CN107840796A - A kind of preparation method of trifluoromethyl alkene ester - Google Patents
A kind of preparation method of trifluoromethyl alkene ester Download PDFInfo
- Publication number
- CN107840796A CN107840796A CN201711106760.0A CN201711106760A CN107840796A CN 107840796 A CN107840796 A CN 107840796A CN 201711106760 A CN201711106760 A CN 201711106760A CN 107840796 A CN107840796 A CN 107840796A
- Authority
- CN
- China
- Prior art keywords
- trifluoromethyl
- alkene ester
- catalyst
- preparation
- cooh
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/04—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides onto unsaturated carbon-to-carbon bonds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C303/00—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides
- C07C303/26—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of esters of sulfonic acids
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C313/00—Sulfinic acids; Sulfenic acids; Halides, esters or anhydrides thereof; Amides of sulfinic or sulfenic acids, i.e. compounds having singly-bound oxygen atoms of sulfinic or sulfenic groups replaced by nitrogen atoms, not being part of nitro or nitroso groups
- C07C313/02—Sulfinic acids; Derivatives thereof
- C07C313/04—Sulfinic acids; Esters thereof
Abstract
The invention discloses a kind of preparation method of trifluoromethyl alkene ester, in the presence of a catalyst, Fluoroacetylenes CF3CH≡CR1With R2COOH reacts to obtain trifluoromethyl alkene ester, and wherein catalyst is tertiary amine, potassium phosphate or alkali metal hydroxide.The invention provides a green high-efficient, it is capable of the synthetic method of large-scale application, mainly for the preparation of trifluoromethyl alkene ester.
Description
Technical field
The invention belongs to fluorine material field, is related to a kind of preparation method of trifluoromethyl alkene ester.
Background technology
In the past few decades, the study on the synthesis for fluorochemical is always the hot fields that chemists pay close attention to.Fluorine
The atom element most strong as electron-withdrawing power, can form the very strong C-F keys of bond energy with carbon atom, and its atomic radius with
Hydrogen atom is close, after atom is introduced into organic matter, can significantly change the physicochemical properties and bioactivity of compound.
Organic fluorocompound is widely used to the fields such as chemicals, agricultural chemicals, photoelectric material, and existing most of organic
Fluorine-containing thing, it is not present in nature, it is necessary to artificial synthesized.Therefore, for the study on the synthesis of organic fluorocompound matter, Neng Goufeng
Species and means rich in fluorine material.
Fluoropolymer is one of important purposes of Fluorine containing olefine class compound, due to fluorine atom have heat endurance, dredge
It is water-based to wait special performance, therefore, it polymerize to obtain fluorinated polymer material by Fluorine containing olefine, has in special material field important
Effect, such as：The hydrophobic material Teflon (polytetrafluoroethylene (PTFE)) for polymerizeing to obtain by tetrafluoroethylene monomer is in industrial circle application
Widely, fluorine-containing alkene ester type compound of the present invention also a kind of fluoropolymer monomer, due to synthetic method
Simply, inexpensively, therefore there is higher prospects for commercial application.
The prior synthesizing method of alkene ester type compound is obtained by the addition reaction of precious metal catalyst alkynoic acids, such as：It is right
A kind of acids addition reaction of gold catalysis alkynes is reported than file (ACS catal.2015,5,6918-6921), is used
It is expensive and be not easy the Au catalyst prepared, it is difficult to large-scale application.
The content of the invention
The technical problem to be solved in the present invention is to be directed to prior art defect, there is provided a kind of green high-efficient, can be extensive
The preparation method of the trifluoromethyl alkene ester of application, the technique convenient post-treatment, production cost are low.
