CN105348048A - Method for preparing aryl trifluoroethoxyl ether - Google Patents

Method for preparing aryl trifluoroethoxyl ether Download PDF

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CN105348048A
CN105348048A CN201510854777.9A CN201510854777A CN105348048A CN 105348048 A CN105348048 A CN 105348048A CN 201510854777 A CN201510854777 A CN 201510854777A CN 105348048 A CN105348048 A CN 105348048A
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aryl
acid
trifluoro ethoxy
boron compound
cdcl
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CN105348048B (en
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卿凤翎
张柯
黄焰根
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Donghua University
National Dong Hwa University
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    • C—CHEMISTRY; METALLURGY
    • 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
    • C—CHEMISTRY; METALLURGY
    • 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
    • C07C231/12—Preparation of carboxylic acid amides by reactions not involving the formation of carboxamide groups
    • C—CHEMISTRY; METALLURGY
    • 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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    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • 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
    • C07C269/06—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 by reactions not involving the formation of carbamate groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • 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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • 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
    • C—CHEMISTRY; METALLURGY
    • 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 invention relates to a method for preparing aryl trifluoroethoxyl ether. The method includes the steps that aryl boron compounds and trifluoroethanol are added to organic solvent, a copper salt catalyst, a ligand and an oxidizing agent are added, a reaction is conducted in a stirring mode for 1-40 hours at the temperature of 0-60 DEG C, filtering is conducted, column chromatography isolation is conducted, and the aryl trifluoroethoxyl ether is obtained. The method is simple in operation, raw materials are easy to obtain, the reaction condition is mild, the substrate universality is wide, the environmental friendliness is achieved, and the method is applicable to industrial application.

Description

A kind of method preparing aryl trifluoro ethoxy ether compound
Technical field
The invention belongs to the synthetic method field of trifluoro ethoxy ether compound, particularly a kind of method preparing aryl trifluoro ethoxy ether compound.
Background technology
Fluorinated organic compound greatly facilitates in the widespread use of medicine, agricultural chemicals and Material Field and introduce fluorine atom and various fluorine-containing functional group in organic molecule.In these functional groups, trifluoro ethoxy is because its higher metabolic stability and good lipotropy make this functional group very common in drug molecule.Comprise the Silodosin for the treatment of benign prostatic hyperplasia at the medicine gone on the market, treat the lansoprazole etc. of ARR flecainide and treatment duodenal ulcer.The compound of this kind of functional group of traditional preparation mainly comprises following two kinds of methods: (1) reacts the trifluoroethylization of phenolic compound; (2) to the nucleophilic substitution reaction of activation aromatic hydrocarbons.Mainly by the reagent such as close electric trifluoroethyl iodine or trifluoroethyl methanesulfonates and phenolic compound, [Camps, F. are reacted to the trifluoroethylization reaction of phenolic compound; Coll, J.; Messeguer, A.; Peric à s, M.A.Synthesis1980,1980,727.], but trifluoroethyl iodine or trifluoroethyl methanesulfonates expensive, and reaction usually needs high temperature make this method condition harsh and lack economy; That the oil of mirbane or fluorobenzene that mainly activate and trifluoroethanol react [(a) Idoux, J.P. to the nucleophilic substitution reaction of activation aromatic hydrocarbons; Madenwald, M.L.; Garcia, B.S.; Chu, D.L.; Gupton, J.T.J.Org.Chem1985,50,1876. (b) foraradicaldisplacementofnitrobenzenes, see:Tejero, I.; Huertas, I.; Gonz á lez-Lafont, ; Lluch, J.M.; Marquet, J.J.Org.Chem2005,70,1718.], but these class methods are limited to the universality of substrate, just have good reactivity when the phenyl ring of oil of mirbane or fluorobenzene must have one or more strong electron-withdrawing group roll into a ball.In recent years, the linked reaction of transition metal-catalyzed/participation becomes the main method preparing trifluoro ethoxy aryl ethers.Document [Vuluga, D.; Legros, J.; Crousse, B.; Bonnet-Delpon, D.Eur.J.Org.Chem.2009,2009,3513.] report the aryl iodide of copper catalysis or the Trifluo-roethoxylation reaction of bromide, but the method needs greatly excessive trifluoroethanol and comparatively high temps.Document [Huang, R.; Huang, Y.; Lin, X.; Rong, M.; Weng, Z.Angew.Chem., Int.Ed.2015,54,5736.] also report the stable trifluoroethanol copper complex [(phen) of aryl iodide or bromide and 1,10-phenanthroline 2cu (OCH 2cF 3)] reaction, prepared a series of trifluoro ethoxy virtue (mixing) based compound, but reaction needed highly basic, [(phen) 2cu (OCH 2cF 3)] preparation need the mantoquita of equivalent and the part of 2 equivalents, 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.; PalSingh, R.Tetrahedron2015,71,8307.] and document [Terrett, J.A.; Cuthbertson, J.D.; Shurtleff, V.W.; MacMillan, D.W.C.Nature2015,524,330.] also report the linked reaction of aryl halide under palladium and nickel catalysis and trifluoroethanol respectively, but be the use of the very expensive catalyzer of cost and part.Based on the importance of this compounds, invention is a kind of simple to operate, with low cost, and the method that the efficient and environmental friendliness of reaction prepares aryl trifluoro ethoxy ether compound seems extremely important and necessary.
Summary of the invention
Technical problem to be solved by this invention is to provide a kind of method preparing aryl trifluoro ethoxy ether compound, this method solve that cost intensive in prior art, condition are harsh, substrate universality narrow with and be not suitable for the defects such as industrial applications.
A kind of method preparing aryl trifluoro ethoxy ether compound of the present invention, comprise: aryl boron compound and trifluoroethanol are joined in organic solvent, add copper salt catalyst, nitrogenous organic ligand and oxygenant, 0 ~ 60 DEG C of stirring reaction 1 ~ 40h, filter, column chromatography for separation, obtains aryl trifluoro ethoxy ether compound; Wherein, the mol ratio of aryl boron compound, trifluoroethanol, nitrogenous organic ligand and copper salt catalyst is 1:0.2-50:0.2-50:0.001-1.
