Table of Contents
Organic Chemistry International
Volume 2014, Article ID 816487, 5 pages
http://dx.doi.org/10.1155/2014/816487
Research Article

Microwave Assisted Solvent-Free Synthesis of Some Imine Derivatives

1Department of Molecular Biology and Genetics, Faculty of Arts and Science, Canik Basarı University, 55080 Samsun, Turkey
2Department of Chemistry, Faculty of Arts and Sciences, Ondokuz Mayis University, 55139 Samsun, Turkey

Received 2 January 2014; Revised 23 February 2014; Accepted 24 February 2014; Published 26 March 2014

Academic Editor: Joseph E. Saavedra

Copyright © 2014 Yunus Bekdemir and Kürşat Efil. This is an open access article distributed under the Creative Commons Attribution License, which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited.

Abstract

Some imine derivatives (1a7d) were synthesized using a rapid and an environmentally friendly method with reaction of aromatic aldehydes (ad) and aromatic amines (17) (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], CeCl37H2O [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 (1a7d) by condensation of some aromatic amines (17) 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, we tested the effect of different microwave power such as 180, 360, 600, 900 W and detected the microwave power of 180 W and 360 W are more appropriate choices for the reaction. Hence, the optimum microwave reaction conditions were determined using 180 and 360 W microwave power and neat and wetting with β-EE for compound 1a. The highest reaction yield (94%) and shorter reaction time (1.5 min.) were obtained at 360 W microwave power with -EE. In the absence of wetting reagent, the reaction yields are 81% for 1.5 minutes and 88% for 5 minutes. It is understood that the reaction yield was increased by wetting reagent that increases the polarity of the reaction medium. The optimization of microwave-assisted conditions was given in Table 1.

tab1
Table 1: The optimization of microwave conditions for compound 1a.
816487.sch.001
Scheme 1

In addition, we have synthesized some imine derivatives (1a, 4a, 1b, 4b, 1c, 4c, 1d, 4d) under classical conditions using a solvent (azeotropic) and traditional heating source (hot plate) for comparison with microwave conditions. Firstly, synthesis of compound 1a under the classical reaction conditions was tested at various periods of time (30, 60, 120, 240, 1300 min) to determine the optimum reaction time, which was determined as 120 minutes. Information on the optimization of the reaction time of compound 1a for classic conditions was presented in Table 2.

tab2
Table 2: The optimization of classical conditions for compound 1a.

The compounds 1a, 4a, 1b, 4b, 1c, 4c, 1d, and 4d were obtained at 76%, 73%, 63%, 79%, 67%, 73%, 67%, and 75% yields, respectively, in 120 minutes under the classical reaction conditions, whereas in microwave conditions, the corresponding reaction yields were 94%, 97%, 95%, 98%, 91%, 97%, 95%, and 96%, respectively, in 1.0–1.5 minutes. All the results such as reactions time, yields, and melting points of the compounds were presented in Table 3. In addition, the yields of microwave and conventional reaction conditions for some imines were expressed graphically in Figure 1.

tab3
Table 3: Synthesis of imine derivatives under microwave irradiation.
816487.fig.001
Figure 1: Comparison of yields under the microwave and classical conditions.

3. Conclusion

In conclusion, we have developed a simple microwave assisted solvent-free method for the synthesis of imines using a wetting reagent (-ethoxyethanol). The method works well for the reaction of this type amines and aldehydes. Because, we have synthesized imine compounds for good yields and fast reaction times in our method. Our method has some advances such as higher reaction yields, shorter reaction times, and green reaction conditions than classical requirements used of a solvent and conventional heat source (like hot plate) and other some microwave methods used of catalyst and solid supports. In addition, some imines were synthesized for the first time by us with this study.

4. Experimental

All of the chemicals were obtained from commercial sources or prepared according to standard methods. Melting points were determined with an Electrothermal 9100 apparatus. The infrared absorption spectrum of the compounds has been recorded in the region at 4000 and 400 cm−1 range using a Bruker Vertex 80/80 v spectrophotometer using KBr pressed pellet technique at room temperature. The 1H NMR and 13C NMR spectra were recorded using a Bruker AC 200 NMR 200 MHz spectrometer in CDCl3- and DMSO- using TMS as the internal standard. Elemental analyses were conducted at the METU Central Laboratory using a LECO, CHNS-932. All syntheses were carried out in A Bosh HMT 812 C modified microwave oven.

