CN109232240B - Method for synthesizing chloroacrylic acid fluoroalcohol ester - Google Patents
Method for synthesizing chloroacrylic acid fluoroalcohol ester Download PDFInfo
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- CN109232240B CN109232240B CN201811292646.6A CN201811292646A CN109232240B CN 109232240 B CN109232240 B CN 109232240B CN 201811292646 A CN201811292646 A CN 201811292646A CN 109232240 B CN109232240 B CN 109232240B
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- reaction
- fluoroalcohol
- acrolein
- chlorine
- chloroacrylic acid
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- -1 chloroacrylic acid fluoroalcohol ester Chemical class 0.000 title claims abstract description 19
- 238000000034 method Methods 0.000 title claims abstract description 16
- 230000002194 synthesizing effect Effects 0.000 title description 2
- HGINCPLSRVDWNT-UHFFFAOYSA-N Acrolein Chemical compound C=CC=O HGINCPLSRVDWNT-UHFFFAOYSA-N 0.000 claims abstract description 32
- 238000006243 chemical reaction Methods 0.000 claims abstract description 19
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims abstract description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000000460 chlorine Substances 0.000 claims abstract description 14
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 14
- AQYSYJUIMQTRMV-UHFFFAOYSA-N hypofluorous acid Chemical compound FO AQYSYJUIMQTRMV-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000003153 chemical reaction reagent Substances 0.000 claims abstract description 10
- 239000003054 catalyst Substances 0.000 claims abstract description 9
- 239000002994 raw material Substances 0.000 claims abstract description 7
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 8
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- KEQGZUUPPQEDPF-UHFFFAOYSA-N 1,3-dichloro-5,5-dimethylimidazolidine-2,4-dione Chemical group CC1(C)N(Cl)C(=O)N(Cl)C1=O KEQGZUUPPQEDPF-UHFFFAOYSA-N 0.000 claims description 5
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 4
- 239000003513 alkali Substances 0.000 claims description 4
- FJDQFPXHSGXQBY-UHFFFAOYSA-L caesium carbonate Chemical group [Cs+].[Cs+].[O-]C([O-])=O FJDQFPXHSGXQBY-UHFFFAOYSA-L 0.000 claims description 4
- 229910000024 caesium carbonate Inorganic materials 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 4
- 238000005886 esterification reaction Methods 0.000 claims description 4
- 230000003647 oxidation Effects 0.000 claims description 4
- 238000007254 oxidation reaction Methods 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- 238000005660 chlorination reaction Methods 0.000 claims description 3
- 239000012039 electrophile Substances 0.000 claims description 3
- 229910052731 fluorine Inorganic materials 0.000 claims description 3
- 239000011737 fluorine Substances 0.000 claims description 3
- 125000001153 fluoro group Chemical group F* 0.000 claims description 3
- ZYMKZMDQUPCXRP-UHFFFAOYSA-N fluoro prop-2-enoate Chemical compound FOC(=O)C=C ZYMKZMDQUPCXRP-UHFFFAOYSA-N 0.000 claims description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 3
- 238000002360 preparation method Methods 0.000 claims description 3
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims description 3
- 150000003852 triazoles Chemical class 0.000 claims description 3
- ZSOPPQGHWJVKJB-UHFFFAOYSA-N 3-chloroprop-2-enal Chemical compound ClC=CC=O ZSOPPQGHWJVKJB-UHFFFAOYSA-N 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 125000003118 aryl group Chemical group 0.000 claims description 2
- 239000002585 base Substances 0.000 claims description 2
- 238000005580 one pot reaction Methods 0.000 claims description 2
- 239000007800 oxidant agent Substances 0.000 claims description 2
- 230000001590 oxidative effect Effects 0.000 claims description 2
- 238000000746 purification Methods 0.000 claims description 2
- 238000000926 separation method Methods 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 2
