CN102408335A - Synthetic method of p-fluorophenyl acetate - Google Patents
Synthetic method of p-fluorophenyl acetate Download PDFInfo
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- CN102408335A CN102408335A CN2010102896631A CN201010289663A CN102408335A CN 102408335 A CN102408335 A CN 102408335A CN 2010102896631 A CN2010102896631 A CN 2010102896631A CN 201010289663 A CN201010289663 A CN 201010289663A CN 102408335 A CN102408335 A CN 102408335A
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- acetic ester
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- fluorophenyl acetic
- fluorophenyl
- acid
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
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Abstract
The invention provides a synthetic method of p-fluorophenyl acetate. The invention relates to the field of chemical synthesis and particularly relates to synthetic method of the p-fluorophenyl acetate. In details, the p-fluorophenyl acetate is obtained through enabling p-fluorophenol and acetic anhydride to be subjected to reaction for 2-6 hours at the temperature of 80-150 DEG C and in the presence of a catalyst. The catalyst is methylsulfonic acid, paratoluenesulfonic acid or sulphamic acid. The catalyst can be repeatedly used. The reaction aftertreatment adopts a straight fractional distillation method to purify, the fractional distillation under normal pressure can be adopted, and the depressurizing fractional distillation can also be adopted. With the adoption of the synthetic method, the p-fluorophenyl acetate with high purity can be obtained, and the p-fluorophenyl acetate can be used as an intermediate in organic synthesis and can also be used as an electrolyte additive of a lithium battery.
Description
Technical field
The present invention relates to the field of chemical synthesis, particularly relate to a kind of compound method the fluorophenyl acetic ester.At length say so p-fluorophenol and aceticanhydride in the presence of catalyzer, under 80～150 ℃ of temperature, react 2～6h, just can obtain the fluorophenyl acetic ester.Catalyzer is methylsulphonic acid, tosic acid, thionamic acid.Catalyzer can be reused, and catalytic effect does not have considerable change.Post-reaction treatment adopts the method for straight-forward fractional distillation to purify, and can adopt the normal pressure fractionation, also can adopt vacuum fractionation.
Background technology
The fluorophenyl acetic ester there are following several kinds of compound methods at present.1) U.S. Pat 4780471 adopts p-fluorophenol, sodium-acetate, aceticanhydride back flow reaction in benzene, and add water then, neutralize with yellow soda ash, layering, organic layer is used anhydrous magnesium sulfate drying, and distillation at last obtains product.This method has used the big carcinogenic benzene of toxicity as reaction solvent, the aftertreatment trouble.2) J.Med.Chem.1987,30:814～819 documents adopt the vitriol oil as catalyzer, and multistep operations such as reaction will neutralize after finishing, extracts, drying obtain the finished product.This method is owing to adopt the vitriol oil as catalyzer, and serious to equipment corrosion, same aftertreatment bothers.3) high chemical engineering journal; 2007; 21 (3): the 442-447 document adopts pyridine as catalyst for reaction; Will obtain final product after removing solvent through hydrochloric acid neutralization, extracted with diethyl ether, sodium hydroxide washing, dried over sodium sulfate, decompression at last, there are shortcomings such as long reaction time, complex operation in this method.
Summary of the invention
The object of the present invention is to provide a kind of simple synthesis to the fluorophenyl acetic ester, processing ease, aftertreatment are simple, can obtain highly purified product easily.This product can be used as the organic reaction midbody, also can be used as a kind of lithium battery electrolytes additive.Synthetic of the present invention to the fluorophenyl acetic ester be with p-fluorophenol, aceticanhydride raw material in the presence of catalyzer, under the condition of heating, react and obtain.Directly carrying out fractionation after reaction finishes just can obtain highly purified to fluorophenyl acetic ester product.
The present invention adopts following technical scheme.
To in fluorophenyl acetic acid synthetic, used raw material is p-fluorophenol, aceticanhydride, and raw material does not need any processing just can directly use.The mol ratio of p-fluorophenol and aceticanhydride is 0.8: 1～1: 1.2, and p-fluorophenol has no particular limits with the ratio row of aceticanhydride, considers that from the cost aspect aceticanhydride is excessive more economical.
