CN102675015A - Decarboxylation and fluorination method for carboxylic acid - Google Patents

Decarboxylation and fluorination method for carboxylic acid Download PDF

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CN102675015A
CN102675015A CN2012101914097A CN201210191409A CN102675015A CN 102675015 A CN102675015 A CN 102675015A CN 2012101914097 A CN2012101914097 A CN 2012101914097A CN 201210191409 A CN201210191409 A CN 201210191409A CN 102675015 A CN102675015 A CN 102675015A
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carboxylic acid
decarboxylation
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CN102675015B (en
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李超忠
王振涛
尹锋
李兆栋
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Shanghai Ruiwa Technology Co., Ltd.
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Shanghai Institute of Organic Chemistry of CAS
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Abstract

The invention relates to a decarboxylation and fluorination method for carboxylic acid. According to the method, fatty acid RCOOH, monovalent silver salt catalyst and fluorinated reagent Selectfluor or hexafluorophosphate derivative thereof are reacted in a solvent at the temperature of between room temperature and 80 DEG C to obtain RF; and by adopting the method, the carboxylic acid is efficiently converted into corresponding decarboxylated and fluorinated product in an aqueous phase. The method is mild in reaction conditions and easy to operate, has good chemical selectivity and functional group compatibility, and is a very practical sp<3> carbon-fluorine bond synthesizing method.

Description

Carboxylic acid decarboxylation fluoric method
Technical field
The present invention relates to the fluorine organic compound field, relate to a kind of carboxylic acid decarboxylation fluoric novel method furtherly.
Background technology
In organic cpds, introduce physics, chemistry and the biological property that fluorine atom can change molecule; Therefore fluorinated organic compound has very important purposes [1.K.M ü ller, C.Faeh, F.Diederich in medicine, agricultural chemicals and field of materials; Science 317,1881 – 1886 (2007); 2.D.O ' Hagan, Chem.Soc.Rev.37,308 – 319 (2008); 3.S.Purser, P.R.Moore, S.Swallow, V.Gouverneur, Chem.Soc.Rev.37,320 – 330 (2008); 4.K.L.Kirk, Org.Process Res.Dev.12,305 – 321 (2008) .].Nearly in the market 25% medicine contains at least one fluorine atom, and nearly 30% agricultural chemicals contains fluorine atom.In addition, contain 18The molecule of F mark has important purposes [5.P.W.Miller, N.J.Long, R.Vilar, A.D.Gee, Angew.Chem., Int.Ed.47,8998 – 9033 (2008) clinically; 6.T.Furuya, C.A.Kuttruff, T.Ritter, Curr.Opin.Drug Discuv.Dev.11,803 – 819 (2008) .].
But the naturally occurring fluorinated organic compound of finding up to now only has 13.The fluorinated organic compound of the overwhelming majority needs synthetic.Therefore, the formation of carbon-fluorine bond becomes a research direction of organic synthesis.In recent years at sp 2The achievement in research [7.V.V.Grushin, Acc.Chem.Res.43, the 160-171 (2010) that attract people's attention have been obtained in the formation of carbon-fluorine bond; 8.T.Furuya, J.E.M.N.Klein, T.Ritter, Synthesis 1804-1821 (2010); 9.T.Furuya, A.S.Kamlet, T.Ritter, Nature 473,470-477 (2011); 10.D.A.Watson, M.Su, G.Teverovskiy, Y.Zhang, J.Garc í a-Fortanet, T.Kinzel, S.L.Buchwald, Science 325,1661 – 1664 (2009); 11.P.Tang, T.Furuya, T.Ritter, J.Am.Chem.Soc.132,12150 – 12154 (2010); 12.E.Lee, A.S.Kamlet, D.C.Powers, C.N.Neumann, G.B.Boursalian, T.Furuya, D.C.Choi, J.M.Hooker, T.Ritter, Science 334,639-642 (2011) .], still, at sp 3Then make slow progress in the formation of carbon-fluorine bond.
1. present sp 3The formation of carbon-fluorine bond mainly contains two kinds of methods: nucleophilic fluoro and close electric fluoro.Aspect the nucleophilic fluoro, because very weak nucleophilicity of fluorine anion and stronger solvation effect make and directly use the substitution reaction inefficiency of fluorion as nucleophilic reagent, suitability narrow [13.S.Young, J.Chem.Soc.39,489-497 (1881); 14.D.W.Kim, C.E.Song, D.Y.Chi, J.Am.Chem.Soc.124,10278 – 10279 (2002); 15.K.-Y.Kim, B.C.Kim, H.B.Lee, H.Shin, J.Org.Chem.73,8106 – 8108 (2008) .].More common nucleophilic fluoro reagent is DAST (diethylin sulfur trifluoride) and analogue thereof, can alcohol be converted into the fluoro product, but this type reagent toxicity is big; Operation is inconvenient, and usually follows generation [16.K.-Y.Kim, the B.C.Kim of side reactions such as elimination, rearrangement; H.B.Lee; H.Shin, J.Org.Chem.73,8106 – 8108 (2008); 17.W.J.Middleton, J.Org.Chem.40,574 – 578 (1975) .].Aspect the electric fluoro of parent; Mainly be the reaction of close electric fluoro reagent and carbanion, close electric fluoro reagent commonly used mainly contains NFSI (N, N-hexichol alkylsulfonyl is fluoridized ammonia) and Selectfluor (1-chloromethyl-4-fluorine diazabicyclo [2; The two a tetrafluoro borates of octane) and analogue 2,2].But synthetic [18.R.P.Singh, J.M.Shreeve, Synthesis 2561 – 2578 (2002) of the general only suitable ortho position of these class methods fluoric carbonyl compound; 19.R.P.Singh, J.M.Shreeve, Acc.Chem.Res.37,31 – 44 (2004); 20.P.T.Nyffeler, S.G.Dur ó n, M.D.Burkart, S.P.Vincent, C.-H.Wong, Angew.Chem., Int.Ed.44,192 – 212 (2005); 21Y.Hamashima, M.Sodeoka, Synlett 1467 – 1478 (2006); 22.V.Rauniyar, A.D.Lackner, G.L.Hamilton, F.D.Toste, Science 334,1681 – 1684 (2011) .].
