CN105017320B - The method preparing the double salt of two fluoro ethyl salt/1,2 vinyls under condition of no solvent - Google Patents

The method preparing the double salt of two fluoro ethyl salt/1,2 vinyls under condition of no solvent Download PDF

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CN105017320B
CN105017320B CN201510381754.0A CN201510381754A CN105017320B CN 105017320 B CN105017320 B CN 105017320B CN 201510381754 A CN201510381754 A CN 201510381754A CN 105017320 B CN105017320 B CN 105017320B
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phenyl
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xenyl
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fluoro ethyl
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张成潘
汪诗梦
董涛
韩家斌
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Wuhan University of Technology WUT
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Abstract

The present invention relates to preparing two fluoro ethyl salt/1 under a kind of condition of no solvent, the simple and easy method of the double salt of 2 vinyls, under condition of no solvent, by organophosphors and difluoro ethylating agent or the mixing of vinylated reagent, stirring reaction 0.5～36h at 20～150 DEG C, after the completion of question response, washs solid, filter, gained solid oil pump is drying to obtain product.The method has good substrate applicability, simple to operate, the easy purification of product, advantages of environment protection.By the structure adjusting reaction temperature and change organic phosphine, the preparation of two fluoro ethyl salt in same system, can also be realized, two fluoro ethyl salt are a class potentially fluorine-containing strippings and slicings, are expected to be used for the synthesis of multiple fluorochemicals.

Description

The method preparing the double salt of two fluoro ethyl salt/1,2- vinyl under condition of no solvent
Technical field
The invention belongs to organic synthesiss, medicine, pesticide and field of functional materials are and in particular under a kind of condition of no solvent Prepare the simple and easy method of the double salt of two fluoro ethyl salt/1,2- vinyl.
Background technology
Quaternary salt has been obtained for being widely applied in chemistry, the field such as biology, material.Quaternary salt can be used as phase transfer and urges Agent and the multiple chemical reaction of Lewis acid catalyst.Quaternary salt with active α-H can be used as phosphorus ylide precursor, In the presence of alkali, aldehyde, ketone can be changed into by corresponding alkene by Wittig reaction.Additionally, the larger aryl quaternary salt of volume There is good chemical stability, fat-soluble and crystallinity, when their aniones special with structure form new ion salt, its Originally the stability of anion, dissolubility and crystallinity can be greatly improved.The ionic liquid being made up of quaternary salt, also Can serve as solvent and the material that can be recycled, meet the requirement of Green Chemistry.At present, in order to meet from industry-by-industry Application demand, the novel salt of a large amount of structures is by synthetic.
Two cationes are connected by the double salt of trans 1,2- vinyl by a vinyl, and at two cationes Antiposition in double bond.The double salt of 1,2- vinyl is easy to hydrolysis and alcoholysis in the basic conditions；1,2- vinyl is double Cation in salt can also be by tert-butyl group anion nucleophilic displacement of fluorine；And with I-And Ph4B-1,2- vinyl for anion Double (triphenyl) salt can serve as the additive of fire proofing material.These interesting phenomenons imply the double salt of 1,2- vinyl also There are much potential, abundant property value must excavate.There is several methods that synthesis of trans 1 at present, the double salt of 2- vinyl, but It is because their the substrate scope of application is narrower, need using the reagent to air or water sensitive, raw materials used synthesis is time-consuming (such as：[IC≡CI][OTf]2(E)-R1R2PCH=CHPR1R2), therefore significantly limit their application.
Content of the invention
It is an object of the invention to provide it is double to prepare two fluoro ethyl salt/trans 1,2- vinyl under a kind of condition of no solvent The simple and easy method of salt, the method wide application range of substrates, agents useful for same is insensitive to air and water, and raw material sources are simple, operation Simplicity, yield is higher, and does not have solvent to participate in, environmental friendliness.
The present invention solves the scheme that adopted of above-mentioned technical problem：Two fluoro ethyl salt/1 are prepared under condition of no solvent, The method of the double salt of 2- vinyl it is characterised in that：Under condition of no solvent, by organophosphors and difluoro ethylating agent or ethylene Base reagent mixes, and wherein organophosphors and the mol ratio of difluoro ethylating agent or vinylated reagent are 1:0.2～5, in -20 Stirring reaction 0.5～36h at～150 DEG C, after the completion of question response, washs solid, filters, gained solid oil pump is drying to obtain product Product.
