CN105348048B - A kind of method for preparing aryl trifluoro ethoxy ether compound - Google Patents

A kind of method for preparing aryl trifluoro ethoxy ether compound Download PDF

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CN105348048B
CN105348048B CN201510854777.9A CN201510854777A CN105348048B CN 105348048 B CN105348048 B CN 105348048B CN 201510854777 A CN201510854777 A CN 201510854777A CN 105348048 B CN105348048 B CN 105348048B
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卿凤翎
张柯
黄焰根
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Donghua University
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    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
    • C07C41/01—Preparation of ethers
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    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C201/00—Preparation of esters of nitric or nitrous acid or of compounds containing nitro or nitroso groups bound to a carbon skeleton
    • C07C201/06—Preparation of nitro compounds
    • C07C201/12—Preparation of nitro compounds by reactions not involving the formation of nitro groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C231/00—Preparation of carboxylic acid amides
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    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C253/00—Preparation of carboxylic acid nitriles
    • C07C253/30—Preparation of carboxylic acid nitriles by reactions not involving the formation of cyano groups
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    • C07C269/00—Preparation of derivatives of carbamic acid, i.e. compounds containing any of the groups, the nitrogen atom not being part of nitro or nitroso groups
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    • C07C319/00—Preparation of thiols, sulfides, hydropolysulfides or polysulfides
    • C07C319/14—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of sulfides
    • C07C319/20—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of sulfides by reactions not involving the formation of sulfide groups
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    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
    • C07C45/64—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by introduction of functional groups containing oxygen only in singly bound form
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    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/30—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group
    • C07C67/31—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by introduction of functional groups containing oxygen only in singly bound form

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Abstract

The present invention relates to a kind of method for preparing aryl trifluoro ethoxy ether compound, including：Aryl boron compound and trifluoroethanol are added in organic solvent, copper salt catalyst, part and oxidant is added, 0~60 DEG C of 1~40h of stirring reaction, filtering, column chromatography for separation, produces.The method of the present invention is simple to operate, and raw material is easy to get, reaction condition is gentle, substrate universality is wide, it is environment-friendly, suitable for industrial applications.

Description

A kind of method for preparing aryl trifluoro ethoxy ether compound
Technical field
The invention belongs to the synthetic method field of trifluoro ethoxy ether compound, more particularly to one kind prepares aryl trifluoro second The method of epoxide ether compound.
Background technology
Fluorinated organic compound has been greatly facilitated into organic molecule in the extensive use of medicine, agricultural chemicals and Material Field Introduce fluorine atom and various fluorine-containing functional groups.In these functional groups, trifluoro ethoxy is because its higher metabolic stability and good Good lipophilicity make it that this functional group is very common in drug molecule.Include the benign forefront for the treatment of in the medicine listed Lansoprazole of the Silodosin of gland hyperplasia, the Flecainide for treating arrhythmia cordis and treatment duodenal ulcer etc..Traditional Preparing the compound of this kind of functional group mainly includes following two methods：(1) trifluoroethylization of phenolic compound is reacted； (2) to the nucleophilic substitution of activation aromatic hydrocarbons.Trifluoroethylization reaction to phenolic compound mainly passes through electrophilic trifluoro The reagent such as ethyl iodide or trifluoroethyl methanesulfonates is reacted [Camps, F. with phenolic compound；Coll,J.； Messeguer,A.；Peric à s, M.A.Synthesis 1980,1980,727.], but trifluoroethyl iodine or trifluoroethyl first Sulphonic acid ester is expensive, and reacts and usually need high temperature so that this method condition is harsh and lack economy；To activation virtue The nucleophilic substitution of hydrocarbon is the nitrobenzene or fluorobenzene and trifluoroethanol reaction [(a) Idoux, J.P. mainly activated； Madenwald,M.L.；Garcia,B.S.；Chu,D.L.；Gupton,J.T.J.Org.Chem 1985,50,1876.(b)for a radical displacement of nitrobenzenes,see:Tejero,I.；Huertas,I.；González- Lafont,；Lluch,J.M.；Marquet, J.J.Org.Chem 2005,70,1718.], but this kind of method is limited to bottom There must be one or more strong electron-withdrawing groups that just there is well anti-when rolling into a ball on the phenyl ring of the universality of thing, nitrobenzene or fluorobenzene Ying Xing.In recent years, the coupling reaction of transition metal-catalyzed/participation turns into the main method for preparing trifluoro ethoxy aryl ether.Text Offer [Vuluga, D.；Legros,J.；Crousse,B.；Bonnet-Delpon,D.Eur.J.Org.Chem.2009,2009, 3513.] the Trifluo- roethoxylation reaction of the aryl iodide or bromide of copper catalysis is reported, but this method needs serious offense The trifluoroethanol and higher temperature of amount.Document [Huang, R.；Huang,Y.；Lin,X.；Rong,M.；Weng, Z.Angew.Chem., Int.Ed.2015,54,5736.] also report aryl iodide or bromide and 1,10- ferrosins are steady Fixed trifluoroethanol copper complex [(phen)2Cu(OCH2CF3)] reaction, it is fragrant (miscellaneous) to be prepared for a series of trifluoro ethoxy Based compound, but reaction needs highly basic, [(phen)2Cu(OCH2CF3)] preparation need the mantoquita of equivalent and matching somebody with somebody for 2 equivalents Body, limit the economy of this reaction.Document [(a) Rangarajan, T.M.；Singh,R.；Brahma,R.；Devi,K.； Singh,R.P.；Singh,R.P.；Prasad,A.K.Chem.Eur.J.2014,20,14218.(b)Rangarajan,T.M.； Devi,K.；Ayushee；Prasad,A.K.；Pal Singh, R.Tetrahedron 2015,71,8307.] and document [Terrett,J.A.；Cuthbertson,J.D.；Shurtleff,V.W.；MacMillan,D.W.C.Nature 2015, 524,330.] palladium and aryl halide and the coupling reaction of trifluoroethanol under nickel catalysis are also reported respectively, but are used Cost very expensive catalyst and part.Based on the importance of this kind of compound, invention is a kind of simple to operate, and cost is cheap, Reaction is efficiently and the environment-friendly method for preparing aryl trifluoro ethoxy ether compound seems extremely important and necessary.