2. by contrast, form sp 3The third side Fa – radical fluoro research of Tan – fluorine bond is very few, and its organic synthesis using value also fails to embody.Existing bibliographical information mainly is to adopt F 2[23.V.Grakauskas, J.Org.Chem.34,2446 – 2450 (1969)] or XeF 2[24.T.B.Patrick, K.K.Johri, D.H.White, J.Org.Chem.48,4158 – 4159 (1983); 25.T.B.Patrick, K.K.Johri, D.H.White, W.S.Bertrand, R.Mokhtar, M.R.Kilbourn, M.J.Welch, Can.J.Chem.64,138 – 141 (1986); 26.T.B.Patrick, S.Khazaeli, S.Nadji, K.Hering-Smith, D.Reif, J.Org.Chem.58,705-708 (1993) .] carry out the decarboxylation fluoro of carboxylic acid, but these reaction efficiencies are low, and the equal severe toxicity of both reagent, operation inconvenience.There is report to utilize tert-butyl acrylate and NFSI reaction recently, generates corresponding decarboxylation fluoro product [27.T.B.Patrick, S.Khazaeli, S.Nadji, K.Hering-Smith, D.Reif, J.Org.Chem.58,705-708 (1993) .].But this method must prepare tert-butyl acrylate from carboxylic acid earlier, and reaction efficiency is on the low side.In addition, owing to the generation at the more active uncle's butoxy free radical of simultaneous that produces alkyl diradical, therefore, the limitation of this reaction is bigger.Therefore, the efficient pervasive decarboxylation fluoro method of development is very necessary.
A kind of brand-new decarboxylation fluoro method of patent report of the present invention; With the monovalence silver salt is catalyzer, 1-chloromethyl-4-fluorine diazabicyclo [2,2; 2] the two a tetrafluoro borates (Selectfluor) of octane are fluorination reagent, at aqueous phase carboxylic acid are converted into corresponding decarboxylation fluoro product efficiently.Reaction conditions is gentle, and very easily operation, and it is compatible with functional group to have a good chemo-selective is the unusual sp of practicality 3Carbon-fluorine bond compound method.
Summary of the invention
The problem that the present invention will solve provides a kind of carboxylic acid decarboxylation fluoric novel method.
Reaction formula of the present invention is following:
Figure BDA00001750774300031
Carboxylic acid: the various lipid acid that do not contain or contain functional group.
Silver salt: Silver Nitrate, silver tetrafluoroborate, silver trifluoromethanesulfonate, Silver monoacetate etc.
Solvent (Solvent): water, water/acetone, water/acetonitrile, water/methylene dichloride etc.
Fluorination reagent (Fluorinating agent): Selectfluor or its hexafluorophosphate analogue
Figure BDA00001750774300032
Reaction formula 1
In the method for the present invention, the R that is suitable for is C1～C100 alkyl, preferred C1～C20 alkyl, and described carboxylic acid comprises various primary carbons, secondary carbon and tertiary carbon carboxylic acid; R can contain a kind of to three kinds of following substituting groups in the carboxylic acid molecules: carbonyl, phenyl, C2～C10 ester group, C1～C10 alkoxyl group; Carboxamido-group, cyanic acid, carboxyl, halogenophenyl; The naphthenic base of C5～C7, halogenated phenoxy, phenylcarbonyl group, Pyrrolidine-2; The 5-diketo, phthalimide-based, halogeno-benzene formyl radical, halogen; Phenyl replaces C1 ~ 4 alkyl, and adamantyl contains five yuan or the hexa-member heterocycle of N, and what perhaps have benzo base, C1 ~ 6 alkyl, halo, C2～C10 ester group, C1～C10 alkoxyl group contains five yuan of N or hexa-member heterocycle or the like.
In another kind of preference, R is selected from the alkyl of C1～C20, substituted alkyl, adamantyl, the substituted naphthenic base of C5～C20, the substituted piperidyl of C6～C20 or substituted six hydrogen piperidyls of C6～C20 of C1～C20 or the like.Described alkyl can be primary carbon, secondary carbon or tertiary carbon alkyl.The substituting group of described substituted alkyl, substituted naphthenic base, substituted piperidyl and substituted six hydrogen piperidyls as previously mentioned; Especially be preferably a kind of naphthenic base, halogenophenyl, halogenated phenoxy, C2～C10 ester group, phenylcarbonyl group, Pyrrolidine-2,5-diketo, phthalimide-based, halogeno-benzene formyl radical or halogen or the like to three kinds of following substituting groups: C1～C10 alkyl, C5～C7.RF is 1-fluorine heptadecane, 3-fluorine pentadecane, 1 for example; 3-dicyclohexyl-2-fluoropropane, 1-fluoro-1-octyl group pentamethylene, 1; 3-two (4-chloro-phenyl-)-2-fluoropropane, 2-fluoro-2-methyl dodecyl, 1-fluoro-1-octyl group hexanaphthene, 1; 3-acetoxyl group-2-fluoro-2-methylpropane, 4-fluoro-4-methylvaleric acid cyclohexyl, 4-fluoro-1-phenyl-1-hexanone, (2-fluorine cyclohexyl) phenyl ketone, (4-fluoro-4-methyl isophthalic acid-piperidyl) phenyl ketone, 1-(2-fluoropropyl) Pyrrolidine-2; 5-diketone, 1-(1-fluorine 2-phenylethyl) Pyrrolidine-2,5-diketone, 2-(fluorine butyl) benzene, N-((4-fluorine cyclohexyl) methyl) phthalic imidine, 4-fluoro-N-(4-chlorobenzene formacyl) six hydrogen piperidines, 1-fluorine tridecane, 1-bromo-10-fluorine certain herbaceous plants with big flowers alkane, N-(5-fluorine amyl group) phthalic imidine, 1-fluorine diamantane, 1-chloro-4-(fluorine methoxyl group) benzene, N-(methyl fluoride) phthalic imidine or the like.