By such scheme, the formula of two described fluoro ethyl salt is：
Wherein, R1、R2、R3And R4、R5、R6For identical or different group, selected from phenyl, p-methylphenyl, a tolyl, neighbour Tolyl, p-methoxyphenyl, m-methoxyphenyl, guaiacyl, rubigan, a chlorphenyl, Chloro-O-Phenyl, to fluorophenyl, Between fluorophenyl, adjacent fluorophenyl, p-trifluoromethyl phenyl, m-trifluoromethylphenyl, o-trifluoromethyl phenyl, 4- xenyl, 3- joins Phenyl, 2- xenyl, cyclohexyl, methyl, any one in ethyl, propyl group, butyl and the tert-butyl group, wherein X are RfnSO3、 RSO3、ArSO3、RfnCO2、RCO2、ArCO2, Cl, Br or I；RfnFluoroalkyl for 1～8 carbon or perfluoroalkyl, R is 1～4 The alkyl of carbon, Ar is phenyl, p-methylphenyl, p-nitrophenyl and five fluorine, tetrafluoro, trifluoro, in difluoro or single fluorine substituted-phenyl Any one.
By such scheme, the formula of the double salt of described 1,2- vinyl is：
Wherein, R1、R2、R3、R4、R5、R6For identical or different group, selected from phenyl, p-methylphenyl, a tolyl, right Anisyl, m-methoxyphenyl, rubigan, a chlorphenyl, to fluorophenyl, a fluorophenyl, p-trifluoromethyl phenyl, a trifluoro Aminomethyl phenyl, 4- xenyl, 3- xenyl, 2- xenyl, cyclohexyl, methyl, arbitrary in ethyl, propyl group, butyl and the tert-butyl group Kind, wherein X is RfnSO3、RSO3、ArSO3、RfnCO2、RCO2、ArCO2, Cl, Br or I；RfnFluoroalkyl or complete for 1～8 carbon Fluoroalkyl, R is the alkyl of 1～4 carbon, and Ar is phenyl, p-methylphenyl, p-nitrophenyl and five fluorine, tetrafluoro, trifluoro, difluoro Or any one in list fluorine substituted-phenyl.
By such scheme, the general structure of described organophosphors is：
Wherein, R1、R2、R3And R4、R5、R6For identical or different group, selected from phenyl, p-methylphenyl, a tolyl, neighbour Tolyl, p-methoxyphenyl, m-methoxyphenyl, guaiacyl, rubigan, a chlorphenyl, Chloro-O-Phenyl, to fluorophenyl, Between fluorophenyl, adjacent fluorophenyl, p-trifluoromethyl phenyl, m-trifluoromethylphenyl, o-trifluoromethyl phenyl, 4- xenyl, 3- joins Phenyl, 2- xenyl, cyclohexyl, methyl, in ethyl, propyl group, butyl and the tert-butyl group any one.
By such scheme, the general structure of described difluoro ethylating agent or vinylated reagent is
Wherein X is RfnSO3、RSO3、ArSO3、RfnCO2、RCO2、ArCO2, Cl, Br or I；RfnFluoroalkyl for 1～8 carbon Or perfluoroalkyl, R is the alkyl of 1～4 carbon, Ar is phenyl, p-methylphenyl, p-nitrophenyl and five fluorine, tetrafluoro, trifluoro, Any one in difluoro or single fluorine substituted-phenyl.
Preparation method of the present invention, can be respectively obtained by the structure adjusting reaction temperature and change organic phosphine Two fluoro ethyl salt and the double salt of 1,2- vinyl.
When using relatively low reaction temperature, all of organic phosphine is completely converted into two fluoro ethyl salt；Raise reaction temperature Degree, two fluoro ethyl salt can continue to be transformed into the double salt of 1,2- vinyl.For triaryl phosphine, replace when ortho position is had on phenyl ring During base, even if at high temperature, reaction also stays at two fluoro ethyl salt phases, and (triaryl phosphine refers to one of organic phosphine class Type).
The present invention prepares two fluoro ethyl salt and the double reaction used by salt of 1,2- vinyl, it is recommended to use following equation Represent：
R1、R2、R3, R4、R5、R6And X, with above-mentioned definition.