The content of the invention
The technical problems to be solved by the invention are to provide a kind of method for preparing aryl trifluoro ethoxy ether compound, should Method solve in the prior art it is costly, condition is harsh, substrate universality it is narrow with and be not suitable for industrial applications etc. Defect.
A kind of method for preparing aryl trifluoro ethoxy ether compound of the present invention, including：By aryl boron compound and three Fluoroethanol is added in organic solvent, addition copper salt catalyst, nitrogenous organic ligand and oxidant, and 0~60 DEG C of stirring reaction 1~ 40h, filtering, column chromatography for separation, obtains aryl trifluoro ethoxy ether compound；Wherein, aryl boron compound, trifluoroethanol, contain The mol ratio of nitrogen organic ligand and copper salt catalyst is 1：0.2-50：0.2-50：0.001-1.
The aryl boron compound is phenyl boron compound, naphthyl boron compound, pyridine radicals boron compound, thienyl boronation Compound, furyl boron compound, oxazolyls boron compound, thiazolyl boron compound or pyrimidine radicals boron compound.
The phenyl boron compound is 2- bromophenylboronic acids, 2- iodophenyl boronic acids, 2- hydroxyphenyl boronic acids, the boron of 1,4- benzene two Acid, 4- bromobenzeneboronic acids, 4- iodobenzenes boric acid, the bromo- 3- Acetvlamino-phenvls boric acid of 4-, the iodo- 3- Acetvlamino-phenvls boric acid of 4- or 3- acetylaminohydroxyphenylarsonic acid 1,4- benzene hypoboric acid；Pyridine radicals boron compound is the pyridine boronic acid of -3 methyl of 2- methylols -4 or 2- chloromethyls -3 The pyridine boronic acid of methyl -4.
When described phenyl boron compound is 2- bromophenylboronic acids, 2- iodophenyl boronic acids or 2- hydroxyphenyl boronic acids, lead to It is the key for preparing medical Silodosin to cross the trifluoro ethoxy aryl trifluoromethoxy ether that this method is efficiently synthesized by the boric acid Intermediate.
Described phenyl boron compound is Isosorbide-5-Nitrae-benzene hypoboric acid, 4- bromobenzeneboronic acids, 4- iodobenzenes boric acid, the bromo- 3- acetyl ammonia of 4- When the iodo- 3- Acetvlamino-phenvls boric acid of base-phenylboric acid, 4- or 3- acetylaminohydroxyphenylarsonic acids Isosorbide-5-Nitrae-benzene hypoboric acid, by this method by The trifluoro ethoxy aryl trifluoromethoxy ether that the boric acid efficiently synthesizes is the key intermediate for preparing medical Flecainide.
Described pyridine radicals boron compound is the pyridine boronic acid of -3 methyl of 2- methylols -4 or the pyridine of -3 methyl of 2- chloromethyls -4 During boric acid, the trifluoro ethoxy pyridine base trifluoromethoxy ether efficiently synthesized by this method by the boric acid is to prepare the blue rope of medicine Draw the key intermediate of azoles.
The organic solvent is dichloromethane, 1,2- dichloroethanes or toluene, added solvent volume and phenyl boronation material Amount is than being 5：1-100:1.
The copper salt catalyst is mantoquita or mol ratio is 0.1-10：1 mantoquita and the complexing with nitrogenous organic ligand Thing.
The mantoquita and with the reaction temperature in the preparation process of the complex compound of nitrogenous organic ligand be -20 DEG C -60 DEG C.
Additive is added before the stirring reaction.
The reaction equation that the preparation method of the present invention is related to is as follows：
Wherein, described X is H, F, Cl, Br, I, NO2、NH2、NR2、SiR3, OH, OR, SR or SO2R；X isUpper list Substitution, two substitutions or trisubstituted group；Alkyl that R is C1-C6, monosubstituted or polysubstituted phenyl；
R1Benzo base, the C1- substituted for H, phenyl, formoxyl, acetyl group, methylsulfonyl, amide groups, C1-C6 alkoxy Phenoxy group, the C1-C6 alkyl or acyl group of C6 alkoxy or nitro substitution；R1ForUpper monosubstituted, two substitutions three take The group in generation；And work as Z1、Z2For CH when, R1 and X total substitution number is no more than 5；Work as Z1、Z2For N when, R1With X total substitution number No more than 3；When working as Z1、Z2For CH and N when, R1It is no more than 4 with X total substitution number；Z1And Z2For identical or different group, it is selected from CH or N；Y is B (OH)2, BF3K or boric acid ester group.
Preferable preparation method is as follows：
Wherein, Ar is naphthalene, pyridine, thiophene, furans, oxazoles, thiazole；Copper catalyst is thiophene -2-carboxylic acid copper.
The copper salt catalyst is monovalence or cupric salt, and cuprous salt is preferably thiophene -2-carboxylic acid copper, and cupric salt is excellent Choosing is trifluoromethayl sulfonic acid copper, copper acetate (containing the crystallization water or without the crystallization water), copper chloride, trifluoracetic acid copper or isooctyl acid copper, Its dosage is the 0.001-1 equivalents of aryl boron compound, and optimum amount is the 0.005-0.2 equivalents of aryl boron compound.
The molar ratio of copper and nitrogenous organic ligand is 0.1-10 in copper salt catalyst, and optimum molar ratio is 0.5-2；Institute The nitrogenous organic ligand stated is pyridine, monosubstituted or polysubstituted pyridine derivate, 1,10- ferrosin, 2-2 ' bipyridyls, 2, 2':6', 2 "-terpyridyl, imidazoles, triethylamine or DIPEA.Copper salt catalyst is by trifluoromethayl sulfonic acid copper, copper acetate (containing crystallization Water or without the crystallization water), trifluoracetic acid copper, isooctyl acid copper or thiophene -2-carboxylic acid copper and pyridine, monosubstituted or polysubstituted pyridine Derivative, 1,10- ferrosin, 2-2 ' bipyridyls or 2,2':6', 2 "-terpyridyl are prepared with 0.5-2 molar ratio； Reaction temperature is -20 DEG C -60 DEG C.
The oxidant is solid oxidizer and gaseous oxidant, when oxidant is silver carbonate, silver acetate, silver nitrate, height Sodium iodate, when Potassiumiodate, TBHP or di-tert-butyl peroxide, its dosage is that phenyl boron compound 0.5-10 works as Amount, optimum amount is 2 equivalents；When oxidant is air or oxygen, its reaction pressure scope is 1-5atm.