The mol ratio of described lipid acid, the agent of monovalence silver catalyst and fluorination reagent is 1:0.1～0.5:1～5.Be recommended as 1:0.1～0.2:1～2.
Used monovalence silver salt is catalytic amount, can be Silver Nitrate, silver tetrafluoroborate or silver trifluoromethanesulfonate, or the like.
Reaction solvent can be a pure water, also can be the mixed solvent that water and organic solvent are formed, like water-acetone, and water-acetonitrile, water-methylene dichloride or water-1, the 2-ethylene dichloride, or the like.
Fluorination reagent can be Selectfluor or its phosphofluoric acid salt derivative.
The reaction generally in room temperature to carrying out 1～20 hour reaction times between the reflux temperature.
(2) typical reaction example
With the Silver Nitrate is catalyzer, and Selectfluor is a fluoro reagent, and the typical reaction example is shown in table one and table two.Can find out that it is compatible that this fluoro-reaction has extraordinary functional group, to the equal effective decarboxylation fluoro of primary carbon, secondary carbon and tertiary carbon carboxylic acid.But aromatic carboxylic acid then is inertia under these conditions.The activity of carboxylic acid is successively decreased by following order: the tertiary carbon carboxylic acid>secondary carbon carboxylic acid>the primary carbon carboxylic acid>aromatic acid.
Table one, be mixed solvent with the acetone, decarboxylation fluoro-reaction under the Silver Nitrate catalysis
Figure BDA00001750774300041
Figure BDA00001750774300051
Figure BDA00001750774300061
Wherein, reflux representes reflux temperature; Rt representes room temperature.
Table two, be solvent with water, decarboxylation fluoro-reaction under the Silver Nitrate catalysis
Figure BDA00001750774300062
Figure BDA00001750774300071
(3) reaction mechanism
Infer that the possible mechanism of reaction is following: at first monovalence silver ions and Selectfluor effect, generate the silver-colored fluorochemical F-Ag (III) of trivalent, this midbody has stronger oxidisability, can alkyl carboxylic acid be oxidized to carboxyl free radical, removes CO then fast 2, produce corresponding alkyl diradical, and F-Ag (III) obtains becoming divalence silver fluorochemical F-Ag (II) behind the electronics; At last, F-Ag (II) carries out fluorine atom again with alkyl diradical to be shifted, thereby obtains final product R-F; The monovalence silver ions of regenerating simultaneously is shown in reaction formula two.
Figure BDA00001750774300081
The possible mechanism of reaction formula 2. reactions
Embodiment
The present invention will be helped to understand through following embodiment, but content of the present invention can not be limited.
Embodiment 1
Synthesizing of 3-fluorine pentadecane (1a)
Under nitrogen atmosphere with 2-ethyl TETRADECONIC ACID (A-1a, 51.2mg, 0.20mmol), AgNO 3(6.8mg, 0.04mmol) and Selectfluor (141.6mg 0.4mmol) adds in the reaction tubes successively.Add each 2 milliliters in acetone and water then.Reaction solution under agitation refluxed 10 hours.System is chilled to room temperature, uses dichloromethane extraction (15mL * 3) then.Organic phase is used anhydrous sodium sulfate drying after merging.Filter, concentrated filtrate, crude product are through purification by silica gel column chromatography, and eluent is a hexane, get product 3-fluorine pentadecane, are colourless liquid, productive rate: 42.7mg (93%) .IR (neat): ν (cm -1) 2926,2855,1465; 1H NMR (400MHz, CDCl 3) δ 0.88 (3H, t, J=7.2Hz), 0.96 (3H, t, J=7.6Hz), 1.26-1.69 (24H, m), 4.29-4.49 (1H, m); 13C NMR (100MHz, CDCl 3) δ 9.4 (d, J=5.9Hz), 14.1,22.7,25.2 (d, J=4.4Hz), 28.1 (d, J=21.2Hz), 29.37,29.43,29.55,29.56,29.6,29.7,29.8,31.9,34.7 (d, J=21.2Hz), 95.7 (d, J=166.2Hz); 19F NMR (282MHz, CDCl 3) δ-181.6 (1F, m); EIMS:m/z (rel intensity) 210 (M-HF, 7), 182 (5), 152 (8), 111 (49), 97 (89), 83 (85), 69 (100), 57 (77), 43 (73); HRMS calculated value (calcd for) C 15H 31F:230.2410, measured value (found) 230.2414.
