CN118047659A - Trifluoro vinyl transfer reagent and preparation method and application thereof - Google Patents
Trifluoro vinyl transfer reagent and preparation method and application thereof Download PDFInfo
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- CN118047659A CN118047659A CN202410147004.6A CN202410147004A CN118047659A CN 118047659 A CN118047659 A CN 118047659A CN 202410147004 A CN202410147004 A CN 202410147004A CN 118047659 A CN118047659 A CN 118047659A
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- trifluoroethylene
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- -1 Trifluoro vinyl Chemical group 0.000 title claims abstract description 83
- 238000012546 transfer Methods 0.000 title claims abstract description 83
- 239000003153 chemical reaction reagent Substances 0.000 title claims abstract description 82
- 238000002360 preparation method Methods 0.000 title abstract description 11
- MIZLGWKEZAPEFJ-UHFFFAOYSA-N 1,1,2-trifluoroethene Chemical group FC=C(F)F MIZLGWKEZAPEFJ-UHFFFAOYSA-N 0.000 claims abstract description 61
- 239000000178 monomer Substances 0.000 claims abstract description 30
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 26
- 150000002367 halogens Chemical group 0.000 claims abstract description 22
- 125000006273 (C1-C3) alkyl group Chemical group 0.000 claims abstract description 18
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 39
- 125000003118 aryl group Chemical group 0.000 claims description 32
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 27
- 238000000034 method Methods 0.000 claims description 24
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 15
- 239000007788 liquid Substances 0.000 claims description 14
- 239000012038 nucleophile Substances 0.000 claims description 11
- 239000012434 nucleophilic reagent Substances 0.000 claims description 11
- 239000003960 organic solvent Substances 0.000 claims description 11
- 239000000243 solution Substances 0.000 claims description 11
- PWGPFNBKVNMDLK-UHFFFAOYSA-N tributyl(1,2,2-trifluoroethenyl)stannane Chemical compound CCCC[Sn](CCCC)(CCCC)C(F)=C(F)F PWGPFNBKVNMDLK-UHFFFAOYSA-N 0.000 claims description 10
- 239000012295 chemical reaction liquid Substances 0.000 claims description 9
- 239000012043 crude product Substances 0.000 claims description 9
- 238000004519 manufacturing process Methods 0.000 claims description 9
- 239000011541 reaction mixture Substances 0.000 claims description 9
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 6
- 238000009835 boiling Methods 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- 150000001408 amides Chemical class 0.000 claims description 4
- 150000001733 carboxylic acid esters Chemical class 0.000 claims description 4
- 238000004108 freeze drying Methods 0.000 claims description 4
- 239000011259 mixed solution Substances 0.000 claims description 4
- 230000001376 precipitating effect Effects 0.000 claims description 3
- 125000005843 halogen group Chemical group 0.000 claims 4
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 abstract description 6
- 229910052740 iodine Inorganic materials 0.000 abstract description 6
- 239000011630 iodine Substances 0.000 abstract description 6
- 230000003647 oxidation Effects 0.000 abstract description 4
- 238000007254 oxidation reaction Methods 0.000 abstract description 4
- 125000000524 functional group Chemical group 0.000 abstract 1
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 30
- 239000000047 product Substances 0.000 description 29
- 238000006243 chemical reaction Methods 0.000 description 18
- 150000001875 compounds Chemical class 0.000 description 15
- 238000000806 fluorine-19 nuclear magnetic resonance spectrum Methods 0.000 description 11
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 11
- 239000003795 chemical substances by application Substances 0.000 description 10
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 9
- 238000003786 synthesis reaction Methods 0.000 description 9
- 230000015572 biosynthetic process Effects 0.000 description 8
- 238000001460 carbon-13 nuclear magnetic resonance spectrum Methods 0.000 description 8
- 125000004205 trifluoroethyl group Chemical group [H]C([H])(*)C(F)(F)F 0.000 description 7
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 5
- 238000004293 19F NMR spectroscopy Methods 0.000 description 5
- 238000005160 1H NMR spectroscopy Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 238000004440 column chromatography Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 4
- 238000000746 purification Methods 0.000 description 4
- 238000006467 substitution reaction Methods 0.000 description 4
- 125000003396 thiol group Chemical class [H]S* 0.000 description 4
- 238000005481 NMR spectroscopy Methods 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- JWAZRIHNYRIHIV-UHFFFAOYSA-N 2-naphthol Chemical compound C1=CC=CC2=CC(O)=CC=C21 JWAZRIHNYRIHIV-UHFFFAOYSA-N 0.000 description 2
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 2
- 239000005751 Copper oxide Substances 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 229910000431 copper oxide Inorganic materials 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 2
- 150000002497 iodine compounds Chemical class 0.000 description 2
- RAMPDACRJWTXEV-UHFFFAOYSA-N methyl 2-cyanobenzoate Chemical compound COC(=O)C1=CC=CC=C1C#N RAMPDACRJWTXEV-UHFFFAOYSA-N 0.000 description 2