Two fluoro ethyl salt of present invention synthesis, its typical structure is：
The double salt of 1,2- vinyl of present invention synthesis, its typical structure is：
The present invention utilizes the gentle, XCH to air-stable2CF2H reagent and organic phosphine reaction, under condition of no solvent, Prepare the double salt of trans 1,2- vinyl.Compared with other synthetic methods, the method has good substrate applicability, simple to operate, The easy purification of product, advantages of environment protection.By the structure adjusting reaction temperature and change organic phosphine, in same system In, the preparation of two fluoro ethyl salt can also be realized, two fluoro ethyl salt are a class potentially fluorine-containing strippings and slicings, are expected to be used for multiple The synthesis of fluorochemical.
Specific embodiment
Will be helpful to understand the present invention by following embodiments, but be not intended to limit present disclosure.
Embodiment 1：(counterparty's formula 1)
By TfOCH2CF2H (0.514g, 2.4mmol) is mixed with triphenylphosphine (0.525g, 2mmol), anti-in 120 DEG C of stirrings Answer 24h, after question response system is cooled to room temperature, gained solid ether, toluene, normal hexane or petroleum ether, filter, then use Oil pump is drained, and obtains final product product (E)-[Ph3PCH=CHPPh3][OTf]2(white solid, 0.66g, 0.78mmol), yield： 78%.1H NMR(CD3COCD3):δ 8.71 (t, J=20.7Hz, 2H), 8.04 (t, J=7.2Hz, 6H), 7.95 (m, 12H), 7.88(m,12H).19F NMR(CD3COCD3):δ-78.8(s,6F).31P NMR(CD3COCD3):δ20.8(s).
Embodiment 2：(counterparty's formula 1)
By TfOCH2CF2H (0.514g, 2.4mmol) is mixed with tricyclohexyl phosphine (1.346g, 4.8mmol), stirs in 120 DEG C Mix reaction 8h, after question response system is cooled to room temperature, gained solid ether, toluene, normal hexane or petroleum ether, filter, Drained with oil pump again, obtain final product product (E)-[(C6H11)3PCH=CHP (C6H11)3][OTf]2(white solid, 1.335g, 1.51mmol), yield：63%.1H NMR:δ 8.03 (t, J=18.1Hz, 2H), 3.08 (m, 6H), 2.02-1.84 (m, 30H), 1.64-1.53(m,24H),1.26(m,6H).19F NMR:δ-78.3(s,6F).31P NMR:δ33.0(s).
Embodiment 3：(counterparty's formula 2)
By TfOCH2CF2H (0.257g, 1.2mmol) is mixed with tricyclohexyl phosphine (0.337g, 1.2mmol), at room temperature Stirring reaction 12h, then gained solid ether, toluene, normal hexane or petroleum ether, filters, then is drained with oil pump, obtain final product Product [(C6H11)3PCH2CF2H] [OTf] (white solid, 0.325g, 0.66mmol) yield：55%.1H NMR:δ6.48 (tdt, J=55.4Hz, J=13.9Hz, J=3.3Hz, 1H), 3.20 (m, 2H), 2.53 (q, J=12.4Hz, 3H), 2.01- 1.95(m,12H),1.86-1.81(m,3H),1.61-1.54(m,6H),1.46-1.38(m,6H),1.36-1.28(m,3H) .19F NMR:δ -78.4 (s, 3F), -107.5 (dm, J=55.6Hz, 2F).31P NMR:δ32.9(s).
Embodiment 4：(counterparty's formula 1)
By TfOCH2CF2H (0.257g, 1.2mmol) is mixed with three (p-methylphenyl) phosphine (0.365g, 1.2mmol), in 120 Stirring reaction 6h at DEG C, then gained solid ether, toluene, normal hexane or petroleum ether, filter, then drained with oil pump, Obtain final product product (E)-[(4-CH3C6H4)3PCH=CHP (4-CH3C6H4)3][OTf]2(white solid, 0.390g, 0.42mmol) produces Rate：70%.1H NMR:δ 8.04 (t, J=20.7Hz, 2H), 7.59-7.53 (m, 24H), 2.51 (s, 18H).19F NMR:δ- 78.4(s,6F).31P NMR:δ20.9(s).