- 238000007039 two-step reaction Methods 0.000 claims description 2
- 125000001183 hydrocarbyl group Chemical group 0.000 claims 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims 2
- 125000003158 alcohol group Chemical group 0.000 claims 1
- 125000000623 heterocyclic group Chemical group 0.000 claims 1
- 230000007613 environmental effect Effects 0.000 abstract description 2
- 238000009776 industrial production Methods 0.000 abstract description 2
- 238000006709 oxidative esterification reaction Methods 0.000 abstract description 2
- 238000003786 synthesis reaction Methods 0.000 abstract description 2
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 12
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 8
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- JRNVZBWKYDBUCA-UHFFFAOYSA-N N-chlorosuccinimide Chemical compound ClN1C(=O)CCC1=O JRNVZBWKYDBUCA-UHFFFAOYSA-N 0.000 description 3
- SZTBMYHIYNGYIA-UHFFFAOYSA-M 2-chloroacrylate Chemical compound [O-]C(=O)C(Cl)=C SZTBMYHIYNGYIA-UHFFFAOYSA-M 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 2
- FZWLAAWBMGSTSO-UHFFFAOYSA-N Thiazole Chemical compound C1=CSC=N1 FZWLAAWBMGSTSO-UHFFFAOYSA-N 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000012044 organic layer Substances 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 238000010898 silica gel chromatography Methods 0.000 description 2
- 238000004809 thin layer chromatography Methods 0.000 description 2
- BYEAHWXPCBROCE-UHFFFAOYSA-N 1,1,1,3,3,3-hexafluoropropan-2-ol Chemical compound FC(F)(F)C(O)C(F)(F)F BYEAHWXPCBROCE-UHFFFAOYSA-N 0.000 description 1
- QXJCOPITNGTALI-UHFFFAOYSA-N 1,1,2,2,3,3,4,4,4-nonafluorobutan-1-ol Chemical compound OC(F)(F)C(F)(F)C(F)(F)C(F)(F)F QXJCOPITNGTALI-UHFFFAOYSA-N 0.000 description 1
- 239000005708 Sodium hypochlorite Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 208000012839 conversion disease Diseases 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 150000002430 hydrocarbons Chemical group 0.000 description 1
- 150000007529 inorganic bases Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 150000007530 organic bases Chemical class 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The invention belongs to the technical field of organic chemical synthesis, and particularly relates to a method for preparing chloroacrylic acid fluoroalcohol ester. The invention takes acrolein, chlorine-containing electrophilic reagent and fluoroalcohol as raw materials, takes azacarbene as a catalyst, and prepares the chloroacrylic acid fluoroalcohol ester through MBH-like reaction and oxidative esterification reaction. The method has the advantages of cheap raw materials, simple and convenient process, greenness, safety, high efficiency and environmental protection, and is suitable for industrial production.
Description
Technical Field
The invention belongs to the technical field of organic chemical synthesis, and particularly relates to a method for preparing chloroacrylic acid fluoroalcohol ester from acrolein, chlorine-containing electrophilic reagent and fluoroalcohol.
Background
The fluoroacrylate chlorohydrate is a compound widely used in the fields of organic chemistry and polymer chemistry, and is useful in various fields as industrial applications such as fine chemicals, raw materials for pharmaceuticals and agricultural chemicals, raw materials for resins and plastics, electronic information materials, and optical materials.
As a method for producing an ester compound, conventionally, a method of obtaining a corresponding ester by dehydrating a carboxylic acid and an alcohol under an acidic condition has been used, and a high temperature is often required, a reaction conversion rate is sometimes low, and a side reaction is sometimes involved. The method adopts direct oxidation esterification of aldehyde and alcohol, has mild conditions and has industrial application prospect.
