CN104803826B - A kind of method utilizing hexafluoropropene that aryl boric acid directly aoxidizes seven fluorine isopropylations - Google Patents

Abstract

The present invention relates to a kind of method utilizing hexafluoropropene that aryl boric acid directly aoxidizes seven fluorine isopropylations.The method includes with Argentous fluoride for fluorine source, under the effect of mantoquita, in room temperature and organic solvent, it is possible to hexafluoropropene and aryl boric acid are converted into a series of compound containing seven fluorine isopropyls, and this reaction is also applied for ene boric acid.The method of the present invention has optionally synthesized a series of compound containing seven fluorine isopropyls by single step reaction height.

Description

A kind of method utilizing hexafluoropropene that aryl boric acid directly aoxidizes seven fluorine isopropylations

Technical field

The present invention relates to a kind of method utilizing hexafluoropropene that aryl boric acid directly aoxidizes seven fluorine isopropylations.

Background technology

The substituted aromatic compound of perfluoroalkyl in the field such as medicine, pesticide and material in occupation of very important effect [Müller K,Faeh C,Diederich F.Fluorine in Pharmaceuticals:Looking Beyond Intuition.Science,2007,317:1881-1886；Bnaks R E.Organofluorine Chemicals and their industrial applications.New York:Halsted,1979,97-120.].This is due to perfluoroalkyl There is the characteristic that other substituent group a lot of is incomparable, such as low polarity, low surface tension, high electronegativity, highly lipophilic and height Biological stability etc.^[[minister in ancient times's phoenix tail feather, Qiu little Long, organic fluorine chemistry, Science Press, 2007 .].And, along with perfluoroalkyl The growth of chain, some of which character shows the most obvious.At present, the perfluoroalkyl being most widely used is trifluoromethyl (Hammett (Hammett) constant σ_RIt is 0.16), and seven fluorine isopropyls have higher electrophilic conjugation, and (Hammett is normal Number σ_RIt is 0.22) [Sheppard W A, The Electronic Properties of Fluoroalkyl Groups.Fluorine p-πInteraction.J.Am.Chem.Soc.,1965,87:2410–2420.](Table 1)。

Table 1. trifluoromethyl and the Hammett constant of seven fluorine isopropyls

σ m represents meta-substituent parameter；σ p represents para-orientation parameter；σ_IInductive effect parameter；σ_RRepresent conjugation Parameter

Seven fluorine isopropyls, as a member of perfluoroalkyl extended family, have been applied at numerous areas, as pesticide, material and [Onishi M, Ikeda K, the Shimaoka T et al.Perfluoroisopropylbenzene such as Catalyst Design Derivative.US 2005113567A1.].Wherein, it is most widely used in the designing and developing of pesticide.Such as, fluorine worm is double Amide (flubendiamide), has another name called Flubendiamide, and trade name ridge is sung, and is that Nihon Nihyaku Co., Ltd was in research and development in 1998 A kind of insecticide [Masanori T, Hayami N, Takashi F, et containing seven fluorine isopropyls al.Flubendiamide,a novel insecticide highly active against lepidopterous insect pests.J.Pestic.Sci.,2005,30:354–360.](Scheme 1).This insecticide and the fish of insect cell Buddhist nun's fourth (Ryanodine) receptor acting, activates ryanodine receptor intracellular calcium release channel, causes the mistake of storage calcium ion The release of control property, in causing insecticide muscular tissue, calcium ion concentration rises, and calcium ion is combined with troponin immediately, and induction muscle is fine Dimension is shunk, and insecticide stops feed until dead.Owing to fipronil bisamide selectively acting is in ryanodine receptor, therefore it is a kind of To the lowest broad spectrum insecticide of mammalian toxicity [Liu Changling. New-type wide-spectrum, the ryanodine receptor insecticide of safety, pesticide, 2005,44:527.]。

The excellent specific property showed due to fipronil bisamide, attracted to include E.I.Du Pont Company, Syngenta Co., Ltd and its The concern of his scientific research institutions.By the modification to phthalic diamides compound, a large amount of similar compounds are designed to synthesize Come that [Chen Zhengwang, the synthesis of Novel ortho diamide compound and insecticidal activity research thereof, Hunan Normal University, master graduates opinion Literary composition, 2011.].Wherein Japan pesticide company developed in 2004 a kind of entitled Pyrifluquinazon (new quinazoline ( Diazine) insecticides) insecticide [Kimura M, Morimoto M, Uehara M, et al.Substituted aminoquinazolinone(thione)derivatives or salts thereof,intermediates thereof, and pest controllers and a method for using the same.EP 1097932A1.]；First just reaching public affairs Department have found the most in an experiment a kind of has the similar bisamide of insecticidal effect as experiment insecticide (experimental insecticide)[Pierre J,Patricia D,William L,et al.insecticidal compounds.WO 2007128410A1.](Scheme 2)。

Nematic temperature can be extended to a great extent owing to introducing fluorine atom on the aromatic rings of liquid crystal mother nucleus structure Degree scope, reduces the fusing point of material and improves their dissolubility, therefore, fluorochemical as liquid crystal material application even LCD (liquid crystal display) Age of Technology can be traced back to.Seven fluorine isopropyls also can be applied to liquid crystal owing to having above feature Exploitation [Kazuo O, Compound having fluoroisopropyl group side chain, the and of material liquid crystal composition containing the same.Jpn.Kokai Tokkyo Koho,JP 2007308483,2007.] (formula Scheme 3).

Introducing fluorine atom or fluoro-containing group such as trifluoromethyl etc. in catalyst molecule can be with modified catalyst molecule Activity and selectivity, this is because by modifying the electronics distribution that can change catalyst molecule and steric effect etc..Seven Fluorine isopropyl substituents can also apply to the modification to catalyst molecule.2012, List et al. [Guin J, Rabalakos C,List B,Highly Enantioselective Hetero-Diels–Alder Reaction of 1,3-Bis- (silyloxy)-1,3-dienes with Aldehydes Catalyzed by Chiral Disulfonimide.Angew.Chem.Int.Ed.2012,51:8859–8863.].Carrying out the most right of diene substrate and aldehyde When claiming oxa-Diels-Alder (diels-alder) reaction, find that trifluoromethyl modifies with the even naphthalene N as mother nucleus structure, The catalyst efficiency that the catalytic efficiency of N-disulfonyl amine chiral catalyst does not has seven fluorine isopropyls to modify is high (Scheme 4).With As a example by substrate 2-naphthaldehyde, under the same terms, it is 77% that the chiral catalyst that trifluoromethyl is modified obtains the productivity of product, and er is (right Reflect body ratio) value is 87:13, and the products collection efficiency that the chiral catalyst that seven fluorine isopropyls are modified obtains is 83%, er value is up to 96:4.By comparing discovery, the activity of chiral catalyst and the enantioselectivity of product that seven fluorine isopropyls are modified are superior to three The chiral catalyst that methyl fluoride is modified.This is because compared to trifluoromethyl, seven fluorine isopropyls have bigger steric hindrance, different The character such as electrically, when regulating and controlling activity and the selectivity of catalyst, has more excellent performance.

