An Efficient FeCl3 Catalyzed Synthesis of N,N’-Diarylformamidines

Abstract

An efficient FeCl3 catalyzed synthesis of N,N-diarylformamidines using triethylorthoformate (1 equivalent) and primary aryl amines (2 equivalents) at ambient temperature has been described. This methodology provides an eco-friendly and simple procedure without using any hazardous and expensive chemicals.

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P. Chakraborty and S. Roy, "An Efficient FeCl3 Catalyzed Synthesis of N,N’-Diarylformamidines," Green and Sustainable Chemistry, Vol. 3 No. 1, 2013, pp. 26-30. doi: 10.4236/gsc.2013.31005.

Conflicts of Interest

The authors declare no conflicts of interest.

References

[1] R. W. Beeman and F. Matsumura, “Chlordimeform: A Pesticide Acting upon Amine Regulatory Mechanisms,” Nature, Vol. 242, No. 5395, 1973, pp. 273-274. doi:10.1038/242273a0
[2] S. A. Aziz and C. O. Knowles, “Inhibition of Monoamine Oxidase by the Pesticides Chlordimeform and Related Compounds,” Nature, Vol. 242, No. 5397, 1973, pp. 417-418. doi:10.1038/242417a0
[3] V. K. S. Leung, T. Y. K. Chan and V. T. F.Yeung, “Ami-Traz Poisining in Humans,” Clinical Toxicology, Vol. 37, No. 4, 1999, pp. 513-514. doi:10.1081/CLT-100102523
[4] A. Nakayama, M. Sukekawa and Y. Eguchi, “Stereochemistry and Active Conformation of a Novel Insecticide, Acetamiprid,” Pesticide Science, Vol. 51, No. 2, 1997, pp. 157-164. doi:10.1002/(SICI)1096-9063(199710)51:2<157::AID-PS620>3.0.CO;2-C
[5] G. D. Baxter and S. C. Barker, “Isolation of a cDNA for an Octopamine-Like, G-Protein Coupled Receptor from the Cattle Tick, Boophilus microplus,” Insect Biochemistry and Molecular Biology, Vol. 29, No. 5, 1999, pp. 461-467. doi:10.1016/S0965-1748(99)00023-5
[6] M. Gall, J. M. McCall, R. E. TenBrink, P. F. Von-Voigtlander and J. S. Mohrland, “Arylformamidines with Antinociceptive Properties,” Journal of Medicinal Chemistry, Vol. 31, No. 9, 1988, pp. 1816-1820. doi:10.1021/jm00117a023
[7] A. Donetti, E. Cereda, E. Bellora, A. Gallazzi, C. Bazzano, P. Vanoni, P. D. Soldato, R. Michelett, F. Pagani and A. Giachetti, “(Lmidazolylphenyl)Formamidines. A Structurally Novel Class of Potent Histamine H2 Receptor Antagonists,” Journal of Medicinal Chemistry, Vol. 27, No. 3, 1984, pp. 380-386. doi:10.1021/jm00369a025
[8] T. Goto, H. Sakashita, K. Murakami, M. Sugiura, T. Kondo and C. Fukaya, “Novel Histamine H3 Receptor Antagonists: Synthesis and Evaluation of Formamidine and S-Methylisothiourea Derivatives,” Chemical & Pharmaceutical Bulletin, Vol. 45, No. 2, 1997, pp. 305-311. doi:10.1248/cpb.45.305
[9] G. K. W. Yim, M. P. Holsapple, W. R. Pfister and R. M. Hollingworth, “Prostaglandin Synthesis Inhebited by Formamidine Pesticides,” Life Sciences, Vol. 23, No. 25, 1978, pp. 2509-2515. doi:10.1016/0024-3205(78)90176-5
[10] D. I. Arnold, F. A. Cotton, J. H. Matonic and C. A. Murillo, “Bis(N,N’-diphenylformamidine)silver(l) Triflate: A Three-Coordinate Silver Formamidine Compound Stabilized by Intramolecular Hydrogen Bonds,” Polyhedron, Vol. 16, No. 11, 1997, pp. 1837-1841. doi:10.1016/S0277-5387(96)00496-2
[11] D. B. Mitzi and K. Liang, “Synthesis, Resistivity, and Thermal Properties of the Cubic Perovskite NH2CH= NH2SnI3 and Related Systems,” Journal of Solid State Chemistry, Vol. 134, No. 2, 1997, pp. 376-381. doi:10.1006/jssc.1997.7593
[12] A. I. Meyers and R. Hutchings, “Asymmetric Dialkylation of Chiral 2-Benzazepine Formamidines,” Heterocycles Vol. 42, No. 2, 1996, pp. 475-478. doi:10.3987/COM-95-S58
[13] M. Matulenko and A. I. Meyers, “Total Synthesis of (-)-Tetrahydropalmatine via Chiral Formamidine Carbanions: Unexpected Behavior with Certain Ortho-Substituted Electrophiles,” The Journal of Organic Chemistry, Vol. 61, No. 2, 1996, pp. 573-580. doi:10.1021/jo951611q
[14] S. J. Benkovic, T. H. Barrows and P. R. Farina, “Studies on Models for Tetrahydrofolic Acid. IV. Reactions of Amines with Formamidinium Tetrahydroquinoxaline Analogs,” Journal of the American Chemical Society, Vol. 95, No. 25, 1973, pp. 8414-8420.
[15] P. S. Furth, M. S. Reitman and A. F. Cook, “A Novel Formamidine Linker for use in Soid-Phase Synthesis,” Tetrahedron Letters, Vol. 38, No. 31, 1997, pp. 5403-5406. doi:10.1016/S0040-4039(97)01200-8
[16] K. Hirano, S. Urban, C. Wang and F. Glorius,” A Modular Synthesis of Highly Substituted Imidazolium Salts,” Organic Letters, Vol. 11, No. 4, 2009, pp. 1019-1022. doi:10.1021/ol8029609
[17] L. Meschede and H-H Limbach,” Dynamic NMR Study of the Kinetic HH/HD/DD Isotope Effects on the Double Proton Transfer in Cyclic Bis(p-fluorophenyl)formamidine Dimers,” The Journal of Physical Chemistry, Vol. 95, No. 25, 1991, pp. 10267-10280. doi:10.1021/j100178a009
[18] R. M. Roberts, “ The Molecular Association of Diarylformamidines. II. Effects of 0- and P-Methyl Groups,” Journal of the American Chemical Society, Vol. 78, No. 11, 1956, pp. 2606-2608. doi:10.1021/ja01592a076
[19] K. M. Kuhn and R. H. Grubbs, “A Facile Preparation of Imidazolinium Chlorides,“ Organic Letters, Vol. 10, No. 10, 2008, pp. 2075-2077. doi:10.1021/ol800628a
[20] H. G. Mandel and A. J. Hill, “The Conversion of Formamides into Formamidines,” Journal of the American Chemical Society, Vol. 76, No. 15, 1954, pp. 3978-3982. doi:10.1021/ja01644a034
[21] R. M. Roberts, R. H. DeWolfe and J. H. Ross, “Ortho Esters, Imidic Esters and Amidines. II. Disproportionation Reactions of Nitrophenyl-, Chlorophenyl- and Tolyl- substituted Formimidates and Formamidines,” Journal of the American Chemical Society, Vol. 73, No. 5, 1951, pp. 2277-2281. doi:10.1021/ja01149a105
[22] C. D. Lewis, R. G. Krupp, H Tieckelmann and H. W. Post, “The Action of Ethyl Orthoformate on Aniline and Certain of its Derivatives,” The Journal of Organic Chemistry, Vol. 12, No. 2, 1947, pp. 303-307. doi:10.1021/jo01166a016
[23] C. Lin, J. D. Protasiewicz, E. T. Smith and T. Ren, “Linear Free Energy Relationships in Dinuclear Compounds. 2. Inductive Redox Tuning via Remote Substituents in Quadruply Bonded Dimolybdenum Compounds,” Inorganic Chemistry, Vol. 35, No. 22, 1996, pp. 6422-6428. doi:10.1021/ic960555o
[24] M. L. Cole, P. C. Junk and L. M. Louis, “Synthesis and Structural Characterisation of Some Novel Lithium and Sodium N,N’-di(para-tolyl)formamidinate Complexes,” Journal of the Chemical Society, Dalton Transacions, No. 20, 2002, pp. 3906-3914. doi:10.1039/b204047f
[25] L.-J. Han, “Redetermination of (E)-N,N’-bis(4-bromophenyl)formamidine,” Acta Crystallographica section E, Vol. 67, No. 5, 2011, p. 1159. doi:10.1107/S600536811013419
[26] K. U. Sadek, A. Alnajjar, R. A. Mekheimer, N. K. Mohamed and H. A. Mohamed, “Cerium (IV) Ammonium Nitrate (CAN) Mediated Reactions IV. A Highly Efficient Synthesis of N,N’-Diarylsubstituted Formamidines in Water at Ambient Temperature,” Green and Sustainable Chemistry, Vol. 1, No. 3, 2011, pp. 92-97. doi:10.4236/gsc.2011.13015

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