微波辅助氢氧化钾催化合成2-(4-羟基苯基)六氟异丙醇

doi:10.3724/SP.J.1095.2013.20590

摘要/Abstract

摘要： 微波辐射下，在水溶液中以KOH催化苯酚与六氟丙酮三水合物（HFA·3H2O）的缩合反应，制备了2-(4-羟-基苯基)六氟异丙醇的异构体混合物；目标产物结构经IR、1H NMR和MS确认。结果表明，与传统加热法相比，微波辐射法可明显缩短反应时间。在n(苯酚)∶n(HFA·3H2O)∶n(KOH)=3.0∶1.0∶0.3及微波功率为300 W条件下，反应时间可由常规加热法的35 h缩短至6 h，总收率由87%提高到90%，目标物产物选择性为94%。

关键词: (羟基苯基)六氟异丙醇, 苯酚, 微波, 氢氧化钾, 六氟丙酮三水合物, 正交实验法

Abstract: With the assistance of microwave, a mixture of 2-(4-hydroxy-phenyl)-1,1,1,3,3,3-hexafluoro-propan-2-ol isomers were obtained via the condensation between hexafluoroacetone trihydrate(HFA·3H2O) and phenol using potassium hydroxide as catalyst. The product was characterized by 1H NMR, IR and MS spectra. The results show that the microwave-assisted process can reduce the reaction time remarkably compared with conventional processes. Under optimal conditions with the microwave power 300 W at n(phenol)∶n(HFA·3H2O)∶n(KOH)=3.0∶1.0∶0.3, the reaction time are shortened from 35 h in conventional heating to 6 h, the total yield is increased from 87% to 90% with 94% selectivity.

Key words: (hydroxy-phenyl)-hexafluoro-propan-ol,phenol, microwave, potassium hydroxide, hexafluoroacetone trihydrate, orthogonal experimental design

中图分类号:

O625.3

戴燕, 吕春绪, 李斌栋, 谭卫红. 微波辅助氢氧化钾催化合成2-(4-羟基苯基)六氟异丙醇[J]. 应用化学, DOI: 10.3724/SP.J.1095.2013.20590.

DAI Yan1,2, LV Chunxu3, LI Bindong3*, TAN Weihong1,2*. Microwave-Assisted Synthesis of 2-(4-Hydroxy-phenyl)-1,1,1,3,3,3-hexafluoro-propan-2-ol via Potassium Hydroxide as the Catalyst[J]. Chinese Journal of Applied Chemistry, DOI: 10.3724/SP.J.1095.2013.20590.

参考文献

[1] Uchiyama Y,Kano N,Kawashima T. Syntheses, Structures, and Thermolyses of Pentacoordinate 1,2-Oxastibetanes:Potential Intermediates in the Reactions of Stibonium Ylides with Carbonyl Compounds[J]. J Org Chem,2006,71(2):659-670.

[2] Hanes R E,Lynch V M,Anslyn E V,et al. Toward a Stable Hydroxyphosphorane[J]. Org Lett,2002,4(2):201-203.

[3] Gómez A,Martínez R,Sancenón F,et al. Functional Aromatic Polyethers:Polymers with Tunable Chromogenic and Fluorogenic Properties[J]. Macromolecules,2010,43(17):7111-7121.

[4] Rebeck N T,Knauss M. Sulfonamide as an Activating Group for the Synthesis of Poly(aryl ether sulfonamide)s by Nucleophilic Aromatic Substitution[J]. Macromolecules,2011,44(17):6717-6723.

[5] Arrhenius T,Chen M,Cheng J F,et al. Malonyl-CoA Decarbosylase Inhibitors Useful as Metabolic Modulators:WO,2002064136.A2[P],2002-08-22.

[6] DAI Yan,LV Chunxu,LI Bindong,et al. New Method for Synthesis of Bisphenol AF[J]. Chinese J Appl Chem,2009,26(11):1292-1296(in Chinese).

戴燕,吕春旭,李斌栋,等. 合成双酚AF的新方法[J]. 应用化学,2009,26(11):1292-1296.

[7] Dang T D,Bai Z,Shumaker J,et al. Synthesis and Characterization of Fully Disulfonated Poly(arylenethioethersulfone)s Containing Hexafluoroisopropylidene Moiety[J]. Polymer,2010,51(2):463-468.

[8] Andjelkovic D D,Sheares V V. Isomeric Hexafluoroisopropylidene-Linked Benzophenone Polymers via Nickel Catalysis[J]. Macromolecules,2007,40(20):7148-7156.

[9] Cassidy P E,Aminabhavi T M,Reddy V S,et al. Polymers Derived from 2-Phenyl-1,1,1,3,3,3-hexafluoropropan-2-ol and Its Drivatives[J]. Eur Polym J,1995,31(4):353-361.

[10] ZHANG Yunming,LI Hong,ZHANG Heng. Fluorinated Functional Material[M]. Beijing:Chemical Industry Press,2006:427-436(in Chinese).

张永明,李虹,张恒. 含氟功能材料[M]. 北京:化学工业出版社,2008:323-341.

[11] Cracowski J M,Sharma B,Brown D K,et al. Perfluorocyclopentenyl(PFCP) Aryl Ether Polymers via Polycondensation of Octafluorocyclopentene with Bisphenols[J]. Macromolecules,2012,45(2):766-771.

[12] Cureton L T,Beyer F L,Turner S R. Synthesis and Characterization of Hexafluoroisopropylidene Bisphenol Poly(arylene ether sulfone) and Polydimethylsiloxane Segmented Block Copolymers[J]. Polymer,2010,51(8):1679-1686.

[13] Liu J,Spraul B K,Topping C,et al. Effect of Hexafluoroisopropylidene on Perfluorocyclobutyl Aryl Ether Copolymer Solution Behavior in Supercritical CO2 and Propane[J]. Macromolecules,2007,40(16):5973-5977.

[14] Lara-estévez J C I,Camacho-zuňiga C,Ruiz-treviňo F A,et al. Gas Transport Properties of Some Fluorine-Containing Polyethers[J]. Ind Eng Chem Res,2010,49(23):11948-11953.

[15] Sterlin S R,Shaposhnikova E N,Postovoi S A,et al. Condensation of Fluorinated Carbonyl Compounds with Halobenzenes[J]. J Fluorine Chem,1998,89(2):137-139.

[16] Gilbert E E,Litt M,Otto J A. Derivatives of Fluorinated Ketones and Process for Producing Same:US,3324185[P],1967-06-06.

[17] Murray J J. Perhalo Ketones:XIV.7,7-Bis(trifluoromethyl)quinonemethide[J]. J Org Chem,1968,33(8):3306-3308.

[18] Farah B S,Gilbert E E,Litt M,et al. Perhalo Ketones:Ⅶ.Phenolic Derivatives of the Perhaloacetones[J]. J Org Chem,1963,30(4):1003-1005.

[19] LIU Hongmei. Research on the Synthesis of Hexafluoroacetone via Oxidation[D]. Nanjing:Nanjing University of Science and Technology,2007( in Chinese).

刘红梅. 氧化合成六氟丙酮的工艺研究[D]. 南京:南京理工大学,2007.