Described aryl boron compound is phenyl boron compound, naphthyl boron compound, pyridyl boron compound, thienylboron compound, furyl boron compound, oxazolyl boron compound, thiazolyl boron compound or pyrimidyl boron compound.
Described phenyl boron compound is 2-bromophenylboronic acid, 2-iodophenyl boronic acid, 2-hydroxyphenyl boronic acid, 1,4-benzene hypoboric acid, 4-bromobenzeneboronic acid, 4-iodobenzene boric acid, 4-bromo-3-Acetvlamino-phenvl boric acid, 4-iodo-3-Acetvlamino-phenvl boric acid or 3-acetylaminohydroxyphenylarsonic acid Isosorbide-5-Nitrae-benzene hypoboric acid; Pyridyl boron compound is 2-methylol-3 methyl-4 pyridine boronic acid or 2-chloromethyl-3 methyl-4 pyridine boronic acid.
When described phenyl boron compound is 2-bromophenylboronic acid, 2-iodophenyl boronic acid or 2-hydroxyphenyl boronic acid, the trifluoro ethoxy aryl trifluoromethoxy ether efficiently synthesized by this boric acid by present method is the key intermediate preparing medical Silodosin.
Described phenyl boron compound is 1,4-benzene hypoboric acid, 4-bromobenzeneboronic acid, 4-iodobenzene boric acid, 4-bromo-3-Acetvlamino-phenvl boric acid, 4-iodo-3-Acetvlamino-phenvl boric acid or 3-acetylaminohydroxyphenylarsonic acid 1, during 4-benzene hypoboric acid, the trifluoro ethoxy aryl trifluoromethoxy ether efficiently synthesized by this boric acid by present method is the key intermediate preparing medical flecainide.
Described pyridyl boron compound be 2-methylol-3 methyl-4 pyridine boronic acid or 2-chloromethyl-3 methyl-4 pyridine boronic acid time, the trifluoro ethoxy pyridine base trifluoromethoxy ether efficiently synthesized by this boric acid by present method is the key intermediate preparing medical lansoprazole.
Described organic solvent is methylene dichloride, 1,2-ethylene dichloride or toluene, and added solvent volume and phenyl boride mass ratio are 5:1-100:1.
Described copper salt catalyst is mantoquita or mol ratio is the mantoquita of 0.1-10:1 and the complex compound with nitrogenous organic ligand.
Described mantoquita and be-20 DEG C-60 DEG C with the temperature of reaction in the preparation process of the complex compound of nitrogenous organic ligand.
Additive is added before described stirring reaction.
The reaction formula that preparation method of the present invention relates to is as follows:
Wherein, described X is H, F, Cl, Br, I, NO 2, NH 2, NR 2, SiR 3, OH, OR, SR or SO 2r; X is upper monosubstituted, two replacement or trisubstituted groups; R is the alkyl of C1-C6, monosubstituted or polysubstituted phenyl;
R 1for H, the phenoxy group that the benzo base that the alkoxyl group of phenyl, formyl radical, ethanoyl, methylsulfonyl, amide group, C1-C6 replaces, the alkoxyl group of C1-C6 or nitro replace, the alkyl of C1-C6 or acyl group; R 1for upper monosubstituted, two replacement or trisubstituted groups; And work as Z 1, Z 2during for CH, total replacement number of R1 and X is no more than 5; Work as Z 1, Z 2during for N, R 13 are no more than with total replacement number of X; When working as Z 1, Z 2during for CH and N, R 14 are no more than with total replacement number of X; Z 1and Z 2for identical or different group, be selected from CH or N; Y is B (OH) 2, BF 3k or boric acid ester group.
Preferred preparation method is as follows:
Wherein, Ar is naphthalene, pyridine, thiophene, furans, oxazole, thiazole; Copper catalyst is thiophene-2-carboxylic acid copper.
Described copper salt catalyst is monovalence or cupric salt, cuprous salt is preferably thiophene-2-carboxylic acid copper, cupric salt is preferably trifluoromethayl sulfonic acid copper, neutralized verdigris (containing crystal water or not containing crystal water), cupric chloride, trifluoracetic acid copper or isocaprylic acid copper, its consumption is the 0.001-1 equivalent of aryl boron compound, and optimum amount is the 0.005-0.2 equivalent of aryl boron compound.
In copper salt catalyst, the molar ratio of copper and nitrogenous organic ligand is 0.1-10, and optimum molar ratio is 0.5-2; Described nitrogenous organic ligand is pyridine, monosubstituted or polysubstituted pyridine derivate, 1,10-phenanthroline, 2-2 ' dipyridyl, 2,2':6', 2 "-terpyridyl, imidazoles, triethylamine or DIPEA.Copper salt catalyst is by trifluoromethayl sulfonic acid copper, neutralized verdigris (containing crystal water or not containing crystal water), trifluoracetic acid copper, isocaprylic acid copper or thiophene-2-carboxylic acid copper and pyridine, monosubstituted or polysubstituted pyridine derivate, 1,10-phenanthroline, 2-2 ' dipyridyl or 2,2':6', 2 "-terpyridyl prepares with the molar ratio of 0.5-2; Temperature of reaction is-20 DEG C-60 DEG C.
Described oxygenant is solid oxidizing agent and gaseous oxidant, when oxygenant is silver carbonate, silver acetate, Silver Nitrate, sodium periodate, when Potassium Iodate, tertbutyl peroxide or ditertiary butyl peroxide, its consumption is phenyl boron compound 0.5-10 equivalent, and optimum amount is 2 equivalents; When oxygenant is air or oxygen, its reaction pressure scope is 1-5atm.
Additive is sodium carbonate, sodium bicarbonate, salt of wormwood, saleratus, potassiumphosphate, potassium primary phosphate, sodium acetate or potassium acetate, and its consumption is the 0.5-10 equivalent of phenyl boron compound, and optimum amount is 2 equivalents.
The relevant aryl trifluoro ethoxy ether synthesized by present method is the key intermediate of preparation medical Silodosin, flecainide and lansoprazole.
Raw material involved in the present invention is that aryl boric acid or aryl fluoride boric acid sylvite all have good reactive behavior, and the present invention has advantage that is simply efficient, mild condition, prepares have various substituent aryl trifluoro ethoxy ether compound by method of the present invention.