Embodiment 2
1,3-dicyclohexyl-2-fluoropropane (1b) synthetic
Method is synthetic with 1a's, 10 hours reaction times.Be yellow oily liquid.Yellow oil.IR (neat): ν (cm -1) 2923,1558,1275,1261,764,750; 1H NMR (400MHz, CDCl 3) δ 0.74-1.76 (26H, m), 4.52-4.75 (1H, m); 13C NMR (100MHz, CDCl 3) δ 25.2,25.3,25.5,31.9,33.0,33.1 (d, J=3.7Hz), 42.5 (d, J=20.5Hz), 89.4 (d, J=164.8Hz); 19F NMR (282MHz, CDCl 3) δ-177.2 (1F, m); EIMS:m/z (rel intensity) 206 (M-HF, 10), 178 (2), 135 (8), 110 (22), 96 (45), 82 (100), 67 (33), 55 (62), 41 (24); HRMS calculated value (calcd for) C 15H 26(M-HF): 206.2035, measured value (found) 206.2032.
Embodiment 3
1,3-two (4-chloro-phenyl-)-2-fluoropropane (1c) synthetic
Method is synthetic with 1a's, 10 hours reaction times.Be yellow oily liquid.IR (neat): ν (cm -1) 2925,1492,1275,1261,1091,1016,805,764,750; 1H NMR (400MHz, CDCl 3) δ 2.73-2.89 (4H, m), 4.66-4.84 (1H, m) 7.06 (4H, d, J=8.4Hz), 7.20 (4H, d, J=8.4Hz); 13C NMR (100MHz, CDCl 3) δ 40.3 (d, J=21.2Hz), 94.0 (d, J=174.3Hz), 128.7,130.8,132.7,135.3 (d, J=3.6Hz); 19F NMR (282MHz, CDCl 3) δ-178.6 (1F, m); EIMS:m/z (rel intensity) 282 (M +, 27), 254 (4), 227 (3), 192 (2), 157 (17), 125 (100), 101 (11), 91 (14), 75 (7), 51 (3); HRMS calculated value (calcd for) C 15H 13Cl 2F:282.0378, measured value (found) 282.0380.
Embodiment 4
Synthesizing of 4-fluoro-1-phenyl-1-hexanone (1d)
Method is synthetic with 1a's, 10 hours reaction times.Be yellow oily liquid.IR (neat): ν (cm -1) 2989,2936,1809,1556,1484,1452,1389,1354,1193,1042,777,712; 1H NMR (400MHz, CDCl 3) δ 1.31 (3H, dd, J=23.6,6.0Hz), 1.88-2.10 (2H, m), 2.98-3.14 (2H, m), 4.57-4.79 (1H, m), 7.38 (2H, t, J=7.6Hz), 7.48 (1H, t, J=7.6Hz), 7.89 (2H, d, J=7.2Hz); 13C NMR (100MHz, CDCl 3) δ 21.1 (d, J=22.6Hz), 31.1 (d, J=20.4Hz), 33.9 (d, J=3.0Hz), 90.3 (d, J=164Hz), 128.0,128.6,133.1,136.9,199.4; 19F NMR (282MHz, CDCl 3) δ-175.5 (1F, m); EIMS:m/z (rel intensity) 180 (M +, 2), 160 (1), 120 (34), 105 (100), 91 (1), 77 (32), 51 (6), 47 (2); HRMS calculated value (calcd for) C 11H 13FO:180.0950, measured value (found) 180.0947.
Embodiment 5
Synthesizing of 2-(fluorine butyl) benzene (1e)
Method is synthetic with 1a's, 10 hours reaction times.Be colourless liquid. 1H?NMR(400MHz,CDCl 3)δ1.00(3H,t,J=7.2Hz),1.53-1.71(2H,m),2.81-3.01(2H,m),4.53-4.70(1H,m),7.21-7.32(5H,m); 13C?NMR(100MHz,CDCl 3)δ9.35(d,J=5.9Hz),27.7(d,J=21.1Hz),41.2(d,J=21.9Hz),95.7(d,J=170.6Hz),126.5,128.4,129.4,137.5; 19F?NMR(282MHz,CDCl 3)δ-180.2(1F,m).
Embodiment 6
Synthesizing of N-((4-fluorine cyclohexyl) methyl) phthalic imidine (1f)
Method is synthetic with 1a's, 10 hours reaction times.This compound is the mixture (trans:cis=1:2.4) of cis-trans-isomer. white solid.Mp 104-106 ℃; IR (KBr): ν (cm -1) 2933,1772,1712,1466,1433,1398,1275,1261,1139,1051,948,764,750,721; 1H NMR (400MHz, CDCl 3) (mixture of two stereoisomers) δ 1.30-1.50 (5H, m), 1.71-1.80 (2H, m), 1.92-2.04 (2H, m); 3.46-3.52 (2H, m), 4.30-4.50 (0.3H, m), 4.71 (0.7H, d; J=48.4Hz), and 7.63-7.66 (2H, m), 7.74-7.78 (2H, m); 13CNMR (100MHz, CDCl 3) δ 24.6,27.8 (d, J=11.2Hz)/30.0 (d, J=21.6Hz), 31.6/35.9,43.0/43.6,88.5 (d, J=167.2Hz), 123.3/123.2,132.0/132.1,134.0/133.9,168.6; 19F NMR (282MHz, CDCl 3) δ-170.8/-184.5 (1F, m); EIMS:m/z (rel intensity) 262 (M ++ 1,31), 241 (1), 200 (1), 160 (100), 148 (26), 130 (14), 104 (15), 77 (17), 50 (4); HRMS calculated value (calcd for) C 15H 16FNO 2: 261.1165, measured value (found) 261.1166.