Additive is sodium carbonate, sodium acid carbonate, potassium carbonate, saleratus, potassium phosphate, potassium dihydrogen phosphate, sodium acetate or second Sour potassium, its dosage are the 0.5-10 equivalents of phenyl boron compound, and optimum amount is 2 equivalents.
The related aryl trifluoro ethoxy ether synthesized by this method is to prepare medical Silodosin, Flecainide and orchid Rope draws the key intermediate of azoles.
Raw material involved in the present invention is that aryl boric acid or aryl potassium fluoborate salt have good reactivity, Yi Jiben Invention has the simple efficient, advantage of mild condition, the virtue with various substituents can be prepared by the method for the present invention Base trifluoro ethoxy ether compound.
What the present invention was realized in：When in organic solvent, presence or absence of additive, reaction temperature is 0-60 DEG C The promotion of reaction, phenyl boron compound or pyridine radicals boron compound or pyrimidine radicals boron compound and trifluoroethanol in mantoquita and part In the presence of oxidant, aryl-trifluoro ethoxy ether compound is prepared with 85% or so yield in reaction 1-40 hours.
Mantoquita involved in the present invention includes monovalence and cupric salt, cuprous salt thiophene -2-carboxylic acid copper and triethylamine, pyrrole Pyridine, monosubstituted or polysubstituted pyridine derivate coordination composition effect are preferable；Cupric salt such as trifluoromethayl sulfonic acid copper, copper acetate (containing the crystallization water or without the crystallization water), copper chloride, trifluoracetic acid copper or isooctyl acid copper and triethylamine, imidazoles, pyridine, it is monosubstituted or Polysubstituted pyridine derivate, 1,10- ferrosin, 2-2 ' bipyridyls or 2,2':6', 2 "-terpyridyl etc. parts composition effect Fruit is preferable, wherein best using isooctyl acid copper or copper acetate and pyridine coordination using effect.
Oxidant involved in the present invention such as silver carbonate, silver acetate, silver nitrate, sodium metaperiodate, Potassiumiodate, t-butyl peroxy Change hydrogen, di-tert-butyl peroxide, air or oxygen can be effectively promoted the progress of reaction, silver carbonate di-tert-butyl peroxide The effect of thing, air and oxygen is outstanding.
Sodium Carbonate Additive involved in the present invention, sodium acid carbonate, potassium carbonate, saleratus etc. can effectively facilitate reaction Carrying out, the Additive effect such as sodium carbonate, sodium acid carbonate is the most obvious, but these additives are to reaction and non-key, In the case of not having additive, reaction can also be carried out, but yield is slightly lower.
In the method for the present invention, had using various aryl boron compounds such as aryl boric acid and aryl potassium fluoborate salt good Good reaction effect, but the reaction effect of aryl-boric acid ester is poor.
Beneficial effect
(1) raw material of the invention is that aryl boric acid or aryl potassium fluoborate salt have good reactivity, and synthesis side Method has the simple efficient, advantage of mild condition；
(2) method of the invention solve in the prior art it is costly, condition is harsh, substrate universality it is narrow with and not The defects of suitable for industrial applications；
(3) method of the invention is simple to operate, and raw material is easy to get, reaction condition is gentle, substrate universality is wide, it is environment-friendly, Suitable for industrial applications.
Embodiment
With reference to specific embodiment, the present invention is expanded on further.It should be understood that these embodiments are merely to illustrate the present invention Rather than limitation the scope of the present invention.In addition, it is to be understood that after the content of the invention lectured has been read, people in the art Member can make various changes or modifications to the present invention, and these equivalent form of values equally fall within the application appended claims and limited Scope.
Embodiment 1
Using air as oxidant, the oxidative coupling reaction of 4- biphenylboronic acids and trifluoroethanol under cuprous salt catalysis.
Using dichloromethane (5ml) as solvent, 4- biphenylboronic acids (0.5mmol), trifluoroethanol (1.0mmol) and three are added Ethamine (1.0mmol) is stirred at room temperature 18 hours under cuprous salt CuTc (0.05mmol) catalysis under air atmosphere.Pass through19F NMR tracking reactions, until reaction progress is complete.Column chromatography for separation obtains corresponding aryl trifluoroethoxy after filtering, removing solvent Base ether compound.Yield is 45%.Related data is as follows：1H NMR(400MHz,CDCl3) δ ppm 7.56 (d, J=7.2Hz, 4H), 7.43 (t, J=7.6Hz, 2H), 7.34 (t, J=7.2Hz, 1H), 7.07 (d, J=8.4Hz, 2H), 4.40 (q, J= 8.2Hz,2H).13C NMR(100MHz,CDCl3)δppm 157.0,140.4,135.8,128.9,128.4,127.1,126.9, 123.5 (q, J=278.0Hz), 115.3,66.0 (q, J=35.4Hz)19F NMR(376MHz,CDCl3)δppm-73.98(t, J=8.1Hz, 3F) .MS (EI):M/z (%) 252 (100), [M]+,252.HRMS(EI-TOF)m/z:[M]+Calcd for C14H11F3O:252.0762；Found:[M]+,252.0757。
Embodiment 2
Using air as oxidant, the oxidative coupling reaction of 4- biphenylboronic acids and trifluoroethanol under cupric salt catalysis.
Using dichloromethane (5ml) as solvent, 4- biphenylboronic acids (0.5mmol), trifluoroethanol (1.0mmol) and pyrrole are added Pyridine (1.0mmol) is at cupric salt Cu (OAc)2Under (0.05mmol) catalysis, it is stirred at room temperature under air atmosphere 18 hours.Pass through19F NMR tracking reactions, until reaction progress is complete.Column chromatography for separation obtains corresponding aryl trifluoroethoxy after filtering, removing solvent Base ether compound, yield 55%.
Embodiment 3
Using silver carbonate as oxidant, the oxidative coupling of 4- biphenylboronic acids and trifluoroethanol under cupric salt catalysis is anti- Should.
Using dichloromethane (5ml) as solvent, 4- biphenylboronic acids (0.5mmol), trifluoroethanol (1.0mmol), carbon are added Sour silver (1.0mmol) and pyridine (1.0mmol) are at cupric salt Cu (OAc)2Under (0.05mmol) catalysis, room temperature under nitrogen atmosphere Stirring 18 hours.Pass through19F NMR tracking reactions, until reaction progress is complete.Column chromatography for separation obtains after filtering, removing solvent Corresponding aryl trifluoro ethoxy ether compound, yield 87%.
