CN104592013A - Method for synthesizing p-fluorobenzoyl chloride - Google Patents
Method for synthesizing p-fluorobenzoyl chloride Download PDFInfo
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- CN104592013A CN104592013A CN201410856211.5A CN201410856211A CN104592013A CN 104592013 A CN104592013 A CN 104592013A CN 201410856211 A CN201410856211 A CN 201410856211A CN 104592013 A CN104592013 A CN 104592013A
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- fluorobenzoyl chloride
- reaction
- synthesizing
- parafluorobenzoic acid
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/58—Preparation of carboxylic acid halides
- C07C51/60—Preparation of carboxylic acid halides by conversion of carboxylic acids or their anhydrides or esters, lactones, salts into halides with the same carboxylic acid part
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- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a method for synthesizing p-fluorobenzoyl chloride. The method is characterized by comprising the following steps: adding bis(trichlormethyl) carbonate into a reaction kettle filled with parafluorobenzoic acid and 1,2-dichloroethane, reacting in the presence of a catalyst, filtering, and performing reduced pressure distillation, thereby obtaining p-fluorobenzoyl chloride. The selected acylating chlorination reagents are green and environment-friendly, the raw materials are low in price and readily available, the synthetic process is mild in conditions, the purity of the finally obtained product can be 99.9 percent, and the product has wide application prospects and industrial values.
Description
Technical field
The present invention relates to the preparation field of fluoro-containing intermediate, be specifically related to a kind of synthetic method of the method to fluorobenzoyl chloride.
Background technology
A kind of important fluoro-containing intermediate to fluorobenzoyl chloride, it is the important intermediate of synthesis Drugs Containing Fluorine flunarizine, lomerizine, almitrine, special application is that it is the important intermediate of monomer 4, the 4'-difluoro benzophenone of special high-performance PEEK (PEEK).
The route openly reported fluorobenzoyl chloride about synthesis is at present a lot, mainly contain following several: US Patent No. 2006/12879A1 reports and reacts obtained with parafluorobenzoic acid and sulfur oxychloride, the shortcoming of this route is that to prepare by product many and produce a large amount of sour gas, larger to the corrodibility of equipment; It is raw material that US Patent No. 6187952B1 reports with p-Fluorobenzenecarboxaldehyde, obtains through chlorination preparation, the shortcoming of this reaction be raw material p-Fluorobenzenecarboxaldehyde price used costly, cause the high cost of this route; Document " organic fluorine industry " 2011,4, it is raw material that 46-47 reports with p-fluorotoluene, chlorine is passed under ultraviolet lamp, obtain fluorine benzenyl trichloride, then obtain product through hydrolysis and distillation, the shortcoming of this route is that experiment employs photoresponse and is unfavorable for large-scale industrial production, and react wayward, easily obtain parafluorobenzoic acid by product; Document Journal of Labelled Compounds and Radiopharmaceuticals, it is starting raw material that 2013,56,309-618 reports with parafluorobenzoic acid, through oxalyl chloride (COCl)
2chlorination, the shortcoming of this reaction is that chlorination reagent cost is higher, is unfavorable for suitability for industrialized production.
In sum, along with the development of society, environmental problem more and more comes into one's own, and develop a kind of green, environmental protection, mild condition and be easy to the route that controls, this industrialized route is produced and had great importance and bright industrial prospect to fluorine trichlorotoluene zotrichloride.
Summary of the invention
The present invention, in order to overcome defect and the deficiency of prior art, provides a kind of cheaper starting materials to be easy to get, and synthetic technological condition is gentle, Reagent evaluation used in building-up process to environmental protection, a kind of method prepared fluorobenzoyl chloride that reaction yield is high.
Technical scheme of the present invention provides a kind of method prepared fluorobenzoyl chloride, it is characterized in that, in the reactor that parafluorobenzoic acid and 1,2-ethylene dichloride be housed, add Solid triphosgene, in the presence of a catalyst after reaction, after filtration, underpressure distillation must to fluorobenzoyl chloride.
According to the method that technique scheme provides, catalyzer is selected from imidazoles, triethylamine, diethylamine or pyridine.
According to the method that technique scheme provides, temperature of reaction is 40-80 DEG C, and the reaction times is 3-8h.
According to the method that technique scheme provides, step 2) in Solid triphosgene, parafluorobenzoic acid, catalyzer the ratio of amount of substance be 1:1.5-2.5:0.01.