Embodiment 7
Synthesizing of (2-fluorine cyclohexyl) phenyl ketone (1g)
Method is synthetic with 1a's, 10 hours reaction times.Product 1g is made up of the cis-trans-isomer of 1:1.Wherein, cis-isomeride: white solid.Mp 80-81 ℃; IR (KBr): ν (cm -1) 2939,1685,1447,1275,1260,764,750; 1H NMR (400MHz, CDCl 3) δ 1.25-1.99 (7H, m), 2.20-2.36 (1H, m), 3.53-3.59 (1H, m), 4.83-5.02 (1H, m), 7.47 (2H, t, J=7.6Hz), 7.57 (1H, t, J=7.2Hz), 7.98 (2H, d, J=7.2Hz); 13C NMR (100MHz, CDCl 3) δ 23.7 (d, J=10.9Hz), 24.6,29.0 (d, J=8.0Hz), 31.8 (d, J=17.5Hz), 50.8 (d, J=18.9Hz), 92.4 (d, J=172.1Hz), 128.4,128.6,133.1,136.9,201.3; 19FNMR (282MHz, CDCl 3) δ-171.3 (1F, m); EIMS:m/z (rel intensity) 206 (M +, 7), 186 (2), 149 (1), 105 (100), 82 (27), 77 (40), 67 (14), 51 (9); HRMS calculated value (calcd for) C 13H 15FO:206.1107, measured value (found) 206.1111. trans-isomer(ide): 103-104 ℃ of White solid.Mp; IR (KBr): ν (cm -1) 2939,2865,1685,1447,1275,1260,764,750; 1H NMR (400MHz, CDCl 3) δ 1.26-2.14 (8H, m), 3.25-3.42 (1H, m), 4.96-5.13 (1H, m), 7.39 (2H, t, J=8.0Hz), 7.48 (1H, t, J=7.6Hz), 7.79 (2H, d, J=7.2Hz); 13C NMR (100MHz, CDCl 3) δ 20.0,22.2,24.3,31.0 (d, J=21.1Hz), 48.8 (d, J=21.1Hz), 89.2 (d, J=175Hz), 128.2,128.7,132.8,136.4,200.2; 19F NMR (282MHz, CDCl 3) δ-193.8 (1F, m); EIMS:m/z (rel intensity) 206 (M +, 3), 186 (4), 151 (1), 133 (1), 105 (100), 77 (38), 67 (17), 51 (8); HRMS calculated value (calcd for) C 13H 15FO:206.1107, measured value (found) 206.1111.
Embodiment 8
Synthesizing of 4-fluoro-N-(4-chlorobenzene formacyl) six hydrogen piperidines (1h)
Under nitrogen atmosphere with the acid of N-(4-chlorobenzene formacyl) six hydrogen piperidines-4-(A-1h, 53.4mg, 0.20mmol), AgNO 3(6.8mg, 0.04mmol) and Selectfluor (141.6mg 0.4mmol) adds in the reaction tubes successively.Add each 2 milliliters in acetone and water then.Reaction solution stirred 10 hours down at 45 ℃.System is chilled to room temperature, uses dichloromethane extraction (15mL * 3) then.Organic phase is used anhydrous sodium sulfate drying after merging.Filter, concentrated filtrate, crude product is through purification by silica gel column chromatography; Eluent is that (1:10 v:v), gets product 4-fluoro-N-(4-chlorobenzene formacyl) six hydrogen piperidines to ethyl acetate/hexane; Be yellow liquid, productive rate: 28.8mg (60%) .Yellow oil.IR (neat): ν (cm -1) 1637,1436,1364,1092,1016,799; 1H NMR (400MHz, CDCl 3) δ 1.68-2.07 (4H, m), 3.29-3.72 (3H, m), 3.89-4.14 (1H, m), 4.81-5.01 (1H, m), 7.35 (2H, d, J=8.8Hz), 7.40 (2H, d, J=8.8Hz); 13CNMR (100MHz, CDCl 3) δ 31.3,43.5,87.5 (d, J=170.6Hz), 128.4,128.8,134.2,135.9,169.4; 19F NMR (282MHz, CDCl 3) δ-184.0 (1F, m); EIMS:m/z (rel intensity) 241 (M +, 19), 240 (49), 209 (7), 191 (10), 167 (14), 139 (100), 111 (31), 91 (7), 75 (12); HRMS calculated value (calcd for) C 12H 13ClFNO:241.0670, measured value (found) 241.0671.
Embodiment 9
Synthesizing of 2-fluoro-2-methyl dodecyl (1i)
Under nitrogen atmosphere with 2,2-dimethyl-laurostearic acid (A-1i, 45.6mg, 0.20mmol), AgNO 3(6.8mg, 0.04mmol) and Selectfluor (141.6mg 0.4mmol) adds in the reaction tubes successively.Add each 2 milliliters in acetone and water then.Reaction solution at room temperature stirred 10 hours.Use dichloromethane extraction (15mL * 3) then.Organic phase is used anhydrous sodium sulfate drying after merging.Filter, concentrated filtrate, crude product are through purification by silica gel column chromatography, and eluent is a hexane, get product 2-fluoro-2-methyl dodecyl, are yellow liquid, productive rate: 33.1mg (82%) .Yellow oil.IR (neat): ν (cm -1) 2926,2855,1467,1384,1373,881,763,750; 1H NMR (400MHz, CDCl 3) δ 0.81 (3H, t, J=6.4Hz), 1.10-1.40 (22H, m), 1.47-1.56 (2H, m); 13C NMR (100MHz, CDCl 3) δ 14.1,22.6,22.7,24.0 (d, J=5.1Hz), 26.6 (d, J=24.8Hz), 29.4,29.5,29.6,29.7,30.0,31.9,41.5 (d, J=22.6Hz), 95.8 (d, J=162.6Hz); 19F NMR (282MHz, CDCl 3) δ-137.4 (1F, m); EIMS:m/z (rel intensity) 182 (M-HF, 8), 167 (6), 154 (15), 126 (19), 111 (22), 97 (30), 83 (34), 69 (65), 56 (100), 43 (36); HRMS calculated value (calcd for) C 13H 26(M-HF): 182.2035, measured value (found) 182.2031.
