A Highly Selective and Efficient Method for the Preparation of Amides from Carboxylic Acids and Amines Using Sodium Hydrogen Sulfate Adsorbed on Silica Gel †
World Journal of Applied Chemistry
Volume 4, Issue 1, March 2019, Pages: 14-18
Received: Feb. 23, 2019;
Accepted: Apr. 23, 2019;
Published: Jun. 17, 2019
Views 153 Downloads 31
Rathod Aravind Kumar, Natural Products Chemistry Division, CSIR- Indian Institute of Chemical Technology, Hyderabad, India; SemiochemicalDivision, CSIR- Indian Institute of Chemical Technology, Hyderabad, India
Nayaki Salvanna, Natural Products Chemistry Division, CSIR- Indian Institute of Chemical Technology, Hyderabad, India; Osmania University Post Graduate College, Medak, India
Biswanath Das, Natural Products Chemistry Division, CSIR- Indian Institute of Chemical Technology, Hyderabad, India
Jajula Kashanna, Natural Products Chemistry Division, CSIR- Indian Institute of Chemical Technology, Hyderabad, India; Department of Chemistry, Rajiv Gandhi University of Knowledge Technologie, Basar, India
The formation of amides from carboxylic acids and amines has been catalyzed efficiently with sodium hydrogen sulfate adsorbed on silica gel (NaHSO4.SiO2) at room temperature to give the products in high yields. The conversion carried out under reflux requires less reaction times and forms the products in higher yields. The reaction is highly selective as it has been found that either or both of the substrates should be aliphatic but it is failure when the acid as well as the amine is aromatic. The method has been utilized for the preparation of a natural phenethyl amide derivative and its analogues.
Rathod Aravind Kumar,
A Highly Selective and Efficient Method for the Preparation of Amides from Carboxylic Acids and Amines Using Sodium Hydrogen Sulfate Adsorbed on Silica Gel †, World Journal of Applied Chemistry.
Vol. 4, No. 1,
2019, pp. 14-18.
I. L. Finar, Organic Chemistry, Vol. 1; The Fundamental Principles, 6th Edn., ELBS and Longman Group Ltd., London, 1973, 658-665.
S. R. Sandler, W. Karo. Organic Functional Group Preparations, 2nd Edn., Academic Press, London, 1983, 1: 316-554.
G. Benz. in. Comprehensive Organic Synthesis, Eds, Trost, B. M.; Fleming, I. Pergamon press, Oxford, 1991, 6, 381-417.
C. Y. Duh, Y. C. Wu, S. K. Wang. Cytotoxic pyridone alkaloids from the leaves of Piper aborescens. J. Nat. Prod. 1990, 53 (6): 1575-1577.
H-M. D. Wang, C-Y. Chen, P-F. Wu. Isophilippinolide A Arrests Cell Cycle Progression and Induces Apoptosis for Anticancer Inhibitory Agents in Human Melanoma Cells. J. Agric. Food Chem. 2014, 62 (5): 1057-1065.
A. L. J. Beckwith. Synthesis of Amides in: The Chemistryof Amides, Ed. Zadrocki, J. Intersience, New York, 1970, 96-105.
O-P. Andrea, G-S. Diego. Recent Developments in Amide Synthesis Using Nonactivated Starting Materials. J. Org. Chem. 2016, 81 (23): 11548–11555.
K. Hyodo, G. Hasegawa, N. Oishi, K. Kuroda, K. Uchida. Direct and Catalytic Amide Synthesis from Ketones via Transoximation and Beckmann Rearrangement under Mild Conditions, J. Org. Chem. 2018, 83 (21): 13080–13087.
C. Chen, Y. Zhang, S. H. Hong. N-Heterocyclic Carbene Based Ruthenium-Catalyzed Direct AmideSynthesis from Alcohols and Secondary Amines: Involvement of Esters, J. Org. Chem. 2011, 76 (24): 10005–10010.
J. Cui, D. I. Chai, C. Miller, J. Hao, C. Thomas, J. Wang, K. A. Scheidt, S. A. Kozmin. Assembly of Four Diverse Heterocyclic Libraries Enabled by Prins Cyclization, Au-CatalyzedEnyneCycloisomerization, and AutomatedAmide Synthesis. J. Org. Chem. 2012, 77 (17): 7435–7470.
S. Masala, M. Taddei. Solid-Supported Chloro [1, 3, 5] triazine. A Versatile New SyntheticAuxiliary for the Synthesis of Amide Libraries. Org. Lett. 1999, 1 (9), 1355–1357
Z. Fu, J. Lee, B. Kang, S. H. Hong . Dehydroge-native Amide Synthesis: Azide as a Nitrogen Source, Org. Lett. 2012, 14 (23): 6028–6031.
J. Zhu, Y. Zhang, F. Shi, Y. Deng. Dehydrogenative amide synthesis from alcohol and amine catalyzed by hydrotalcite-supported gold nanoparticles. Tetrahedron Letters. 2012, 53 (25): 3178-3180.
L. Zhang, X. J. Wang, J. Wang, N. Grinberg, D. K. Krishnamurthy, C. H. Senanayake. An improved method of amide synthesis using acyl chlorides. Tetrahedron Letters. 2009, 50 (24): 2964-2966.
L. E. Barstow, V. J. Hruby. Simple method for the synthesis of amides. J. Org. Chem. 1971, 36: 1305-1306.
A. Garecka, M. leplawy, J. Zabrocki, A. Zwierzak. Diethyl Phosphorobromidate- An Effective New Peptide-Forming Agent. Synthesis. 1978, 6: 474-476.
J. D. Meseguer, A. L. P. Coll, J. R. F. Lizabre, A. Z. Bilbao. A New Reagent for Activating Carboxyl Groups; Preparation and Reactions of N, N-Bis [2-oxo-3-ox-azolidinyl] phosphorodiamidic Chloride. Synthesis. 1980, 7: 547-551.
T. Kubota, S. Miyashita, T. Kitazume, N. Ishikawa. Novel synthetic reactions using bis (2, 2, 2-trifluoroethoxy) triphenylphosphorane. J. Org. Chem. 1980, 45 (25): 5052-5057.
T. Kunieda, Y. Abe, T. Higuchi, M. Hirobe. A new reagent for activating carboxyl groups: diphenyl 2-oxo-3-oxazolinylphosphonate. Tetrahedron Lett. 1981, 22: 1257-1258.
G. Trapani, A. Reho, A. Latrofa. Trimethylamine-Borane as Useful Reagent in the N-Acylation or N-Alkylation of Amines by Carboxylic Acids. Synthesis. 1983, 12: 1013-1014.
T. Ogawa, T. Hikasa, T. Ikegami, N. Ono, H. Suzuki. Selective activation of primary carboxylic acids by electron-rich triarylbismuthanes. Application to amide and ester synthesis under neutral conditions. J. Chem. Soc. Perkin Trans1. 1994, 3473-3478.
I. Azumaya, T. Okamoto, F. Imabeppu, H. Takayanagi. Simple and convenient synthesis of tertiary benzanilides using dichlorotriphenylphosphorane. Tetrahedron. 2003, 59: 2325-2331.
D. M. Shendge, R. Froehlich, G. Haufe. Highly Efficient Stereoconservative Amidation and Deamidation of α-Amino Acids. Org. Lett. 2004, 6 (21): 3675-3678.
M. Hossaini-Sarvave, H. Sharghi. ZnO as a New Catalyst for N-Formylation of Amines under Solvent-Free Conditions. J. Org. Chem. 2006, 71 (17): 6652-6654.
J. Bures, M. Martin, F. Urpi, J. Vilarrasa. Catalytic Staudinger-Vilarrasa Reaction for the Direct Ligation of Carboxylic Acids and Azides. J. Org. Chem. 2009, 74 (5): 2203-2206.
B. Das, B. Venkataiah, A. Kashinatham. Venkatasin, A new CoumarinoLignoid from jatropha Gassypifolia. Nat. Prod. Lett. 1999, 13 (4): 293-297.
B. Das, B. Venkataiah, P. Madhusudhan. A Simple and Efficient Selective Esterification of Aliphatic Carboxylic Acids in the Presence of Aromatic Carboxylic Acids. Synlett. 2000, 59-60.
C. Ramesh, N. Ravindranath, B. Das. J. Org. Chem. 2003, 68 (18): 7101-7103.
C. Ramesh, J. Benerji, R. Pal, B. Das. Silica Supported Sodium Hydrogen Sulfate and Amberlyst‐15: Two Efficient Heterogeneous Catalysts for Facile Synthesis of Bis‐ and Tris (1H‐indol‐3‐yl) methanes from Indoles and Carbonyl Compounds. Adv. Synth. Catal. 2003, 345 (5): 557-559.
B. Das, K. Venkataiah, G. Mahender, I. Mahender. A simple and efficient method for α-bromination of carbonyl compounds using N-bromosuccinimide in the presence of silica-supported sodium hydrogen sulfate as a heterogeneous catalyst. Tetrahedron Lett. 2005, 46: 3041-3044.
B. Das, K. R. Reddy, P. Thirupathi. A simple, efficient and highly selective deprotection of t-butyldimethylsilyl (TBDMS) ethers using silica supported sodium hydrogen sulfate as a heterogeneous catalyst. Tetrahedron Lett. 2006, 47: 5855.
B. Das, N. Chowddhury, K. Damodar, K. R. Reddy. Efficient Conjugate Addition of 1H-Indoles to Electron-Deficient Olefines Catalyzed by Silica-Supported Sodium Hydrogen Sulfate (NaHSO4.SiO2). Helv. Chem. Acta. 2007, 90: 340-345.
B. Das, Ch. R. Reddy, D. N. Kumar, M. Krishnaiah, R. Narender. A Simple, Advantageous Synthesis of 5-Substituted 1H-Tetrazoles. Synlett. 2010, 391-394.
K. Boroczky, H. Laatsch, I. Wagner-Dobler, K. Stritzke, S. Schulz. Chem analysis as selection and dereplication tool for the identification of new natural compounds from large sample sets. Chem. Biodiversity. 2006, 3: 622-634.
T. H. Jones, H. M. Garraffo, T. F. Spande, N. R. Andriamaharavo, J. S. T. Gorman, A. J. Snyder, A. W. Jeter, J. A. Torres, R. R. Snelling, J. W. Daly. Caste-Specific Tyramides from Myrmicine Ants. J. Nat. Prod. 2010, 71 (3): 313-316.
Z. J. Lin, X. M. Lu, T. J. Zhu, Y. C. Fang, Q. Q. Gu, W. Zhu. GPR12 selections of the metabolites from an endophytic Streptomyces sp. associated with Cistanches deserticola. Arch. Pharm. Res. 2008, 31 (9): 1108-1114.
N. Ullah, K. M. Arafch. The first total synthesis of aplysamine 6, an inhibitor of isoprenylcysteine carboxy methyltransferase. Tetrahedron Lett. 2009, 50: 158-160.
A. S. B. Prasad, J. V. B. Kanth, M. Periasamy. Convenient methods for the reduction of amides, nitriles, carboxylic esters, acids and hydroboration of alkenes using NaBH4/I2system. Tetrahedron. 1992, 48: 4623-4628.
G. W. Breton. Selective Monoacetylation of Unsymmetrical Diols Catalyzed by Silica Gel-Supported Sodium Hydrogen Sulfate. J. Org. Chem. 1997, 62 (25): 8952-8954.