The water used in embodiments of the present invention is deionized water.
The term "or" that the present invention uses represents alternatives, if properly, they can be combined, and that is, term "or" comprises each listed independent alternatives and their combination.Such as, " described catalyzer is selected from imidazoles, triethylamine, diethylamine or pyridine " represents that catalyzer can be the one among imidazoles, triethylamine, diethylamine or pyridine, also can be its more than one combination.
Unless explicitly stated otherwise in contrast, otherwise all scopes that the present invention quotes comprise end value.Such as, " temperature of reaction of described reaction is 40-80 DEG C ", represents that the scope of temperature T is 40 DEG C≤T≤80 DEG C.
Beneficial effect of the present invention is:
The present invention has abandoned existing synthesis technique, have selected a kind of newly synthesize fluorobenzoyl chloride to the chloride reagent Solid triphosgene of fluorobenzoyl chloride, this chloride reagent green, environmental protection, inexpensive.Be starting raw material with parafluorobenzoic acid in the present invention, with 1,2-ethylene dichloride is the solvent of reaction, Solid triphosgene (BTC) is chloride reagent, use conventional organic bases be reaction catalyzer through chloride obtain purity be 99.9% to fluorobenzoyl chloride, the purity of this product meets synthesis 4, and 4 '-difluoro benzophenone is to the purity requirement of substrate.
In preparation technology of the present invention, raw materials used cheap and easy to get, synthetic technological condition is gentle, and Reagent evaluation used in building-up process, to environmental protection, has broad application prospects and industrial value.
Embodiment
The following stated be the preferred embodiment of the present invention, what the present invention protected is not limited to following preferred implementation.It should be pointed out that on the basis of conceiving in these innovation and creation for a person skilled in the art, the some distortion made and improvement, all belong to protection scope of the present invention.Raw material used in embodiment all can be obtained by commercial sources.
Embodiment 1
Take solid phosgene (BTC) 89.1g (0.3mol) and parafluorobenzoic acid 63g (0.45mol) in there-necked flask, add solvent 1.2-ethylene dichloride 500mL, add catalyst of triethylamine 0.3g (0.003mol), the slow temperature to 60 DEG C raising reaction, at this temperature react 4 hours, reaction solution after filtration, except desolventizing, obtain being about 60g to fluorobenzoyl chloride finally by underpressure distillation, yield 95.1%.
Embodiment 2
Take solid phosgene (BTC) 89.1g (0.3mol) and parafluorobenzoic acid 84g (0.6mol) in there-necked flask, add solvent 1.2-ethylene dichloride 500mL, add catalyst pyridine 0.24g (0.003mol), the slow temperature to 60 DEG C raising reaction, react 4 hours at this temperature, reaction solution is after filtration, except desolventizing, obtain being about 75.8g to fluorobenzoyl chloride finally by underpressure distillation, yield 80.1%
Embodiment 3
Take solid phosgene (BTC) 89.1g (0.3mol) and parafluorobenzoic acid 105g (0.75mol) in there-necked flask, add solvent 1.2-ethylene dichloride 500mL, add catalyzer imidazoles 0.2g (0.003mol), the slow temperature to 60 DEG C raising reaction, at this temperature react 4 hours, reaction solution after filtration, except desolventizing, obtain being about 100.6g to fluorobenzoyl chloride finally by underpressure distillation, yield 85.0%.
Claims (4)
1. prepare the method to fluorobenzoyl chloride, it is characterized in that, in the reactor that parafluorobenzoic acid and 1,2-ethylene dichloride be housed, add Solid triphosgene, in the presence of a catalyst after reaction, after filtration, underpressure distillation must to fluorobenzoyl chloride.
2. the preparation method to fluorobenzoyl chloride according to claim 1, is characterized in that, described catalyzer is selected from imidazoles, triethylamine, diethylamine or pyridine.
3. the preparation method to fluorobenzoyl chloride according to claim 1, is characterized in that, the temperature of reaction of described reaction is 40-80 DEG C, and the reaction times is 3-8h.