Embodiment 10
Synthesizing of 1-fluoro-1-octyl group pentamethylene (1j)
Method is synthetic with 1i's.Be yellow oily liquid.IR (neat): ν (cm -1) 2927,2855,1466; 1H NMR (400MHz, CDCl 3) δ 0.88 (3H, t, J=7.2Hz), 1.28-1.92 (22H, m); 13C NMR (100MHz, CDCl 3) δ 14.1,22.7,23.9,24.5 (d, J=3.7Hz), 29.3,29.6,30.1,31.9,37.5 (d, J=24.0Hz), 38.6 (d, J=24.1Hz), 107.3 (d, J=171.4Hz); 19F NMR (282MHz, CDCl 3) δ-143.1 (1F, m); EIMS:m/z (rel intensity) 180 (M-HF, 7), 152 (4), 123 (18), 109 (12), 82 (100), 67 (74), 55 (32), 41 (32); HRMS calculated value (calcd for) for C 13H 24(M-HF): 180.1878, measured value (found) 180.1879.
Embodiment 11
Synthesizing of 1-fluoro-1-octyl group hexanaphthene (1k)
Method is synthetic with 1i's.Be yellow oily liquid.IR (neat): ν (cm -1) 2931,2855,1450; 1H NMR (400MHz, CDCl 3) δ 0.88 (3H, t, J=7.2Hz), 1.20-1.63 (22H, m), 1.76-1.82 (2H, m); 13C NMR (100MHz, CDCl 3) δ 14.1,22.1 (d, J=2.9Hz), 22.7,22.9 (d, J=4.4Hz), 25.5,29.3,29.6,30.1,31.9,35.1 (d, J=22.6Hz), 40.4 (d, J=22.6Hz), 96.0 (d, J=168.4Hz); 19F NMR (282MHz, CDCl 3) δ-155.9 (1F, m); EIMS:m/z (rel intensity) 194 (M-HF, 14), 166 (5), 138 (3), 101 (53), 81 (100), 67 (13), 55 (21), 43 (10); HRMS calculated value (calcd for) C 14H 26(M-HF): 194.2035, measured value (found) 194.2037.
Embodiment 12
Synthesizing of 4-fluoro-4-methylvaleric acid cyclohexyl (1l)
Method is synthetic with 1i's.Be yellow oily liquid.IR (neat): ν (cm -1) 2939,1732,1456,1387,1260,1174,1124,1016,750; 1H NMR (400MHz, CDCl 3) δ 1.13-1.95 (18H, m), 2.34 (2H, t, J=8.0Hz), 4.66-4.71 (1H, m); 13C NMR (100MHz, CDCl 3) δ 23.7,25.4,26.5 (d, J=24.1Hz), 29.4 (d, J=4.4Hz), 31.6,36.1 (d, J=23.3Hz), 72.6,94.6 (d, J=165.5Hz), 172.8; 19F NMR (282MHz, CDCl 3) δ-141.1 (1F, m); EIMS:m/z (rel intensity) 196 (M-HF, 1), 171 (1), 143 (2), 115 (100), 97 (90), 82 (45), 69 (57), 55 (31); HRMS calculated value (calcd for) C 12H 20O 2(M-HF): 196.1463, measured value (found) 196.1460.
Embodiment 13
Synthesizing of (4-fluoro-4-methyl isophthalic acid-piperidyl) phenyl ketone (1m)
Method is synthetic with 1i's.Be yellow oily liquid.IR (neat): ν (cm -1) 2922,1634,1444,1380,1278,1261,967,764,750; 1H NMR (400MHz, CDCl 3) δ 1.40 (3H, d, J=21.2Hz), 1.53-1.94 (4H, m), 3.09-3.60 (3H, m), 4.39-4.63 (1H, m), 7.39 (5H, br); 13C NMR (100MHz, CDCl 3) δ 27.0 (d, J=24.1Hz), 36.2,37.2,38.4,43.8,92.2 (d, J=167.7Hz), 126.9,128.5,129.7,136.1,170.5; 19F NMR (282MHz, CDCl 3) δ-154.2 (1F, m); EIMS:m/z (rel intensity) 221 (M +, 30), 220 (70), 200 (5), 160 (3), 134 (1), 105 (100), 77 (43), 51 (9), 42 (4); HRMS calcd forC 13H 16FNO:221.1216, measured value (found) 221.1212.
Embodiment 14
1,3-acetoxyl group-2-fluoro-2-methylpropane (1n) synthetic
Method is synthetic with 1h's.Be yellow oily liquid.IR (neat): ν (cm -1) 1747,1387,1275,1259,1053,902,764,750; 1H NMR (400MHz, CDCl 3) δ 1.34 (3H, d, J=21.6Hz), 2.04 (6H, s), 4.06-4.20 (4H, m); 13C NMR (100MHz, CDCl 3) δ 19.4 (d, J=22.6Hz), 20.6,65.6 (d, J=27.0Hz), 93.0 (d, J=174.3Hz), 170.4; 19F NMR (282MHz, CDCl 3) δ-161.2 (1F, m); EIMS:m/z (rel intensity) 192 (M ++ 1,1), 181 (1), 130 (7), 112 (3), 103 (35), 73 (6), 60 (15), 43 (100); HRMS calcd for C 8H 13FO 4: 192.0798, measured value (found) 192.0802.