The present invention relates to a kind of preparation method of trifluoromethyl alkene ester, the formula such as formula (I) of trifluoromethyl alkene ester is shown：
Comprise the following steps：
With CF3CH≡CR1And R2COOH is raw material, and in the presence of a catalyst, synthesis obtains trifluoromethyl alkene ester, reaction side
Formula is as follows：
Raw material CF3CH≡CR1And R2COOH, in the presence of a catalyst, Fluoroacetylenes CF3CH≡CR1With R2COOH reacts
To trifluoromethyl alkene ester (I), wherein, raw material and R in product1For hydrogen, perfluoroalkyl, alkyl or aryl, R2For hydrogen, alkyl or virtue
Base, catalyst are tertiary amine, metal phosphate or hydroxide, reaction condition：CF3CH≡CR1With R2COOH is material molar ratio
For 1~5:1, catalyst and R2COOH mol ratio is 0.01~2.01:1, reaction temperature is 0~180 DEG C, the reaction time 1
~48h.
The Fluoroacetylenes CF3CH≡CR1For 1,1,1,4,4,4- hexafluoro -2- butine, trifluoropropyne, 4- trifluoromethylbenzenes
Acetylene or 2- acetenyl benzotrifluorides.
The R2COOH be P-methoxybenzoic acid, caprylic acid, to benzene methanesulfonic acid, to methoxyl group sulfinic acid.
The catalyst is triethylamine, diisopropylethylamine, potassium phosphate or cesium hydroxide.
The preferred reaction conditions：CF3CH≡CR1With R2COOH mol ratios are 1~3:1, catalyst and R2COOH mole
Than for 0.05~1.1:1, reaction temperature is 25~120 DEG C, and the reaction time is 2~16h.
The advantage of the invention is that：
(1) Au catalyst of costliness is employed in documents, and the present invention can be carried out in the case where being participated in without metal, it is greener
Color, efficiently.
(2) present invention uses relatively inexpensive base catalyst, not only post-process more convenient, and can answer on a large scale
With.(3) raw material Fluoroacetylenes are Fluorine contained chemicals, cheap and easy to get.
Embodiment
The present invention is described in further detail below by specific embodiment, but not the present invention done any formal
Limitation.
Embodiment 1：
Dichloromethane 2mL, triethylamine 0.025g, P-methoxybenzoic acid 0.152g are added into 25mL Schlenk pipes,
After liquid nitrogen cooling, vacuumize, suction 1,1, Isosorbide-5-Nitrae, 4,4- hexafluoro -2- butine 0.2-0.3g, reacted 10 hours in 25 DEG C, decompression is steamed
Target product, yield 99% are obtained after evaporating.
Embodiment 2~4：
Embodiment 2~4 prepares trifluoromethyl alkene ester according to identical preparation method in embodiment 1, except that implementing
Trifluoromethyl alkynes in example 1 is 1,1, Isosorbide-5-Nitrae, 4,4- hexafluoro -2- butine, and in embodiment 2~4 is respectively trifluoropropyne, 4-
Trifluoromethyl phenylacetylene or 2- acetenyl benzotrifluorides.The reaction result of embodiment 2~4 is as shown in table 1.
The reaction result of the trifluoromethyl alkynes of table 1
| Embodiment | Alkynes | Catalyst | Yield (%) |
| 2 | Trifluoropropyne | Triethylamine | 95 |
| 3 | 4- trifluoromethyl phenylacetylenes | Diisopropylethylamine | 91 |
| 4 | 2- acetenyl benzotrifluorides | Diisopropylethylamine | 76 |
Embodiment 5~7：
Embodiment 5~7 prepares trifluoromethyl alkene ester according to identical preparation method in embodiment 1, except that implementing
Trifluoromethyl alkynes in example 1 is 1,1, Isosorbide-5-Nitrae, 4,4- hexafluoro -2- butine, and raw material 2- bromine trifluoropropyls are used in embodiment 5~7
Alkene, 2- chlorine trifluoro propene or 1- chlorine trifluoro propenes.The reaction result of embodiment 5~7 is as shown in table 2.