- 230000000269 nucleophilic effect Effects 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000005086 pumping Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 2
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- XJFFUXNWVUZUIF-UHFFFAOYSA-N 4-ethenylisoindole-1,3-dione Chemical compound C=CC1=CC=CC2=C1C(=O)NC2=O XJFFUXNWVUZUIF-UHFFFAOYSA-N 0.000 description 1
- 239000005711 Benzoic acid Substances 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- MWVGKTUELQKXEN-UHFFFAOYSA-K [Li+].[Mg++].[Cl-].[Cl-].[Cl-] Chemical compound [Li+].[Mg++].[Cl-].[Cl-].[Cl-] MWVGKTUELQKXEN-UHFFFAOYSA-K 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- 229950011260 betanaphthol Drugs 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- JILPJDVXYVTZDQ-UHFFFAOYSA-N lithium methoxide Chemical compound [Li+].[O-]C JILPJDVXYVTZDQ-UHFFFAOYSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000005580 one pot reaction Methods 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000000750 progressive effect Effects 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- ITCQYXAJRANQQZ-UHFFFAOYSA-N tributyl(2,2,2-trifluoroethyl)stannane Chemical compound CCCC[Sn](CCCC)(CCCC)CC(F)(F)F ITCQYXAJRANQQZ-UHFFFAOYSA-N 0.000 description 1
- 125000001889 triflyl group Chemical group FC(F)(F)S(*)(=O)=O 0.000 description 1
- KOZCZZVUFDCZGG-UHFFFAOYSA-N vinyl benzoate Chemical compound C=COC(=O)C1=CC=CC=C1 KOZCZZVUFDCZGG-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The application provides a trifluoro vinyl transfer reagent, a preparation method and application thereof, the trifluoro vinyl transfer reagent has a structural formula as shown in a formula 1,Wherein R 1、R2、R3、R4、R5 is independently selected from at least one of H, halogen and halogen substituted C1-C3 alkyl. The trifluoroethylene group transfer reagent with the structural formula has the characteristics of higher oxidation energy and leaving capacity by utilizing the trivalent iodine reagent, and the trifluoroethylene group is used as a leaving group, so that the trifluoroethylene group functional group can be efficiently introduced into molecules under milder conditions, and different trifluoroethylene compound monomers can be obtained.
Description
Technical Field
The application relates to the technical field of organic synthesis, in particular to a trifluoro vinyl transfer reagent and a preparation method and application thereof.
Background
The compound with the trifluoro vinyl group is unstable and is extremely easy to generate polymerization reaction to generate high molecular polymer, and can be processed and molded by various methods, and the excellent chemical stability, radiation resistance, insulativity, heat resistance (flame resistance and heat stability), acid resistance, alkali resistance and organic solvent (except halide) of the compound can be widely applied to the fields of production and living, defending industry and some advanced high technology as a structural material, so that the compound has extremely important research and application values.
Therefore, there is a need to improve the research and development ability of the domestic trifluoroethylene-based polymer.
Based on this, it is desired to provide a method for efficiently introducing a trifluoroethylene group into a molecule.
Disclosure of Invention
The application provides a trifluoro vinyl transfer reagent, a preparation method and application thereof, wherein the trifluoro vinyl transfer reagent can efficiently introduce trifluoro vinyl functional groups into molecules under mild conditions so as to obtain different trifluoro vinyl compound monomers.
In a first aspect, the present application provides a trifluoroethyl transfer agent having a structural formula as shown in formula 1,
Wherein R 1、R2、R3、R4、R5 is independently selected from at least one of H, halogen and halogen substituted C1-C3 alkyl.
According to the trifluoroethylene transfer reagent with the structural formula, by utilizing the characteristic that the trivalent iodine reagent has higher oxidation energy and leaving capacity and taking the trifluoroethylene as a leaving group, the trifluoroethylene functional group can be efficiently introduced into molecules under milder conditions, so that different trifluoroethylene compound monomers can be obtained.
In some embodiments, R 1、R5 is each independently selected from at least one of Br, halogen substituted C1-C3 alkyl.
In some embodiments, the trifluoroethyl transfer agent has the structural formula
In a second aspect, the present application provides a process for preparing a trifluoroethylene transfer reagent comprising the steps of:
s10: reacting cyano (aryl) -lambda 3 -iodo trifluoro methanesulfonate with trifluoro vinyl tributyltin in an organic solvent under nitrogen atmosphere at-10-0 ℃ until the reaction liquid is clear liquid to obtain a reaction mixture; wherein the structural formula of the cyano (aryl) -lambda 3 -iodo trifluoro methanesulfonate is shown in a formula 2, R 1、R2、R3、R4、R5 is independently selected from at least one of H, halogen and halogen substituted C1-C3 alkyl;
s20: removing the organic solvent from the reaction mixture by freeze drying to obtain a crude product;
S30: dispersing the crude product by diethyl ether at the temperature of-10 to 0 ℃, and then precipitating and washing the crude product by using diethyl ether/low boiling point liquid alkane mixed solution to obtain the trifluoro vinyl transfer reagent.