Embodiment 15
Synthesizing of 1-fluorine margaric synthetic (1o)
Under nitrogen atmosphere with stearic acid (A-1o, 56.9mg, 0.20mmol), AgNO 3(6.8mg, 0.04mmol) and Selectfluor (283.2mg 0.8mmol) adds in the reaction tubes successively.Add 2 milliliters in acetone then, 0.5 milliliter in water.Reaction solution under agitation refluxed 10 hours.Be chilled to room temperature then, with dichloromethane extraction (15mL * 3).Organic phase is used anhydrous sodium sulfate drying after merging.Filter, concentrated filtrate, crude product are through purification by silica gel column chromatography, and eluent is a hexane, get product 1-fluorine heptadecane, are yellow liquid, productive rate: 28.9mg (56%) .Yellow oil.IR (neat): ν (cm -1) 2925,2854,1466,1261,1015,804,750; 1H NMR (400MHz, CDCl 3) δ 0.88 (3H, t, J=6.8Hz), 1.18-1.73 (30H, m), 4.43 (2H, dt, J=47.2,6.4Hz); 13C NMR (100MHz, CDCl 3) δ 14.1,22.7,25.1,25.2,29.2,29.3,29.4,29.5,29.6,29.7,29.8,30.3,30.5,31.9,35.2 (d, J=20.5Hz), 84.2 (d, J=162.6Hz); 19F NMR (282MHz, CDCl3) δ-215.5 (1F, m); EIMS:m/z (rel intensity) 258 (M+, 1), 240 (2), 182 (2), 154 (3), 125 (9), 111 (20), 97 (37), 71 (64), 57 (100); HRMS calculated value (calcd for) C 17H 35F:258.2723, measured value (found) 258.2720.
Embodiment 16
(1p's) of 1-fluorine tridecane is synthetic
Method is synthetic with 1o's.Be colourless liquid. 1H?NMR(400MHz,CDCl 3)δ0.88(3H,t,J=6.4Hz),1.25-1.41(20H,m),1.63-1.74(2H,m),4.43(2H,dt,J=47.2,6.4Hz); 13C?NMR(100MHz,CDCl 3)δ14.1,22.7,25.1(d,J=5.8Hz),29.3,29.4,29.5,29.56,29.64,29.7,30.4(d,J=20.7Hz),31.9,84.2(d,J=163.3Hz); 19F?NMR(282MHz,CDCl 3)δ-218.4(1F,m).
Embodiment 17
Synthesizing of 1-bromo-10-fluorine certain herbaceous plants with big flowers alkane (1q)
Method is synthetic with 1o's, 10 hours reaction times.Be colourless oil liquid. 1H?NMR(400MHz,CDCl 3)δ1.25-1.45(12H,m),1.63-1.75(2H,m),1.81-1.89(2H,m),3.40(2H,t,J=7.2Hz),4.43(2H,dt,J=47.2,6.4Hz); 13C?NMR(100MHz,CDCl 3)δ25.1(d,J=5.1Hz),28.2,28.7,29.2,29.3,29.4,30.4(d,J=20.7Hz),32.8,33.7,84.2(d,J=162.6Hz); 19F?NMR(282MHz,CDCl 3)δ-218.5(1F,m).
Embodiment 18
Synthesizing of N-(5-fluorine amyl group) phthalic imidine (1r) [28]
Under nitrogen atmosphere, with N-(5-hydrogen-oxygen carbonyl) phthalic imidine (A-1r, 52.2mg, 0.20mmol), AgNO 3(6.8mg, 0.04mmol), Selectfluor (141.6mg 0.4mmol) adds in the reaction tubes successively. and add 2 milliliters of reaction solutions of entry then and stirred 10 hours down at 55 ℃.System is chilled to room temperature, uses dichloromethane extraction (15mL * 3) then.Organic phase is used anhydrous sodium sulfate drying after merging.Filter, concentrated filtrate, crude product are through purification by silica gel column chromatography, and eluent is acetate ester/sherwood oil, get product N-(5-fluorine amyl group) phthalic imidine, are colourless liquid, productive rate: 37.6mg (80%). 1H?NMR(400MHz,CDCl 3)δ1.42-1.51(2H,m),1.67-1.82(4H,m),3.71(2H,t,J=7.2Hz),4.43(2H,dt,J=47.2,6.0Hz),7.70-7.72(2H,m),7.83-7.85(2H,m); 13C?NMR(100MHz,CDCl 3)δ22.6(d,J=5.8Hz),28.2,29.9(d,J=19.0Hz),37.8,83.8(d,J=163.3Hz),123.2,132.2,133.9,168.4; 19F?NMR(282MHz,CDCl 3)δ-218.8(1F,m)。
Embodiment 19
1-(2-fluoropropyl) Pyrrolidine-2,5-diketone (1s) synthetic
Method is synthetic with 1r's, 10 hours reaction times.Be colourless oil liquid.IR (neat): ν (cm -1) 2959,2930,1702,1424,1403,1326,1260,1197,1122,1090,750; 1H NMR (400MHz, CDCl 3) δ 1.30 (3H, dd, J=23.6,6.4Hz), 2.68 (4H, s), 3.38-3.50 (1H, m), 3.71-3.81 (1H, m), 4.70-4.90 (1H, m); 13C NMR (100MHz, CDCl 3) δ 18.6 (J=21.1Hz), 28.1,43.7 (J=22.6Hz), 87.0 (J=169.9Hz), 177.0; 19F NMR (282MHz, CDCl 3) δ-181.1 (1F, m); ESI-MS:m/z 182 (M+Na) .HRMS calculated value (calcd for) C 7H 10FNNaO 2(M+Na) 182.0588, measured value (found) 182.0591.