Embodiment 4
Using air as oxidant, the oxidation of 4- biphenylboronic acids, trifluoroethanol, divalent copper catalyst under additive promotion Coupling reaction.
Solvent be used as with dichloromethane (5ml) (yield change is little when with 1,2- dichloroethanes being solvent), 4- is added and joins Phenyl boric acid (0.5mmol), trifluoroethanol (1.0mmol), sodium carbonate (1.0mmol) and pyridine (1.0mmol) (change into triethylamine or During imidazoles, yield slightly reduces) at cupric salt Cu (OAc)2Under (0.05mmol) catalysis, it is small to be stirred at room temperature 18 under air atmosphere When.Pass through19F NMR tracking reactions, until reaction progress is complete.Column chromatography for separation obtains corresponding virtue after filtering, removing solvent Base trifluoro ethoxy ether compound, yield 85%.
Embodiment 5
Using air as oxidant, 4- biphenyl fluoboric acid sylvite, trifluoroethanol, divalent copper catalyst are under additive promotion Oxidative coupling reaction.
Using dichloromethane (5ml) as solvent, 4- biphenyl fluoboric acid sylvite (0.5mmol), trifluoroethanol are added (1.0mmol), sodium carbonate (1.0mmol) and pyridine (1.0mmol), at cupric salt Cu (OAc)2Under (0.05mmol) catalysis, It is stirred at room temperature under air atmosphere 18 hours.Pass through19F NMR tracking reactions, until reaction progress is complete.After filtering, removing solvent Column chromatography for separation obtains corresponding aryl trifluoro ethoxy ether compound, yield 89%.
Embodiment 6
Coupling reaction of the phenylboric acid with trifluoroethanol under cupric salt catalysis with different substituents.
Using dichloromethane (5ml) as solvent, the phenylboric acid (0.5mmol) with different substituents, trifluoro second are added Alcohol (1.0mmol), sodium carbonate (1.0mmol) and pyridine (1.0mmol), at cupric salt Cu (OAc)2(0.05mmol) is catalyzed Under, it is stirred at room temperature 18 hours under air atmosphere or [under silver carbonate (0.4mmol)/nitrogen atmosphere].Pass through19F NMR tracking reactions, Until reaction is carried out completely.Column chromatography for separation obtains corresponding aryl trifluoro ethoxy ether compound after filtering, removing solvent.
Wherein, when the phenylboric acid of different substituents is 2- biphenylboronic acids, gained compound is 2- biphenyl trifluoroethoxies Base ether (44.2mg), yield：35%.
Related data is：White solid,1H NMR(400MHz,CDCl3) δ ppm 7.52 (d, J=7.5Hz, 2H), 7.43- 7.29 (m, 5H), 7.14 (t, J=7.5Hz, 1H), 6.98 (d, J=8.2Hz, 1H), 4.23 (q, J=8.2Hz, 2H)13CNMR (100MHz,CDCl3)δppm 154.50,137.49,132.02,131.41,129.39,128.68,128.13,127.29, 123.35 (q, J=279.4Hz), 123.29,114.50,66.80 (q, J=35.4Hz)19F NMR(376MHz,CDCl3)δ Ppm-73.93 (t, J=8.2Hz, 3F) .IR (KBr) υmax 3063,2941,1482,1287,1168,976,862,752, 668cm-1.MS(EI):M/z (%) 252 (100), [M]+,252.HRMS(EI-TOF)m/z:[M]+Theoretical calculation (Calcd for)C14H11F3O:252.0762；Experiment value (Found):[M]+,252.0765.
Wherein, when the phenylboric acid of different substituents is 4- phenoxy group phenyl boric acids, gained compound is 4- phenoxy groups-benzene Base trifluoro ethoxy ether (93.5mg), yield：70%.
Related data is：White solid, fusing point：119-121℃.1H NMR(400MHz,CDCl3) δ ppm 7.32 (t, J= 7.6Hz, 2H), 7.08 (t, J=7.4Hz, 1H), 7.01-6.97 (m, 3H), 6.93 (t, J=7.6Hz, 3H), 4.33 (q, J= 8.2Hz,2H).13C NMR(100MHz,CDCl3) δ ppm 157.94,153.59,152.03,129.75,123.3 (q, J= 287.2Hz), 122.96,120.63,118.12,116.41,66.65 (q, J=35.5Hz)19F NMR(376MHz,CDCl3)δ Ppm-74.06 (t, J=8.2Hz, 3F) .IR (KBr) υmax 3042,2943,1590,1490,1285,1221,1168,1103, 975,842,750,692cm-1.MS(EI):M/z (%) 268 (100), [M]+,268.HRMS(EI-TOF)m/z:[M]+Theory meter Calculate (Calcd for) C14H11F3O2:268.0711；Experiment value (Found):[M]+,268.0712.
Wherein, when the phenylboric acid of different substituents is 4- methylthio phenyl boric acid, gained compound is 4- methyl mercaptos-benzene Base trifluoro ethoxy ether (87.6mg), yield：79%.
Related data is：Colourless viscous liquid,1H NMR(400MHz,CDCl3) δ ppm 7.25 (d, J=8.8Hz, 2H), 6.88 (d, J=8.8Hz, 2H), 4.31 (q, J=8.2Hz, 3H), 2.44 (s, 3H)13C NMR(100MHz,CDCl3)δ Ppm155.75,131.51,129.52,123.31 (q, J=278.1Hz), 115.73,66.11 (q, J=35.5Hz), 17.34.19FNMR(376MHz,CDCl3) δ ppm-74.02 (t, J=8.2Hz, 3F) .IR (KBr) υmax 2923,1595,1492, 1288,1236,1169,1074,973,821,691cm-1.MS(EI):M/z (%) 222 (100), [M]+,222.HRMS(EI- TOF)m/z:[M]+Theoretical calculation (Calcd for) C9H9F3OS:222.0326；Experiment value (Found):[M]+,222.0329.
Wherein, when the phenylboric acid of different substituents is 4- tert-butylbenzeneboronic acids, gained compound is the 4- tert-butyl groups-benzene Base trifluoro ethoxy ether (83.5mg), yield：72%.