In some embodiments, R 1、R2、R3、R4、R5 is independently selected from at least one of H, halogen substituted C1-C3 alkyl; preferably, R 1、R5 is independently selected from at least one of Br, halogen substituted C1-C3 alkyl; preferably, the cyano (aryl) -lambda 3 -iodo trifluoro methanesulfonate has the structural formula
In some embodiments, in the step S10: the concentration of the cyano (aryl) -lambda 3 -iodo trifluoro methanesulfonate in the reaction liquid is 0.1-0.7 mol/L.
In some embodiments, in the step S10: the molar ratio of the cyano (aryl) -lambda 3 -iodo trifluoro-methanesulfonate to trifluoro-vinyl tributyltin is 1:1-1.3.
In some embodiments, the step S10 specifically includes:
S11: dispersing cyano (aryl) -lambda 3 -iodotrifluoromethanesulfonate in an organic solvent under nitrogen atmosphere to obtain cyano (aryl) -lambda 3 -iodotrifluoromethanesulfonate solution;
s12: dropwise adding trifluoro vinyl tributyltin into the cyano (aryl) -lambda 3 -iodo trifluoro methanesulfonate solution in nitrogen atmosphere at the temperature below minus 30 ℃, and then heating to the temperature of minus 10-0 ℃ to react until the reaction liquid is clear liquid, thus obtaining the reaction mixture.
In a third aspect, the present application provides a process for preparing a trifluorovinyl compound monomer comprising the steps of:
The trifluoroethylene compound monomer is obtained by reacting a trifluoroethylene group transfer reagent according to any one of the embodiments of the first aspect or a trifluoroethylene group transfer reagent prepared according to any one of the embodiments of the second aspect with a nucleophile.
In some embodiments, the nucleophile comprises at least one of a carboxylic acid, a carboxylic acid ester, an amide, and a sulfhydryl compound.
Compared with the prior art, the application has the beneficial effects that: by utilizing the characteristic of high oxidation energy and leaving capability of the trivalent iodine reagent, the trifluoro vinyl is taken as a leaving group, and the trifluoro vinyl functional group can be efficiently introduced into the molecule under a milder condition so as to obtain different trifluoro vinyl compound monomers; in particular, by optimizing the structure of the aryl group in the trifluoroethylene group transfer reagent, the selectivity of the trifluoroethylene group transfer can be effectively improved, thereby improving the yield of the produced trifluoroethylene compound monomer.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this specification, illustrate embodiments consistent with the application and together with the description, serve to explain the principles of the application.
FIG. 1 is a 1 H NMR spectrum of a trifluoroethylene transfer reagent 1a obtained in example 1 of the present application;
FIG. 2 is a 19 F NMR spectrum of a trifluoroethylene transfer reagent 1a obtained in example 1 of the present application;
FIG. 3 is a 13 C NMR chart of a trifluoroethylene transfer reagent 1a obtained in example 1 of the present application;
FIG. 4 is a single crystal structure diagram of the trifluoroethylene transfer reagent 1a according to example 1 of the present application;
FIG. 5 is a 1 H NMR spectrum of a trifluoroethylene transfer reagent 1b obtained in example 2 of the present application;
FIG. 6 is a 19 F NMR spectrum of a trifluoroethylene transfer reagent 1b obtained in example 2 of the present application;
FIG. 7 is a 13 C NMR chart of a trifluoroethylene transfer reagent 1b obtained in example 2 of the present application;
FIG. 8 is a 1 H NMR spectrum of the product 1, 2-trifluorovinyl benzoate of example 3;
FIG. 9 is a 19 F NMR spectrum of the product 1, 2-trifluorovinyl benzoate of example 3;
FIG. 10 is a 13 C NMR chart of the product 1, 2-trifluorovinyl benzoate of example 3;
FIG. 11 is a 1 H NMR spectrum of the product 1, 2-trifluoroethyl-2-naphthyl sulfide of example 4;
FIG. 12 is a 19 F NMR spectrum of the product 1, 2-trifluoroethyl-2-naphthyl sulfide of example 4;
FIG. 13 is a 13 C NMR spectrum of the product 1, 2-trifluoroethyl-2-naphthyl sulfide of example 4.
FIG. 14 is a 1 H NMR spectrum of the product N-1, 2-trifluoroethyl-phthalimide of example 5.
FIG. 15 is a 19 F NMR spectrum of the product N-1, 2-trifluoroethyl-phthalimide of example 5.
FIG. 16 is a 13 C NMR spectrum of the product N-1, 2-trifluoroethyl-phthalimide of example 5.
Specific embodiments of the present application have been shown by way of the above drawings and will be described in more detail below. The drawings and the written description are not intended to limit the scope of the inventive concepts in any way, but rather to illustrate the inventive concepts to those skilled in the art by reference to the specific embodiments.
Detailed Description
Each example or embodiment in this specification is described in a progressive manner, each example focusing on differences from other examples.
In the description of the present specification, reference to the terms "one embodiment," "some embodiments," "illustrative embodiments," "examples," "specific examples," or "some examples," etc., means that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the application. In this specification, schematic representations of the above terms do not necessarily refer to the same embodiments or examples. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.
