CN109232240A - The synthetic method of chloroacrylic acid fluorine alcohol ester - Google Patents
The synthetic method of chloroacrylic acid fluorine alcohol ester Download PDFInfo
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- CN109232240A CN109232240A CN201811292646.6A CN201811292646A CN109232240A CN 109232240 A CN109232240 A CN 109232240A CN 201811292646 A CN201811292646 A CN 201811292646A CN 109232240 A CN109232240 A CN 109232240A
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- chloroacrylic acid
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
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Abstract
The invention belongs to organic chemical synthesis technical fields, and in particular to a kind of method of chloroacrylic acid fluorine alcohol ester preparation.The present invention is using methacrylaldehyde, electrophilic reagent containing chlorine and fluorinated alcohols as raw material, and using azepine Cabbeen as catalyst, chloroacrylic acid fluorine alcohol ester is made through class MBH reaction and oxidative esterification reaction.Raw material of the present invention is cheap, simple process, and green safe, high-efficiency environment friendly is suitable for industrialized production.
Description
Technical field
The invention belongs to organic chemical synthesis technical fields, and in particular to one kind is by methacrylaldehyde, electrophilic reagent containing chlorine and fluorine
The method for preparing chloroacrylic acid fluorine alcohol ester for alcohol.
Background technique
Chloroacrylic acid fluorine alcohol ester is widely used in the compound of organic chemistry and chemical field, as fining
The industrial uses such as drug, medical pesticide material, resin and plastic raw material, electronic information material, optical material are learned, in numerous areas
It is useful.
As the preparation method of ester type compound, traditional strategy is dehydrated and obtains in acid condition using carboxylic acid and alcohol
Corresponding ester generally requires higher temperature, and reaction conversion ratio is lower sometimes, and with side reaction.This patent using aldehyde with
Alcohol direct oxidation esterification, mild condition have prospects for commercial application.
Summary of the invention
The purpose of the present invention is to provide be using methacrylaldehyde, electrophilic reagent containing chlorine and fluorinated alcohols as raw material with azepine Cabbeen
Catalyst, the method that chloroacrylic acid fluorine alcohol ester is made through class MBH reaction and oxidative esterification reaction.The reaction is one pot continuous
Two-step reaction, first step reaction are the chlorination reaction of class MBH reaction, and methacrylaldehyde and excessive electrophilic reagent containing chlorine are in azepine Cabbeen
Chloropropene aldehyde is generated under catalyst action；Second step reaction, upper step after reaction, separating-purifying, is not directly added into fluorine
For alcohol, the above excessive chloro-containing reagent of step occurs oxidative esterification reaction and obtains as oxidant, azepine Cabbeen as catalyst at this time
To chloroacrylic acid fluorine alcohol ester, reaction equation is as follows:
The electrophilic reagent containing chlorine is chlorine, N- chlorosuccinimide (CAS 128-09-6), sodium hypochlorite and dichloro
One of Dimethyl Hydan (CAS 118-52-5) or several combinations.
The fluorinated alcohols, which refer on hydrocarbyl chain, has one or more hydrogen by fluorine-substituted alcohol, such as perfluor n-butanol, hexafluoro
Isopropanol, 1H, 1H, 2H, 2H- perfluor hex- 1- alcohol etc., but not limited to this.
The azepine carbone catalyst is that the quaternary ammonium salt of common imidazoles, the thiazole or triazole scene of reacting with alkali is raw
At.Wherein shown in imidazoles quaternary ammonium salt such as structure (3), shown in thiazole quaternary ammonium salt such as structure (4), triazole quaternary ammonium salt such as structure (5)
It is shown:
Wherein R1, R2, R3, R4For alkyl, aryl or heterocycle.
In addition, alkali is potassium carbonate, cesium carbonate, potassium tert-butoxide, sodium methoxide, 1,8- diazabicylo, 11 carbon -7- alkene (DBU)
Etc. one of common inorganic base or organic base or several combinations.
Solvent used in reacting is water, ethyl alcohol, methanol, toluene, tetrahydrofuran, ether, acetonitrile, acetone, dimethyl sulfoxide
Or one of n,N-Dimethylformamide or several.