Related data is：Colourless liquid,1H NMR(400MHz,CDCl3) δ ppm 7.33 (d, J=8.8Hz, 2H), 6.87 (d, J=8.8Hz, 2H), 4.32 (q, J=8.2Hz, 2H), 1.30 (s, 9H)13C NMR(100MHz,CDCl3)δppm (155.26,145.39,126.52,123.45 q, J=278.2Hz), 114.50,66.07 (q, J=35.4Hz), 34.19, 31.44.19F NMR(376MHz,CDCl3) δ ppm-74.09 (t, J=8.2Hz, 3F) .IR (KBr) υmax 2964,1513, 1286,1239,1165,1078,975,829cm-1.MS(EI):M/z (%) 217 (100), [M]+,232.HRMS(EI-TOF)m/ z:[M]+Theoretical calculation (Calcd for) C12H15F3O:232.1075；Experiment value (Found):[M]+,232.1081.
Wherein, when the phenylboric acid of different substituents is 3- acetamidobenzeneboronic acids, gained compound is 3- trifluoro second Epoxide-antifebrin (60.3mg), yield：52%.
Related data is：White solid, fusing point：108-109℃.1H NMR(400MHz,CDCl3) δ ppm 7.41 (d, J= 2.3Hz, 1H), 7.32 (bs, 1H), 7.26-7.17 (m, 2H), 6.96 (d, J=8.1Hz, 1H), 6.68 (dd, J=8.2, 2.5Hz, 1H), 4.33 (q, J=8.1Hz, 2H), 2.16 (s, 3H)13C NMR(100MHz,CDCl3)δppm 169.02, (157.81,139.45,129.91,123.30 q, J=277.8Hz), 113.74,110.68,106.84,65.75 (q, J= 35.6Hz),24.50.19F NMR(376MHz,CDCl3) δ ppm-74.00 (t, J=8.1Hz, 3F) .IR (KBr) υmax 3306, 1670,1602,1447,1278,1161,974,869,770,684cm-1.MS(EI):M/z (%) 191 (100), [M]+, 233.HRMS(EI-TOF)m/z:[M]+Theoretical calculation (Calcd for) C10H10F3NO2:233.0664；Experiment value (Found): [M]+,233.0659.
Wherein, when the phenylboric acid of different substituents is 3,4- methylene-benzene boric acid, gained compound is 3,4- methylenes Base epoxide-phenyl trifluoromethanesulfonate ethyoxyl ether (76.5mg), yield：69%.
Related data is：White solid, fusing point：53-55℃.1H NMR(400MHz,CDCl3) δ ppm.6.70 (d, J= 8.4Hz, 1H), 6.53 (d, J=2.6Hz, 1H), 6.35 (dd, J=8.4,2.6Hz, 1H), 5.92 (s, 2H), 4.25 (q, J= 8.2Hz,2H).13C NMR(100MHz,CDCl3) δ ppm 152.94,148.48,143.14,123.33 (q, J=278.1Hz), (107.95,106.63,101.49,98.96,67.15 q, J=35.3Hz)19F NMR(376MHz,CDCl3)δppm-74.16 (t, J=8.2Hz, 3F) .IR (KBr) υmax 2898,1488,1288,1170,1039,973,941,857,816cm-1.MS (EI):M/z (%) 201, [M]+,201.HRMS(EI-TOF)m/z:[M]+Theoretical calculation (Calcd for) C9H7F3O3: 220.0347；Experiment value (Found):[M]+,220.0344.
Wherein, when the phenylboric acid of different substituents is 4- vinylphenylboronic acids, gained compound is 4- vinyl-benzene Base trifluoro ethoxy ether (75.5mg), yield：75%.
Related data is：Colourless liquid,1H NMR(400MHz,CDCl3) δ ppm 7.36 (d, J=8.8Hz, 2H), 6.89 (d, J=8.8Hz, 2H), 6.65 (dd, J=17.6,10.9Hz, 1H), 5.64 (dd, J=17.6,0.9Hz, 1H), 5.17 (dd, J=10.9,0.9Hz, 1H), 4.33 (q, J=8.1Hz, 2H)13C NMR(100MHz,CDCl3)δppm 157.07,135.83, (132.29,127.58,123.33 q, J=278.0Hz), 114.98,112.76,65.92 (q, J=35.6Hz)19F NMR (376MHz,CDCl3) δ ppm-74.02 (t, J=8.2Hz, 3F) .IR (KBr) υmax 2940,1607,1510,1320,1239, 1163,1080,975,834,659cm-1.MS(EI):M/z (%) 202 (100), [M]+,202.HRMS(EI-TOF)m/z:[M]+ Theoretical calculation (Calcd for) C10H9F3O:202.0605；Experiment value (Found):[M]+,202.0602.
Wherein, when different substituents phenylboric acid for 4- methyl -3- chloro- phenyl boric acids when, gained compound be 4- methyl - The chloro- phenyl trifluoromethanesulfonate ethyoxyl ethers (90.6mg) of 3-, yield：81%.
Related data is：Colourless liquid,1H NMR(400MHz,CDCl3) δ ppm 7.14 (d, J=8.4,1H), 6.95 (d, J=2.7Hz, 1H), 6.75 (dd, J=8.4,2.7Hz, 1H), 4.29 (q, J=8.1Hz, 2H), 2.30 (s, 3H)13C NMR (100MHz,CDCl3) δ ppm 156.00,134.86,131.48,130.12,123.20 (q, J=278.3Hz), 115.88, (113.52,66.18 q, J=35.7Hz), 19.10.19F NMR(376MHz,CDCl3) δ ppm-74.05 (t, J=8.1Hz, 3F).IR(KBr)υmax 2928,1609,1496,1288,1165,1085,976,909,836,812,660cm-1.MS(EI):m/ Z (%) 224 (100), [M]+,224.HRMS(EI-TOF)m/z:[M]+Theoretical calculation (Calcd for) C9H8ClF3O: 224.0216；Experiment value (Found):[M]+,224.0220.
Wherein, when the phenylboric acid of different substituents phenyl boric acid bromo- for 4-, gained compound is the bromo- phenyl trifluoromethanesulfonates of 4- Ethyoxyl ether (91.5mg), yield：72%.
