intermediate and a pesticide intermediate at present, and is used as a synthetic raw material of a rubber additive and a photographic photosensitive material.
In addition, the synthetic precursor pivaloyl chloride (also called trimethyl acetyl chloride) adopted in the process route is also an important acylation reagent, and has wide application in synthesizing various medicines (antiviral agents and anti-inflammatory agents) and pesticide products. It can also be used to synthesize polymer initiators.
The final product of the invention, chloro pivaloyl chloride, is an intermediate in the synthesis of, for example, a novel highly effective herbicide clomazone, for its use as a pesticidal intermediate alone. In recent years, with the popularization and promotion of chemical weeding technology, chemical herbicides are recognized and welcomed by farmers, but the current situation of high production cost of clomazone herbicides is caused by high cost of chloro pivaloyl chloride raw materials for synthesizing clomazone, so that the popularization and application of the products are not facilitated.
The pivaloyl chloride as the precursor of the present invention is used mainly as a medical intermediate and as a main raw material in the preparation of many amides and phenolics; the method is currently used for producing drugs such as benzyl hydroxylamine penicillin, cefaclor benzyl, cefazolin, and dual valeryl adrenals, and is also used for producing peracid ester initiators of polyvinyl chloride, photographic sensitive materials and the like. Therefore, the implementation of the invention can also provide the pivaloyl chloride with high quality and low price, reduce the related industrial cost and also have important social and economic benefits.
The synthesis of chloro pivaloyl chloride has been reported in many ways. The existing industrial production processes employ, for example, the following three methods: firstly, isobutene and carbon monoxide are used as initial raw materials to synthesize pivalic acid under high pressure, the pivalic acid is reacted with a chlorinating agent, and generated pivaloyl chloride is catalyzed and chlorinated by chlorine gas to generate chloro pivaloyl chloride. Secondly, tert-butyl chloride and formic acid are used as initial raw materials to synthesize pivalic acid, the pivalic acid reacts with a chlorinating agent, and generated pivaloyl chloride is catalyzed and chlorinated by chlorine gas to generate substituted pivaloyl chloride. Thirdly, in the presence of a catalyst such as aluminum trichloride or ferric trichloride, tert-butyl chloride and carbon monoxide are used as starting materials, the tert-butyl chloride is subjected to carbonylation to prepare pivaloyl chloride, and then chlorination reaction is carried out to generate chloro pivaloyl chloride. (see, e.g., US 4770821; US 5312982; FR 2623496A; CN 1227836A; J.AM. CHEM. SOC.54, PP 3438-41; tetrahedron Lett. (1988), 29(36), 4569-72; fine petrochemical, 1997(1), PP 15-18).
In the former two methods, the chlorinating agent is used in foreign countries such as phosgene, sulfuryl chloride, carbon trichloride, thionyl chloride which are all toxic substances and difficult to operate and process, and the purity and yield of the intermediate pivaloyl chloride are high. Another drawback of the second method is the need to use formic acid of high purity (e.g. 99%). For the third method, since it is necessary to use a catalyst for obtaining better selectivity and increasing yield, it is possible to form impurities or to subject the formed reaction product to a reverse reaction. In addition, for the gas phase high pressure reaction, the equipment investment is large, the material requirement is high, the pressurization is needed in the operation process, the equipment leakage corrosion is easily caused, the reaction temperature is high, and byproducts are easily generated. The above-mentioned method can only reach 98% of product purity when rectifying, and also contain higher quantity of impurity, such as pivaloyl chloride and dichloro pivaloyl chloride, each of which is greater than 0.5%, and its energy consumption is very large. Other manufacturers at home and abroad do not break through the method, and the produced chloro-pivaloyl chloride product has unstable quality and high cost.
In order to overcome the defects of the method, people always find a more ideal process route for synthesizing the chloro pivaloyl chloride. In recent years, documents on this point have reported, for example, in US5872290, a process route using pivalaldehyde and chlorine gas as starting materials, which employs chlorine gas to chlorinate pivalaldehyde in the absence of a catalyst, an initiator and with or without light to produce pivalaoyl chloride, followed by chlorination to produce chloro pivalaoyl chloride; CN1272104A discloses a process route starting from lactones and chlorinating agents by reacting the corresponding lactones with chlorinating agents in the presence of a catalyst such as a urea compound to prepare chloro pivaloyl chloride; CN1227836A discloses the following method: pivalic acid and trichloromethyl benzene are catalytically reacted to produce pivaloyl chloride, which is then chlorinated to produce chloro pivaloyl chloride. Although the above-mentioned method can avoid orpartially avoid the disadvantages of the prior art in the industrial production process, it is not an ideal industrial production method due to the price of raw materials or the limitation of process conditions.