4., according to the preparation method to fluorobenzoyl chloride according to claim 1, it is characterized in that, step 2) in Solid triphosgene, parafluorobenzoic acid, catalyzer the ratio of amount of substance be 1:1.5-2.5:0.01.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410856211.5A CN104592013A (en) | 2014-12-31 | 2014-12-31 | Method for synthesizing p-fluorobenzoyl chloride |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410856211.5A CN104592013A (en) | 2014-12-31 | 2014-12-31 | Method for synthesizing p-fluorobenzoyl chloride |
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| CN104592013A true CN104592013A (en) | 2015-05-06 |
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| CN201410856211.5A Pending CN104592013A (en) | 2014-12-31 | 2014-12-31 | Method for synthesizing p-fluorobenzoyl chloride |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105384641A (en) * | 2015-10-26 | 2016-03-09 | 安徽广信农化股份有限公司 | Wastewater treatment process for paranitrobenzoyl chloride |
| CN105481687A (en) * | 2016-01-27 | 2016-04-13 | 浙江汇能生物股份有限公司 | Preparing method for o-methoxybenzoyl chloride |
| CN110143917A (en) * | 2019-07-09 | 2019-08-20 | 郑州大学第一附属医院 | A kind of rich preparation method for Buddhist nun's metabolin of card |
| CN111548263A (en) * | 2020-05-26 | 2020-08-18 | 江苏巨莱生物医药有限公司 | Process method for preparing o-ethoxy benzoyl chloride |
| CN113501755A (en) * | 2021-07-03 | 2021-10-15 | 江苏万隆化学有限公司 | Environment-friendly halogenated benzoyl chloride manufacturing process |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1995003A (en) * | 2006-12-26 | 2007-07-11 | 浙江工业大学 | Chemical synthesis method for undecanoyl chloride and lauroyl chloride |
| CN103833724A (en) * | 2012-11-20 | 2014-06-04 | 上海医药工业研究院 | Preparation method of 5-penphene-2-formyl chloride |
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2014
- 2014-12-31 CN CN201410856211.5A patent/CN104592013A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1995003A (en) * | 2006-12-26 | 2007-07-11 | 浙江工业大学 | Chemical synthesis method for undecanoyl chloride and lauroyl chloride |
| CN103833724A (en) * | 2012-11-20 | 2014-06-04 | 上海医药工业研究院 | Preparation method of 5-penphene-2-formyl chloride |
Non-Patent Citations (4)
| Title |
|---|
| MARY E. NEUBERT ET AL.: "Syntheses of Liquid Crystal Intermediates: 4-Alkylbenzoyl Chlorides", 《MOLECULAR CRYSTALS AND LIQUID CRYSTALS》, vol. 53, no. 12, 31 December 1979 (1979-12-31), pages 101 - 110 * |
| 宋夏辉等: "4,4’-二氟二苯甲酮的合成研究", 《江西化工》, no. 3, 30 September 2006 (2006-09-30), pages 107 - 110 * |
| 杜晓华等: "绿色氯化技术在农药中间体合成中的应用", 《现代农药》, vol. 8, no. 1, 28 February 2009 (2009-02-28) * |
| 郎咸坤等: "苯甲酰氯合成工艺研究", 《齐齐哈尔大学学报》, vol. 22, no. 6, 30 November 2006 (2006-11-30), pages 15 - 17 * |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105384641A (en) * | 2015-10-26 | 2016-03-09 | 安徽广信农化股份有限公司 | Wastewater treatment process for paranitrobenzoyl chloride |
| CN105481687A (en) * | 2016-01-27 | 2016-04-13 | 浙江汇能生物股份有限公司 | Preparing method for o-methoxybenzoyl chloride |
| CN110143917A (en) * | 2019-07-09 | 2019-08-20 | 郑州大学第一附属医院 | A kind of rich preparation method for Buddhist nun's metabolin of card |
| CN110143917B (en) * | 2019-07-09 | 2020-03-31 | 郑州大学第一附属医院 | Preparation method of cabozantinib metabolite |
| CN111440119A (en) * | 2019-07-09 | 2020-07-24 | 郑州大学第一附属医院 | Preparation method of cabozantinib intermediate |
| CN111440119B (en) * | 2019-07-09 | 2021-08-24 | 郑州大学第一附属医院 | Preparation method of cabozantinib intermediate |
| CN111548263A (en) * | 2020-05-26 | 2020-08-18 | 江苏巨莱生物医药有限公司 | Process method for preparing o-ethoxy benzoyl chloride |
| CN113501755A (en) * | 2021-07-03 | 2021-10-15 | 江苏万隆化学有限公司 | Environment-friendly halogenated benzoyl chloride manufacturing process |
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Application publication date: 20150506 |