Related data is：White solid, fusing point：38-40℃.1H NMR(400MHz,CDCl3) δ ppm 7.41 (d, J= 9.1Hz, 2H), 6.81 (d, J=9.1Hz, 2H), 4.30 (q, J=8.1Hz, 2H)13C NMR(100MHz,CDCl3)δ Ppm156.51,132.63,123.16 (q, J=278.1Hz), 116.80,114.98,66.06 (q, J=35.8Hz)19F NMR (376MHz,CDCl3) δ ppm-73.99 (t, J=8.1Hz, 3F) .IR (KBr) υmax 3050,2937,1597,1513,1452, 1156,1076,974,830,670cm-1.MS(EI):M/z (%) 168 (100), [M]+,254.HRMS(EI-TOF)m/z:[M]+ Theoretical calculation (Calcd for) C8H6BrF3O:253.9554；Experiment value (Found):[M]+,253.9560.
Wherein, when the phenylboric acid of different substituents phenyl boric acid iodo- for 4-, gained compound is the iodo- phenyl trifluoromethanesulfonates of 4- Ethyoxyl ether (102.5mg), yield：68%.
Related data is：Colourless liquid,1H NMR(400MHz,CDCl3) δ ppm 7.59 (d, J=8.2Hz, 2H), 6.70 (d, J=8.2Hz, 2H), 4.30 (q, J=8.1Hz, 2H)13C NMR(100MHz,CDCl3)δppm 157.28,138.60, 123.16 (q, J=278.2Hz), 117.26,85.06,65.86 (q, J=35.9Hz)19F NMR(376MHz,CDCl3)δ Ppm-73.95 (t, J=8.1Hz, 3F) .IR (KBr) υmax 2940,1586,1485,1289,1236,1164,1057,1004, 975,819,681cm-1.MS(EI):M/z (%) 302 (100), [M]+,302.HRMS(EI-TOF)m/z:[M]+Theoretical calculation (Calcd for)C8H6IF3O:301.9415；Experiment value (Found):[M]+,301.9420.
Wherein, when the phenylboric acid of different substituents is 4- carbethoxyl group phenyl boric acids, gained compound is 4- trifluoro second Epoxide-ethyl benzoate (93.1mg), yield：75%.
Related data is：White solid, fusing point：58-60℃.1H NMR(400MHz,CDCl3) δ ppm 8.02 (d, J= 8.8Hz, 2H), 6.94 (d, J=8.8Hz, 2H), 4.39 (q, J=8.1Hz, 2H), 4.34 (q, J=7.2Hz, 2H), 1.37 (t, J=7.1Hz, 4H)13C NMR(100MHz,CDCl3)δppm 165.95,160.65,131.71,124.82,123.10(q,J =277.9Hz), 114.31,65.52 (q, J=36.3Hz), 60.89,14.31.19F NMR(376MHz,CDCl3)δppm- 73.90 (t, J=8.1Hz, 3F) .IR (KBr) υmax 2988,1701,1608,1511,1282,1168,1106,974,847, 769,741,695cm-1.MS(EI):M/z (%) 203 (100), [M]+,248.HRMS(EI-TOF)m/z:[M]+Theoretical calculation (Calcd for):C11H11F3O3:248.0660；Experiment value (Found):[M]+,248.0659.
Wherein, when the phenylboric acid of different substituents is 4- benzyloxycarbonyl group phenyl boric acids, gained compound is 4- trifluoro second Epoxide-Ergol (128.0mg), yield：78%.
Related data is：White solid, fusing point：67-68℃.1H NMR(400MHz,CDCl3) δ ppm 8.05 (d, J= 9.0Hz, 2H), 7.47-7.28 (m, 5H), 6.95 (d, J=9.0Hz, 2H), 5.33 (s, 2H), 4.39 (q, J=8.0Hz, 2H) .13CNMR(100MHz,CDCl3)δppm 165.79,160.84,136.12,131.95,128.64,128.30,128.21, 124.44,123.48 (q, J=278.7Hz), 114.41,66.66,65.51 (q, J=36.0Hz)19F NMR(376MHz, CDCl3) δ ppm-73.87 (t, J=8.0Hz, 3F) .IR (KBr) υmax 2949,1718,1607,1509,1456,1288, 1101,975,865,752,696cm-1.MS(EI):M/z (%) 203 (100), [M]+,310.HRMS(EI-TOF)m/z:[M]+ Theoretical calculation (Calcd for) C16H13F3O3:310.0817；Experiment value (Found):[M]+,310.0815.
Wherein, when the phenylboric acid of different substituents is 4- acetylbenzene boric acid, gained compound is 4- trifluoroethoxies Base-acetophenone (73.0mg), yield：67%.
Related data is：White solid, fusing point：72-73℃.1H NMR(400MHz,CDCl3) δ ppm 7.97 (d, J= 8.9Hz, 2H), 6.99 (d, J=8.9Hz, 2H), 4.42 (q, J=8.0Hz, 2H), 2.58 (s, 3H)13C NMR(100MHz, CDCl3) δ ppm 196.56,160.82,131.90,130.69,123.06 (q, J=277.8Hz), 114.47,65.53 (q, J =36.2Hz), 26.39.19F NMR(376MHz,CDCl3) δ ppm-73.87 (t, J=8.0Hz, 3F) .MS (EI):M/z (%) 203(100),[M]+,218.HRMS(EI-TOF)m/z:[M]+Theoretical calculation (Calcd for) C10H9F3O2:218.0555；It is real Test value (Found):[M]+,218.0559.
Wherein, when the phenylboric acid of different substituents is 4- formylphenylboronic acids, gained compound is 4- trifluoroethoxies Base-benzaldehyde (62.3mg), yield：61%.
Related data is：Colourless liquid,1H NMR(400MHz,CDCl3) δ ppm 9.94 (s, 1H), 7.89 (d, J= 8.7Hz, 2H), 7.07 (d, J=8.7Hz, 2H), 4.45 (q, J=8.0Hz, 2H)13C NMR(100MHz,CDCl3)δ Ppm190.56,161.84,132.01,131.41,122.99 (q, J=277.9Hz), 115.06,65.57 (q, J= 36.3Hz).19FNMR(376MHz,CDCl3) δ ppm-73.83 (t, J=8.0Hz, 3F) .IR (KBr) υmax 2833,1700, 1601,1509,1289,1245,1162,1072,975,896,831,678cm-1.MS(EI):M/z (%) 203 (100), [M]+, 204.HRMS(EI-TOF)m/z:[M]+Theoretical calculation (Calcd for) C9H7F3O2:204.0398；Experiment value (Found):[M ]+,204.0397.