The present invention is achieved in that in organic solvent, during presence or absence additive, temperature of reaction is 0-60 DEG C of reaction, phenyl boron compound or pyridyl boron compound or pyrimidyl boron compound and trifluoroethanol under mantoquita and the promotion of part and the effect of oxygenant, react 1-40 hour with about 85% yield prepare aryl-trifluoro ethoxy ether compound.
Mantoquita involved in the present invention comprises monovalence and cupric salt, and cuprous salt thiophene-2-carboxylic acid copper and triethylamine, pyridine, that monosubstituted or polysubstituted pyridine derivate coordination forms effect is better; Cupric salt is as trifluoromethayl sulfonic acid copper, neutralized verdigris (containing crystal water or not containing crystal water), cupric chloride, trifluoracetic acid copper or isocaprylic acid copper and triethylamine, imidazoles, pyridine, monosubstituted or polysubstituted pyridine derivate, 1,10-phenanthroline, 2-2 ' dipyridyl or 2,2':6', 2 "-terpyridyl etc. part composition effect is better, wherein uses isocaprylic acid copper or neutralized verdigris and pyridine coordination result of use best.
Oxygenant involved in the present invention is as silver carbonate, silver acetate, Silver Nitrate, sodium periodate, Potassium Iodate, tertbutyl peroxide, ditertiary butyl peroxide, air or oxygen all effectively can promote the carrying out reacted, and the effect of silver carbonate ditertiary butyl peroxide, air and oxygen is outstanding.
Sodium Carbonate Additive involved in the present invention, sodium bicarbonate, salt of wormwood, saleratus etc. effectively can promote the carrying out reacted, the Additive such as sodium carbonate, sodium bicarbonate effect is the most obvious, but these additives to reaction and non-key, when there is no additive, reaction also can be carried out, but productive rate is slightly low.
In method of the present invention, use various aryl boron compound such as aryl boric acid and aryl fluoride boric acid sylvite to have good reaction effect, but the reaction effect of aryl-boric acid ester is poor.
beneficial effect
(1) raw material of the present invention is that aryl boric acid or aryl fluoride boric acid sylvite all have good reactive behavior, and synthetic method has advantage that is simply efficient, mild condition;
(2) method of the present invention solve that cost intensive in prior art, condition are harsh, substrate universality narrow with and be not suitable for the defects such as industrial applications;
(3) method of the present invention is simple to operate, and raw material is easy to get, and reaction conditions is gentle, substrate universality wide, environmental friendliness, be applicable to industrial applications.
Embodiment
Below in conjunction with specific embodiment, set forth the present invention further.Should be understood that these embodiments are only not used in for illustration of the present invention to limit the scope of the invention.In addition should be understood that those skilled in the art can make various changes or modifications the present invention, and these equivalent form of values fall within the application's appended claims limited range equally after the content of having read the present invention's instruction.
Embodiment 1
Using air as oxygenant, 4-biphenylboronic acid and the oxidative coupling reaction of trifluoroethanol under cuprous salt catalysis.
Using methylene dichloride (5ml) as solvent, add 4-biphenylboronic acid (0.5mmol), trifluoroethanol (1.0mmol) and triethylamine (1.0mmol) under cuprous salt CuTc (0.05mmol) catalysis, stirring at room temperature 18 hours under air atmosphere.Pass through 19fNMR follows the tracks of reaction, until reaction is carried out completely.Filter, obtain corresponding aryl trifluoro ethoxy ether compound except desolventizing rear pillar chromatographic separation.Productive rate is 45%.Related data is as follows: 1hNMR (400MHz, CDCl 3) δ ppm7.56 (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). 13cNMR (100MHz, CDCl 3) δ ppm157.0,140.4,135.8,128.9,128.4,127.1,126.9,123.5 (q, J=278.0Hz), 115.3,66.0 (q, J=35.4Hz). 19fNMR (376MHz, CDCl 3) δ ppm-73.98 (t, J=8.1Hz, 3F) .MS (EI): m/z (%) 252 (100), [M] +, 252.HRMS (EI-TOF) m/z:[M] +calcdforC 14h 11f 3o:252.0762; Found:[M] +, 252.0757.
Embodiment 2
Using air as oxygenant, 4-biphenylboronic acid and the oxidative coupling reaction of trifluoroethanol under cupric salt catalysis.
Using methylene dichloride (5ml) as solvent, add 4-biphenylboronic acid (0.5mmol), trifluoroethanol (1.0mmol) and pyridine (1.0mmol) at cupric salt Cu (OAc) 2(0.05mmol) under catalysis, stirring at room temperature 18 hours under air atmosphere.Pass through 19fNMR follows the tracks of reaction, until reaction is carried out completely.Filter, except desolventizing rear pillar chromatographic separation obtains corresponding aryl trifluoro ethoxy ether compound, productive rate is 55%.
Embodiment 3
Using silver carbonate as oxygenant, 4-biphenylboronic acid and the oxidative coupling reaction of trifluoroethanol under cupric salt catalysis.
Using methylene dichloride (5ml) as solvent, add 4-biphenylboronic acid (0.5mmol), trifluoroethanol (1.0mmol), silver carbonate (1.0mmol) and pyridine (1.0mmol) are at cupric salt Cu (OAc) 2(0.05mmol) under catalysis, stirring at room temperature 18 hours under nitrogen atmosphere.Pass through 19fNMR follows the tracks of reaction, until reaction is carried out completely.Filter, except desolventizing rear pillar chromatographic separation obtains corresponding aryl trifluoro ethoxy ether compound, productive rate is 87%.
Embodiment 4
Using air as oxygenant, 4-biphenylboronic acid, trifluoroethanol, the divalent copper catalyst oxidative coupling reaction under additive promotes.
With methylene dichloride (5ml) (with 1, when 2-ethylene dichloride is solvent, productive rate change is little) as solvent, add 4-biphenylboronic acid (0.5mmol), trifluoroethanol (1.0mmol), sodium carbonate (1.0mmol) and pyridine (1.0mmol) (when changing triethylamine or imidazoles into, productive rate slightly reduces) are at cupric salt Cu (OAc) 2(0.05mmol) under catalysis, stirring at room temperature 18 hours under air atmosphere.Pass through 19fNMR follows the tracks of reaction, until reaction is carried out completely.Filter, except desolventizing rear pillar chromatographic separation obtains corresponding aryl trifluoro ethoxy ether compound, productive rate is 85%.