General Procedure for Preparation of 1a7d. Aldehyde (1mmoL), amine (1mmoL) and two drops of -ethoxyethanol as a wetting reagent were mixed in a beaker. Then the beaker was placed in the microwave oven and was exposed to microwave irradiation (360 W). The product obtained by reaction was washed with cold ethanol. Then, it was recrystallized in ethanol. The physical and spectra data of the compounds 3a, 2b, 3b, 2c, 3c, 2d, and 3d are as follows.

N-(Salicylidene)-2-hydroxy-4-methylaniline (3a). M.p. 199-202°C. IR: 3033, 2965, 2916, 2858, 1612 (C=N), 1592, 1527, 1486, 1422, 1278, 1221, 1141, 1113, 1012, 869, 788, 754, 720, 622, 587, 556 cm−1. 1H NMR (DMSO-d6): δ 8.94 (s, 1H, N=CH), 13.90 (s, 1H, OH), 9.65 (s, 1H, OH). 13C NMR (DMSO-d6): δ 160.54, 160.36, 150.82, 137.56, 132.36, 132.25, 131.92, 120.17, 119.46, 119.14, 118.46, 116.93, 116.48. Elemental Anal. Calcd. for C14H13NO2: C, 73.99; H, 5.77; N, 6.16. Found: C, 72.81; H, 5.64; N, 6.16%.

N-(p-Chlorobenzylidene)-2-hydroxy-5-chloroaniline (2b). M.p. 123–125°C. IR: 3367, 3086, 3071, 3059, 2910, 2894, 1626 (C=N), 1588, 1569, 1478, 1424, 1370, 1274, 1234, 1194, 1154, 1087, 1011, 911, 857, 815, 799 (C–Cl), 697, 658, 608, 548, 533 cm−1. 1H NMR (CDCl3): δ 8.66 (s, 1H, N=CH), 7.91 (d, J = 8.4 Hz, 2H, Ar), 7.54 (d, J = 8.4 Hz, 2H, Ar), 7.34 (s, 1H, Ar), 7.24 (d, J = 8.6 Hz, 1H, Ar), 7.02 (d, J = 8.6 Hz, 1H, Ar). 13C NMR (CDCl3): δ 156.75 (N=C), 150.94, 138.21, 135.86, 133.87, 130.06, 129.28, 128.77, 125.07, 116.19, 116.16. Elemental Anal. Calcd. for C13H9Cl2NO: C, 58,67; H, 3,41; N, 5,26. Found: C, 57.74; H, 3.42; N, 5.26%.

N-(p-Chlorobenzylidene)-2-hydroxy-4-methylaniline (3b). M.p. 134–137°C. IR: 3367, 3063, 3049, 3028, 2907, 2857, 1629 (C=N), 1576, 1569, 1497, 1370, 1344, 1295, 1242, 1169, 1154, 1080, 1011, 947, 874, 857, 828, 808 (C–Cl), 793, 733, 687, 610, 591, 579 cm−1. 1H NMR (CDCl3): δ 8.72 (s, 1H, N=CH), 7.92 (d, J = 8.3 Hz, 2H, Ar), 7.53 (d, J = 8.4 Hz, 2H, Ar), 7.29 (d, J = 8.1 Hz, 1H, Ar), 6.92 (s, 1H, Ar), 6.80 (d, J = 8.0 Hz, 1H, Ar), 2.42 (s, 3H, CH3). 13C NMR (CDCl3): δ 154.09 (N=C), 152.34, 139.81, 137.40, 134.54, 132.60, 129.72, 129.16, 120.93, 115.67, 115.36, 21.48. Elemental Anal. Calcd. for C14H12ClNO: C, 68.44; H, 4.92; N, 5.70. Found: C, 67.64; H, 4.89; N, 5.69%.

N-(p-Methoxybenzylidene)-2-hydroxy-5-chloroaniline (2c). M.p. 86–88°C. IR: 3323, 3017, 2970, 2954, 2927, 2840, 1626 (C=N), 1599, 1569, 1511, 1453, 1312, 1250, 1165, 1027, 804, 650, 594 cm−1. 1H NMR (CDCl3): δ 9.88 (s, 1H, OH), 8.55 (s, 1H, N=CH), 7.85 (d, J = 8.5 Hz, 2H, Ar), 7.23 (s, 1H, Ar), 7.11 (d, J = 8.6 Hz, 1H, Ar), 6.99 (d, J = 8.5 Hz, 2H, Ar), 6.90 (d, J = 8.6 Hz, 1H, Ar), 3.88 (s, 3H, OCH3). 13C NMR (CDCl3): δ 162.92, 157.76 (N=C), 150.70, 136.69, 130.85, 128.49, 127.81, 124.91, 116.08, 115.77, 114.33, 55.49. Elemental Anal. Calcd. for C14H12ClNO2: C, 64.25; H, 4.62; N, 5,35. Found: C, 62.92; H, 4.57; N, 5.45%.