The ratio between amount of the methacrylaldehyde, electrophilic reagent containing chlorine and fluoro alcohol matter is 1:2:1；The alkali and imidazoles, thiazole
Or the amount of the substance of the quaternary ammonium salt of triazole is the 5~20% of methacrylaldehyde.
The invention has the benefit that
(1) chloroacrylic acid fluorine alcohol ester synthetic method provided by the invention, the cheap, simple process with raw material, industrially
The advantages of easily preparing.
(2) this patent prepares chloroacrylic acid fluorine alcohol ester, this method green with methacrylaldehyde, electrophilic reagent containing chlorine and fluorinated alcohols
Safety, high-efficiency environment friendly are suitable for industrialized production.
Specific embodiment
Embodiment one:
Solvent chloroform 100ml is sequentially added in the reaction tube of 250ml, to 5.6 grams of methacrylaldehyde (0.1mol), triazole salt
0.7 gram (0.005mol), 1.63 grams of cesium carbonate (0.005mol) and 1, bis- 39.4 grams of chloro- 5,5- Dimethyl Hydan of 3-
(0.2mol), normal-temperature reaction completely disappear (about 24 hours) using thin-layer chromatography tracking reaction to methacrylaldehyde.CF is added3(CF2)7CH2CH2After OH46.4 grams (0.1mol), reaction 12 hours, with water and ethyl acetate extraction, removes water layer three times, and organic layer is used
Anhydrous sodium sulfate is dry.Solvent is removed with Rotary Evaporators, it is then passed through into silica gel chromatograph (ethyl acetate/petroleum ether=1/
10) it purifies, obtains 43.1 grams pure of chloroacrylic acid fluorine alcohol ester, yield 78%.
Embodiment two:
Solvent chloroform 100ml is sequentially added in the reaction tube of 250ml, to 5.6 grams of methacrylaldehyde (0.1mol), triazole salt
0.7 gram (0.005mol), 1.63 grams of cesium carbonate (0.005mol) and 1, bis- 39.4 grams of chloro- 5,5- Dimethyl Hydan of 3-
(0.2mol), normal-temperature reaction completely disappear (about 24 hours) using thin-layer chromatography tracking reaction to methacrylaldehyde.CF is added2H
(CF2)3CH2After OH23.2 grams (0.1mol), reaction 12 hours, with water and ethyl acetate extraction, removes water layer, organic layer three times
It is dry with anhydrous sodium sulfate.With Rotary Evaporators remove solvent, then by its by silica gel chromatograph (ethyl acetate/petroleum ether=
1/10) it purifies, obtains 26.6 grams pure of chloroacrylic acid fluorine alcohol ester, yield 83%.
Claims (9)
1. the preparation method of chloroacrylic acid fluorine alcohol ester, which is characterized in that step include: with methacrylaldehyde, electrophilic reagent containing chlorine and
Fluorinated alcohols are raw material, and using azepine Cabbeen as catalyst, chloroacrylic acid fluorine alcohol is made through class MBH reaction and oxidative esterification reaction
Ester.
2. the preparation method of chloroacrylic acid fluorine alcohol ester according to claim 1, which is characterized in that the methacrylaldehyde is such as
Following formula (1) compound represented:
。
3. the preparation method of chloroacrylic acid fluorine alcohol ester according to claim 1, which is characterized in that the electrophilic examination containing chlorine
Agent is chlorine, N- chlorosuccinimide (CAS 128-09-6), sodium hypochlorite and dichloro-dimethyl glycolylurea (CAS 118-
One of 52-5) or several combinations.
4. the preparation method of chloroacrylic acid fluorine alcohol ester according to claim 1, which is characterized in that the fluorinated alcohols refer to
There is one or more hydrogen by fluorine-substituted alcohol on hydrocarbyl chain, such as perfluor n-butanol, hexafluoroisopropanol, 1H, 1H, 2H, 2H- perfluor
Hex- 1- alcohol etc., but not limited to this.
5. the preparation method of chloroacrylic acid fluorine alcohol ester according to claim 1, which is characterized in that the product chloro third
Olefin(e) acid fluorine alcohol ester such as following formula (2) compound represented:
Wherein x, y, z is integer more than or equal to 1, indicate the compound from the alkyl of alcohol part be have on hydrocarbyl chain one or
The multiple hydrogen of person are by fluorine-substituted structure.