Embodiment 5
Using air as oxygenant, 4-biphenyl fluoroboric acid sylvite, trifluoroethanol, the divalent copper catalyst oxidative coupling reaction under additive promotes.
Using methylene dichloride (5ml) as solvent, add 4-biphenyl fluoroboric acid sylvite (0.5mmol), trifluoroethanol (1.0mmol), sodium carbonate (1.0mmol) and pyridine (1.0mmol), at cupric salt Cu (OAc) 2(0.05mmol) under catalysis, stirring at room temperature 18 hours under air atmosphere.Pass through 19fNMR follows the tracks of reaction, until reaction is carried out completely.Filter, except desolventizing rear pillar chromatographic separation obtains corresponding aryl trifluoro ethoxy ether compound, productive rate is 89%.
Embodiment 6
There is phenyl-boron dihydroxide and the linked reaction of trifluoroethanol under cupric salt catalysis of different substituents.
Using methylene dichloride (5ml) as solvent, add phenyl-boron dihydroxide (0.5mmol), the trifluoroethanol (1.0mmol) with different substituents, sodium carbonate (1.0mmol) and pyridine (1.0mmol), at cupric salt Cu (OAc) 2(0.05mmol) under catalysis, under air atmosphere or [under silver carbonate (0.4mmol)/nitrogen atmosphere] stirring at room temperature 18 hours.Pass through 19fNMR follows the tracks of reaction, until reaction is carried out completely.Filter, obtain corresponding aryl trifluoro ethoxy ether compound except desolventizing rear pillar chromatographic separation.
Wherein, when the phenyl-boron dihydroxide of different substituents is 2-biphenylboronic acid, gained compound is 2-biphenyl trifluoro ethoxy ether (44.2mg), productive rate: 35%.
Related data is: white solid, 1hNMR (400MHz, CDCl 3) δ ppm7.52 (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, CDCl 3) δ ppm154.50,137.49,132.02,131.41,129.39,128.68,128.13,127.29,123.35 (q, J=279.4Hz), 123.29,114.50,66.80 (q, J=35.4Hz). 19fNMR (376MHz, CDCl 3) δ ppm-73.93 (t, J=8.2Hz, 3F) .IR (KBr) υ max3063,2941,1482,1287,1168,976,862,752,668cm -1.MS (EI): m/z (%) 252 (100), [M] +, 252.HRMS (EI-TOF) m/z:[M] +theoretical Calculation (Calcdfor) C 14h 11f 3o:252.0762; Experimental value (Found): [M] +, 252.0765.
Wherein, when the phenyl-boron dihydroxide of different substituents is 4-phenoxy group phenylo boric acid, gained compound is 4-Phenoxy-phenyl trifluoro ethoxy ether (93.5mg), productive rate: 70%.
Related data is: white solid, fusing point: 119-121 DEG C. 1hNMR (400MHz, CDCl 3) δ ppm7.32 (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). 13cNMR (100MHz, CDCl 3) δ ppm157.94,153.59,152.03,129.75,123.3 (q, J=287.2Hz), 122.96,120.63,118.12,116.41,66.65 (q, J=35.5Hz). 19fNMR (376MHz, CDCl 3) δ ppm-74.06 (t, J=8.2Hz, 3F) .IR (KBr) υ max3042,2943,1590,1490,1285,1221,1168,1103,975,842,750,692cm -1.MS (EI): m/z (%) 268 (100), [M] +, 268.HRMS (EI-TOF) m/z:[M] +theoretical Calculation (Calcdfor) C 14h 11f 3o 2: 268.0711; Experimental value (Found): [M] +, 268.0712.
Wherein, when the phenyl-boron dihydroxide of different substituents is 4-methylthio phenyl boric acid, gained compound is 4-methylthio group-phenyl trifluoromethanesulfonate oxyethyl group ether (87.6mg), productive rate: 79%.
Related data is: colourless viscous liquid, 1hNMR (400MHz, CDCl 3) δ ppm7.25 (d, J=8.8Hz, 2H), 6.88 (d, J=8.8Hz, 2H), 4.31 (q, J=8.2Hz, 3H), 2.44 (s, 3H). 13cNMR (100MHz, CDCl 3) 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, CDCl 3) δ ppm-74.02 (t, J=8.2Hz, 3F) .IR (KBr) υ max2923,1595,1492,1288,1236,1169,1074,973,821,691cm -1.MS (EI): m/z (%) 222 (100), [M] +, 222.HRMS (EI-TOF) m/z:[M] +theoretical Calculation (Calcdfor) C 9h 9f 3oS:222.0326; Experimental value (Found): [M] +, 222.0329.
Wherein, when the phenyl-boron dihydroxide of different substituents is 4-tert-butylbenzeneboronic acid, gained compound is 4-tbutyl-phenyl trifluoro ethoxy ether (83.5mg), productive rate: 72%.
Related data is: colourless liquid, 1hNMR (400MHz, CDCl 3) δ ppm7.33 (d, J=8.8Hz, 2H), 6.87 (d, J=8.8Hz, 2H), 4.32 (q, J=8.2Hz, 2H), 1.30 (s, 9H). 13cNMR (100MHz, CDCl 3) δ ppm155.26,145.39,126.52,123.45 (q, J=278.2Hz), 114.50,66.07 (q, J=35.4Hz), 34.19,31.44. 19fNMR (376MHz, CDCl 3) δ ppm-74.09 (t, J=8.2Hz, 3F) .IR (KBr) υ max2964,1513,1286,1239,1165,1078,975,829cm -1.MS (EI): m/z (%) 217 (100), [M] +, 232.HRMS (EI-TOF) m/z:[M] +theoretical Calculation (Calcdfor) C 12h 15f 3o:232.1075; Experimental value (Found): [M] +, 232.1081.
Wherein, when the phenyl-boron dihydroxide of different substituents is 3-acetamidobenzeneboronic acid, gained compound is 3-trifluoro ethoxy-Acetanilide (60.3mg), productive rate: 52%.