The present inventors have made intensive studies and, as a result, have found that the present invention can overcome the drawbacks of the prior art by synthesizing chloro-pivaloyl chloride using isobutanol (or t-butanol) and formic acid as starting materials and selecting an appropriate chlorinating agent and reaction conditions. The process route has the advantages of cheap and easily-obtained raw materials of isobutanol, formic acid, concentrated sulfuric acid, phosphorus trichloride and chlorine, mild process conditions, simple and convenient operation, easy control of reaction, good stability, few byproducts, high yield and the like, and is low in equipment investment, low in corrosion degree of the process to equipment and free of three-waste discharge, so that the process is very suitable for industrial production.
Disclosure of Invention
The invention aims to provide a method for preparing chloro-pivaloyl chloride by using isobutanol (or tert-butanol) as a starting material.
The technological process of the present invention includes the reaction of isobutanol (or tert-butanol) and formic acid as initial material in the presence of sulfuric acid to synthesize 2, 2-dimethyl propionic acid, the reaction of the 2, 2-dimethyl propionic acid with phosphorus trichloride as chlorinating reagent, the intermittent liquid phase photocatalytic chlorination of the product pivaloyl chloride under micro negative pressure, and the rectification to obtain the product.
FIG. 1 is a process flow diagramfor the synthesis of chloro pivaloyl chloride.
The synthetic route adopted by the invention is as follows:
(1) 2, 2-methylpropanoic acid is synthesized by the reaction of isobutanol (or tert-butanol) and formic acid in the presence of sulfuric acid, taking isobutanol as an example, and the reaction formula is as follows:
(2) the 2, 2-dimethyl propionic acid is chloridized by phosphorus trichloride to prepare the pivaloyl chloride, and the reaction formula is as follows:
(3) the chloro pivaloyl chloride is prepared by adopting intermittent kettle type liquid phase chlorination and rectification, and the reaction equation is as follows:
in a particular embodiment of the process of the present invention,
in the reaction step (1), the molar ratio of isobutanol or tert-butanol to formic acid is 1: 1.3-1.5, concentrated sulfuric acid is added dropwise under stirring, the temperature is controlled at 10-15 ℃, after the addition, the temperature is kept and the stirring is continued for 2-4 hours, and ice water is added into the reaction solution to form two phases. Vacuum fractionating the organic phase, and collecting 77-80 deg.C fraction to obtain refined 2, 2-dimethyl propionic acid.
In the reaction step (2), the molar ratio of the 2, 2-dimethyl propionic acid to the phosphorus trichloride is 1: 0.35-0.45, the 2, 2-dimethyl propionic acid in the reactor is heated to 60 ℃ while stirring, thephosphorus trichloride is dripped for 3-4 hours, the heat preservation and the stirring are continued for 2.5-3 hours, the supernatant is separated, the rectification is carried out, and the fraction with the temperature of 104 ℃ and 105 ℃ is collected, so that the fine pivaloyl chloride is obtained.
In the reaction step (3), the pivaloyl chloride in the reactor is heated to 100 ℃, chlorine is slowly introduced, the reaction temperature is kept at 100-115 ℃, and when the content of monochlorotripivaloyl chloride is 38-40%, the chlorine introduction is stopped. Cooling to 60 ℃, transferring the material to a rectifying still, keeping the vacuum at 0.05-0.06MPa, heating to discharge, adjusting the reflux ratio, and collecting the finished product when the chloro pivaloyl chloride reaches 99%.
Step (3) is preferably carried out in the absence of a diluent. But may also be carried out in the presence of suitable inert agents such as chloroform or carbon tetrachloride.
If desired, the halogenation of pivaloyl chloride may also be carried out with the addition of various catalysts suitable for such halogenation reactions, such as free radical catalysts, e.g. peroxides or azo compounds, to obtain better selectivity and improved yields. However, the addition of the catalyst often has the problems of difficult recycling and separation treatment, and therefore, the reaction is generally catalyzed by a chemical cleaning catalyst such as a conventional UV light source. The irradiation can be carried out using water-cooled high-pressure mercury vapor lamps, and the halogen lamps used can be immersed or externally mounted. Care is required in the installation of the lamp so that the light can reach the halogenation region. All high-pressure mercury vapor lamps conventionally used for halogenation can be used in the present invention. Of course, other lamp sources suitable for these halogenation reactions may also beused.