Embodiment 5：(counterparty's formula 1)
By TfOCH2CF2H (0.257g, 1.2mmol) and three (tolyl) phosphine (0.365g, 1.2mmol) mixes, in 120 Stirring reaction 6h at DEG C, then gained solid ether, toluene, normal hexane or petroleum ether, filter, then drained with oil pump, Obtain final product product (E)-[(3-CH3C6H4)3PCH=CHP (3-CH3C6H4)3][OTf]2(white solid, 0.447g, 0.48mmol) produces Rate：80%.1H NMR:δ 8.23 (t, J=20.7Hz, 2H), 7.66-7.60 (m, 12H), 7.53-7.47 (m, 12H), 2.45 (s,18H).19F NMR:δ-78.6(s,6F).31P NMR:δ20.5(s).
Embodiment 6：(counterparty's formula 2)
By TfOCH2CF2H (0.257g, 1.2mmol) is mixed with three (o-tolyl) phosphine (0.365g, 1.2mmol), in 120 Stirring reaction 6h at DEG C, then gained solid ether, toluene, normal hexane or petroleum ether, filter, then drained with oil pump, Obtain final product product [(2-CH3C6H4)3PCH2CF2H] [OTf] (white solid, 0.306g, 0.59mmol) yield：49%.1H NMR:δ 7.75-7.68 (m, 6H), 7.55-7.48 (m, 6H), 6.41 (tdt, J=55.0Hz, J=14.6Hz, J=2.9Hz, 1H), 4.34 (q, J=14.1Hz, 2H), 2.24 (s, 9H).19F NMR:δ -78.4 (s, 3F), -109.5 (dm, J=55.0Hz, 2F) .31P NMR:δ19.2(s).
Embodiment 7：(counterparty's formula 1)
By ICH2CF2H (0.192g, 1.0mmol) is mixed with triphenylphosphine (0.262g, 1.0mmol), stirs at 120 DEG C Reaction 24h, then gained solid ether, toluene, normal hexane or petroleum ether, filters, then is drained with oil pump, obtain final product product (E)-[Ph3PCH=CHPPh3]I2(yellow solid, 0.349g, 0.43mmol) yield：87%.1H NMR:δ 8.71 (t, J= 21.1Hz, 2H), 8.04 (t, J=7.2Hz, 6H), 7.95 (m, 12H), 7.88 (m, 12H).31P NMR(CD3COCD3):δ20.8 (s).
Embodiment 8：(counterparty's formula 1)
By TsOCH2CF2H (0.236g, 1.0mmol) is mixed with triphenylphosphine (0.262g, 1.0mmol), stirs at 120 DEG C Mix reaction 24h, then gained solid ether, toluene, normal hexane or petroleum ether, filter, then drained with oil pump, obtain final product product Product (E)-[Ph3PCH=CHPPh3][OTs]2(light yellow solid, 0.221g, 0.25mmol) yield：50%.1H NMR:δ8.49 (t, J=21.1Hz, 2H), 7.82-7.76 (m, 12H), 7.74-7.65 (m, 12H), 7.55-7.52 (m, 6H), 7.50-7.46 (m,8H),2.17(s,6H).
Embodiment 9：(counterparty's formula 1)
By CF3COOCH2CF2H (0.356g, 2.0mmol) is mixed with triphenylphosphine (0.525g, 2.0mmol), in 120 DEG C Lower stirring reaction 24h, then gained solid ether, toluene, normal hexane or petroleum ether, filters, then is drained with oil pump, that is, Obtain product (E)-[Ph3PCH=CHPPh3][OCOCF3]2(light yellow solid, 0.038g, 0.05mmol) yield：5%.1H NMR: δ 8.46 (t, J=21.1Hz, 2H), 7.81 (t, J=7.3Hz, 6H), 7.75-7.71 (m, 12H), 7.69-7.66 (m, 12H).19F NMR:δ-75.6(s,6F).
Embodiment 10：(counterparty's formula 2)
By TfOCH2CF2H (0.107g, 0.5mmol) is mixed with tri-n-butyl phosphine (0.101g, 0.5mmol), at room temperature Stirring reaction 6h, then gained liquid ether, toluene, normal hexane or petroleum ether, filters, then is drained with oil pump, obtain final product Product [(t-Bu)3PCH2CF2H] [OTf] (colourless liquid, 0.162g, 0.39mmol) yield：78%.1H NMR(CDCl3):δ 6.39 (tdt, J=55.2Hz, J=13.7Hz, J=3.3Hz, 1H), 3.30-3.11 (m, 2H), 2.45-2.22 (m, 6H), 1.73-1.37 (m, 12H), 0.98 (dt, J=12.6Hz, J=7.0Hz, 9H).19F NMR(CDCl3):δ-78.4(s,3F),- 107.5 (dm, J=55.6Hz, 2F).