Wherein, when the phenylboric acid of different substituents is 4- nitrobenzene boronic acids, gained compound is 4- nitro-phenyls three Fluorine ethyoxyl ether (60.2mg), yield：55%.
Related data is：White solid,1H NMR(400MHz,CDCl3) 8.24 (d, J=9.2Hz, 2H), 7.06 (d, J= 9.2Hz, 2H), 4.49 (q, J=7.9Hz, 2H)13C NMR(100MHz,CDCl3)δppm 161.81,142.79,126.01, 122.85 (q, J=278.0Hz), 114.88,65.76 (q, J=36.2Hz)19F NMR(376MHz,CDCl3)δppm-73.85 (t, J=7.9Hz, 3F) .MS (EI):M/z (%) 221 (100), [M]+,221.HRMS(EI-TOF)m/z:[M]+Calcd for C8H6F3NO3:221.0300；Experiment value (Found):[M]+,221.0298.
Wherein, when the phenylboric acid of different substituents is 3- nitrobenzene boronic acids, gained compound is 3- nitro-phenyls three Fluorine ethyoxyl ether (78.5mg), yield：71%.
Related data is：White solid, fusing point：58-59℃.1H NMR(400MHz,CDCl3)δppm 7.96–7.92(m, 1H), 7.79 (t, J=2.3Hz, 1H), 7.52 (t, J=8.2Hz, 1H), 7.34-7.30 (m, 1H), 4.46 (q, J=7.9, 2H).13CNMR(100MHz,CDCl3)δppm 19F NMR(376MHz,CDCl3) δ ppm-73.83 (t, J=7.9Hz, 3F) .IR (KBr)υmax 3103,1585,1533,1483,1353,1321,1163,1066,973,859,801,738,658cm-1.MS (EI):M/z (%) 221 (100), [M]+,221.HRMS(EI-TOF)m/z:[M]+Theoretical calculation (Calcd for) C8H6F3NO3: 221.0300；Experiment value (Found):[M]+,221.0307.
Wherein, when the phenylboric acid of different substituents is 4- itrile group phenyl boric acids, gained compound is 4- itrile groups-phenyl three Fluorine ethyoxyl ether (58.1mg), yield：58%.
Related data is：White solid,1H NMR(400MHz,CDCl3) δ ppm 7.65 (d, J=8.9Hz, 2H), 7.04 (d, J=8.9Hz, 2H), 4.44 (q, J=7.9Hz, 2H)13C NMR(100MHz,CDCl3)δppm 160.3,134.2, 122.9 (q, J=277.9Hz), 118.6,115.5,106.1,65.6 (q, J=36.3Hz)19F NMR(376MHz,CDCl3)δ Ppm-73.83 (t, J=7.9Hz, 3F) .MS (EI):M/z (%) 201 (100), [M]+,201.HRMS(EI-TOF)m/z:[M]+ Theoretical calculation (Calcd for) C9H6F3NO:201.0401；Experiment value (Found):[M]+,201.0399.
Wherein, when the phenylboric acid of different substituents is 9,9- dimethyl fluorene -2- boric acid, gained compound is 9,9- bis- Methyl -2- trifluoro ethoxies fluorenes (87.2mg), yield：60%.
Related data is：Colourless liquid,1H NMR(400MHz,CDCl3) δ ppm 7.65 (dd, J=8.0,4.3Hz, 2H), 7.42 (d, J=8.0Hz, 1H), 7.38-7.26 (m, 2H), 7.04 (d, J=2.4Hz, 1H), 6.90 (dd, J=8.3,2.4Hz, 1H), 4.41 (q, J=8.1Hz, 2H), 1.48 (s, 6H)13C NMR(100MHz,CDCl3)δppm 157.34,155.81, (153.32,138.65,133.98,127.09,126.68,123.46 q, J=278.0Hz), 122.57,120.93,119.52, (113.41,110.02,66.29 q, J=35.3Hz), 46.99,27.19.19F NMR(376MHz,CDCl3)δppm-73.95 (t, J=8.1Hz, 3F) .IR (KBr) υmax 2961,1611,1488,1426,1260,1165,1088,974,775,758, 735,665cm-1.MS(EI):M/z (%) 277 (100), [M]+,292.HRMS(EI-TOF)m/z:[M]+Theoretical calculation (Calcdfor)C17H15F3O:292.1075；Experiment value (Found):[M]+,292.1070.
Wherein, when the phenylboric acid of different substituents is 6- methoxynaphthalene -2- boric acid, gained compound is 2- methoxies Base -6- trifluoro ethoxies naphthalene (89.2mg), yield：70%.
Related data is：White solid, fusing point：91-92℃.1H NMR(400MHz,CDCl3) δ ppm 7.67 (d, J= 8.9Hz, 1H), 7.63 (d, J=8.9Hz, 1H), 7.19-7.12 (m, 2H), 7.11 (d, J=2.8Hz, 2H), 4.43 (q, J= 8.0Hz,2H),3.89(s,3H).13C NMR(100MHz,CDCl3)δppm 156.78,153.86,130.67,129.30, (128.66,128.33,123.44 d, J=278.0Hz), 119.44,118.60,108.21,106.05,66.06 (q, J= 35.8Hz),55.33.19F NMR(376MHz,CDCl3) δ ppm-73.89 (t, J=8.0Hz, 3F) .IR (KBr) υmax 2966, 1606,1395,1283,1164,1029,975,853,663cm-1.MS(EI):M/z (%) 256 (100), [M]+,256.HRMS (EI-TOF)m/z:[M]+Theoretical calculation (Calcd for) C13H11F3O2:256.0711；Experiment value (Found):[M]+, 256.0709. wherein, when the phenylboric acid of different substituents is quinoline -3- boric acid, gained compound is 3- trifluoro ethoxies Quinoline (73.5mg), yield：65%.