Generally, the selectivity and the completion degree of the reaction are controlled by the raw material proportion under certain reaction conditions or the gas introduction amount relative to the liquid raw material within a certain time, and the product quantitative method is adopted in the invention to control the introduction amount of the chlorine gas and determine the reaction time, thereby ensuring the selectivity of the reaction.
The process of the invention can be realized by adopting conventional fractionation, rectification and chlorination devices and also by adopting a device which is suitable for the process and is specially designed and improved.
In addition, the by-products of the present invention can be comprehensively utilized. In the first step, dilute sulfuric acid is produced, in the second step, phosphorous acid is produced, and in the third step, hydrogen chloride is produced. The by-product 60% dilute sulfuric acid can be sold, and can also be neutralized by quick lime to obtain by-product gypsum for sale; 328 tons of phosphorous acid can be sold and can also be used for producing sodium phosphite; the hydrogen chloride is absorbed by water and can be sold as hydrochloric acid. Therefore, the method belongs to a clean synthesis process and belongs to the development direction of green environmental protection in the world at present.
Therefore, the raw materials of isobutanol, formic acid, concentrated sulfuric acid, phosphorus trichloride and chlorine gas adopted in the process route are cheap and easy to obtain, the process conditions are mild, the operation is simple and convenient, the control is easy, the safety and reliability are realized, the by-products are few, the yield is high, the equipment investment is low, the corrosion degree of the process on equipment is low, and three wastes are not discharged, sothat the process is very suitable for industrial production.
The production process technology adopted by the invention has the advantages of simple process, low production temperature and pressure, easy operation, convenient control, good and stable quality and high yield, greatly reduces the production cost and provides guarantee for the large-scale production of the chloro pivaloyl chloride.
By adopting the process route of the invention, the product purity can reach more than 99 percent during rectification, and the product also contains low-content impurities such as pivaloyl chloride and dichloro pivaloyl chloride which are respectively less than 0.5 percent, and the chloro pivaloyl chloride product has stable quality and low cost. The product produced by the production process has international market competitiveness in both price and quality aspects.
Examples
Industrial EXAMPLES production of 1 ton of chloro-pivaloyl chloride having a content of 99% or more
1. In the first step, 2-dimethyl propionic acid (also called pivalic acid, structural formula)Is (CH)3)3CCOOH, molecular formula C5H10O2Molecular weight 102).
The raw material ① has isobutanol content of more than or equal to 98 percent, ② formic acid content of more than or equal to 88 percent, and ③ concentrated sulfuric acid content of more than or equal to 98 percent.
At 5m3850kg of isobutanol and 882kg of formic acid are added into the reaction kettle, 3.5 liters of concentrated sulfuric acid is added dropwise under the stirring condition, the temperature is controlled to be 10-15 ℃, then the stirring is continued for 2-4 hours, and ice water is added into the reaction solution to form two phases. Standing for layering, removing the lower layer, washing the upper organic phase with saturated saline water and water, dewatering, transferring, vacuum fractionating, and collecting 77-80 deg.C fraction to obtain refined pivalic acid 937kg with content of 98% and yield of 90%.
2. In the second step of reaction, the produced trimethylacetyl chloride (also called pivaloyl chloride) has a structural formula of (CH)3)3CCOCl) has the molecular formula C5H9ClO, molecular weight: 120.5).
The used raw material ① 2, 2-dimethyl propionic acid, ② phosphorus trichloride with the content of more than or equal to 98 percent and the content of 98 percent.
At 3m3937kg of 2, 2-dimethylpropanol is added into the reaction kettleHeating the acid to 60 ℃, starting to dropwise add 505kg of phosphorus trichloride after stirring for about 3.5-4 hours, controlling the temperature at 60-62 ℃, keeping the temperature and stirring for 2 hours, standing and separating supernatant, rectifying, and collecting 104-105 ℃ fraction to obtain 886kg of refined pivaloyl chloride with the content of 98 percent and the yield of more than 90 percent.
3. In the third step of reaction, the final product 3-chloro-2, 2-dimethylpropionyl chloride (also called chloro pivaloyl chloride, the structural formula is ClCH)2(CH3)2CCOCl, molecular formula: c5H8Cl2O, molecular weight: 155).