Embodiment 11：(counterparty's formula 3)
By [Ph3PCH2CF2H] [OTf] (0.238g, 0.5mmol) and three (p-methylphenyl) phosphine (0.152g, 0.5mmol) mix Close, stirring reaction 6h at 120 DEG C, then gained solid ether, toluene, normal hexane or petroleum ether, filter, then with oily Pumping is done, and obtains final product product (E)-[(4-CH3C6H4)3PCH=CHPPh3] [OTf] [F] (light yellow solid, 0.104g, 0.12mmol) yield：48%.1H NMR:δ 8.00 (t, J=21.0Hz, 2H), 7.74-7.70 (m, 12H), 7.60-7.54 (m, 15H),2.50(s,9H).19F NMR:δ-78.6(s,3F),-137.3(s,1F).
Embodiment 12：(counterparty's formula 3)
By [Ph3PCH2CF2H] [OTf] (0.238g, 0.5mmol) and three (p-methoxyphenyl) phosphine (0.176g, 0.5mmol) Mixing, stirring reaction 6h at 120 DEG C, then gained solid ether, toluene, normal hexane or petroleum ether, filters, then uses Oil pump is drained, and obtains final product product (E)-[(4-CH3OC6H4)3PCH=CHPPh3] [OTf] [F] (light yellow solid, 0.161g, 0.17mmol) yield：68%.1H NMR:δ 8.00 (t, J=21.3Hz, 2H), 7.90-7.79 (m, 6H), 7.77-7.66 (m, 12H),7.61-7.56(m,9H),3.96(s,9H).19F NMR:δ-75.6(s,6F),-137.3(s,1F).

Claims (2)

1. under condition of no solvent the double salt of preparation 1,2- vinyl method it is characterised in that：Under condition of no solvent, will be organic Phosphorus and the mixing of vinylated reagent, wherein organophosphors are 1 with the mol ratio of vinylated reagent:0.2～5, in -20～150 DEG C Lower stirring reaction 0.5～36h, after the completion of question response, washs solid, filters, gained solid oil pump is drying to obtain product；Described The general structure of vinylated reagent be
Wherein X is RfnSO3、RSO3、ArSO3、RfnCO2、RCO2、ArCO2, Cl, Br or I；RfnFor the fluoroalkyl of 1～8 carbon, R is The alkyl of 1～4 carbon, Ar is phenyl, p-methylphenyl, p-nitrophenyl and five fluorine, tetrafluoro, trifluoro, difluoro or single fluorine replace Any one in phenyl；
The formula of the double salt of described 1,2- vinyl is：
Wherein, R1、R2、R3、R4、R5、R6For identical or different group, selected from phenyl, p-methylphenyl, a tolyl, to methoxy Phenyl, m-methoxyphenyl, rubigan, a chlorphenyl, to fluorophenyl, a fluorophenyl, p-trifluoromethyl phenyl, m-trifluoromethyl Phenyl, 4- xenyl, 3- xenyl, 2- xenyl, cyclohexyl, methyl, in ethyl, propyl group, butyl and the tert-butyl group any one, its Middle X is RfnSO3、RSO3、ArSO3、RfnCO2、RCO2、ArCO2, Cl, Br or I；RfnFor the fluoroalkyl of 1～8 carbon, R is 1～4 The alkyl of carbon, Ar is phenyl, p-methylphenyl, p-nitrophenyl and five fluorine, tetrafluoro, trifluoro, in difluoro or single fluorine substituted-phenyl Any one.
2. method according to claim 1 is it is characterised in that the general structure of described organophosphors is：
Wherein, R1、R2、R3And R4、R5、R6For identical or different group, selected from phenyl, p-methylphenyl, a tolyl, to methoxy Phenyl, m-methoxyphenyl, rubigan, a chlorphenyl, to fluorophenyl, a fluorophenyl, p-trifluoromethyl phenyl, m-trifluoromethyl Phenyl, 4- xenyl, 3- xenyl, 2- xenyl, cyclohexyl, methyl, in ethyl, propyl group, butyl and the tert-butyl group any one.
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