To in fluorophenyl acetic acid synthetic, catalyzer is methylsulphonic acid, tosic acid, thionamic acid, preferred tosic acid.Catalyst consumption is 0.5～10% (weight ratio) of p-fluorophenol amount, preferred 2～5%.Catalyzer is repeatedly reusable, and catalytic effect does not significantly reduce.Catalyzer can directly be reused, and need not pass through any processing.Finish aftercut in reaction and extracted the fluorophenyl acetic ester, catalyst residue after the cooling, just can be carried out catalyzed reaction than adding new p-fluorophenol and aceticanhydride according to metering once more in reaction kettle, need not add new catalyzer.
To in fluorophenyl acetic ester synthetic, temperature of reaction is too low, long reaction time, and also reaction is not exclusively; Temperature of reaction is too high, and the reaction mass color is dark, and is influential to product quality, and energy consumption is also high.So best temperature of reaction is 80～150 ℃, preferred 120～130 ℃.Under above-mentioned temperature condition, 2～6h just can accomplish reaction.
After reaction finishes, directly carry out fractionation and purify, can adopt the normal pressure fractionation, also can adopt vacuum fractionation, the required temperature of normal pressure fractionation is higher, possibly influence the quality of product, preferred vacuum fractionation.In the fractionation purification process, at first steam by product acetic acid, then steam excessive aceticanhydride, unreacted p-fluorophenol and various lower boiling impurity.Receive the cut of positive boiling point at last, be product the fluorophenyl acetic ester.Through such fractionation handle just can obtain 99.5% above purity to the fluorophenyl acetic ester.
To in fluorophenyl acetic acid synthetic, do not adopt any other organic solvent and chemical reagent, can exempt the problem of aspects such as the cost that with an organic solvent brings, safety, recovery like this.
Embodiment
Through specific embodiment the present invention is done further description below, but the present invention not only is defined in these instances.
Embodiment 1
In the 1000ml there-necked flask of TM, electric mixer, reflux condensing tube is housed, add 450g p-fluorophenol, 450g aceticanhydride, add the agent of 20g Catalyzed by p-Toluenesulfonic Acid then, at 120 ℃ of following stirring reaction 3.5h.Method with vacuum fractionation after reaction finishes obtains 550g to the fluorophenyl acetic ester, purity 99.78% (GC).
Embodiment 2
Extracted among the embodiment 1 behind the fluorophenyl acetic ester, the temperature of reaction flask has been reduced to room temperature, and then added 450g p-fluorophenol, 450g aceticanhydride, no longer added any catalyzer, at 125 ℃ of following stirring reaction 4h.Method with vacuum fractionation after reaction finishes obtains 535g to the fluorophenyl acetic ester, purity 99.70% (GC).
Embodiment 3
In the 500ml there-necked flask of TM, electric mixer, reflux condensing tube is housed, add 112g p-fluorophenol, 122g aceticanhydride, the agent of 5g catalyzed by amino sulfonic acid, at 115 ℃ of following stirring reaction 4h.Method with vacuum fractionation after reaction finishes obtains 123.3g to the fluorophenyl acetic ester, purity 99.65% (GC).
Embodiment 4
In the 5000ml there-necked flask of TM, electric mixer, reflux condensing tube is housed, add 1700g p-fluorophenol, 1750g aceticanhydride, 120g tosic acid, above-mentioned material is at 130 ℃ of following stirring reaction 4h.Method with vacuum fractionation after reaction finishes obtains 2030g to the fluorophenyl acetic ester, purity 99.83% (GC).
Claims (6)
1. compound method to the fluorophenyl acetic ester; It is characterized in that: p-fluorophenol and aceticanhydride are in the presence of catalyzer; Under 80～150 ℃ of temperature, react 2～6h, directly carry out fractionation after reaction finishes and just can obtain highly purifiedly to the fluorophenyl acetic ester, catalyzer is reusable.
2. a kind of compound method to the fluorophenyl acetic ester as claimed in claim 1 is characterized in that: described catalyzer is methylsulphonic acid, tosic acid, thionamic acid, preferred tosic acid.
3. according to claim 1 or claim 2 a kind of compound method to the fluorophenyl acetic ester, it is characterized in that: said catalyst consumption is 0.5～10% of a p-fluorophenol weight, preferred 2～5%.
4. like claim 1 and 2 described a kind of compound methods to the fluorophenyl acetic ester, it is characterized in that: described catalyzer can be reused, and reaction finishes the back and directly uses without any processing.