Furthermore, the terms "first," "second," and the like, are used for descriptive purposes only and are not to be construed as indicating or implying a relative importance or implicitly indicating the number of technical features indicated. Thus, a feature defining "a first" or "a second" may explicitly or implicitly include at least one such feature. In the description of the present application, the meaning of "plurality" means at least two, for example, two, three, etc., unless specifically defined otherwise.
As described in the background art above, the polytrifluorovinyl compound has excellent properties, but the preparation of the trifluoroethyl compound monomer is difficult, and there is a certain technical bottleneck.
The existing methods for synthesizing the trifluoro vinyl compound monomer mainly comprise three methods: the first method is to synthesize a trifluorovinyl metal reagent and then react with a corresponding nucleophile to obtain the corresponding trifluorovinyl compound monomer. However, the trifluoro vinyl metal reagent has complex synthesis operation, high environmental requirement, special sensitivity to oxygen, water and temperature, difficult storage, need to be used at present and have metal residues in the product. The second method is to synthesize the organic reagent of trifluoroethylene element, and then react with the corresponding nucleophilic reagent under the action of catalyst to obtain the corresponding trifluoroethylene compound monomer. However, most of the trifluoroethylene organic reagents are complex in synthesis operation, and general trifluoroethylene organic reagents are good in stability and poor in reactivity, can only occur under the catalysis of metal, and some of the trifluoroethylene organic reagents also need harsh conditions such as heating, so that metal residues are unavoidable in the product. The third method is to directly use tetrafluoroethylene gas to react with the corresponding compound under the catalysis of transition metal to obtain the corresponding trifluoro vinyl compound monomer, but the method needs to use inert and high-pressure tetrafluoroethylene gas, and can only happen under the catalysis of transition metal, and also needs harsh conditions such as heating, and metal residues are necessarily remained in the product.
Based on the above, the application provides a trifluoroethylene group transfer reagent, a preparation method and application thereof, and the trifluoroethylene group transfer reagent can efficiently introduce a trifluoroethylene group into molecules under mild conditions so as to obtain different trifluoroethylene compound monomers. The following describes specific embodiments of the present application in detail.
It is noted that abbreviations and terms of partial functionality in the context of the present application have the meaning well known in the art, including but not limited to: OTf represents trifluoromethanesulfonyl, me represents methyl, bu represents butyl, halogen represents at least one of F, cl, br, I, aryl represents a group containing a benzene ring, C1-C3 alkyl represents an alkyl group having 1-3 carbon atoms, and "substitution" may be complete substitution or partial substitution.
Trifluoro vinyl transfer reagent
In a first aspect, the present application provides a trifluoroethyl transfer agent having a structural formula as shown in formula 1,Wherein R 1、R2、R3、R4、R5 is independently selected from at least one of H, halogen and halogen substituted C1-C3 alkyl.
According to the trifluoroethylene transfer reagent with the structural formula, by utilizing the characteristic that the trivalent iodine reagent has higher oxidation energy and leaving capacity and taking the trifluoroethylene as a leaving group, the trifluoroethylene functional group can be efficiently introduced into molecules under milder conditions, so that different trifluoroethylene compound monomers can be obtained.
Specifically, the trifluoro vinyl transfer reagent belongs to an organic trivalent iodine compound, and has stronger electrophilic activity due to the special structure of the organic trivalent iodine compound, and can react with a nucleophilic reagent under milder conditions to graft trifluoro vinyl on the nucleophilic reagent, thereby obtaining trifluoro vinyl compound monomers. As an example, nucleophiles include, but are not limited to, carboxylic acids, carboxylic esters, amides, and thiols, whereby the trifluorovinyltransfer reagent can be reacted with nucleophiles having different structures to provide the corresponding trifluorovinyl compound monomers. In addition, R 1、R2、R3、R4、R5 in the formula 1 is independently selected from at least one of H, halogen and halogen substituted C1-C3 alkyl, so that the trifluoro vinyl transfer reagent can be ensured to have better stability.
In some embodiments, R 1、R5 is each independently selected from at least one of Br, halogen substituted C1-C3 alkyl.
In some embodiments, R 1、R5 is ortho to trivalent iodine on the benzene ring, and R 1、R5 is respectively and independently selected from Br and at least one of C1-C3 alkyl substituted by halogen, the reaction of the trifluoro vinyl transfer reagent and the nucleophilic reagent has better selectivity, and the trifluoro vinyl is more easily grafted on the nucleophilic reagent. The inventor found that when the trifluoroethylene group transfer reagent reacts with the nucleophilic reagent, besides the separation transfer grafting of the trifluoroethylene group on the nucleophilic reagent, side reaction of aryl transfer grafting on the trifluoroethylene group transfer reagent on the nucleophilic reagent can occur, so that the selectivity of the reaction is poor, and the yield of the trifluoroethylene compound monomer can be reduced. When a substituent group with larger steric hindrance is introduced on the ortho position of the aryl group and the trivalent iodine, the trifluoro vinyl fragment can be selectively transferred under the action of steric hindrance, and the aryl iodobenzene part is not easy to transfer, so that the yield of preparing the trifluoro vinyl compound monomer by the reaction of the fluoro vinyl transfer reagent and the nucleophilic reagent can be obviously improved.