Disclosure of Invention
The invention aims to provide a method for preparing chloroacrylic acid fluoroalcohol ester by using acrolein, chlorine-containing electrophilic reagent and fluoroalcohol as raw materials and using azacarbene as a catalyst through MBH-like reaction and oxidative esterification reaction. The reaction is a one-pot continuous two-step reaction, the first step is a chlorination reaction of MBH-like reaction, and acrolein and excessive chlorine-containing electrophilic reagents generate chloroacrolein under the action of an aza-carbene catalyst; and (2) a second step of reaction, wherein after the reaction in the previous step is finished, the fluoroalcohol is directly added without separation and purification, the excessive chlorine-containing reagent in the previous step is used as an oxidant, the azacarbene is used as a catalyst, and the oxidation esterification reaction is carried out to obtain the chloroacrylic acid fluoroalcohol ester, wherein the reaction formula is as follows:
the chlorine-containing electrophilic reagent is one or a combination of more of chlorine, N-chlorosuccinimide (CAS No. 128-09-6), sodium hypochlorite and dichlorodimethyl hydantoin (CAS No. 118-52-5).
The fluoroalcohol refers to an alcohol in which one or more hydrogens of the hydrocarbon chain are replaced with fluorine, such as perfluoron-butanol, hexafluoroisopropanol, 1H, 2H-perfluorohex-1-ol, and the like, but is not limited thereto.
The aza-carbene catalyst is generated by reacting common imidazole, thiazole or triazole quaternary ammonium salt with alkali on site. Wherein the imidazole quaternary ammonium salt is shown in a structure (3), the thiazole quaternary ammonium salt is shown in a structure (4), and the triazole quaternary ammonium salt is shown in a structure (5):
wherein R is1，R2，R3，R4Is alkyl, aryl or heterocyclic radical.
The base is one or more of common inorganic bases or organic bases such as potassium carbonate, cesium carbonate, potassium tert-butoxide, sodium methoxide, 1, 8-diazabicycloundecen-7-ene (DBU), and the like.
The solvent used in the reaction is one or more of water, ethanol, methanol, toluene, tetrahydrofuran, diethyl ether, acetonitrile, acetone, dimethyl sulfoxide or N, N-dimethylformamide.
The ratio of the amounts of acrolein, chlorine-containing electrophile and fluoroalcohol species is 1: 2: 1; the amount of the substance of the alkali and the quaternary ammonium salt of imidazole, thiazole or triazole is 5-20% of that of the acrolein.
The invention has the beneficial effects that:
(1) the synthesis method of the chloroacrylic acid fluoroalcohol ester provided by the invention has the advantages of cheap raw materials, simple and convenient process and easy industrial preparation.
(2) This patent prepares chloroacrylic acid fluorine alcohol ester with acrolein, chlorine electrophilic reagent and fluoroalcohol, and this method is green safety, and high-efficient environmental protection is applicable to the industrial production.
Detailed Description
The first embodiment is as follows:
100ml of chloroform, 5.6 g (0.1mol) of acrolein, 0.7 g (0.005mol) of triazazole salt, 1.63 g (0.005mol) of cesium carbonate, and 39.4 g (0.2mol) of 1, 3-dichloro-5, 5-dimethylhydantoin were sequentially added to a 250ml reaction tube, and the reaction was followed by thin layer chromatography at room temperature until acrolein was completely disappeared (about 24 hours). Adding CF3(CF2)7CH2CH2OH46.4 g (0.1mol), after 12 hours of reaction, extracted three times with water and ethyl acetate, the aqueous layer was removed and the organic layer was dried over anhydrous sodium sulfate. The solvent was removed by rotary evaporator and purified by silica gel chromatography (ethyl acetate/petroleum ether-1/10) to give pure fluoroalcohol chloroacrylate 43.1 g, 78% yield.
Example two:
100ml of chloroform, 5.6 g (0.1mol) of acrolein, 0.7 g (0.005mol) of triazazole salt, 1.63 g (0.005mol) of cesium carbonate, and 39.4 g (0.2mol) of 1, 3-dichloro-5, 5-dimethylhydantoin were sequentially added to a 250ml reaction tube, and the reaction was followed by thin layer chromatography at room temperature until acrolein was completely disappeared (about 24 hours). Adding CF2H(CF2)3CH2OH23.2 g (0.1mol), after 12 hours of reaction, extracted three times with water and ethyl acetate, the aqueous layer was removed and the organic layer was dried over anhydrous sodium sulfate. Removal of solvent by rotary evaporatorThis was then purified by silica gel chromatography (ethyl acetate/petroleum ether ═ 1/10) to give pure fluoroalcohol chloroacrylate 26.6 g, 83% yield.