The reaction result of the variety classes alkene of table 2
| Embodiment | Alkene | Catalyst | Yield (%) |
| 5 | 2- bromine trifluoro propenes | Triethylamine | 83 |
| 6 | 2- chlorine trifluoro propenes | Triethylamine | 71 |
| 7 | 1- chlorine trifluoro propenes | Cesium hydroxide | 65 |
Embodiment 8~10：
Embodiment 8~10 prepares trifluoromethyl alkene ester according to identical preparation method in embodiment 1, except that implementing
Reactant in example 1 is P-methoxybenzoic acid, and the reactant in embodiment 8~10 is caprylic acid, p-methyl benzenesulfonic acid or right
Methoxyl group sulfinic acid.The reaction result of embodiment 8~10 is as shown in table 3.
The catalyst amount of table 3 influences
| Embodiment | Reactant | Catalyst | Yield (%) |
| 8 | Caprylic acid | Cesium hydroxide | 71 |
| 9 | P-methyl benzenesulfonic acid | Triethylamine | 89 |
| 10 | To methoxyl group sulfinic acid | Diisopropylethylamine | 81 |
Embodiment 11~13：
Embodiment 11~13 prepares trifluoromethyl alkene ester according to identical preparation method in embodiment 1, except that real
It is catalyst to apply in example 1 using triethylamine, and selects diisopropylethylamine in embodiment 11~13 respectively, potassium phosphate or hydroxide
Caesium is that catalyst is reacted.The reaction result of embodiment 11~13 is as shown in table 4.
The reaction time of table 4 influences on reaction
| Embodiment | Catalyst | Yield (%) |
| 11 | Diisopropylethylamine | 99 |
| 12 | Potassium phosphate | 65 |
| 13 | Cesium hydroxide | 71 |
Claims (5)
- A kind of 1. preparation method of trifluoromethyl alkene ester, shown in trifluoromethyl alkene ester formula such as formula (I)：Comprise the following steps：In the presence of a catalyst, Fluoroacetylenes CF3CH≡CR1With R2COOH reacts to obtain trifluoromethyl alkene ester (I), wherein, R in raw material and product1For hydrogen, perfluoroalkyl, alkyl or aryl, R2For hydrogen, alkyl or aryl, catalyst is three-level Amine, metal phosphate or hydroxide, reaction condition：CF3CH≡CR1With R2COOH is that material molar ratio is 1~5:1, catalyst With R2COOH mol ratio is 0.01~2.01:1, reaction temperature is 0~180 DEG C, and the reaction time is 1~48h.
- 2. the preparation method of trifluoromethyl alkene ester according to claim 1, it is characterised in that Fluoroacetylenes CF3CH≡CR1For 1,1,1,4,4,4- hexafluoro -2- butine, trifluoropropyne, 4- trifluoromethyls phenylacetylene or 2- acetenyl benzotrifluorides.
- 3. the preparation method of trifluoromethyl alkene ester according to claim 1, it is characterised in that the R2COOH is to methoxyl group Benzoic acid, caprylic acid, to benzene methanesulfonic acid, to methoxyl group sulfinic acid.
- 4. the preparation method of trifluoromethyl alkene ester according to claim 1, it is characterised in that catalyst is triethylamine, two different Propylethylamine, potassium phosphate or cesium hydroxide.
