芳甲酸氰基芳甲酯的合成

doi:10.11944/j.issn.1000-0518.2019.01.180092

摘要/Abstract

摘要：

芳甲酸氰基芳甲酯是重要的有机合成中间体,其现有合成方法采用剧毒氰化物为氰源来合成。本研究以K₄[Fe(CN)₆]为绿色氰化试剂,芳酰氯为原料,采用一锅两步反应合成芳甲酸氰基芳甲酯。通过改变第二步反应温度、反应时间、硼氢化钠和催化剂的用量获得最佳反应条件,以61.7%~80.3%的产率合成了10种芳甲酸氰基芳甲酯(2a~2j),产物结构通过傅里叶变换红外光谱仪(FTIR)、核磁共振波谱仪(NMR)分析确认。根据实验结果,提出了可能的反应机理。该法避免了对剧毒氰化剂的使用,具有产率高、操作简单、后处理方便等优点。

关键词: 芳甲酸氰基芳甲酯, K₄[Fe(CN)₆], 氰化反应, 绿色合成

Abstract:

Aryl formic acid cyano aryl methyl esters are important organic synthesis intermediate presently obtained from highly toxic cyanide. In this study, K₄[Fe(CN)₆] as a green cyanide source combined with acyl chlorine was used to synthesize this type of cyanohydrin ester in a one pot two-steps reaction. Optimized reaction condition was obtained by changing the temperature in second step, the reaction time, the dosages of sodium borohydride and the catalysts,Ten aryl formic acid cyano aryl methyl esters(2a~2j) were synthesized in 61.7%~80.3% yield. Their structures were confirmed by Fourier transform infrared spectrometer(FTIR) and nuclear magnetic resonance spectrometer(NMR). A possible reaction mechanism was also proposed. This method avoids the use of highly toxic cyanide, and benefits from high yield, simple operation, and convenient post-processing.

Key words: aryl formic acid cyano aryl methyl esters, potassium hexacyanoferrate(Ⅱ);, acyanide reaction, green synthesis

周立王, 赵宙兴. 芳甲酸氰基芳甲酯的合成[J]. 应用化学, 2019, 36(1): 10-15.

ZHOU Liwang, ZHAO Zhouxing. Synthesis of Aryl Formic Acid Cyano Aryl Methyl Esters[J]. Chinese Journal of Applied Chemistry, 2019, 36(1): 10-15.

参考文献

[1]	Belokon Y N,Blacker A J,Carta P,et al. Synthetic and Mechanistic Studies on Asymmetric Cyanohydrin Synthesis Using a Titanium(salen) Bimetallic Catalyst[J]. Tetrahedron,2004,60(46):10433-10447.
[2]	Gregory R J H. Cyanohydrins in Nature and the Laboratory:Biology, Preparations,and Synthetic Applications[J]. Chem Rev,1999,99(12):3649-3682.
[3]	Veum L,Pereira S R M,Waal J C,et al. Cholinium-Based Supported Ionic Liquid Membranes:A Sustainable Route for Carbon Dioxide Separation[J]. Org Chem,2006,16(64):110-113.
[4]	Hoffmann H M R,Ismail Z M,Hollweg R,et al. DABCO-Mediated Synthesis and Biological Activity of Cyanohydrin Esters[J]. Chem Soc Jpn,1990,63(6):1807-1810.
[5]	Zhang W,Shi M.Alkyl Phosphines Promoted Reductive Coupling of Acyl Cyanides:Formation of O-Acyl Cyanohydrins[J]. Tetrahedron,2006,62(37):8715-8719.
[6]	Zhang W,Shi M.DBU Catalyzed Cyanoacylation of Ketones with Acyl Cyanides[J]. Org Biomol Chem,2006,4(9):1671-1674.
[7]	Iwanami K,Aoyagi M,Oriyama T.An Efficient and Facile One-Pot Synthesis of Cyanohydrin Esters from Carbonyl Compounds Catalyzed by Iron(Ⅲ) Chloride[J]. Tetrahedron Lett,2005,46(44):7487-7490.
[8]	Chenevert R,Plante R,Voyer N.Crown Ether Catalysis in Synthesis of Cyanohydrin Derivatives[J]. Synth Commun,1983,13(5):403-409.
[9]	Photis J M.A New Synthesis of Cyanohydrin Esters[J]. Org Chem,1981,12(25):182-184.
[10]	Warmerdam E G J C,Brussee J,Kruse C G,et al. Inversion of the Configuration of Cyanohydrins by a Mitsunobu Esterification Reaction[J]. Tetrahedron,1993,49(5):1063-1070.
[11]	Acharyya K,Acharyya K,Howlader P,et al. Molecular Cage Impregnated Palladium Nanoparticles:Efficient, Additive-Free Heterogeneous Catalysts for Cyanation of Aryl Halides[J]. J Am Chem Soc,2016,138(5):1709-1716.
[12]	Hajipour A R,Rafiee F,Ruoho A E.Microwave-Enhanced Synthesis of Aryl Nitriles Using Dimeric Orthopalladated Complex of Tribenzylamine and K4[Fe(CN)6][J]. Tetrahedron Lett,2012,53(5):526-529.
[13]	Hajipour A R,Abrisham F,Tavakoli G.Microwave-Enhanced Cyanation of Aryl Halides with a Dimeric Ortho-Palladated Complex Catalyst[J]. Transit Metal Chem,2011,36(7): 725-730.
[14]	Li Z,Shi S.AgI-PEG400-KI Catalyzed Environmentally Benign Synthesis of Aroyl Cyanides Using Potassium Hexacyanoferrate(Ⅱ) as the Cyanating Agent[J]. Synlett,2006,38(3):2495-2497.
[15]	Li Z,Tian G,Ma Z.One-Pot Three-component Solvent-Free Cyanoaroylation of Aldehydes Using Potassium Hexacyanoferrate(Ⅱ) as Environmentally Benign Cyanide Source[J]. Synlett,2010,41(52):2164-2168.