In some embodiments, the trifluoroethyl transfer agent is of the formula
In some embodiments, the structural formula of the trifluoroethylene transfer reagent is specifically defined, and the trifluoroethylene transfer reagent with the structure has better stability and is more easily synthesized besides better selective transfer of the trifluoroethylene fragment.
Method for preparing trifluoro-vinyl transfer agent
In a second aspect, the present application provides a process for preparing a trifluoroethylene transfer reagent comprising the steps of:
S10: under the nitrogen atmosphere, cyano (aryl) -lambda 3 -iodo trifluoro methanesulfonate and trifluoro vinyl tributyltin react in an organic solvent at the temperature of minus 30 ℃ to minus 10 ℃ to 0 ℃ until the reaction liquid is clear liquid, so as to obtain a reaction mixture; wherein the structural formula of the cyano (aryl) -lambda 3 -iodo trifluoro methanesulfonate is shown in a formula 2, R 1、R2、R3、R4、R5 is independently selected from at least one of H, halogen and halogen substituted C1-C3 alkyl;
S20: removing the organic solvent from the reaction mixture by freeze drying to obtain a crude product;
S30: dispersing the crude product with diethyl ether at-10-0 deg.c, and precipitating and washing with mixed diethyl ether/low boiling point liquid alkane solution to obtain trifluoro vinyl transferring reagent.
According to the present application, the trifluoroethylene transfer reagent obtained by using the above-described method has the same structural formula as that of the trifluoroethylene transfer reagent in any one of the embodiments of the first aspect, and thus has the advantageous effects of the first aspect. Meanwhile, the preparation raw materials in the method are simple and easy to obtain, the synthesis method is simple, the reaction operation is simple and convenient, the product yield is high, and the method can be used for mass preparation and is suitable for industrial production and application.
Specifically, the chemical reaction equation for preparing the trifluoroethylene transfer reagent by the above method is as follows:
Because the product has stronger electrophilic activity and poorer stability in a reaction system, the preparation process needs to be carried out under the condition of low temperature, no water and no oxygen, and under the condition, the yield of the trifluoro vinyl transfer reagent can be effectively improved. Steps S20 and S30 can effectively improve the purity of the trifluoroethylene transfer reagent.
In addition, it should be noted that, as the structure of the trifluoroethylene transfer reagent prepared from cyano (aryl) -lambda 3 -iodo-trifluoromethane sulfonate with different structures is also different, the polarity of the product will be changed due to the substituent on the aryl, in the step S30, the reaction product can be precipitated and washed by controlling the mixed solution of diethyl ether and low boiling point liquid alkane with different proportions, so as to improve the yield of the trifluoroethylene transfer reagent. Wherein the low boiling liquid alkane includes, but is not limited to, hexane or pentane.
In some embodiments, R 1、R5 is each independently selected from at least one of Br, halogen substituted C1-C3 alkyl.
In some of the above embodiments, when Br or halogen substituted C1-C3 alkyl group having a larger steric hindrance is introduced at the ortho position of the benzene ring to trivalent iodine, the trifluoroethylene transfer agent is more stable, and the corresponding trifluoroethylene transfer agent as in the partial embodiment of the first aspect can be obtained, and the yield of the production of the trifluoroethylene compound monomer can be improved by the steric hindrance effect. Further preferred, the cyano (aryl) -lambda 3 -iodotrifluoromethane sulfonate is of the formula
In some embodiments, in step S10: the concentration of cyano (aryl) -lambda 3 -iodo trifluoro methanesulfonate in the reaction liquid is 0.1-0.7 mol/L. Suitable concentrations facilitate further increases in the yield of the trifluoroethylene transfer reagent.
In some embodiments, in step S10: the molar ratio of cyano (aryl) -lambda 3 -iodo trifluoro-methanesulfonate to trifluoro-vinyl tributyltin is 1:1-1.3. A suitable excess of trifluoroethyl tributyltin is advantageous for increasing the efficiency of ligand exchange while increasing the conversion of cyano (aryl) -lambda 3 -iodotrifluoro methanesulfonate.
In some embodiments, the organic solvent includes, but is not limited to, methylene chloride.
In some embodiments, step S10 specifically includes:
S11: dispersing cyano (aryl) -lambda 3 -iodotrifluoromethanesulfonate in an organic solvent under nitrogen atmosphere to obtain cyano (aryl) -lambda 3 -iodotrifluoromethanesulfonate solution;
S12: dropwise adding trifluoro vinyl tributyltin into cyano (aryl) -lambda 3 -iodo trifluoro methanesulfonate solution in nitrogen atmosphere at the temperature below minus 30 ℃, and then heating to the temperature of minus 10-0 ℃ to react until the reaction liquid is clear liquid, thus obtaining the reaction mixture.
In some of the above embodiments, the yield of the trifluoroethylene transfer agent may be further improved by dropwise adding trifluoroethylene tributyltin to a cyano (aryl) -lambda 3 -iodotrifluoromethane sulfonate solution under nitrogen low temperature conditions.