Related data is: white solid, fusing point: 108-109 DEG C. 1hNMR (400MHz, CDCl 3) δ ppm7.41 (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). 13cNMR (100MHz, CDCl 3) δ ppm169.02,157.81,139.45,129.91,123.30 (q, J=277.8Hz), 113.74,110.68,106.84,65.75 (q, J=35.6Hz), 24.50. 19fNMR (376MHz, CDCl 3) δ ppm-74.00 (t, J=8.1Hz, 3F) .IR (KBr) υ max3306,1670,1602,1447,1278,1161,974,869,770,684cm -1.MS (EI): m/z (%) 191 (100), [M] +, 233.HRMS (EI-TOF) m/z:[M] +theoretical Calculation (Calcdfor) C 10h 10f 3nO 2: 233.0664; Experimental value (Found): [M] +, 233.0659.
Wherein, when the phenyl-boron dihydroxide of different substituents is 3,4-methylene-benzene boric acid, gained compound is 3,4-methylene radical oxygen base-phenyl trifluoromethanesulfonate oxyethyl group ether (76.5mg), productive rate: 69%.
Related data is: white solid, fusing point: 53-55 DEG C. 1hNMR (400MHz, CDCl 3) 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). 13cNMR (100MHz, CDCl 3) δ ppm152.94,148.48,143.14,123.33 (q, J=278.1Hz), 107.95,106.63,101.49,98.96,67.15 (q, J=35.3Hz). 19fNMR (376MHz, CDCl 3) δ ppm-74.16 (t, J=8.2Hz, 3F) .IR (KBr) υ max2898,1488,1288,1170,1039,973,941,857,816cm -1.MS (EI): m/z (%) 201, [M] +, 201.HRMS (EI-TOF) m/z:[M] +theoretical Calculation (Calcdfor) C 9h 7f 3o 3: 220.0347; Experimental value (Found): [M] +, 220.0344.
Wherein, when the phenyl-boron dihydroxide of different substituents is 4-vinylphenylboronic acid, gained compound is 4-vinyi-phenyl trifluoro ethoxy ether (75.5mg), productive rate: 75%.
Related data is: colourless liquid, 1hNMR (400MHz, CDCl 3) δ ppm7.36 (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). 13cNMR (100MHz, CDCl 3) δ ppm157.07,135.83,132.29,127.58,123.33 (q, J=278.0Hz), 114.98,112.76,65.92 (q, J=35.6Hz). 19fNMR (376MHz, CDCl 3) δ ppm-74.02 (t, J=8.2Hz, 3F) .IR (KBr) υ max2940,1607,1510,1320,1239,1163,1080,975,834,659cm -1.MS (EI): m/z (%) 202 (100), [M] +, 202.HRMS (EI-TOF) m/z:[M] +theoretical Calculation (Calcdfor) C 10h 9f 3o:202.0605; Experimental value (Found): [M] +, 202.0602.
Wherein, when the phenyl-boron dihydroxide of different substituents is the chloro-phenylo boric acid of 4-methyl-3-, gained compound is 4-methyl-3-chloro-phenyl trifluoromethanesulfonate oxyethyl group ether (90.6mg), productive rate: 81%.
Related data is: colourless liquid, 1hNMR (400MHz, CDCl 3) δ ppm7.14 (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). 13cNMR (100MHz, CDCl 3) δ ppm156.00,134.86,131.48,130.12,123.20 (q, J=278.3Hz), 115.88,113.52,66.18 (q, J=35.7Hz), 19.10. 19fNMR (376MHz, CDCl 3) δ ppm-74.05 (t, J=8.1Hz, 3F) .IR (KBr) υ max2928,1609,1496,1288,1165,1085,976,909,836,812,660cm -1.MS (EI): m/z (%) 224 (100), [M] +, 224.HRMS (EI-TOF) m/z:[M] +theoretical Calculation (Calcdfor) C 9h 8clF 3o:224.0216; Experimental value (Found): [M] +, 224.0220.
Wherein, when the phenyl-boron dihydroxide of different substituents is the bromo-phenylo boric acid of 4-, gained compound is 4-bromo-phenyl trifluoromethanesulfonate oxyethyl group ether (91.5mg), productive rate: 72%.
Related data is: white solid, fusing point: 38-40 DEG C. 1hNMR (400MHz, CDCl 3) δ ppm7.41 (d, J=9.1Hz, 2H), 6.81 (d, J=9.1Hz, 2H), 4.30 (q, J=8.1Hz, 2H). 13cNMR (100MHz, CDCl 3) δ ppm156.51,132.63,123.16 (q, J=278.1Hz), 116.80,114.98,66.06 (q, J=35.8Hz). 19fNMR (376MHz, CDCl 3) δ ppm-73.99 (t, J=8.1Hz, 3F) .IR (KBr) υ max3050,2937,1597,1513,1452,1156,1076,974,830,670cm -1.MS (EI): m/z (%) 168 (100), [M] +, 254.HRMS (EI-TOF) m/z:[M] +theoretical Calculation (Calcdfor) C 8h 6brF 3o:253.9554; Experimental value (Found): [M] +, 253.9560.
Wherein, when the phenyl-boron dihydroxide of different substituents is the iodo-phenylo boric acid of 4-, gained compound is 4-iodo-phenyl trifluoromethanesulfonate oxyethyl group ether (102.5mg), productive rate: 68%.
Related data is: colourless liquid, 1hNMR (400MHz, CDCl 3) δ ppm7.59 (d, J=8.2Hz, 2H), 6.70 (d, J=8.2Hz, 2H), 4.30 (q, J=8.1Hz, 2H). 13cNMR (100MHz, CDCl 3) δ ppm157.28,138.60,123.16 (q, J=278.2Hz), 117.26,85.06,65.86 (q, J=35.9Hz). 19fNMR (376MHz, CDCl 3) δ ppm-73.95 (t, J=8.1Hz, 3F) .IR (KBr) υ max2940,1586,1485,1289,1236,1164,1057,1004,975,819,681cm -1.MS (EI): m/z (%) 302 (100), [M] +, 302.HRMS (EI-TOF) m/z:[M] +theoretical Calculation (Calcdfor) C 8h 6iF 3o:301.9415; Experimental value (Found): [M] +, 301.9420.