N-(p-Methoxybenzylidene)-2-hydroxy-4-methylaniline (3c). M.p. 86–87°C. IR: 3344, 3066, 3018, 2974, 2934, 2907, 2840, 1622 (C=N), 1593, 1567, 1509, 1481, 1423, 1378, 1245, 1162, 1026, 969, 909, 861, 835, 809, 761, 666, 617, 559 cm−1. 1H NMR (CDCl3): δ 8.59 (s, 1H, N=CH), 7.83 (d, J = 8.7 Hz, 2H, Ar), 7.16 (d, J = 8.1 Hz, 1H, Ar), 6.97 (d, J = 8.7 Hz, 2H, Ar), 6.81 (s, 1H, Ar), 6.68 (d, J = 7.8 Hz, 1H, Ar), 3.86 (s, 3H, OCH3), 2.31 (s, 3H, CH3). 13C NMR (CDCl3): δ 162.52, 155.25 (N=C), 152.02, 138.71, 133.68, 130.36, 129.13, 120.74, 115.34, 115.26, 114.30, 55.45, 21.41. Elemental Anal. Calcd. for C15H15NO2: C, 74.67; H, 6.27; N, 5.81. Found: C, 74.63; H, 6.41; N, 6.21%.

N-(Cinnamylidene)-2-hydroxy-5-chloroaniline (2d). M.p. 91–93°C. IR: 3344, 3064, 3013, 2964, 2911, 2881, 2839, 1621 (C=N), 1577, 1501, 1483, 1445, 1366, 1240, 1154, 1082, 979, 837, 804, 742, 683, 661, 593 cm−11H NMR (CDCl3): δ 8.41 (d, J = 8.2 Hz, 1H, N=CH), 7.54 (d, J = 5.2, 2H, Ar), 7.43–7.00 (m, 5H, Ar & CH=CH), 7.29 (s, 1H, Ar), 7.22 (d, J = 8.1 Hz, 1H, Ar), 6.90 (d, J = 8.6 Hz, 1H, Ar). 13C NMR (CDCl3): δ 159.36, 150.95 (N=C), 145.23, 136.47, 135.35, 129.99, 128.99, 128.36, 128.11, 127.69, 124.94, 115.99, 115.86. Elemental Anal. Calcd, for C15H12ClNO: C, 69.91; H, 4.69; N, 5.43. Found: C, 68.80; H, 4.72; N, 5.36%.

N-(Cinnamylidene)-2-hydroxy-4-methylaniline (3d). M.p. 97-98°C. IR: 3350, 3061, 3012, 2963, 2912, 2880, 2840, 1624 (C=N), 1577, 1541, 1498, 1447, 1368, 1257, 1157, 1092, 975, 836, 804, 749, 686, 630, 552 cm−1   1H NMR (CDCl3): δ 8.57 (d, J = 6.6 Hz, 1H, N=CH), 7.66 (dd, J = 6.0, 1.9 Hz, 2H, Ar), 7.54–7.12 (m, 5H, Ar & CH=CH), 7.30 (d, J = 7.9 Hz, 1H, Ar), 6.93 (s, 1H, Ar), 6.80 (d, J = 8.1 Hz, 1H, Ar), 2.43 (s, 3H, Ar). 13C NMR (CDCl3): δ 156.85, 152.28 (N=C), 143.26, 139.38, 135.71, 133.20, 129.53, 128.92, 128.73, 127.46, 120.75, 115.48, 115.04, 21.46. Elemental Anal. Calcd, for C16H15NO: C, 80.98; H, 6.37; N, 5,26. Found: C, 79.22; H, 6.18; N, 5.90%.

Conflict of Interests

The authors declare that there is no conflict of interests regarding the publication of this paper.

Acknowledgments

The authors would like to thank the Middle East Technical University analysis Center (Türkiye) for elemental analyses and Özgür Özdamar (Assistant Professor) and Hasan Saral (Assistant Professor) for the analysis, NMR, and IR of some imine compounds.

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