Claims (6)
1. The preparation method of the chloroacrylic acid fluoroalcohol ester is characterized by comprising the following steps: acrolein, chlorine-containing electrophilic reagents and fluoroalcohol are used as raw materials, aza-carbene is used as a catalyst, and chlorination reaction and oxidation esterification reaction are carried out to prepare chloroacrylic acid fluoroalcohol ester;
wherein the product of the chloroacrylic acid fluoroalcohol ester is a compound shown as the following formula (2):
wherein x, y, z are integers of 1 or more, which means that the hydrocarbyl group of the compound from the alcohol moiety is a structure having one or more hydrogens on the hydrocarbyl chain replaced with fluorine;
the chlorine-containing electrophilic reagent is 1, 3-dichloro-5, 5-dimethylhydantoin;
the aza-carbene catalyst is generated by the reaction of quaternary ammonium salt of triazole and alkali on site;
the triazole quaternary ammonium salt is shown as a structure (5):
R1，R2，R4is alkyl, aryl or heterocyclyl;
the base is cesium carbonate.
2. The method according to claim 1, wherein the acrolein is a compound represented by the following formula (1):
3. the method of claim 1, wherein the fluoroalcohol is an alcohol having one or more hydrogens on the hydrocarbyl chain replaced with fluorine.
4. The process for the preparation of fluoroacrylate chloride according to claim 1 wherein the reaction is a one-pot two-step reaction, the first step being a chlorination reaction, acrolein being reacted with excess chlorine-containing electrophile over an azacarbene catalyst to form chloroacrolein; and (2) a second step of reaction, wherein after the previous step of reaction is finished, the fluoroalcohol is directly added without separation and purification, the excessive chlorine-containing reagent in the previous step is used as an oxidant, and the azacarbene is used as a catalyst, so that the oxidation esterification reaction is carried out to obtain the chloroacrylic acid fluoroalcohol ester.
5. The method for preparing fluoroacrylate chloride according to claim 1, wherein the solvent used in the reaction is one or more selected from water, ethanol, methanol, toluene, tetrahydrofuran, diethyl ether, acetonitrile, acetone, dimethylsulfoxide and N, N-dimethylformamide.
6. The method according to claim 1, wherein the ratio of the amounts of acrolein, chlorine-containing electrophile and fluoroalcohol species is 1: 2: 1; the amount of the substance of the quaternary ammonium salt of the alkali and the triazole is 5-20% of that of the acrolein.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811292646.6A CN109232240B (en) | 2018-11-01 | 2018-11-01 | Method for synthesizing chloroacrylic acid fluoroalcohol ester |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811292646.6A CN109232240B (en) | 2018-11-01 | 2018-11-01 | Method for synthesizing chloroacrylic acid fluoroalcohol ester |
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| Publication Number | Publication Date |
|---|---|
| CN109232240A CN109232240A (en) | 2019-01-18 |
| CN109232240B true CN109232240B (en) | 2022-01-04 |
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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 |
|---|
| Chemoselective conversion of alpha-unbranched aldehydes to amides, esters, and carboxylic acids by NHC-catalysis;Kuwano, Satoru et al.;《Chemical Communications》;20121231;第48卷(第1期);第145-147页 * |
| Cycloaddition of acyclic conjugated dienes with a tetrachloro-substituted oxyallyl intermediate generated from pentachloroacetone;Fohlisch, B et al.;《European Journal Of Organic Chemistry》;20000430;第2000卷(第7期);第1335-1344页 * |
| Selective and Efficient Oxidation of Benzylic Alcohols to Benzaldehydes and Methyl Benzoates by Dibromo-5,5-dimethylhydantoin;Li, Zhongzhou et al.;《Synthetic Communications》;20140418;第44卷(第8期);第1155-1164页 * |
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