- 5. the preparation method of trifluoromethyl alkene ester according to claim 1, it is characterised in that reaction condition：CF3CH≡CR1 With R2COOH mol ratios are 1~3:1, catalyst and R2COOH mol ratio is 0.05~1.1:1, reaction temperature is 25~120 DEG C, the reaction time is 2~16h.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711106760.0A CN107840796B (en) | 2017-11-10 | 2017-11-10 | Preparation method of trifluoromethyl alkenyl ester |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711106760.0A CN107840796B (en) | 2017-11-10 | 2017-11-10 | Preparation method of trifluoromethyl alkenyl ester |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN107840796A true CN107840796A (en) | 2018-03-27 |
| CN107840796B CN107840796B (en) | 2020-12-15 |
Family
ID=61682576
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201711106760.0A Active CN107840796B (en) | 2017-11-10 | 2017-11-10 | Preparation method of trifluoromethyl alkenyl ester |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107840796B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113277959A (en) * | 2020-12-18 | 2021-08-20 | 武汉大学 | Synthesis method of ortho-perfluoroalkyl substituted azide compound |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3898252A (en) * | 1973-02-26 | 1975-08-05 | Us Agriculture | Preparation of enol esters |
-
2017
- 2017-11-10 CN CN201711106760.0A patent/CN107840796B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3898252A (en) * | 1973-02-26 | 1975-08-05 | Us Agriculture | Preparation of enol esters |
Non-Patent Citations (2)
| Title |
|---|
| ALBERT L. HENNE等: "Addition of Acetic Acid to Perfluoro-2-butyne", 《JOURNAL OF THE AMERICAN CHEMICAL SOCIETY》 * |
| XIANJUN XU等: "Direct Amidation of Carboxylic Acids through an Active α‑Acyl Enol Ester Intermediate", 《J. ORG. CHEM.》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113277959A (en) * | 2020-12-18 | 2021-08-20 | 武汉大学 | Synthesis method of ortho-perfluoroalkyl substituted azide compound |
Also Published As
| Publication number | Publication date |
|---|---|
| CN107840796B (en) | 2020-12-15 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102432414B (en) | Low temperature ethylene oligomerization method | |
| CN103232365B (en) | Schiff base compound, and synthesis method and application thereof | |
| CN101648122B (en) | Preparation method for fluorine-contained emulsifier | |
| CN101168493B (en) | Preparation method for fluorochlorobenzene | |
| CN109574812B (en) | Method for preparing perfluoroolefin with high selectivity | |
| CN105622369A (en) | Method for preparing cyclopropyl methyl ketone | |
| CN104418690B (en) | A kind of method of ethylene oligomerization | |
| CN107840796A (en) | A kind of preparation method of trifluoromethyl alkene ester | |
| CN102964388A (en) | Preparation method of benzoyl-substituted 1,10-phenanthroline complex and catalytic application in ethylene oligomerization | |
| CN102399119A (en) | Method for catalyzing ethylene oligomerization by using butyryl-substituted 1,10-phenanthroline complex | |
| CN109957049A (en) | Asymmetric (alpha-diimine) nickel alkene catalyst and its preparation method and application | |
| CN103788363A (en) | Method for preparing perfluoropolyether with high molecular weight | |
| CN106495985A (en) | A kind of environment-friendly preparation process of solvent method synthesizing perfluoroalkyl ethanol | |
| CN113816824A (en) | Preparation method and application of perfluoroolefin oligomer | |
| CN104326862A (en) | Preparation method of 2,4-dichloro-1,1,1-trifluorobutane derivative | |
| CN102407158A (en) | Preparation method of ethylene oligomerization catalyst and use thereof | |
| CN103965023B (en) | A kind of preparation method of fluoro-alkyl vinyl ethers | |
| CN212524041U (en) | Continuous production equipment for hexafluoropropylene oxide oligomer | |
| CN103641692B (en) | Preparation of novel fluorine-containing bisphenol compound | |
| CN107400040A (en) | A kind of preparation method of the propane diols of 2,2 difluoro 1,3 | |
| CN107619368A (en) | A kind of preparation method of trifluoromethyl alkene ether | |
| CN103086819B (en) | Chlorination 2-positive propionyl-1,10-phenanthroline contracting amine is used to close the method for the low-temperature catalyzed ethylene oligomerization of rear transition metal | |
| CN103804428A (en) | Preparation method and application of complex | |
| CN102558242B (en) | Preparation of isobutyryl substituted 1,10-phenanthroline complex and application of complex serving as catalyst | |
| CN105753661A (en) | Polyether-type hydrofluoroether and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |