Some imine derivatives (1a–7d) were synthesized using a rapid and an environmentally friendly method with reaction of aromatic aldehydes (a–d) and aromatic amines (1–7) (in 1?:?1 molar ratio) in the presence of -ethoxyethanol as a wetting reagent (2 drops) under solvent-free conditions using microwave heating. 1. Introduction Compounds containing the –C=N– (azomethine group) structure are known as Schiff bases, usually synthesized from the condensation of primary amines and active carbonyl groups [1]. The reaction is acid-catalyzed and is generally carried out by refluxing the carbonyl compound and amine, with an azeotroping agent if necessary, and separating the water as formed [2]. Schiff bases are well known for their biological applications as antibacterial, antifungal, anticancer, and antiviral agents; furthermore, they have been used as intermediates in medical substrates and as ligands in complex formation with some metal ions [1, 3]. The synthesis of imines was firstly reported by Hugo Schiff in 1864 and they have been known since then [4]. The imine compounds have been prepared using molecular sieves [5, 6], infrared irradiation [7], Mg(ClO4)2 [8], P2O5/SiO2 [9], ZnCl2 [10], CaO under microwave power [11], ethyl lactate as a tunable solvent [12], K10 clay [13], TiCl4 [14], alumina [15], CeCl3 7H2O [16], ultrasound irradiation [17], polymer-supported [18], nanotube TiO2 (in sunlight) [19], and Ti(OEt)4 [20, 21]. The present work reveals the comparative aspects of condensation of some aromatic amines with aldehyde derivatives using microwave and conventional methods. The amine and aldehyde compounds as starting materials, -ethoxyethanol ( -EE) as wetting reagent and microwave power as an effective source of heating are used in this study. The corresponding imine compounds were prepared in high yields and short reaction times using this effective and environment friendly method. 2. Results and Discussion In this work, we synthesized quickly and efficiently a series imine derivatives (1a–7d) by condensation of some aromatic amines (1–7) and aldehyde derivatives such as salicylaldehyde (a), p-chlorobenzaldehyde (b), p-methoxybenzaldehyde (c) and cinnamaldehyde (d) under microwave-assisted solvent-free conditions using -EE as wetting reagent. -EE that is a polar molecule quickly absorbs microwaves and therefore heats up and heats around effectively. As a result, -EE, which increases the polarity of the reaction medium, has an active role in the heating of the reaction medium by microwaves. The general reaction was summarized in Scheme 1. In addition,
References
[1]
A. M. Asiri and S. A. Khan, “Synthesis and anti-bacterial activities of some novel schiff bases derived from aminophenazone,” Molecules, vol. 15, no. 10, pp. 6850–6858, 2010.
[2]
R. W. Layer, “The chemistry of imines,” Chemical Reviews, vol. 63, pp. 489–510, 1963.
[3]
H.-K. Fun, R. Kia, A. M. Vijesh, and A. M. Isloor, “5-Diethylamino-2-[(E)-(4-methyl-3-nitrophenyl)iminomethyl]phenol: a redetermination,” Acta Crystallographica E: Structure Reports Online, vol. 65, no. 2, pp. o349–o350, 2009.
[4]
H. Schiff, “Sur quelques dérivés phéniques des aldéhydes,” Annali Di Chimica, vol. 131, p. 118, 1864.
[5]
K. Taguchi and F. H. Westheimer, “Catalysis by molecular sieves in the preparation of ketimines and enamines,” Journal of Organic Chemistry, vol. 36, no. 11, pp. 1570–1572, 1971.
[6]
M. E. Kuehne, “The application of enamines to a new synthesis of β-ketonitriles,” Journal of the American Chemical Society, vol. 81, no. 20, pp. 5400–5404, 1959.
[7]
M. á. Vázquez, M. Landa, L. Reyes, R. Miranda, J. Tamariz, and F. Delgado, “Infrared irradiation: effective promoter in the formation of N-benzylideneanilines in the absence of solvent,” Synthetic Communications, vol. 34, no. 15, pp. 2705–2718, 2004.
[8]
A. K. Chakraborti, S. Bhagat, and S. Rudrawar, “Magnesium perchlorate as an efficient catalyst for the synthesis of imines and phenylhydrazones,” Tetrahedron Letters, vol. 45, no. 41, pp. 7641–7644, 2004.
[9]
H. Naeimi, H. Sharghi, F. Salimi, and K. Rabiei, “Facile and efficient method for preparation of Schiff bases catalyzed by P2O5/SiO2 under free Solvent conditions,” Heteroatom Chemistry, vol. 19, no. 1, pp. 43–47, 2008.
[10]
J. H. Billman and K. M. Tai, “Reduction of Schiff bases. II: benzhydrylamines and structurally related compounds,” Journal of Organic Chemistry, vol. 23, no. 4, pp. 535–539, 1958.