Wherein, when the phenyl-boron dihydroxide of different substituents is 4-ethoxycarbonyl phenylo boric acid, gained compound is 4-trifluoro ethoxy-ethyl benzoate (93.1mg), productive rate: 75%.
Related data is: white solid, fusing point: 58-60 DEG C. 1hNMR (400MHz, CDCl 3) δ ppm8.02 (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). 13cNMR (100MHz, CDCl 3) δ ppm165.95,160.65,131.71,124.82,123.10 (q, J=277.9Hz), 114.31,65.52 (q, J=36.3Hz), 60.89,14.31. 19fNMR (376MHz, CDCl 3) δ ppm-73.90 (t, J=8.1Hz, 3F) .IR (KBr) υ max2988,1701,1608,1511,1282,1168,1106,974,847,769,741,695cm -1.MS (EI): m/z (%) 203 (100), [M] +, 248.HRMS (EI-TOF) m/z:[M] +theoretical Calculation (Calcdfor): C 11h 11f 3o 3: 248.0660; Experimental value (Found): [M] +, 248.0659.
Wherein, when the phenyl-boron dihydroxide of different substituents is 4-carbobenzoxy-(Cbz) phenylo boric acid, gained compound is 4-trifluoro ethoxy-peruscabin (128.0mg), productive rate: 78%.
Related data is: white solid, fusing point: 67-68 DEG C. 1hNMR (400MHz, CDCl 3) δ ppm8.05 (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, CDCl 3) δ ppm165.79,160.84,136.12,131.95,128.64,128.30,128.21,124.44,123.48 (q, J=278.7Hz), 114.41,66.66,65.51 (q, J=36.0Hz). 19fNMR (376MHz, CDCl 3) δ ppm-73.87 (t, J=8.0Hz, 3F) .IR (KBr) υ max2949,1718,1607,1509,1456,1288,1101,975,865,752,696cm -1.MS (EI): m/z (%) 203 (100), [M] +, 310.HRMS (EI-TOF) m/z:[M] +theoretical Calculation (Calcdfor) C 16h 13f 3o 3: 310.0817; Experimental value (Found): [M] +, 310.0815.
Wherein, when the phenyl-boron dihydroxide of different substituents is 4-acetylbenzene boric acid, gained compound is 4-trifluoro ethoxy-methyl phenyl ketone (73.0mg), productive rate: 67%.
Related data is: white solid, fusing point: 72-73 DEG C. 1hNMR (400MHz, CDCl 3) δ ppm7.97 (d, J=8.9Hz, 2H), 6.99 (d, J=8.9Hz, 2H), 4.42 (q, J=8.0Hz, 2H), 2.58 (s, 3H). 13cNMR (100MHz, CDCl 3) δ ppm196.56,160.82,131.90,130.69,123.06 (q, J=277.8Hz), 114.47,65.53 (q, J=36.2Hz), 26.39. 19fNMR (376MHz, CDCl 3) 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 (Calcdfor) C 10h 9f 3o 2: 218.0555; Experimental value (Found): [M] +, 218.0559.
Wherein, when the phenyl-boron dihydroxide of different substituents is 4-formylphenylboronic acid, gained compound is 4-trifluoro ethoxy-phenyl aldehyde (62.3mg), productive rate: 61%.
Related data is: colourless liquid, 1hNMR (400MHz, CDCl 3) δ ppm9.94 (s, 1H), 7.89 (d, J=8.7Hz, 2H), 7.07 (d, J=8.7Hz, 2H), 4.45 (q, J=8.0Hz, 2H). 13cNMR (100MHz, CDCl 3) 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, CDCl 3) δ ppm-73.83 (t, J=8.0Hz, 3F) .IR (KBr) υ max2833,1700,1601,1509,1289,1245,1162,1072,975,896,831,678cm -1.MS (EI): m/z (%) 203 (100), [M] +, 204.HRMS (EI-TOF) m/z:[M] +theoretical Calculation (Calcdfor) C 9h 7f 3o 2: 204.0398; Experimental value (Found): [M] +, 204.0397.
Wherein, when the phenyl-boron dihydroxide of different substituents is 4-nitrobenzene boronic acid, gained compound is 4-nitro-phenyl trifluoro ethoxy ether (60.2mg), productive rate: 55%.
Related data is: white solid, 1hNMR (400MHz, CDCl 3) 8.24 (d, J=9.2Hz, 2H), 7.06 (d, J=9.2Hz, 2H), 4.49 (q, J=7.9Hz, 2H). 13cNMR (100MHz, CDCl 3) δ ppm161.81,142.79,126.01,122.85 (q, J=278.0Hz), 114.88,65.76 (q, J=36.2Hz). 19fNMR (376MHz, CDCl 3) δ ppm-73.85 (t, J=7.9Hz, 3F) .MS (EI): m/z (%) 221 (100), [M] +, 221.HRMS (EI-TOF) m/z:[M] +calcdforC 8h 6f 3nO 3: 221.0300; Experimental value (Found): [M] +, 221.0298.
Wherein, when the phenyl-boron dihydroxide of different substituents is 3-nitrobenzene boronic acid, gained compound is 3-nitro-phenyl trifluoro ethoxy ether (78.5mg), productive rate: 71%.
Related data is: white solid, fusing point: 58-59 DEG C. 1hNMR (400MHz, CDCl 3) δ ppm7.96 – 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, CDCl 3) δ ppm 19fNMR (376MHz, CDCl 3) δ ppm-73.83 (t, J=7.9Hz, 3F) .IR (KBr) υ max3103,1585,1533,1483,1353,1321,1163,1066,973,859,801,738,658cm -1.MS (EI): m/z (%) 221 (100), [M] +, 221.HRMS (EI-TOF) m/z:[M] +theoretical Calculation (Calcdfor) C 8h 6f 3nO 3: 221.0300; Experimental value (Found): [M] +, 221.0307.
Wherein, when the phenyl-boron dihydroxide of different substituents is 4-itrile group phenylo boric acid, gained compound is 4-itrile group-phenyl trifluoromethanesulfonate oxyethyl group ether (58.1mg), productive rate: 58%.
Related data is: white solid, 1hNMR (400MHz, CDCl 3) δ ppm7.65 (d, J=8.9Hz, 2H), 7.04 (d, J=8.9Hz, 2H), 4.44 (q, J=7.9Hz, 2H). 13cNMR (100MHz, CDCl 3) δ ppm160.3,134.2,122.9 (q, J=277.9Hz), 118.6,115.5,106.1,65.6 (q, J=36.3Hz). 19fNMR (376MHz, CDCl 3) 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 (Calcdfor) C 9h 6f 3nO:201.0401; Experimental value (Found): [M] +, 201.0399.
Wherein, when the phenyl-boron dihydroxide of different substituents is 9,9-dimethyl fluorene-2-boric acid, gained compound is 9,9-dimethyl-2-trifluoro ethoxy fluorenes (87.2mg), productive rate: 60%.
Related data is: colourless liquid, 1hNMR (400MHz, CDCl 3) δ ppm7.65 (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). 13cNMR (100MHz, CDCl 3) δ ppm157.34,155.81,153.32,138.65,133.98,127.09,126.68,123.46 (q, J=278.0Hz), 122.57,120.93,119.52,113.41,110.02,66.29 (q, J=35.3Hz), 46.99,27.19. 19fNMR (376MHz, CDCl 3) δ ppm-73.95 (t, J=8.1Hz, 3F) .IR (KBr) υ max2961,1611,1488,1426,1260,1165,1088,974,775,758,735,665cm -1.MS (EI): m/z (%) 277 (100), [M] +, 292.HRMS (EI-TOF) m/z:[M] +theoretical Calculation (Calcdfor) C 17h 15f 3o:292.1075; Experimental value (Found): [M] +, 292.1070.
Wherein, when the phenyl-boron dihydroxide of different substituents is 6-methoxynaphthalene-2-boric acid, gained compound is 2-methoxyl group-6-trifluoro ethoxy naphthalene (89.2mg), productive rate: 70%.
Related data is: white solid, fusing point: 91-92 DEG C. 1hNMR (400MHz, CDCl 3) δ ppm7.67 (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). 13cNMR (100MHz, CDCl 3) δ ppm156.78,153.86,130.67,129.30,128.66,128.33,123.44 (d, J=278.0Hz), 119.44,118.60,108.21,106.05,66.06 (q, J=35.8Hz), 55.33. 19fNMR (376MHz, CDCl 3) δ ppm-73.89 (t, J=8.0Hz, 3F) .IR (KBr) υ max2966,1606,1395,1283,1164,1029,975,853,663cm -1.MS (EI): m/z (%) 256 (100), [M] +, 256.HRMS (EI-TOF) m/z:[M] +theoretical Calculation (Calcdfor) C 13h 11f 3o 2: 256.0711; Experimental value (Found): [M] +, wherein, when the phenyl-boron dihydroxide of different substituents is quinoline-3-boric acid, gained compound is 3-trifluoro ethoxy quinoline (73.5mg) to 256.0709., productive rate: 65%.
Related data is: white solid, fusing point: 63-65 DEG C. 1hNMR (400MHz, CDCl 3) δ ppm8.71 (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). 13cNMR (100MHz, CDCl 3) 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). 19fNMR (376MHz, CDCl 3) δ ppm-73.67 (t, J=8.0Hz, 3F) .IR (KBr) υ max3028,1608,1443,1283,1161,978,855,749,653cm -1.MS (EI): m/z (%) 116 (100), [M] +, 227.HRMS (EI-TOF) m/z:[M] +theoretical Calculation (Calcdfor) C 11h 8f 3nO:227.0558; Experimental value (Found): [M] +, 227.0560.
Wherein, when the phenyl-boron dihydroxide of different substituents is 4-(9H-carbazole-9-base) phenylo boric acid, gained compound is N-(4-trifluoro ethoxy phenyl) carbazole (139.5mg), productive rate: 82%.
Related data is: white solid, fusing point: 117-118 DEG C. 1hNMR (400MHz, CDCl 3) δ ppm8.16 (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). 13cNMR (100MHz, CDCl 3) δ ppm156.51,141.19,132.19,128.80,126.01,123.33 (q, J=278.0Hz), 123.29,120.37,119.95,116.25,109.62,66.17 (q, J=35.9Hz). 19fNMR (376MHz, CDCl 3) δ ppm-73.83 (t, J=8.1Hz, 3F) .IR (KBr) υ max2943,1580,1453,1236,1165,966,753,727cm -1.MS (EI): m/z (%) 341 (100), [M] +, 341.HRMS (EI-TOF) m/z:[M] +theoretical Calculation (Calcdfor) C 20h 14f 3nO:341.1027; Experimental value (Found): [M] +, 341.1020.
Wherein, when the phenyl-boron dihydroxide of different substituents is dibenzothiophene-4-boric acid, gained compound is 4-trifluoro ethoxy dibenzothiophene (49.3mg), productive rate: 35%.
Related data is: white solid, fusing point: 50-51 DEG C. 1hNMR (400MHz, CDCl 3) δ ppm8.17 – 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). 13cNMR (100MHz, CDCl 3) δ ppm152.44,139.86,137.96,135.56,128.83,123.26 (d, J=278.1Hz), 127.06,125.60,124.48,123.03,122.00,116.04,108.75,66.37 (q, J=36.1Hz). 19fNMR (376MHz, CDCl 3) δ ppm-73.84 (t, J=8.1Hz, 3F) .IR (KBr) υ max2968,1568,1443,1287,1248,1166,1075,973,748cm -1.MS (EI): m/z (%) 171 (100), [M] +, 282.HRMS (EI-TOF) m/z:[M] +theoretical Calculation (Calcdfor) C 14h 9f 3oS:282.0326; Experimental value (Found): [M] +, 282.0321.
Wherein, when the phenyl-boron dihydroxide of different substituents is (R)-(during 3-(3-((tert-butoxycarbonyl) (1-naphthalene ethyl) is amino) propyl group) phenylo boric acid, gained compound is (R)-N-tert-butoxycarbonyl-N-1-(1-naphthyl)-ethyl-(3-trifluoro ethoxy phenyl) propylamine (163.5mg), productive rate: 67%.