Embodiment 20
Synthesizing of 1-fluorine diamantane (1t)
Method is synthetic with 1r's.3 hours reaction times.White solid.Mp?199-200℃(lit.200-204℃); 1HNMR(400MHz,CDCl 3)δ1.59-1.66(6H,m),1.88(6H,br),2.23(3H,br); 13C?NMR(100MHz,CDCl 3)δ31.5(d,J=9.5Hz),35.9,42.8(d,J=16.8Hz),92.5(d,J=180.8Hz); 19FNMR(282MHz,CDCl 3)δ-128.8(1F，s).
Embodiment 21
Synthesizing of 1-chloro-4-(fluorine methoxyl group) benzene (1u)
Method is synthetic with 1r's.1 hour reaction times.Be colourless liquid. 1H?NMR(400MHz,CDCl 3)δ5.60(2H,d,J=54.4Hz),6.94(2H,d,J=8.8Hz),7.21(2H,d,J=8.8Hz); 13C?NMR(100MHz,CDCl 3)δ100.8(d,J=218.0Hz),118.1,128.7,129.7,155.4; 19F?NMR(282MHz,CDCl 3)δ-145.2(1F,t,J=53.3Hz).
Embodiment 22
Synthesizing of N-(methyl fluoride) phthalic imidine (1v)
Method is synthetic with 1r's.1 hour reaction times.White solid.Mp?93-94℃(lit.mp.93.5℃); 1HNMR(400MHz,CDCl 3)δ5.77(2H,d,J=52.0Hz),7.82(2H,dd,J=3.2,5.6Hz),7.96(2H,dd,J=3.2,5.6Hz); 13C?NMR(100MHz,CDCl 3)δ74.9(d,J=197.6Hz),124.2,131.7,134.9,166.5; 19F?NMR(282MHz,CDCl 3)δ-174.5(1F,t,J=50.8Hz).
Embodiment 23
1-(1-fluorine 2-phenylethyl) Pyrrolidine-2,5-diketone (1w) synthetic
Method is synthetic with 1r's.8 hours reaction times.White solid.Mp 115-117 ℃; IR (KBr): ν (cm -1) 1788,1712,1456,1386,1229,1170,1057,1039,974,860,819,731,697; 1H NMR (400MHz, CDCl 3) δ 2.65 (4H, s), 3.49-3.74 (2H, m), 6.18 (1H, dt, J=46.8,7.2Hz), 7.20-7.32 (5H, m); 13C NMR (100MHz, CDCl 3) δ 27.9,36.8 (d, J=26.3Hz), 90.7 (d, J=203.4Hz), 127.4,128.8,129.2,134.5 (d, J=7.3Hz), 175.7; 19F NMR (282MHz, CDCl 3) δ-152.1 (1F, m); EIMS:m/z (rel intensity) 201 (M-HF, 63), 178 (1), 165 (3), 139 (3), 122 (100), 102 (5), 91 (21), 74 (6), 55 (16); HRMS calculated value (calcd for) C 12H 11NO 2(M-HF): 201.0790, measured value (found) 201.0787.

Claims (4)

1. carboxylic acid decarboxylation fluoric method, it is characterized in that in solvent with room temperature under reflux temperature, lipid acid RCOOH, the agent of monovalence silver catalyst and fluorination reagent reaction obtained RF in 1～20 hour;
Wherein, R be contain among C1～C100 alkyl, the R a kind of to three kinds of following substituting groups: carbonyl, phenyl, C2～C10 ester group, C1～C10 alkoxyl group; Carboxamido-group, cyanic acid, carboxyl, halogenophenyl; The naphthenic base of C5～C7, halogenated phenoxy, phenylcarbonyl group, Pyrrolidine-2; The 5-diketo, phthalimide-based, halogeno-benzene formyl radical, halogen; Phenyl replaces C1 ~ 4 alkyl, and adamantyl contains five yuan or the hexa-member heterocycle of N, perhaps has five yuan or the hexa-member heterocycle containing N of benzo base, C1 ~ 6 alkyl, halo, C2～C10 ester group, C1～C10 alkoxyl group;
The mol ratio of described lipid acid, the agent of monovalence silver catalyst and fluorination reagent is 1:0.1～0.5:1～5; Be recommended as 1:0.1～0.2:1～2;
Described monovalence silver salt is a Silver Nitrate, silver tetrafluoroborate or silver trifluoromethanesulfonate;
Described fluorination reagent is Selectfluor or its phosphofluoric acid salt derivative with following structural formula:
Figure FDA00001750774200011
Described solvent is the mixed solvent of pure water or water and organic solvent composition.
2. a kind of carboxylic acid decarboxylation fluoric method as claimed in claim 1, the mol ratio that it is characterized in that described lipid acid, the agent of monovalence silver catalyst and fluorination reagent is 1:0.1～0.2:1～2.
3. a kind of carboxylic acid decarboxylation fluoric method as claimed in claim 1 is characterized in that described R is C1～C20 alkyl.
4. a kind of carboxylic acid decarboxylation fluoric method as claimed in claim 1 is characterized in that described organic solvent is acetone, acetonitrile, methylene dichloride or 1, the 2-ethylene dichloride.
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