5. a kind of compound method to the fluorophenyl acetic ester as claimed in claim 1 is characterized in that: the temperature of reaction is 80～150 ℃, preferred 120～130 ℃.
6. a kind of compound method to the fluorophenyl acetic ester as claimed in claim 1 is characterized in that: described method of purification, can adopt the fractionated method of normal pressure, and also can adopt the method for vacuum fractionation, the method for preferred vacuum fractionation.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010102896631A CN102408335A (en) | 2010-09-21 | 2010-09-21 | Synthetic method of p-fluorophenyl acetate |
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| Application Number | Priority Date | Filing Date | Title |
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| CN2010102896631A CN102408335A (en) | 2010-09-21 | 2010-09-21 | Synthetic method of p-fluorophenyl acetate |
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| CN102408335A true CN102408335A (en) | 2012-04-11 |
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| CN2010102896631A Pending CN102408335A (en) | 2010-09-21 | 2010-09-21 | Synthetic method of p-fluorophenyl acetate |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108069892A (en) * | 2017-12-13 | 2018-05-25 | 盐城师范学院 | A kind of preparation method of 4-acetoxyl group piperidine hydrochlorate |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4780471A (en) * | 1986-07-01 | 1988-10-25 | Shionogi & Co., Ltd. | Fungicidal azole derivatives |
| US5808130A (en) * | 1996-06-27 | 1998-09-15 | Henkel Corporation | Esterification of phenols |
| WO2000027787A1 (en) * | 1998-11-06 | 2000-05-18 | Eastman Chemical Company | Method of producing acetoxyaryl carboxylic acids |
| CN1566070A (en) * | 2003-06-12 | 2005-01-19 | 中国石化上海石油化工股份有限公司 | Preparation method of linalyl acetate |
| CN101234971A (en) * | 2008-02-29 | 2008-08-06 | 中国烟草总公司郑州烟草研究院 | Method for synthesizing phenylacetic acid ester derivatives and application for products thereof |
| CN101774917A (en) * | 2010-02-05 | 2010-07-14 | 江苏工业学院 | Method for preparing methyl acetylricinolate |
| CN101781204A (en) * | 2010-02-11 | 2010-07-21 | 华东理工大学 | Method for continuously preparing phenyl acetate |
-
2010
- 2010-09-21 CN CN2010102896631A patent/CN102408335A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4780471A (en) * | 1986-07-01 | 1988-10-25 | Shionogi & Co., Ltd. | Fungicidal azole derivatives |
| US5808130A (en) * | 1996-06-27 | 1998-09-15 | Henkel Corporation | Esterification of phenols |
| WO2000027787A1 (en) * | 1998-11-06 | 2000-05-18 | Eastman Chemical Company | Method of producing acetoxyaryl carboxylic acids |
| CN1566070A (en) * | 2003-06-12 | 2005-01-19 | 中国石化上海石油化工股份有限公司 | Preparation method of linalyl acetate |
| CN101234971A (en) * | 2008-02-29 | 2008-08-06 | 中国烟草总公司郑州烟草研究院 | Method for synthesizing phenylacetic acid ester derivatives and application for products thereof |
| CN101774917A (en) * | 2010-02-05 | 2010-07-14 | 江苏工业学院 | Method for preparing methyl acetylricinolate |
| CN101781204A (en) * | 2010-02-11 | 2010-07-21 | 华东理工大学 | Method for continuously preparing phenyl acetate |
Non-Patent Citations (2)
| Title |
|---|
| RAINER HENNING等: "《Synthesis and Neuroleptic Activity of a Series of 1- [ 1- (Benz o- 1,4-dioxan-2-ylmeht y 1) -4-piperidinylJ ben zimidazolone Derivatives》", 《J.MED.CHEM.》 * |
| 赵地顺: "《精细有机合成原理及应用》", 31 March 2009, 化学工业出版社 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108069892A (en) * | 2017-12-13 | 2018-05-25 | 盐城师范学院 | A kind of preparation method of 4-acetoxyl group piperidine hydrochlorate |
| CN108069892B (en) * | 2017-12-13 | 2021-11-23 | 盐城师范学院 | Preparation method of 4-acetoxypiperidine hydrochloride |
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Application publication date: 20120411 |