In some embodiments, in step S30, after the crude product is dispersed with diethyl ether, freeze drying may be performed again to remove diethyl ether, and the process is repeated three more times, and then precipitation and washing are performed using diethyl ether/low boiling liquid alkane mixed solution. In this case, the purity of the trifluoroethylene transfer reagent can be further improved.
Process for preparing trifluorovinyl compound monomer
In a third aspect, the present application provides a process for preparing a trifluorovinyl compound monomer comprising the steps of:
the trifluoroethylene compound monomer is obtained by reacting a trifluoroethylene group transfer reagent according to any one of the embodiments of the first aspect or a trifluoroethylene group transfer reagent prepared according to any one of the embodiments of the second aspect with a nucleophilic reagent.
According to the present application, there is an advantageous effect of the first aspect or the second aspect because it gives a trifluorovinyl compound monomer by reacting a trifluorovinyl transfer reagent prepared by using any one of the embodiments according to the first aspect or a trifluorovinyl transfer reagent prepared by the method according to any one of the embodiments of the second aspect with a nucleophile.
In some embodiments, the trifluoroethylene transfer reagent and the nucleophile may be mixed directly in a solvent and reacted directly in one pot to produce the trifluoroethylene compound monomer.
In some embodiments, the nucleophile comprises at least one of a carboxylic acid, a carboxylic acid ester, an amide, and a sulfhydryl. It will be appreciated that the carboxylic acid-based compound refers to a compound containing a carboxyl group, the carboxylic acid-based compound refers to a compound containing a carboxylic ester bond, the amine-based compound refers to a compound containing an amide bond, the mercapto-based compound refers to a compound containing a mercapto group, and the trifluoroethyl group transfer agent may be reacted with a compound having a different structure from the above nucleophilic group, and a trifluoroethyl group may be introduced into the nucleophilic agent to obtain a trifluoroethyl group compound monomer.
Hereinafter, embodiments of the present application are described. The following examples are illustrative only and are not to be construed as limiting the application. The examples are not to be construed as limiting the specific techniques or conditions described in the literature in this field or as per the specifications of the product. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.
Example 1
Synthesis of trifluorovinyl transfer reagent:
under nitrogen protection, 1.90g (5.0 mmol) of the compound of formula Adding cyano (phenyl) -lambda 3 -iodo trifluoro methanesulfonate into a 100mL Schlenk tube, adding 10mL ultra-dry dichloromethane, cooling to below-30 ℃, then dropwise adding 1.87g (5 mmol) trifluoro vinyl tributyltin reagent into a mixed system under the protection of nitrogen and stirring, slowly heating to-10 ℃ to 0 ℃ after the addition of the materials is finished until the solid in the reaction system is completely dissolved, immediately pumping the solvent in the system on an oil pump by using a method of adding cold trap at low temperature and under the condition of no water and no oxygen, adding 5mL diethyl ether for dispersion, pumping again for 3 times, finally adding the frozen diethyl ether/hexane solution for separating out solid, washing with diethyl ether/hexane solution, and filtering to obtain the pure trifluoro vinyl transfer reagent 1a, wherein the structural formula is/>The product obtained was a white solid with a yield of 78%, 1 H NMR spectrum of the product was shown in fig. 1, 19 F NMR spectrum was shown in fig. 2, 13 C NMR spectrum was shown in fig. 3, and single crystal structure diagram was shown in fig. 4.
1H NMR(400MHz,CDCl3)δ8.04(d,J＝7.9Hz,2H),7.72(t,J＝7.3Hz,1H),7.58–7.52(m,2H);13C NMR(101MHz,CDCl3)δ155.11(ddd,J＝312.4,287.1,32.9Hz),135.48,133.45,132.65,119.80(q,J＝318.7Hz),115.00,103.46(ddd,J＝321.7,63.1,26.8Hz);19F NMR(376MHz,CDCl3)δ-78.44(d,J＝6.8Hz),-81.14–-82.12(m),-100.85(dd,J＝127.1,33.5Hz),-158.02(ddd,J＝126.3,57.1,10.9Hz).
Example 2
Synthesis of trifluorovinyl transfer reagent:
The preparation was carried out in the same manner as in example 1 except that the cyano (phenyl) -lambda 3 -iodotrifluoro methanesulfonate salt had the structural formula The product is trifluoro vinyl transfer reagent 1b with the structural formula ofThe product obtained was a pale yellow solid with 66% yield, 1 H NMR spectrum of the product was shown in fig. 5, 19 F NMR spectrum was shown in fig. 6, 13 C NMR spectrum was shown in fig. 7.
1H NMR(400MHz,CDCl3)δ8.37(d,J＝8.3Hz,1H),8.13(s,1H),7.70(d,J＝8.1Hz,1H);13C NMR(101MHz,CDCl3)δ155.44(ddd,J＝313.3,288.5,31.3Hz),140.25,137.23(q,J＝34.2Hz),131.07(d,J＝3.2Hz),128.38,127.54(d,J＝3.1Hz),124.57,122.12(q,J＝274.9Hz),119.62(q,J＝318.4Hz),104.52(ddd,J＝324.0,63.9,27.4Hz);19F NMR(376MHz,CDCl3)δ-63.47,-78.43,-80.07(dd,J＝59.1,28.8Hz),-98.54(dd,J＝125.8,28.8Hz),-157.60(dd,J＝125.8,59.5Hz).