TMS represents trimethyl silicane；Me represents methyl；Cat. catalyst is represented；Et₂O represents ether；Then then represents； TFA represents trifluoroacetic acid；Mol represents mole；R_fRepresent fluoro-containing group；Yield represents productivity

Although seven fluorine isopropyl substituents apply wide model, but introduce the method phase of seven fluorine isopropyls in substrate molecule To limited.Applying seven most fluorine isopropylating agents at present is seven fluorine isopropyl iodides [Xu Yuwei, Xu Weiguo, seven fluorine isopropyls Iodine application in fluorine-containing organic chemicals synthesizes, Organic fluoride industry, 2005,16-18.].

Insecticide, liquid crystal material and asymmetric catalyst that seven fluorine isopropyls of above-mentioned actual application are modified all pass through Seven fluorine isopropyl iodides introduce.Under normal circumstances, in substrate molecule, introduce seven fluorine isopropyls have following two ways: (a) leads to Cross sulfinatodehalogenation mode introduce [Huang Weiyuan, sulfinatodehalogenation and application thereof, Hebei education publishing house, 2003.] (Scheme 5)；B () introduces [Jwanro H, Marc S, Christel G, et by Ullmann reaction (ullmann reaction) al.Aryl-aryl bond formation one century after the discovery of the Ullmann reaction.Chem.Rev.2002,102:1359-1469.](Scheme 6).Wherein first kind of way application is the most universal, Electron rich aromatic compound such as phenol compound, aromatic amine compounds, carbon-carbon double bond, triple carbon-carbon bonds etc. try at sulfinatodehalogenation Agent, such as NaHCO₃-Na₂S₂O₄Effect under, pass through free radical proceed, it is achieved the seven fluorine isopropylations to substrate.And Ullmann reaction is then that iodo or aryl bromide and seven fluorine isopropyl iodides (or seven fluorine isopropyl bromides) are at elemental copper or list Under the effect of matter zinc, obtain seven fluorine isopropylation products.Ullmann reaction is generally carried out under higher reaction temperatures, needs Metal reagent is also equivalent.

Et al represents other

2009, MacMillan group [Nagib D A, Scott M E, MacMillan D W C, Enantioselective r-Trifluoromethylation of Aldehydes via Photoredox Organocatalysis.J.Am.Chem.Soc.2009,131:10875 10877.] develop one with seven fluorine isopropyl iodides The α position to aldehyde for reagent introduces the method (Scheme 7) of seven fluorine isopropyls.At MacMillan catalyst and photocatalyst iridium Under the synergism of metal, by illumination, seven fluorine isopropyls can be obtained with the productivity of 72% and the enantioselectivity of 98% Change product.The method achieve and in substrate molecule, introduce seven fluorine isopropyls with catalyzed version.

Me represents methyl；Catalyst represents catalyst；T-Bu represents the tert-butyl group；Photocatalyst represents photocatalysis Agent；N-hex represents n-hexyl；Household light represents home lighting light source；TFA represents trifluoroacetic acid；Lutidine table Show that lutidines, DMF represent DMF；Ee represents optical purity

Formula 7

It is seven fluorine isopropyl metal reagents (Scheme 8) that Equations of The Second Kind studies seven more fluorine isopropylating agents.Wherein, That be in the news at first is seven fluorine isopropyl lithium [(CF₃)₂CFLi], seven fluorine isopropyl magnesium bromide [(CF₃)₂CFMgBr] and seven fluorine Isopropyl zinc iodide [(CF₃)₂CFZnI dioxane] (dioxane represents dioxane) [Chambers R D, Musgrave W K R,Savory J,Organornetallic and Metalloid Compounds Made from Heptafluoro- 2-iodopropane,and their Properties.J.Chem.Soc.1962,1993-1999.].Under cryogenic, Seven fluorine isopropyl lithium [(CF₃)₂CFLi] and seven fluorine isopropyl magnesium bromide [(CF₃)₂CFMgBr] alkyl lithium reagents can be passed through respectively React with seven fluorine isopropyl iodides with Grignard reagent and obtain.And seven fluorine isopropyl zinc iodide [(CF₃)₂CFZnI dioxane] then may be used To be heated to reflux obtaining in dioxane by seven fluorine isopropyl iodides and zinc powder, owing to the seven fluorine isopropyl zinc iodides obtained are lived Property relatively low, synthesis be worth less.Subsequently, seven fluorine isopropyl hydrargyrum { [(CF₃)₂CF]₂Hg}[Miller W T,Freedman M B, Substitution and Addition Reactions of theV.The Electrophilic Addition of Mercuric Fluoride to Fluoropropenes in Hydrogen Fluoride.J.Am.Chem.Soc.,1963,85:180–183；Aldrich P E,Howard E G,Linn W J,et al.Secondary and TertiaryCompounds.J.Org.Chem.,1963,28:184– 188；Dyatkin B L,Sterlin S R,Martynov B I,et al.Reaction of perfluoroalkyl Carbanions with mercury salts.Tetrahedron, 1971,27:2843 2849.] and seven fluorine isopropyls silver [(CF₃)₂CFAg·CH₃CN](CH₃CN represents acetonitrile) [Miller W T, Burnard R J, Perfluoroalkylsilver compounds.J.Am.Chem.Soc.,1968,90:7367–7368；Dyatkin B L,Martynov B I,Martynova L G,On the enteraction of perfluoroalkyl carbanions with silver Salts.J.Organomet.Chem.1973,57:423-433.], reacted with corresponding metal fluoride by perfluoropropene Arrive.Seven fluorine isopropyl chromium reagent { [(CF₃)₂CF]₂Cd·2CH₃CN} then passes through dimethyl cadmium and seven fluorine isopropyl iodides in acetonitrile Reaction obtains [Lange H, Naumann D, Bis (perfluororgano) cadmium-Verbindungen:Ein einfaches darstellungsverfahren[1].J.Fluorine Chem.1976,26:1-18.].Seven fluorine isopropyls Cupferron is then the seven fluorine isopropyl cadmiums examinations generated with DMF solvent situ by monovalence copper such as CuI, CuCl, CuBr, CuCN etc. Agent metal exchange obtain [Nair H K, Burton D J, Perfluoroisopropylcadmium and copper: preparation,stability and reactivity.J.Fluorine Chem.1992,56:341-351.]。

N-Bu represents normal-butyl；Ph represents phenyl；Et represents ethyl；Pentane represents pentane；Reflux represents backflow

3rd class seven fluorine isopropylating agent is perfluoropropene.Owing to perfluoropropene can occur the fluorine anion pair of uniqueness Reaction together with two fluoroolefins generates seven fluorine isopropyl anion, obtains with reaction such as highly active substrate such as acyl chlorides, aldehyde etc. the most again Corresponding product, there are potassium fluoride (Scheme 9) [Loska R, Ma ü kosza M, Synthesis of in wherein conventional fluorine source Perfluoroalkyl-Substituted Azines via Nucleophilic Substitution of Hydrogen With Perfluoroisopropyl Carbanions.J.Org.Chem.2007,72:1354-1365.], Mercury difluoride., fluorination Silver etc..Additionally, under the effect of four (dimethylamino) ethylene (TDAE) of electron rich [Chambersa R D, Graya W K, Korn S R,Reactions involving fluoride ion.Part 40¹.Amines as initiators of Fluoride ion catalysed reactions.Tetrahedron, 1995,51:283-290.], the fluoro virtue of electron deficiency Cycle compound can react with perfluoropropene and obtain the seven substituted products of fluorine isopropyl (Scheme 10).It is noted that it is complete Fluoropropene is that F-22 (Freon-12 11) Pintsch process prepares the by-product of tetrafluoroethene through difluorocarbene's intermediate Thing, but it is but the raw material of application and preparation widely seven fluorine isopropyl iodide.In addition perfluoropropene propylene can also be used to system Standby multiple fluorine-containing fine chemical product, extinguishing chemical, fluoro-containing macromolecule material etc. (Scheme 11).

PMB represents methoxy-benzyl

Side reaction represents side reaction

Additionally, chemists have been also carried out the trial of other seven fluorine isopropylating agents synthesis.The sixties in last century, seven fluorine Isopropyl silica reagent has been synthesized (Scheme 12).But relevant application report and almost without.

Diglyme represents diethylene glycol dimethyl ether

1986, Umemoto group [Umemoto T, Kuriu Y, Shuyama H, et al.Syntheses and properties of(perfluoroalkyl)phenyliodonium triflates(FITS reagents)and their Analogs.J.Fluorine Chem.1986,31:37-56.] design synthesized the class high price iodine containing seven fluorine isopropyls FITS reagent (Scheme 13).But, this reagent is applied in synthesis and is not the most complied with one's wishes, as with malonic acid esters substrate reactions Time be only capable of obtaining the products collection efficiency of 3%；With the products collection efficiency that silyl enol ether substrate reactions also can only obtain 32%.

In sum, although seven fluorine isopropyl iodides can be reacted to substrate molecule by sulfinatodehalogenation and Ullmann Middle introducing seven fluorine isopropyl substituents, but sulfinatodehalogenation experience is free radical proceed, and reaction is difficult to control to, usually Obtain the mixture of isomer, and substrate requirements is higher, it is necessary to for electron rich aromatic hydrocarbons.Ullmann reaction then needs equivalent Metal participate in, and reaction temperature is generally the highest, and condition is harsh.Despite polytype seven fluorine isopropyl metal reagent quilts Be synthesized, but owing to they are not sufficiently stable a bit, need lower temperature, and in view of as seven fluorine isopropyl chromium reagent, The high toxicity of seven fluorine isopropyl mercury reagents etc., so by little for the example of its successful Application.

It is desirable to provide a kind of method utilizing hexafluoropropene that aryl boric acid directly aoxidizes seven fluorine isopropylations.I.e. A kind of simplicity with hexafluoropropene, aryl boric acid direct oxidation seven fluorine isopropylation obtains containing accordingly the product of seven fluorine isopropyls The method of thing.

The method of the present invention can include with aryl boric acid and hexafluoropropene as raw material, in the reagent effect of another one fluorine source Under carry out, under room temperature and catalyst action, optionally synthesized a series of seven fluorine isopropyls of containing by single step reaction height Compound.Described fluorine source reagent include lithium fluoride, sodium fluoride, potassium fluoride, cesium fluoride, Mercury difluoride., cadmium fluoride, Argentous fluoride, two Copper fluoride or alkyl ammonium；Catalyst is the first subgroup, the second subgroup or the compound of the 8th race's element.The method of the present invention It is also applied for ene boric acid.

The method of the present invention further describes: with Argentous fluoride for fluorine source, under the effect of mantoquita, at room temperature and organic solvent In, it is possible to perfluoropropene and aryl boric acid are converted into a series of compound containing seven fluorine isopropyls.Reaction equation is as follows:

HFP represents perfluoropropene；Evaporation represents evaporation；Arylboronic acid table aryl boric acid

The method of the present invention ties up in organic solvent and under room temperature, the seven fluorine isopropyls that perfluoropropene and Argentous fluoride prepare Silver, CuI, Z substituted boric acid ZB (OH)₂, and copper acetate reaction overnight obtain containing the compound of seven fluorine isopropyls；Described Z takes The mol ratio of the boric acid in generation, seven fluorine isopropyl silver, CuI and copper acetate is 1:1.0-2.0:0.3-1.0:0.1-1.0；Recommendation mole Ratio is 1:1.5-2.0:0.8-1.0:0.3-0.6.

Described Z substituent group can be the substituted aryl of R, substituted oxygen-containing, the nitrogen of R or thia aryl or styryl；Institute The aryl stated can be phenyl, naphthyl or xenyl；Described oxygen-containing, nitrogen or thia aryl can be；Described R is H, C_1-6 Alkyl (such as Me, tBu etc.), phenyl, benzo base, halogen (F, Cl, Br, I), cyano group, nitro, C_1-4Hydroxyl, C_1-4Aldehyde radical, C_1-4Carboxyl, C_1-4Carboxyl secondary amine, C_1-4Ester group, C_1-4Alkoxy carbonyl group, C_2-10Hydrocarbon thiazolinyl, hydroxyl C_1-4Alkyl；Described R substituent can be that R is monosubstituted, R is disubstituted or R trisubstituted aryl, R is monosubstituted, R is disubstituted or R trisubstituted oxygen-containing, Nitrogen or thia aryl；Described oxygen-containing, nitrogen or thia aryl can be pyridine radicals, indyl, indenyl, benzimidazolyl, fluorenyl, Carbazyl, dibenzofuran base, dibenzothiophen base or 1,2-methylenedioxybenzenes；Described halogen is F, Cl, Br or I.

Described organic solvent can be DMF, ether, petroleum ether, CH₃CN etc..

Reaction terminates, and can use organic solvent extraction, washing, is dried, and rotation is steamed, and column chromatography purification seven fluorine isopropylation is produced Thing.As added diluted ethyl acetate, then filtering, filtrate adds the dilution of a large amount of water, and ethyl acetate extracts, and merges organic facies, washes, Anhydrous magnesium sulfate is dried.Then filter rotation to steam, seven fluorine isopropylation products of residue rapid column chromatography.Biphenylboronic acid is utilized to examine Examined reaction condition, draw optimization reaction condition be: seven fluorine isopropyl argentum reagents of 2 equivalents, the substituted boric acid of Z of 1 equivalent, 1 The Hydro-Giene (Water Science). of equivalent, the copper acetate of 0.5 equivalent, with DMF as solvent, reaction temperature is room temperature, and the response time is overnight.

According to the condition filtered out, by a series of aryl boric acid seven fluorine isopropylation, result is as follows:

A: productivity PhCF₃Make internal standard by¹⁹F NMR (Enantiomeric excess) measures

B: separate productivity

Above-mentioned seven fluorine isopropyls silver, can at the scene under room temperature, utilize fill the balloon of perfluoropropene at ambient pressure to The organic solvent solution of Argentous fluoride is slowly filled with perfluoropropene, is then stirred for reaction until solution clarification, about reaction 2 are little Time, obtain the organic solution of seven fluorine isopropyl silver, then reduced pressure at room temperature is evaporated and prepares seven fluorine isopropyl silver, reclaims simultaneously and has Machine solvent and the perfluoropropene of excess.Described Argentous fluoride and the mol ratio of perfluoropropene are 1:1-5；Recommendation mol ratio is 1:1- 2.Above-mentioned organic solvent can be CH₃CN etc..

When using the method for the present invention, it is recommended that it is different that on-the-spot employing said method prepares seven fluorine by perfluoropropene and Argentous fluoride Propyl group silver is preferably.The inventive method high can optionally synthesize a series of compound containing seven fluorine isopropyls.

Detailed description of the invention

Following embodiment will assist in and understands the present invention, but is not limiting as present disclosure.

Implementing regulations:

Typical implementing regulations are as described below, and other substrates are all in this feeding sequence and ratio, under the same reaction conditions Carry out.

The preparation of seven fluorine isopropyl argentum reagents: at 25 DEG C, is slowly filled with perfluoropropene in the acetonitrile solution of Argentous fluoride, stirs Mix reaction until solution clarification, obtain seven fluorine isopropyls silver acetonitrile solution, then by prepare seven fluorine isopropyls silver Acetonitrile solution reduced pressure at room temperature is evaporated, and is subsequently adding DMF solution, is then separately added into CuI, aryl boric acid and copper acetate.This mixes Stirring under compound room temperature, until reaction terminates, adds diluted ethyl acetate, then filters, and filtrate adds the dilution of a large amount of water, acetic acid second Ester extracts, and merges organic facies, and washing, anhydrous magnesium sulfate is dried.Then filter rotation to steam, seven fluorine isopropyls of residue rapid column chromatography Base product.

1 adds Argentous fluoride (50.8mg, 0.4mmol) and acetonitrile 5mL, lucifuge condition in flame-dried Schlenk pipe Under utilize balloon to be filled with enough perfluoropropenes, stir after clarifying to solution, solvent under reduced pressure be evaporated, add 3mLDMF, the most again Add CuI (38mg, 0.2mmol), 4-biphenylboronic acid (39.6mg, 0.2mmol), copper acetate (36.4mg, 0.2mol), under room temperature It is stirred overnight.Adding diluted ethyl acetate after question response is complete, then filter, filtrate adds the dilution of a large amount of water, and ethyl acetate extracts, and closes And organic facies, washing, anhydrous magnesium sulfate is dried.Then filtering rotation to steam, residue rapid column chromatography obtains seven fluorine isopropylation products 54mg。

1 raw material: 4-biphenylboronic acid (4-biphenylboronic acid)

Product: 4-(perfluoropropan-2-yl)-1,1'-biphenyl (4-seven fluorine isopropyl biphenyl)

White solid White solid, mp:89-91 DEG C；

¹H NMR(400MHz,CDCl₃) δ 7.69 (q, J=8.7Hz, 4H), 7.64 7.56 (m, 2H), 7.47 (m, 2H), 7.41(m,1H)；¹⁹F NMR(376MHz,CDCl₃) δ-75.66 (d, J=7.4Hz) ,-182.49 (hept, J=7.2Hz)；¹³C NMR(100MHz,CDCl₃) δ 144.02,139.64,129.01,128.21,127.55 (d, J=2.0Hz), 127.25, 126.18 (d, J=10.4Hz), 125.60 (d, J=20.6Hz), 120.75 (qd, J=285.3,26.4Hz), 91.65 (dq, J =201.8,31.1Hz)；IR(KBr,cm^-1):ν3078,1446,1280,1218,1101,981,835,736,697；MS(EI) m/z(relative intensity)322[M⁺],253(100)；

HRMS (EI) value of calculation calcd.For C₁₅H₉F₇: 322.0592, measured value Found:322.0590.

2 raw materials: benzeneboronic acid (phenylboric acid)

Product: (perfluoropropan-2-yl) benzene (sevoflurane isopropyl)

MS (EI) m/z (relative intensity intensity) 246 [M⁺],127(100)；

3 raw materials: 4-tert-butylbenzeneboronic acid (4-tert-butyl group boric acid)

Product: 1-(tert-butyl)-4-(perfluoropropan-2-yl) benzene (the 4-tert-butyl group seven fluorine isopropyl Base benzene)

Colourless liquid Colourless liquid；¹H NMR(400MHz,CDCl₃)δ7.59–7.46(m,4H),1.34(s, 9H)；¹⁹F NMR(376MHz,CDCl₃) δ-75.85 (d, J=7.3Hz) ,-182.59-182.76 (m)；¹³C NMR(100MHz, CDCl₃) δ 154.26,125.80,125.39 (d, J=10.2Hz), 123.75 (d, J=20.7Hz), 120.71 (qd, J= 286.8,28.5Hz),92.90-89.92(m),34.76,31.05；IR(film,cm^-1):ν2968,1611,1308,1218, 1100,982,832,711；MS(EI)m/z(relative intensity)302[M⁺],287(100)；HRMS (EI) value of calculation calcd.For C₁₃H₁₃F₇: 302.0905, measured value Found:302.0906.

4 raw materials: 4-iodophenylboronic acid (4-iodobenzene boric acid)

Product: 1-iodo-4-(perfluoropropan-2-yl) benzene (4-iodine sevoflurane isopropyl)

Colourless liquid Colourless liquid；¹H NMR(400MHz,CDCl₃) δ 7.86 (d, J=8.3Hz, 2H), 7.33 (d, J=8.5Hz, 2H)；¹⁹F NMR(376MHz,CDCl₃) δ-75.74 (d, J=7.3Hz) ,-182.91 (hept, J= 7.2Hz)；¹³C NMR(100MHz,CDCl₃) δ 138.20,127.31 (d, J=10.5Hz), 126.47 (d, J=20.8Hz), 120.33 (qd, J=287.8,27.5Hz), 97.91,93.72 88.83 (m)；IR(film,cm^-1):ν2926,1591,1491, 1301,1213,984,950,816,748；MS(EI)m/z(relative intensity)372(100)[M⁺]；HRMS(EI) Value of calculation calcd.For C₉H₄F₇I:371.9246, measured value Found:371.9250.

5 raw materials: (4-acetylphenyl) boronic acid (4-acetylbenzene boric acid)

Product: 1-(4-(perfluoropropan-2-yl) phenyl) ethanone (4-sevoflurane isopropyl ethyl ketone)

Colourless liquid Colourless liquid；¹H NMR(400MHz,CDCl₃) δ 8.09 (d, J=8.3Hz, 2H), 7.74 (d, J=8.4Hz, 2H), 2.65 (s, 3H)；¹⁹F NMR(376MHz,CDCl₃) δ-75.58 (d, J=7.3Hz) ,- 182.66 (hept, J=7.1Hz)；¹³C NMR(100MHz,CDCl₃) δ 196.87,139.09,131.07 (d, J=20.5Hz), 128.61 (d, J=2.1Hz), 126.13 (d, J=10.6Hz), 120.36 (qd, J=285.8,28.3Hz), 93.04-89.70 (m),26.63；IR(film,cm^-1):ν3372,3008,1696,1613,1414,1362,1273,1214,1103,985,830, 708；MS(EI)m/z(relative intensity)288[M⁺],273(100)；HRMS (EI) value of calculation calcd.For C₁₁H₇OF₇: 288.0385, measured value Found:288.0388.

6 raw materials: (4-cyanophenyl) boronic acid (4-cyanophenylboronic acid)

Product: 4-(perfluoropropan-2-yl) benzonitrile (4-sevoflurane isopropyl formonitrile HCN)

Colourless liquid Colourless liquid；¹H NMR(400MHz,CDCl₃) δ 7.83 (d, J=8.4Hz, 2H), 7.77 (d, J=8.6Hz, 2H)；¹⁹F NMR(376MHz,CDCl₃) δ-75.38 (d, J=7.3Hz) ,-182.69 (hept, J= 7.2Hz)；IR(film,cm^-1):ν2911,1611,1510,1497,1453,1307,1277,1095,1044,979,755；MS (EI)m/z(relative intensity)271(7)[M⁺],221(100)；HRMS (EI) value of calculation calcd.For C₁₀H₄NF₇: 271.0232, measured value Found:271.0230.

7 raw materials: (4-vinylphenyl) boronic acid (4-vinylphenylboronic acid)

Product: 1-(perfluoropropan-2-yl)-4-vinylbenzene (4-sevoflurane isopropyl ethylene)

Colourless liquid Colourless liquid；¹H NMR(400MHz,CDCl₃) δ 7.57 (d, J=8.5Hz, 2H), 7.51 (d, J=8.7Hz, 2H), 6.75 (dd, J=17.6,10.9Hz, 1H), 5.85 (dd, J=17.6,0.5Hz, 1H), 5.39 (dd, J=10.9,0.5Hz, 1H)；¹⁹F NMR(376MHz,CDCl₃) δ-75.74 (d, J=7.3Hz) ,-182.54 (hept, J =7.2Hz)；¹³C NMR(100MHz,CDCl₃) δ 140.25,135.50,126.55 (d, J=2.1Hz), 125.92 (d, J= 10.5Hz), 125.70,120.59 (qd, J=287.2,27.8Hz), 116.44,93.97 89.07 (m)；IR(film,cm^-1): ν2922,1513,1277,1212,1103,983,750；MS(EI)m/z(relative intensity)272(45)[M⁺], 203(100)；HRMS (EI) value of calculation calcd.For C₁₁H₇F₇: 272.0436, measured value Found:272.0439.

8 raw materials: benzo [d] [1,3] dioxol-5-ylboronic acid (3,4-methylene-dioxy phenylboric acid)

Product: 5-(perfluoropropan-2-yl) benzo [d] [1,3] dioxole 3,4-(methylene-dioxy) seven Fluorine cumene

Colourless liquid Colourless liquid；¹H NMR(400MHz,CDCl₃) δ 7.11 (d, J=8.3Hz, 1H), 7.04 (s, 1H), 6.90 (d, J=8.3Hz, 1H), 6.05 (s, 2H)；¹⁹F NMR(376MHz,CDCl₃) δ-75.90 (d, J= 7.2Hz) ,-180.50 (hept, J=7.1Hz)；IR(film,cm^-1):ν2934,2237,1508,1310,1277,1212, 986,836,749,705；MS(EI)m/z(relative intensity)290(13)[M⁺],193(100)；HRMS (EI) counts Calculation value calcd.For C₁₀H₅O₂F₇: 290.0178, measured value Found:290.0176.

9 raw materials: (3-acetamidophenyl) boronic acid (3-acetamidobenzeneboronic acid)

Product: N-(3-(perfluoropropan-2-yl) phenyl) acetamide 3-seven fluorine isopropyl acetanilide

White solid White solid；mp:78-81℃；¹H NMR(400MHz,CDCl₃) δ 7.82 (d, J=8.4Hz, 1H), 7.70 (s, 1H), 7.61 (s, 1H), 7.45 (t, J=8.1Hz, 1H), 7.34 (d, J=8.0Hz, 1H), 2.20 (s, 3H) ；¹⁹F NMR(376MHz,CDCl₃) δ-75.66 (d, J=7.2Hz) ,-182.42 (hept, J=7.1Hz)；¹³C NMR (100MHz,CDCl₃) δ 169.36,138.76,129.58,127.46 (d, J=20.5Hz), 122.50,121.24 (d, J= 9.9Hz), 120.50 (qd, J=286.3,28.2Hz), 117.07 (d, J=11.7Hz), 93.83 87.74 (m), 24.27；IR (KBr,cm^-1):ν3274,1673,1558,1281,1224,982,750,727；MS(EI)m/z(relative intensity) 303(21)[M⁺],261(100)；HRMS (EI) value of calculation calcd.For C₁₁H₈NOF₇: 303.0494, measured value Found: 303.0495.

10 raw materials: (4-(hydroxymethyl) phenyl) boronic acid (4-methylol phenylboric acid)

Product: (4-(perfluoropropan-2-yl) phenyl) methanol (4-seven fluorine isopropylbenzyl alcohol)

Colourless liquid Colourless liquid；¹H NMR(400MHz,CDCl₃) δ 7.61 (d, J=8.3Hz, 2H), 7.50 (d, J=8.2Hz, 2H), 4.77 (s, 2H), 1.91 (s, 1H)；¹⁹F NMR(376MHz,CDCl₃) δ-75.77 (d, J= 7.3Hz) ,-182.57 (hept, J=7.1Hz)；¹³C NMR(100MHz,CDCl₃) δ 143.97,128.81,127.06 (d, J= 2.1Hz), 125.90 (d, J=10.8Hz), 120.59 (qd, J=286.4,28.1Hz), 93.54 89.23 (m), 64.40；IR (film,cm^-1):ν3314,1276,1261,1213,984,751；MS(EI)m/z(relative intensity)276(44) [M⁺],107(100)；HRMS (EI) value of calculation calcd.For C₁₀H₇OF₇: 276.0385, measured value Found:276.0388.

11 raw materials: (4-hydroxyphenyl) boronic acid (4-hydroxy benzenes boric acid)

Product: 4-(perfluoropropan-2-yl) phenol (4-sevoflurane isopropyl phenol)

Colourless liquid Colourless liquid；¹H NMR(400MHz,CDCl₃) δ 7.48 (d, J=8.8Hz, 2H), 6.94 (d, J=8.5Hz, 2H)；¹⁹F NMR(376MHz,CDCl₃) δ-76.00 (d, J=7.4Hz) ,-181.75 (hept, J= 7.2Hz)；¹³C NMR(100MHz,CDCl₃) δ 157.68,127.51 (d, J=10.6Hz), 120.66 (qd, J=287.2, 28.3Hz), 118.83 (d, J=20.8Hz), 115.79 (d, J=1.9Hz), 93.30 89.70 (m)；IR(film,cm^-1):ν 3251,1519,1450,1276,981,764,750；MS(EI)m/z(relative intensity)262(43)[M⁺],193 (100)；HRMS (EI) value of calculation calcd.For C₉H₅OF₇: 262.0229, measured value Found:262.0232.

12 raw materials: (E)-styrylboronic acid (E)-stvrYlboronic acid

Product: (E)-(3,4,4,4-tetrafluoro-3-(trifluoromethyl) but-1-en-1-yl) The fluoro-3-trifluoromethyl of benzene (E)-3,4,4,4-four--1-butylene base benzene

Colourless liquid Colourless liquid；¹H NMR(400MHz,CDCl₃)δ7.48-7.46(m,2H),7.44– 7.35 (m, 3H), 7.14 (d, J=16.1Hz, 1H), 6.14 (dd, J=20.1,16.1Hz, 1H)；¹⁹F NMR(376MHz, CDCl₃) δ-77.10 (d, J=7.7Hz) ,-186.02-186.28 (m)；¹³C NMR(100MHz,CDCl₃)δ138.53(d,J =10.8Hz), 133.87,129.85,128.94,127.37,125.43 115.31 (m), 120.39 (qd, J=287.0, 27.5Hz),92.78–88.83(m)；IR(film,cm^-1):ν3003,1275,1261,764,750；MS(EI)m/z (relative intensity)272(73)[M⁺],203(100)；HRMS (EI) value of calculation calcd.For C₁₁H₇F₇: 272.0436, measured value Found:272.0434.

13 raw materials: (4-formylphenyl) boronic acid (4-formylphenylboronic acid)

Product: 4-(perfluoropropan-2-yl) benzaldehyde (4-sevoflurane isopropyl formaldehyde)

Colourless liquid Colourless liquid；¹H NMR(400MHz,CDCl₃) δ 10.10 (s, 1H), 8.02 (d, J= 8.2Hz, 2H), 7.81 (d, J=8.2Hz, 2H)；¹⁹F NMR(376MHz,CDCl₃) δ-75.40 (d, J=7.2Hz) ,-182.33 (hept, J=7.1Hz)；¹³C NMR(100MHz,CDCl₃) δ 190.93,138.13,132.41 (d, J=20.5Hz), 129.83,126.59 (d, J=10.5Hz), 120.33 (qd, J=287.6,27.9Hz), 93.34 88.47 (m)；IR(film, cm^-1):ν2853,1709,1276,1261,984,750；MS(EI)m/z(relative intensity)274[M⁺],273 (100)；HRMS(EI)calcd.For C₁₀H₅OF₇: 274.0229, measured value Found:274.0228.

14 raw materials: naphthalen-2-ylboronic acid (2-boric acid naphthalene)

Product: 2-(perfluoropropan-2-yl) naphthalene (2-seven fluorine isopropyl naphthalene)

White solid White solid, mp:65-66 DEG C；¹H NMR(400MHz,CDCl₃)δ8.14(s,1H),8.07– 7.82(m,3H),7.74–7.51(m,3H)；¹⁹F NMR(376MHz,CDCl₃) δ-75.43 (d, J=7.3Hz) ,-181.92 (hept, J=7.2Hz)；¹³C NMR(100MHz,CDCl₃) δ 133.99,132.44 (d, J=2.1Hz), 128.85 (d, J= 2.3Hz), 128.71,127.96,127.67,127.13,126.44 (d, J=11.9Hz), 123.96 (d, J=20.3Hz), 121.56 (d, J=9.4Hz), 120.70 (qd, J=287.4,27.8Hz), 94.09 88.83 (m)；IR(KBr,cm^-1):ν 3060,1276,1220,981,907,751；MS(EI)m/z(relative intensity)296(71)[M⁺],177(100)； HRMS (EI) value of calculation calcd.For C₁₃H₇F₇: 296.0436, measured value Found:296.0431.

15 raw materials: (4-fluorophenyl) boronic acid (4-fluorobenzoic boric acid)

Product: 1-fluoro-4-(perfluoropropan-2-yl) benzene (4-fluorine sevoflurane isopropyl)

MS(EI)m/z(relative intensity)264[M⁺]；

16 raw materials: 4-boronobenzoic acid (4-boric acid benzoic acid)

Product: 4-(perfluoropropan-2-yl) benzoic acid (4-sevoflurane isopropyl formic acid)

¹H NMR(400MHz,CDCl₃) δ 9.03 (b, 1H), 8.24 (d, J=8.4Hz, 2H), 7.74 (d, J=8.3Hz, 2H)；¹⁹F NMR(376MHz,CDCl₃) δ-75.55 (d, J=7.2Hz) ,-182.59 (hept, J=7.2Hz)；¹³C NMR (100MHz,CDCl₃) δ 163.66,132.52,131.47 (d, J=20.5Hz), 130.43 (d, J=2.0Hz), 125.88 (d, J=10.5Hz), 120.33 (qd, J=287.5,27.9Hz), 93.01 89.25 (m) .IR (film, cm^-1):ν2934,1693, 1422,1211,1105,985,755,722；MS(EI)m/z(relative intensity)290(51)[M⁺],171(100)； HRMS (EI) value of calculation calcd.For C₁₀H₅O₂F₇: 290.0178, measured value Found:290.0181.

17 raw materials: (4-(methoxycarbonyl) phenyl) boronic acid 4-(methoxycarbonyl) phenylboric acid

Product: methyl 4-(perfluoropropan-2-yl) benzoate (4-sevoflurane isopropyl methyl formate)

Colourless liquid Colourless liquid；¹H NMR(400MHz,CDCl₃) δ 8.17 (d, J=8.3Hz, 2H), 7.71 (d, J=8.4Hz, 2H), 3.96 (s, 3H)；¹⁹F NMR(376MHz,CDCl₃) δ-75.55 (d, J=7.0Hz) ,- 182.59 (hept, J=7.1Hz)；¹³C NMR(100MHz,CDCl₃) δ 165.81,132.75,131.02 (d, J=20.5Hz), 129.94 (d, J=2.3Hz), 125.83 (d, J=10.7Hz), 120.33 (qd, J=287.8,28.3Hz), 93.02 89.41 (m),52.45；IR(film,cm^-1):ν2958,1736,1439,1279,1212,1105,985,956,723；MS(EI)m/z (relative intensity)304(24)[M⁺],273(100)；HRMS (EI) value of calculation calcd.For C₁₁H₇O₂F₇: 304.0334, measured value Found:304.0333.

18 raw materials: (3,4,5-trimethoxyphenyl) boronic acid (3,4,5-trimethoxy phenylboric acid)

Product: 1,2,3-trimethoxy-5-(perfluoropropan-2-yl) benzene (5-seven fluorine isopropyl-1, 2,3-trimethoxy-benzene)

Colourless liquid Colourless liquid；¹H NMR(400MHz,CDCl₃)δ6.79(s,2H),3.90(s,3H), 3.89(s,6H)；¹⁹F NMR(376MHz,CDCl₃) δ-75.68 (d, J=7.2Hz) ,-181.23 (hept, J=7.1Hz)；¹³C NMR(100MHz,CDCl₃) δ 153.45 (d, J=2.1Hz), 140.12,121.57 (d, J=20.7Hz), 120.52 (qd, J= 286.9,27.9Hz), 103.09 (d, J=11.4Hz), 93.77 89.17 (m), 60.78,56.20；IR(film,cm^-1):ν 2945,1595,1514,1465,1422,1290,1168,980,835,727；MS(EI)m/z(relative intensity) 336(100)[M⁺]；HRMS (EI) value of calculation calcd.For C₁₂H₁₁O₃F₇: 336.0596, measured value Found:336.0593.

19 raw materials: (3-(ethoxycarbonyl) phenyl) boronic acid (3-ethoxy carbonyl phenylboric acid)

Product: ethyl 3-(perfluoropropan-2-yl) benzoate (3-sevoflurane isopropyl Ethyl formate)

Colourless liquid Colourless liquid；¹H NMR(400MHz,CDCl₃) δ 8.31 (s, 1H), 8.23 (d, J= 7.9Hz, 1H), 7.80 (d, J=7.9Hz, 1H), 7.60 (t, J=7.9Hz, 1H), 4.43 (q, J=7.1Hz, 2H), 1.42 (t, J=7.1Hz, 3H)；¹⁹F NMR(376 MHz,CDCl₃) δ-75.67 (d, J=7.3Hz) ,-182.48 (hept, J=7.2Hz) ；¹³C NMR(100MHz,CDCl₃) δ 165.26,132.05,131.52 (d, J=2.2Hz), 129.67 (d, J=10.1Hz), 129.06 (d, J=2.2Hz), 127.25 (d, J=20.8Hz), 126.87 (d, J=11.5Hz), 120.40 (qd, J= 286.4,28.0Hz),93.04–89.25(m),61.53,14.19；IR(film,cm^-1):ν2986,1728,1281,1206, 984,723；MS(EI)m/z(relative intensity)318(15)[M⁺],273(100)；HRMS (EI) value of calculation calcd.For C₁₂H₉O₂F₇: 318.0491, value of calculation Found:318.0494.

20 raw materials: (6-methoxynaphthalen-2-yl) boronic acid (6-methoxyl group-2-naphthalene boronic acids)

(2-methoxyl group-6-seven fluorine is different for product: 2-methoxy-6-(perfluoropropan-2-yl) naphthalene Propyl group naphthalene)

White solid White solid, mp:53-55 DEG C；¹H NMR(400MHz,CDCl₃)δ8.04(s,1H),7.84(d, J=8.3Hz, 1H), 7.81 (d, J=8.7Hz, 1H), 7.59 (d, J=8.8Hz, 1H), 7.32 7.20 (m, 1H), 7.17 (d, J =2.3Hz, 1H), 3.94 (s, 3H)；¹⁹F NMR(376MHz,CDCl₃) δ-75.74 (d, J=7.2Hz) ,-182.51 (hept, J =7.2Hz)；¹³C NMR(100MHz,CDCl₃) δ 159.22,135.51,130.19,127.95 (d, J=2.2Hz), 127.55 (d, J=2.3Hz), 126.09 (d, J=11.8Hz), 122.16 (d, J=9.4Hz), 121.53 (d, J=20.5Hz), 120.40 (qd, J=285.4,28.0Hz), 120.15,105.39,93.64 89.22 (m), 55.33；IR(KBr,cm^-1):ν 2962,1637,1610,1488,1277,1220,1102,981,900,854,724；MS(EI)m/z(relative intensity)326(53)[M⁺],257(100)；HRMS (EI) value of calculation calcd.For C₁₄H₉OF₇: 326.0542, measured value Found:326.0541.

21 raw materials: (4-nitrophenyl) boronic acid (4-nitrobenzene boronic acid)

Product: 1-nitro-4-(perfluoropropan-2-yl) benzene (4-nitro sevoflurane isopropyl)

Colourless liquid Colourless liquid；¹H NMR(400MHz,CDCl₃) δ 8.38 (d, J=8.7Hz, 2H), 7.85 (d, J=8.8Hz, 2H)；¹⁹F NMR(376MHz,CDCl₃) δ-75.36 (d, J=7.3Hz) ,-181.96 (hept, J= 7.2Hz)；¹³C NMR(100MHz,CDCl₃) δ 149.61,132.91 (d, J=20.7Hz), 127.22 (d, J=10.8Hz), 124.01 (d, J=2.2Hz), 120.12 (qd, J=286.9,27.2Hz), 93.28 89.60 (m)；IR(film,cm^-1):ν 3118,1611,1536,1276,1217,1106,986,854,760；MS(EI)m/z(relative intensity)291[M⁺],145(100)；HRMS (EI) value of calculation calcd.For C₉H₄NO₂F₇: 291.0130, measured value Found:291.0133.

22 raw materials: o-tolylboronic acid (2-toluene boric acid)

Product: 1-methyl-2-(perfluoropropan-2-yl) benzene (2-methyl sevoflurane isopropyl)

MS(EI)m/z(relative intensity)260[M⁺],191(100)；

23 raw materials: dibenzo [b, d] thiophen-2-ylboronic acid (B-2-dibenzothiophenes ylboronic acid)

(2-seven fluorine isopropyl diphenyl is also for product: 2-(perfluoropropan-2-yl) dibenzo [b, d] thiophene Thiophene)

White solid White solid, mp:102-103 DEG C；¹H NMR(400MHz,CDCl₃)δ8.39(s,1H),8.29– 8.17 (m, 1H), 7.98 (d, J=8.6Hz, 1H), 7.93 7.83 (m, 1H), 7.67 (d, J=8.5Hz, 1H), 7.62 7.47 (m,2H)；¹⁹F NMR(376 MHz,CDCl₃) δ-75.54 (d, J=7.3Hz) ,-181.49 (hept, J=7.2Hz)；¹³C NMR (100MHz,CDCl₃) δ 142.30,139.84,135.85 (d, J=2.3Hz), 134.66,127.61,124.84,123.34 (d, J=2.2Hz), 123.19 (d, J=9.9Hz), 122.96 (d, J=20.5Hz), 122.90,120.70 (qd, J= 288.7,27.8Hz)；(121.84,119.03 d, J=12.1Hz), 93.63 89.89 (m)；IR(KBr,cm^-1):ν3066, 1945,1899,1470,1280,1221,1104,980,765,729；MS(EI)m/z(relative intensity)352 (77)[M⁺],233(100)；HRMS (EI) value of calculation calcd.For C₁₅H₇SF₇: 352.0157, measured value Found: 352.0161.

24 raw materials: (1H-indol-5-yl) boronic acid (1H-indole-5-boric acid)

Product: 5-(perfluoropropan-2-yl)-1H-indole (5-seven fluorine isopropyl-1H-indole)

White solid White solid, mp:100-101 DEG C；¹H NMR(400MHz,CDCl₃)δ8.31(b,1H),7.93 (s, 1H), 7.48 (d, J=8.8Hz, 1H), 7.41 (d, J=8.7Hz, 1H), 7.36 7.28 (m, 1H), 6.64 (d, J= 2.2Hz,1H)；¹⁹F NMR(376MHz,CDCl₃) δ-75.70 (d, J=7.2Hz) ,-180.53 (hept, J=7.1Hz)；¹³C NMR(100MHz,CDCl₃) δ 136.63,127.67 (d, J=2.3Hz), 125.74,120.98 (qd, J=286.9, 27.9Hz), 118.96 (d, J=8.1Hz), 118.85 (d, J=6.7Hz), 117.96 (d, J=20.2Hz), 111.39 (d, J =2.3Hz), 103.46,93.98 89.99 (m)；IR(KBr,cm^-1):ν3476,3388,2248,1476,1280,1216, 1097,978,909,733；MS(EI)m/z(relative intensity)285(48)[M⁺],216(100)；HRMS (EI) counts Calculation value calcd.For C₁₁H₆NF₇: 285.0388, measured value Found:285.0392.

25 raw materials: (6-bromopyridin-3-yl) boronic acid (6-bromopyridine-3-boric acid)

Product: 2-bromo-5-(perfluoropropan-2-yl) pyridine (2-bromo-5-seven fluorine isopropyl pyridine)

Colourless liquid Colourless liquid；¹H NMR(400MHz,CDCl₃) δ 8.63 (d, J=2.2Hz, 1H), (7.78 dd, J=8.5,2.4Hz, 1H), 7.68 (d, J=8.5Hz, 1H)；¹⁹F NMR(376MHz,CDCl₃)δ-75.91(d,J =7.7Hz) ,-184.73 (hept, J=7.6Hz)；¹³C NMR(100MHz,CDCl₃)δ148.43–146.59(m),145.61 (d, J=1.1Hz), 135.69 (d, J=9.9Hz), 128.34 (d, J=2.3Hz), 122.53 (d, J=20.9Hz), 120.02 (qd, J=287.3,27.5Hz), 93.15 87.51 (m)；MS(EI)m/z(relative intensity)325(100,⁷⁹Br) [M⁺],327(97,⁸¹Br)[M⁺]；HRMS (EI) value of calculation calcd.For C₈H₃F₇NBr:324.9337, measured value Found: 324.9341。

Claims (6)

1. the method utilizing hexafluoropropene that aryl boric acid directly aoxidizes seven fluorine isopropylations, is characterized in that using following step Suddenly (1)-(2), or two kinds of methods acquisitions of (2):

(1) at room temperature with in organic solvent, Argentous fluoride and perfluoropropene react 1-3 hour and prepare seven fluorine isopropyl silver；Described Argentous fluoride and the mol ratio of perfluoropropene be 1:1-5；

(2) in organic solvent with under room temperature, seven fluorine isopropyl silver, CuI, Z substituted boric acid ZB (OH)₂, and copper acetate reacted Night obtains the compound containing seven fluorine isopropyls；The substituted boric acid of described Z, seven fluorine isopropyl silver, CuI and the mol ratio of copper acetate For 1:1.0-2.0:0.3-1.0:0.1-1.0；Described Z substituent group is that R is monosubstituted, R is disubstituted or R trisubstituted aryl, and R is mono- Replace, R is disubstituted or trisubstituted oxygen-containing, the nitrogen of R or thia aryl, or styryl；Described aryl is phenyl, naphthyl or connection Phenyl；Described oxygen-containing, nitrogen or thia aryl are pyridine radicals, indyl, indenyl, benzimidazolyl, fluorenyl, carbazyl, dibenzofuran Base, dibenzothiophen base or 1,2-methylene dioxy phenyl group；Described R be the alkyl of H, C1-6, phenyl, benzo base, halogen, cyano group, nitro, The hydroxyl of C1-4, the aldehyde radical of C1-4, the carboxyl of C1-4, the carboxyl secondary amine of C1-4, the ester group of C1-4, the alkoxy carbonyl group of C1-4, The thiazolinyl of C2-10, hydroxyl C1-4 alkyl；Described halogen is F, Cl, Br or I.

2. the method for claim 1, is characterized in that the reaction of step (1) is slowly to fill in the organic solvent of Argentous fluoride Enter excess perfluoropropene, be then stirred for reaction until solution is clarified.

3. the method for claim 1, is characterized in that in step (2), the substituted boric acid of described Z, seven fluorine isopropyls silver, The mol ratio of CuI and copper acetate is 1:1.5-2.0:0.8-1.0:0.3-0.6.

4. the method for claim 1, it is characterized in that described organic solvent be DMF, ether, petroleum ether or CH3CN。

5. the method for claim 1, is characterized in that in step (1), described product is evaporated process through reduced pressure at room temperature.

6. the method for claim 1, is characterized in that in step (2), described product is through organic solvent extraction, water Washing, be dried, rotation is steamed, column chromatography purification.