① used as raw material of trimethyl acetyl chloride (pivaloyl chloride), ② chlorine with the content not less than 98 percent
At 3m3886kg of pivaloyl chloride was charged into the reaction vessel, and the cooling water of the condenser was turned on. Heating to 100 deg.C, closing heating system, slowly introducing chlorine gas under UV irradiation, controlling reaction temperature at 100-115 deg.C, and stopping introducing chlorine when monochlorotritanoyl chloride content reaches 38-40%. Cooling to 60 ℃, transferring the reaction liquid into a rectifying still, keeping the vacuum at 0.05-0.06MPa, heating to discharge, adjusting the reflux ratio, and when the content of the chloro pivaloyl chloride reaches 99%, starting to collect the finished product to obtain 1015kg of refined product, wherein the content is more than or equal to 99%, and the yield is more than 90%.
Claims (1)
1. A process for the preparation of chloro pivaloyl chloride comprising the steps of:
(1) in the presence of sulfuric acid, synthesizing 2, 2-methylpropanoic acid by using isobutanol or tert-butanol and formic acid with the molar ratio of 1: 1.3-1.5, and controlling the reaction temperature at 10-15 ℃;
(2) the mol ratio of the 2, 2-dimethyl propionic acid to the phosphorus trichloride is 1: 0.35-0.45, the reaction temperature is 60-62 ℃, and pivaloyl chloride is prepared by chlorination;
(3) the method comprises the steps of chlorinating pivaloyl chloride by a gap kettle type liquid phase photocatalysis method, heating the pivaloyl chloride in a reactor to 100 ℃, slowly introducing chlorine gas, keeping the reaction temperature at 100-115 ℃, stopping introducing chlorine when the content of monochloropentanyl chloride is 38-40%, cooling to 60 ℃, transferring the material to a rectifying kettle, keeping the vacuum at 0.05-0.06MPa, heating to discharge, adjusting the reflux ratio, and starting to collect a finished product when the content of monochloropentanyl chloride reaches 99%.
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| CNB021465908A CN1304353C (en) | 2002-10-24 | 2002-10-24 | Process for preparing chloro pivaloyl chloride |
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| CN1304353C true CN1304353C (en) | 2007-03-14 |
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Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101311155B (en) * | 2007-05-25 | 2011-10-05 | 江苏建农农药化工有限公司 | Process for preparing chloro-pivalyl chloride |
| CN108689834A (en) * | 2017-04-11 | 2018-10-23 | 江苏联化科技有限公司 | A kind of preparation method of the chloro- 2,2- dimethylpropionic acid chlorides of 3- |
| CN110452112B (en) * | 2018-12-03 | 2022-03-25 | 山东民基新材料科技有限公司 | Catalytic hydrogenation treatment process for chloro pivaloyl chloride rectification residual liquid |
| 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 |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4770821A (en) * | 1985-06-05 | 1988-09-13 | Ihara Nikkei Chemical Industry Co., Ltd. | Method for preparing β-chloropivaloyl chloride |
| US5321982A (en) * | 1990-12-12 | 1994-06-21 | Institut Francais Du Petrole | Method for measuring the rate of penetration of an equipment progressing in a well |
| US5872290A (en) * | 1997-11-07 | 1999-02-16 | Occidental Chemical Corporation | Preparation of acid chlorides |
| CN1227836A (en) * | 1997-12-23 | 1999-09-08 | 埃勒夫阿托化学有限公司 | Continuous process for preparation of pivaloyl chloride and of aroyl chloride |
-
2002
- 2002-10-24 CN CNB021465908A patent/CN1304353C/en not_active Expired - Lifetime
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4770821A (en) * | 1985-06-05 | 1988-09-13 | Ihara Nikkei Chemical Industry Co., Ltd. | Method for preparing β-chloropivaloyl chloride |
| US5321982A (en) * | 1990-12-12 | 1994-06-21 | Institut Francais Du Petrole | Method for measuring the rate of penetration of an equipment progressing in a well |
| US5872290A (en) * | 1997-11-07 | 1999-02-16 | Occidental Chemical Corporation | Preparation of acid chlorides |
| CN1227836A (en) * | 1997-12-23 | 1999-09-08 | 埃勒夫阿托化学有限公司 | Continuous process for preparation of pivaloyl chloride and of aroyl chloride |
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