Example 3
Synthesis of 1, 2-trifluorovinyl benzoate:
Benzoic acid (0.22 mmol,26.8 mg) and ultra-dry acetonitrile (2 mL) were sequentially added to a 25 mL-sealed tube with a stirrer in advance under nitrogen atmosphere, lithium methoxide (0.22 mmol,8.4 mg) was added under stirring at room temperature and kept under nitrogen atmosphere for 2H, then the trifluoro vinyl transfer reagent 1a (0.20 mmol,86.8 mg) prepared in example 1 was added to the reaction system, the stirring reaction was continued at room temperature for 2H, and after the reaction was completed, the column chromatography purification was performed to obtain 1, 2-trifluoro vinyl benzoate, and the obtained product was a colorless oily liquid with a yield of 92%, the 1 H NMR spectrum of the product was shown in FIG. 8, the 19 F NMR spectrum was shown in FIG. 9, and the 13 C NMR spectrum was shown in FIG. 10.
1H NMR(400MHz,CDCl3)δ8.14(dt,J＝8.6,1.4Hz,2H),7.73–7.67(m,1H),7.56–7.50(m,2H);13C NMR(101MHz,CDCl3)δ162.08–161.91(m),147.62(ddd,J＝280.2,274.0,55.7Hz),135.18,130.96,130.49(ddd,J＝263.5,50.6,42.9Hz),129.08,126.54;19F NMR(376MHz,CDCl3)δ-117.59(dd,J＝95.3,60.6Hz),-124.79(dd,J＝110.6,95.5Hz),-134.42(dd,J＝110.6,60.7Hz).
Example 4
Synthesis of 1, 2-trifluoroethyl-2-naphthyl sulfide:
2-Naphthol (0.22 mmol,35.2 mg), ultra-dry acetonitrile/tetrahydrofuran (2 mL, v/v=1/1) were sequentially added to a 25 mL-tube sealer with a stirrer placed therein in advance and cooled to 0℃under nitrogen atmosphere, a2, 6-tetramethylpiperidyl magnesium chloride lithium complex (0.22mmol,1.0M in THF,220. Mu.L) was added thereto under stirring and kept under nitrogen atmosphere at 0℃for 2 hours, then the trifluorovinyl transfer reagent 1a (0.20 mmol,86.8 mg) prepared in example 1 was added to the reaction system, the reaction was continued to be stirred at 0℃for 1 hour, and after the completion of the reaction, column chromatography purification gave 1, 2-trifluorovinyl-2-naphthalene sulfide as a colorless oily liquid in 86% yield, and 1 H NMR spectra of the product were shown in FIG. 11, 19 F NMR spectra were shown in FIG. 12, 13 C NMR spectra were shown in FIG. 13.
1H NMR(400MHz,CDCl3)δ8.05(d,J＝1.7Hz,1H),7.90(dd,J＝6.0,3.5Hz,1H),7.86(dd,J＝9.2,4.2Hz,2H),7.66–7.60(m,3H);13C NMR(101MHz,CDCl3)δ156.24(ddd,J＝302.4,280.4,53.7Hz),133.70,132.77,129.44,129.01,128.62(q,J＝3.7Hz),127.83,127.55,126.98,126.77,126.56,124.50(ddd,J＝279.7,50.0,24.3Hz);19F NMR(376MHz,CDCl3)δ-87.48(dd,J＝43.3,34.7Hz),-105.47–-106.12(m),-148.46(dd,J＝123.5,34.7Hz).
Example 5
Synthesis of N-1, 2-trifluoroethyl-phthalimide:
Methyl 2-cyanobenzoate (0.20 mmol,33.6 mg), copper oxide (0.04 mmol,3.2 mg) and the trifluoro vinyl transfer reagent 1b (0.20 mmol,116.0 mg) prepared in the method in example 2 were sequentially added to a 25mL sealed tube with a stirrer in advance, and the mixture was placed at 80 ℃ for stirring reaction for 2 hours under nitrogen atmosphere, after the reaction was completed, the N-1, 2-trifluoro vinyl-phthalimide was obtained after column chromatography purification, the obtained product was a white solid with the yield of 44%, the 1 H NMR spectrum of the product was shown in FIG. 14, the 19 F NMR spectrum was shown in FIG. 15, and the 13 C NMR spectrum was shown in FIG. 16.
1H NMR(400MHz,CDCl3)δ7.96(dt,J＝6.9,3.5Hz,1H),7.85(dq,J＝6.7,3.8Hz,1H);13C NMR(101MHz,CDCl3)δ164.52,152.39(ddd,J＝290.7,280.3,56.3Hz),135.50,131.33,124.76,115.77(ddd,J＝249.4,50.9,37.7Hz);19F NMR(376MHz,CDCl3)δ-99.29(dd,J＝61.0,49.4Hz),-113.85(dd,J＝114.3,61.9Hz),-147.14(dd,J＝114.8,47.7Hz).