Related data is: light yellow viscous liquid. 1hNMR (400MHz, CDCl 3) δ ppm8.17 (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). 13cNMR (100MHz, CDCl 3) 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. 19fNMR (376MHz, CDCl 3) δ ppm-74.03 (t, J=8.2Hz, 3F) .IR (KBr) υ max2874,2543,1681,1587,1454,1407,1301,1250,1157,973,781cm -1.MS (EI): m/z (%) 155 (100), [M] +, 487.HRMS (EI-TOF) m/z:[M] +theoretical Calculation (Calcdfor) C 28h 32f 3nO 3: 487.2334, experimental value (Found): [M] +, 487.2338.

Claims (11)

1. prepare the method for aryl trifluoro ethoxy ether compound for one kind, comprise: aryl boron compound and trifluoroethanol are joined in organic solvent, add copper salt catalyst, nitrogenous organic ligand and oxygenant, 0 ~ 60 DEG C of stirring reaction 1 ~ 40h, filter, column chromatography for separation, obtains aryl trifluoro ethoxy ether compound; Wherein, the mol ratio of aryl boron compound, trifluoroethanol, nitrogenous organic ligand and copper salt catalyst is 1:0.2-50:0.2-50:0.001-1.
2. a kind of method preparing aryl trifluoro ethoxy ether compound according to claim 1, is characterized in that, the ratio of described aryl boron compound and copper salt catalyst is 1:0.005-0.2.
3. a kind of method preparing aryl trifluoro ethoxy ether compound according to claim 1, it is characterized in that, described aryl boron compound is phenyl boron compound, naphthyl boron compound, pyridyl boron compound, thienylboron compound, furyl boron compound, oxazolyl boron compound, thiazolyl boron compound or pyrimidyl boron compound.
4. a kind of method preparing aryl trifluoro ethoxy ether compound according to claim 3, it is characterized in that, described phenyl boron compound is 2-bromophenylboronic acid, 2-iodophenyl boronic acid, 2-hydroxyphenyl boronic acid, 1,4-benzene hypoboric acid, 4-bromobenzeneboronic acid, 4-iodobenzene boric acid, 4-bromo-3-Acetvlamino-phenvl boric acid, 4-iodo-3-Acetvlamino-phenvl boric acid or 3-acetylaminohydroxyphenylarsonic acid Isosorbide-5-Nitrae-benzene hypoboric acid; Pyridyl boron compound is 2-methylol-3 methyl-4 pyridine boronic acid or 2-chloromethyl-3 methyl-4 pyridine boronic acid.
5. a kind of method preparing aryl trifluoro ethoxy ether compound according to claim 1, is characterized in that, described organic solvent is methylene dichloride, 1,2-ethylene dichloride or toluene, and added solvent volume and phenyl boride mass ratio are 5:1-100:1.
6. a kind of method preparing aryl trifluoro ethoxy ether compound according to claim 1, is characterized in that, described copper salt catalyst is mantoquita or mol ratio is the mantoquita of 0.1-10:1 and the complex compound with nitrogenous organic ligand.
7. a kind of method preparing aryl trifluoro ethoxy ether compound according to claim 6, is characterized in that, described mantoquita is trifluoromethayl sulfonic acid copper, neutralized verdigris, cupric chloride, trifluoracetic acid copper, isocaprylic acid copper or thiophene-2-carboxylic acid copper.
8. a kind of method preparing aryl trifluoro ethoxy ether compound according to claim 1 or 6, it is characterized in that, described nitrogenous organic ligand is pyridine, monosubstituted or polysubstituted pyridine derivate, 1,10-phenanthroline, 2-2 ' dipyridyl, 2,2':6', 2 "-terpyridyl, imidazoles, triethylamine or DIPEA.
9. a kind of method preparing aryl trifluoro ethoxy ether compound according to claim 1, is characterized in that, described oxygenant is solid oxidizing agent and gaseous oxidant; Wherein, solid oxidizing agent is silver carbonate, silver acetate, Silver Nitrate, sodium periodate, Potassium Iodate, tertbutyl peroxide or ditertiary butyl peroxide, and the ratio of add-on and aryl boron compound is 0.5-10:1; Gaseous oxidant is air or oxygen, and reaction pressure scope is 1-5atm.
10. a kind of method preparing aryl trifluoro ethoxy ether compound according to claim 1, is characterized in that, add additive before described stirring reaction.
11. a kind of methods preparing aryl trifluoro ethoxy ether compound according to claim 10, it is characterized in that, described additive is sodium carbonate, sodium bicarbonate, salt of wormwood, saleratus, potassiumphosphate, potassium primary phosphate, sodium acetate or potassium acetate, and consumption is 0.5-10 times of equivalent of aryl boron compound.
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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107200681A (en) * 2017-06-19 2017-09-26 常州大学 A kind of synthetic method of trifluoro ethoxy aryl ether derivatives
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
CN109232289A (en) * 2018-09-10 2019-01-18 绍兴文理学院 A kind of preparation method of N, N- diaryl amide derivatives

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1962603A (en) * 2006-12-04 2007-05-16 中国药科大学 Method for preparing 2-(2,2,2-trifluoroethoxy)phenol
CN102531856A (en) * 2011-12-22 2012-07-04 温州大学 Method for synthesizing asymmetric diaryl ether derivative

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1962603A (en) * 2006-12-04 2007-05-16 中国药科大学 Method for preparing 2-(2,2,2-trifluoroethoxy)phenol
CN102531856A (en) * 2011-12-22 2012-07-04 温州大学 Method for synthesizing asymmetric diaryl ether derivative

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
RUIXIN WANG, ET AL.: "Facile synthesis of trifluoroethyl aryl ethers through copper-catalyzed coupling of CF3CH2OH with aryl- and heteroaryl boronic acids", 《TETRAHEDRON LETTERS》 *
TAN D. QUACH AND ROBERT A. BATEY: "Copper(II)-Catalyzed Ether Synthesis from Aliphatic Alcohols and Potassium Organotrifluoroborate Salts", 《ORGANIC LETTERS》 *

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107200681A (en) * 2017-06-19 2017-09-26 常州大学 A kind of synthetic method of trifluoro ethoxy aryl ether derivatives
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
CN109232289A (en) * 2018-09-10 2019-01-18 绍兴文理学院 A kind of preparation method of N, N- diaryl amide derivatives
CN109232289B (en) * 2018-09-10 2021-04-13 绍兴文理学院 Preparation method of N, N-diaryl amide derivative

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