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Decarboxylation and fluorination method for carboxylic acid

A technology of decarboxylation and fluorination, carboxylic acid, applied in the preparation of carboxylic acid esters, organic chemistry methods, chemical instruments and methods, etc.

Active Publication Date: 2014-11-05
上海睿瓦科技有限公司
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

However, this type of method is generally only suitable for the synthesis of ortho-fluorinated carbonyl compounds [18.R.P.Singh, J.M.Shreeve, Synthesis 2561-2578 (2002); 19.R.P.Singh, J.M.Shreeve, Acc.Chem.Res.37,31 –44 (2004); 20. P.T. Nyffeler, S.G. Durón, M.D. Burkart, S.P. Vincent, C.-H. Wong, Angew. Chem., Int. Ed. 44, 192–212 (2005); 21 Y. Hamashima, M. Sodeoka , Synlett 1467–1478 (2006); 22. V. Rauniyar, A.D. Lackner, G.L. Hamilton, F.D. Toste, Science 334, 1681–1684 (2011).]
[0005] 2. In contrast, the formation of sp 3 The third method of carbon-fluorine bond-radical fluorination has little research, and its application value in organic synthesis has not been reflected
But, this method must prepare tert-butyl peracid from carboxylic acid earlier, and reaction efficiency is on the low side
In addition, since the generation of alkyl radicals is accompanied by the generation of more active tert-butoxy radicals, the reaction is more limited

Method used

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  • Decarboxylation and fluorination method for carboxylic acid
  • Decarboxylation and fluorination method for carboxylic acid
  • Decarboxylation and fluorination method for carboxylic acid

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0039] Synthesis of 3-fluoropentadecane (1a)

[0040] 2-Ethyltetradecanoic acid (A-1a, 51.2mg, 0.20mmol), AgNO 3 (6.8mg, 0.04mmol) and Selectfluor (141.6mg, 0.4mmol) were sequentially added to the reaction tube. Then 2 ml each of acetone and water were added. The reaction solution was refluxed for 10 hours with stirring. The system was cooled to room temperature, and then extracted with dichloromethane (15 mL×3). The organic phases were combined and dried over anhydrous sodium sulfate. Filtrate, concentrate the filtrate, and purify the crude product by silica gel column chromatography with hexane as the eluent to obtain the product 3-fluoropentadecane as a colorless liquid. Yield: 42.7 mg (93%). IR (neat): ν(cm -1 )2926,2855,1465; 1 H NMR (400MHz, CDCl 3 )δ0.88(3H,t,J=7.2Hz),0.96(3H,t,J=7.6Hz),1.26-1.69(24H,m),4.29-4.49(1H,m); 13 C NMR (100MHz, CDCl 3 )δ9.4(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....

Embodiment 2

[0042] Synthesis of 1,3-dicyclohexyl-2-fluoropropane (1b)

[0043] The method is the same as that of 1a, and the reaction time is 10 hours. It is yellow oily liquid. Yellow oil.IR(neat):ν(cm -1 )2923,1558,1275,1261,764,750; 1 H NMR (400MHz, CDCl 3 )δ0.74-1.76(26H,m),4.52-4.75(1H,m); 13 C NMR (100MHz, CDCl 3 )δ25.2,25.3,25.5,31.9,33.0,33.1(d,J=3.7Hz),42.5(d,J=20.5Hz),89.4(d,J=164.8Hz); 19 F 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 15 h 26 (M-HF): 206.2035, measured value (found) 206.2032.

Embodiment 3

[0045] Synthesis of 1,3-bis(4-chlorophenyl)-2-fluoropropane (1c)

[0046] The method is the same as that of 1a, and the reaction time is 10 hours. It is yellow oily liquid. IR(neat):ν(cm -1 )2925,1492,1275,1261,1091,1016,805,764,750; 1 H NMR (400MHz, CDCl 3 )δ2.73-2.89(4H,m),4.66-4.84(1H,m)7.06(4H,d,J=8.4Hz),7.20(4H,d,J=8.4Hz); 13 C NMR (100MHz, CDCl 3 )δ40.3(d,J=21.2Hz),94.0(d,J=174.3Hz),128.7,130.8,132.7,135.3(d,J=3.6Hz); 19 F 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 15 h 13 Cl 2 F: 282.0378, measured value (found) 282.0380.

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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

technical field [0001] The invention relates to the field of fluorine organic compounds, and furthermore relates to a new method for decarboxylation and fluorination of carboxylic acid. Background technique [0002] The introduction of fluorine atoms into organic compounds can change the physical, chemical and biological properties of molecules, so fluorine-containing organic compounds have very important uses in the fields of medicine, pesticides and materials [1.K.Müller, C.Faeh, F.Diederich, 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 25% of drugs currently on the market contain at least one fluorine atom, and nearly 30% of pesticides contain fluorine atoms. In addition, including 18 F-labeled molecules have important clinical applications [5.P.W.Miller, N.J.Long, R.Vilar, A.D.Ge...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): C07B39/00C07C17/363C07C19/08C07C22/00C07C22/08C07C23/08C07C23/10C07C19/14C07C23/38C07C49/80C07C49/813C07C45/65C07D209/48C07D207/452C07D211/38C07C69/63C07C67/32C07C67/297C07C43/225C07C41/22
Inventor 李超忠王振涛尹锋李兆栋
Owner 上海睿瓦科技有限公司
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