Related data is：White solid, fusing point：63-65℃.1HNMR(400MHz,CDCl3) δ ppm 8.71 (d, J= 2.8Hz, 1H), 8.05 (d, J=8.3Hz, 1H), 7.70 (d, J=8.1Hz, 1H), 7.59 (t, J=7.6Hz, 1H), 7.51 (t, J=7.5Hz, 1H), 7.39 (d, J=2.8Hz, 1H), 4.46 (q, J=8.0Hz, 2H)13C NMR(100MHz,CDCl3)δ Ppm150.74,144.24,143.77,129.24,128.19,127.78,127.58,126. 86,123.07 (q, J= 278.1Hz), 114.47,65.92 (q, J=36.0Hz)19F NMR(376MHz,CDCl3) δ ppm-73.67 (t, J=8.0Hz, 3F).IR(KBr)υmax 3028,1608,1443,1283,1161,978,855,749,653cm-1.MS(EI):M/z (%) 116 (100),[M]+,227.HRMS(EI-TOF)m/z:[M]+Theoretical calculation (Calcd for) C11H8F3NO:227.0558；Experiment value (Found):[M]+,227.0560.
Wherein, when the phenylboric acid of different substituents is 4- (9H- carbazole -9- bases) phenyl boric acid, gained compound is N- (4- trifluoro ethoxies phenyl) carbazole (139.5mg), yield：82%.
Related data is：White solid, fusing point：117-118℃.1H NMR(400MHz,CDCl3) δ ppm 8.16 (d, J= 7.8Hz,2H),7.53–7.46(m,2H),7.45–7.40(m,2H),7.36–7.27(m,4H),7.19–7.11(m,2H), 4.44 (q, J=8.1Hz, 2H)13C NMR(100MHz,CDCl3)δppm 156.51,141.19,132.19,128.80, (126.01,123.33 q, J=278.0Hz), 123.29,120.37,119.95,116.25,109.62,66.17 (q, J= 35.9Hz).19F NMR(376MHz,CDCl3) δ ppm-73.83 (t, J=8.1Hz, 3F) .IR (KBr) υmax 2943,1580, 1453,1236,1165,966,753,727cm-1.MS(EI):M/z (%) 341 (100), [M]+,341.HRMS(EI-TOF)m/ z:[M]+Theoretical calculation (Calcd for) C20H14F3NO:341.1027；Experiment value (Found):[M]+,341.1020.
Wherein, when the phenylboric acid of different substituents is dibenzothiophenes -4- boric acid, gained compound is 4- trifluoro second Epoxide dibenzothiophenes (49.3mg), yield：35%.
Related data is：White solid, fusing point：50-51℃.1H NMR(400MHz,CDCl3)δppm 8.17–8.08(m, 1H), 7.89-7.84 (m, 2H), 7.51-7.43 (m, 2H), 7.41 (t, J=7.9Hz, 1H), 6.91 (d, J=7.9Hz, 1H), (4.56 q, J=8.1Hz, 2H)13C NMR(100MHz,CDCl3)δppm 152.44,139.86,137.96,135.56, (128.83,123.26 d, J=278.1Hz), 127.06,125.60,124.48,123.03,122.00,116.04,108.75, 66.37 (q, J=36.1Hz)19F NMR(376MHz,CDCl3) δ ppm-73.84 (t, J=8.1Hz, 3F) .IR (KBr) υmax 2968,1568,1443,1287,1248,1166,1075,973,748cm-1.MS(EI):M/z (%) 171 (100), [M]+, 282.HRMS(EI-TOF)m/z:[M]+Theoretical calculation (Calcd for) C14H9F3OS:282.0326；Experiment value (Found):[M ]+,282.0321.
Wherein, when the phenylboric acid of different substituents is (R)-(3- (3- ((tert-butoxycarbonyl) (1- naphthalenes ethyl) amino) Propyl group) phenyl boric acid when, gained compound is (R)-N- tert-butoxycarbonyls-N-1- (1- naphthyls)-ethyl-(3- trifluoro ethoxies Phenyl) propylamine (163.5mg), yield：67%.
Related data is：Light yellow viscous liquid1H NMR(400MHz,CDCl3) δ ppm 8.17 (d, J=8.2Hz, 1H), 7.85 (d, J=7.7,1H), 7.79 (dd, J=6.7,2.7Hz, 1H), 7.59-7.44 (m, 2H), 7.43-7.38 (m, 2H), 7.07 (t, J=7.9Hz, 1H), 6.65 (dd, J=8.2,2.6Hz, 1H), 6.42 (d, J=7.7Hz, 1H), 6.22- 6.20 (m, 1H), 4.22 (q, J=8.2Hz, 2H), 2.96 (m, 1H), 2.75 (m, 1H), 2.10 (m, 2H), 1.60 (s, 3H) 1.58(s,3H),1.51(s,6H),1.34–1.20(m,1H),0.83–0.67(m,1H).13C NMR(100MHz,CDCl3)δ ppm157.27,155.39,143.77,136.69,133.69,132.40,129.30,128.63,128.48,126.47, (125.85,125.00,124.28 s, 2C), 123.47 (q, J=278.0Hz), 122.38,114.68,111.95,79.67, 65.73 (q, J=35.3Hz), 49.43,42.09,33.22,30.81,28.57,17.13.19F NMR(376MHz,CDCl3)δ Ppm-74.03 (t, J=8.2Hz, 3F) .IR (KBr) υmax 2874,2543,1681,1587,1454,1407,1301,1250, 1157,973,781cm-1.MS(EI):M/z (%) 155 (100), [M]+,487.HRMS(EI-TOF)m/z:[M]+Theoretical calculation (Calcd for)C28H32F3NO3:487.2334；Experiment value (Found):[M]+,487.2338.

Claims (1)

1. a kind of method for preparing aryl trifluoro ethoxy ether compound, including：
Using air as oxidant, the oxygen of 4- biphenyl fluoboric acid sylvite, trifluoroethanol, divalent copper catalyst under additive promotion Change coupling reaction：
Using 5ml dichloromethane as solvent, 0.5mmol 4- biphenyl fluoboric acid sylvite, 1.0mmol trifluoroethanols are added, 1.0mmol sodium carbonate and pyridine 1.0mmol, in 0.05mmol cupric salts Cu (OAc)2Under catalysis, room temperature is stirred under air atmosphere Mix 18 hours；Pass through19F NMR tracking reactions, until reaction progress is complete；Column chromatography for separation obtains phase after filtering, removing solvent The aryl trifluoro ethoxy ether compound answered, yield 89%.
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CN108218735A (en) * 2018-02-08 2018-06-29 陕西师范大学 The preparation method of 1,4- aminoalcohol derivatives
CN108383748A (en) * 2018-02-08 2018-08-10 陕西师范大学 The process for selective oxidation of amino acid derivativges
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