6. the preparation method of chloroacrylic acid fluorine alcohol ester according to claim 1, which is characterized in that the azepine Cabbeen is urged
Agent, which is reacted for the quaternary ammonium salt of common imidazoles, thiazole or triazole with alkali, to be locally produced.Wherein imidazoles quaternary ammonium salt such as structure
(3) shown in, shown in thiazole quaternary ammonium salt such as structure (4), shown in triazole quaternary ammonium salt such as structure (5):
Wherein R1, R2, R3, R4For alkyl, aryl or heterocycle.
In addition, alkali is that potassium carbonate, cesium carbonate, potassium tert-butoxide, sodium methoxide, 1,8- diazabicylo, 11 carbon -7- alkene (DBU) etc. are normal
One of inorganic base or organic base for seeing or several combinations.
7. the preparation method of chloroacrylic acid fluorine alcohol ester according to claim 1, which is characterized in that the reaction is one pot of company
Continuous two-step reaction, first step reaction are the chlorination reaction of class MBH reaction, and methacrylaldehyde and excessive electrophilic reagent containing chlorine are in azepine
Carbone catalyst effect is lower to generate chloropropene aldehyde；Second step reaction, upper step after reaction, not separating-purifying directly adds
Enter fluorinated alcohols, oxidative esterification occurs for the above excessive chloro-containing reagent of step anti-as catalyst as oxidant, azepine Cabbeen at this time
It should obtain chloroacrylic acid fluorine alcohol ester.
8. the preparation method of chloroacrylic acid fluorine alcohol ester according to claim 1, which is characterized in that molten used in reaction
Agent is in water, ethyl alcohol, methanol, toluene, tetrahydrofuran, ether, acetonitrile, acetone, dimethyl sulfoxide or n,N-Dimethylformamide
It is one or several kinds of.
9. the preparation method of chloroacrylic acid fluorine alcohol ester according to claim 1, which is characterized in that the methacrylaldehyde contains
The ratio between amount of chlorine electrophilic reagent and fluoro alcohol matter is 1:2:1；The object of the quaternary ammonium salt of the alkali and imidazoles, thiazole or triazole
The amount of matter is the 5~20% of methacrylaldehyde.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201811292646.6A CN109232240B (en) | 2018-11-01 | 2018-11-01 | Method for synthesizing chloroacrylic acid fluoroalcohol ester |
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| CN201811292646.6A CN109232240B (en) | 2018-11-01 | 2018-11-01 | Method for synthesizing chloroacrylic acid fluoroalcohol ester |
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104710309A (en) * | 2015-02-05 | 2015-06-17 | 浙江普洛医药科技有限公司 | Synthetic methods of loxoprofen sodium and intermediate thereof |
| CN108348909A (en) * | 2015-11-19 | 2018-07-31 | 赢创罗姆有限公司 | For the Au-based catalyst by oxidation of aldehydes esterification at carboxylate |
-
2018
- 2018-11-01 CN CN201811292646.6A patent/CN109232240B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104710309A (en) * | 2015-02-05 | 2015-06-17 | 浙江普洛医药科技有限公司 | Synthetic methods of loxoprofen sodium and intermediate thereof |
| CN108348909A (en) * | 2015-11-19 | 2018-07-31 | 赢创罗姆有限公司 | For the Au-based catalyst by oxidation of aldehydes esterification at carboxylate |
Non-Patent Citations (3)
| Title |
|---|
| FOHLISCH, B ET AL.: "Cycloaddition of acyclic conjugated dienes with a tetrachloro-substituted oxyallyl intermediate generated from pentachloroacetone", 《EUROPEAN JOURNAL OF ORGANIC CHEMISTRY》 * |
| KUWANO, SATORU ET AL.: "Chemoselective conversion of alpha-unbranched aldehydes to amides, esters, and carboxylic acids by NHC-catalysis", 《CHEMICAL COMMUNICATIONS》 * |
| LI, ZHONGZHOU ET AL.: "Selective and Efficient Oxidation of Benzylic Alcohols to Benzaldehydes and Methyl Benzoates by Dibromo-5,5-dimethylhydantoin", 《SYNTHETIC COMMUNICATIONS》 * |
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