Example 6
Synthesis of N-1, 2-trifluoroethyl-phthalimide:
Methyl 2-cyanobenzoate (0.20 mmol,33.6 mg), copper oxide (0.04 mmol,3.2 mg) and the trifluoroethyl transfer reagent 1a (0.20 mmol,116.0 mg) prepared in example 1 were sequentially added to a 25 mL-sealed tube with a stirrer in advance and placed at 80℃for stirring reaction for 2 hours under nitrogen atmosphere, and after completion of the reaction, the N-1, 2-trifluoroethyl-phthalimide was obtained by column chromatography purification as a white solid in 8% yield, and 1H NMR、19 F NMR and 13 C NMR spectra of the product were the same as those of example 5.
According to examples 3 to 6, the trifluoroethylene group transfer reagent provided by the application can react with different nucleophiles under milder conditions to transfer the trifluoroethylene group to the nucleophile, so as to obtain the corresponding trifluoroethylene group compound monomer.
Further, as is clear from examples 5 and 6, when the same trifluoroethylene compound monomer was produced, the yield of the product obtained by using the trifluoroethylene transfer reagent 1b obtained in example 2 was higher, which revealed that the introduction of a group having a large steric hindrance at the ortho position of trivalent iodine on the benzene ring in the trifluoroethylene transfer reagent was effective for improving the selectivity of the trifluoroethylene transfer and the yield of the trifluoroethylene compound monomer.
Finally, it should be noted that: the above embodiments are only for illustrating the technical solution of the present application, and not for limiting the same; although the application has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some or all of the technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit of the application.
Claims (10)
1. A trifluoro vinyl transfer reagent is characterized in that the trifluoro vinyl transfer reagent has a structural formula as shown in a formula 1,
Wherein R 1、R2、R3、R4、R5 is independently selected from at least one of H, halogen and halogen substituted C1-C3 alkyl.
2. The trifluorovinyltransfer reagent according to claim 1, wherein R 1、R5 is independently selected from at least one of Br and halogen substituted C1-C3 alkyl.
3. The trifluoroethylene transfer reagent according to claim 1, wherein the trifluoroethylene transfer reagent has a structural formula of
4. A process for preparing a trifluoroethylene transfer reagent comprising the steps of:
S10: under the nitrogen atmosphere, cyano (aryl) -lambda 3 -iodo trifluoro methanesulfonate and trifluoro vinyl tributyltin react in an organic solvent at the temperature of minus 30 ℃ to minus 10 ℃ to 0 ℃ until the reaction liquid is clear liquid, so as to obtain a reaction mixture; wherein the structural formula of the cyano (aryl) -lambda 3 -iodo trifluoro methanesulfonate is shown in a formula 2,
R 1、R2、R3、R4、R5 is independently selected from at least one of H, halogen and halogen substituted C1-C3 alkyl;
s20: removing the organic solvent from the reaction mixture by freeze drying to obtain a crude product;
S30: dispersing the crude product by diethyl ether at the temperature of-10 to 0 ℃, and then precipitating and washing the crude product by using diethyl ether/low boiling point liquid alkane mixed solution to obtain the trifluoro vinyl transfer reagent.
5. The method of claim 4, wherein R 1、R5 is independently selected from at least one of Br, halogen substituted C1-C3 alkyl;
Preferably, the cyano (aryl) -lambda 3 -iodo trifluoro methanesulfonate has the structural formula
6. The method according to claim 4, wherein in the step S10:
The concentration of the cyano (aryl) -lambda 3 -iodo trifluoro methanesulfonate in the reaction liquid is 0.1-0.7 mol/L.
7. The method according to claim 4 or 5, wherein in step S10:
The molar ratio of the cyano (aryl) -lambda 3 -iodo trifluoro-methanesulfonate to trifluoro-vinyl tributyltin is 1:1-1.3.
8. The method according to claim 4, wherein the step S10 specifically includes:
S11: dispersing cyano (aryl) -lambda 3 -iodotrifluoromethanesulfonate in an organic solvent under nitrogen atmosphere to obtain cyano (aryl) -lambda 3 -iodotrifluoromethanesulfonate solution;
s12: dropwise adding trifluoro vinyl tributyltin into the cyano (aryl) -lambda 3 -iodo trifluoro methanesulfonate solution in nitrogen atmosphere at the temperature below minus 30 ℃, and then heating to the temperature of minus 10-0 ℃ to react until the reaction liquid is clear liquid, thus obtaining the reaction mixture.
9. A process for preparing a trifluoroethylene compound monomer, comprising the steps of:
a trifluoroethylene compound monomer obtained by reacting a trifluoroethylene group transfer reagent according to claims 1 to 3 or a trifluoroethylene group transfer reagent produced by the method according to any one of claims 4 to 8 with a nucleophilic reagent.
10. The method of claim 9, wherein the nucleophile comprises at least one of a carboxylic acid, a carboxylic acid ester, an amide, and a sulfhydryl compound.
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