[11]
M. Gopalakrishnan, P. Sureshkumar, V. Kanagarajan, and J. Thanusu, “New environmentally-friendly solvent-free synthesis of imines using calcium oxide under microwave irradiation,” Research on Chemical Intermediates, vol. 33, no. 6, pp. 541–548, 2007.
[12]
J. S. Bennett, K. L. Charles, M. R. Miner et al., “Ethyl lactate as a tunable solvent for the synthesis of aryl aldimines,” Green Chemistry, vol. 11, no. 2, pp. 166–168, 2009.
[13]
R. S. Varma, R. Dahiya, and S. Kumar, “Clay catalyzed synthesis of imines and enamines under solvent-free conditions using microwave irradiation,” Tetrahedron Letters, vol. 38, no. 12, pp. 2039–2042, 1997.
[14]
W. A. White and H. Weingarten, “A versatile new enamine synthesis,” Journal of Organic Chemistry, vol. 32, no. 1, pp. 213–214, 1967.
[15]
F. Texier-Boullet, “A simple, convenient and mild synthesis of imines on alumina surface without solvent,” Synthesis, vol. 1985, no. 6-7, pp. 679–681, 1985.
[16]
L. Ravishankar, S. A. Patwe, N. Gosarani, and A. Roy, “Cerium(III)-catalyzed synthesis of schiff bases: a green approach,” Synthetic Communications, vol. 40, no. 21, pp. 3177–3180, 2010.
[17]
K. P. Guzen, A. S. Guarezemini, A. T. G. órf?o, R. Cella, C. M. P. Pereira, and H. A. Stefani, “Eco-friendly synthesis of imines by ultrasound irradiation,” Tetrahedron Letters, vol. 48, no. 10, pp. 1845–1848, 2007.
[18]
R. Annunziata, M. Benaglia, M. Cinquini, and F. Cozzi, “Poly(ethylene glycol)-supported 4-alkylthio-substituted aniline: a useful starting material for the soluble polymer-supported synthesis of imines and 1,2,3,4-tetrahydroquinolines,” European Journal of Organic Chemistry, no. 7, pp. 1184–1190, 2002.
[19]
M. Hosseini-Sarvari, “Nano-tube TiO2 as a new catalyst for eco-friendly synthesis of imines in sunlight,” Chinese Chemical Letters, vol. 22, no. 5, pp. 547–550, 2011.
[20]
G. Dutheuil, S. Couve-Bonnaire, and X. Pannecoucke, “Diastereomeric fluoroolefins as peptide bond mimics prepared by asymmetric reductive amination of α-fluoroenones,” Angewandte Chemie: International Edition, vol. 46, no. 8, pp. 1290–1292, 2007.
[21]
J. F. Collados, E. Toledano, D. Guijarro, and M. Yus, “Microwave-assisted solvent-free synthesis of enantiomerically pure N-(tert-Butylsulfinyl)imines,” Journal of Organic Chemistry, vol. 77, Article ID 300919, pp. 5744–5750, 2012.
[22]
E. Tauer and K. H. Grellmann, “Photochemical and thermal reactions of aromatic Schiff bases,” Journal of Organic Chemistry, vol. 46, no. 21, pp. 4252–4258, 1981.
[23]
R. J. Argauer and C. E. White, “Effect of substituent groups on fluorescence of metal chelates,” Analytical Chemistry, vol. 36, no. 11, pp. 2141–2148, 1964.
[24]
J. D. Margerum and J. A. Sousa, “Spectroscopic studies of substituted benzalanilines,” Applied Spectroscopy, vol. 19, pp. 91–97, 1965.
[25]
J. E. Kuder, H. W. Gibson, and D. Wychick, “Electrochemical characterization of salicylaldehyde anils,” Journal of Organic Chemistry, vol. 40, no. 7, pp. 875–879, 1975.
[26]
F. F. Stephens and J. D. Bower, “The preparation of benziminazoles and benzoxazoles from Schiff's bases. Part I,” Journal of the Chemical Society, pp. 2971–2972, 1949.
[27]
J. Schmeyers, F. Toda, J. Boy, and G. Kaupp, “Quantitative solid-solid synthesis of azomethines,” Journal of the Chemical Society: Perkin Transactions 2, no. 4, pp. 989–993, 1998.
[28]
W. Xu, S. Zhang, S. Yang et al., “Asymmetric synthesis of α-aminophosphonates using the inexpensive chiral catalyst 1,1′-binaphthol phosphate,” Molecules, vol. 15, no. 8, pp. 5782–5796, 2010.
[29]
Y. M. S. A. Al-Kahraman, H. M. F. Madkour, D. Ali, and M. Yasinzai, “Antileishmanial, antimicrobial and antifungal activities of some new aryl azomethines,” Molecules, vol. 15, no. 2, pp. 660–671, 2010.