General Papers
ARKIVOC 2016 (v) 318-326
23.04, 120.83, 130.77, 133.58, 145.69, 148.96, 162.54, 173.70, 181.11; Anal. calcd. for C17H20N8OS: C, 53.11, H, 5.24, N, 29.15, S, 8.34. Found: C, 53.02, H, 5.36, N, 29.34, S, 8.42 %. Synthesis of 6-[4-(5-Amino-1,3,4-thiadiazol-2-yl)phenoxy]-N,N′-dicyclopropyl-1,3,5triazine-2,4-diamine (5). A mixture of thiosemicarbazone derivative 4 (1.22 g, 0.0032 mol) and ferric ammonium sulfate (3.18 g, 0.012 mol) in water (20 ml) was refluxed for 10 h, the reaction mixture was then poured into crushed ice and basified with 10% aq. NaOH to pH 5. The product formed was extracted with ethyl acetate, after removing the solvent in vacuum it was purified by a silica gel column (CHCl3/CH3OH/AcOH 9:1:0.02). White solid (0.95 g, 78%), mp 240-241 oC. IR (KBr) νmax/ cm-1 3369 - 3219 cm-1 (NH2 str.), 3010 cm-1 (C-H Ar str.), 1495 cm-1 (C=C str.), 1632 cm-1 (C=N str.), 1580(NH2 bending) 1330 cm-1 (CO-C str.), 760 cm-1 (C-S), 825 cm-1 (s-triazine); 1H NMR (400 MHz, DMSO-d6, δ, ppm); 0.41 – 0.55 (4H, m, CH2 (cyclopropyl ring)), 2.40 (1H, m, CH (cyclopropyl ring)), 3.44 (1H, m, NH cyclopropylamino), 4.41 (2H, s, NH2), 7.04 (2H, d, J 7.5 Hz, phenoxyl), 7.49 (2H, d, J 7.5 Hz, phenoxyl); 13C NMR (100 MHz, DMSO-d6, δ, ppm): 8.94, 23.04, 119.28, 124.43, 127.27, 152.41, 162.54, 161.74, 173.61, 173.70; Anal. calcd. for C17H18N8OS: C, 53.39, H, 4.74, N, 29.30, S, 8.38. Found: C, 53.42, H, 4.80, N, 29.49, S, 8.47 %. Synthesis of 4-(4,6-Dichloro-1,3,5-triazin-2-yloxy)benzonitrile (6). Mixture of cyanuric chloride 1 (0.184 g., 0.001 mol) and p-hydroxybenzonitrile (0.14 g, 0.0012 mol) in DMF (15 mL) were mixed with potassium tertiary butoxide (0.22 g., 0.002 mol) and stirred at 0 – 5 oC for 3 h. The reaction was monitored by TLC (in toluene: acetone 7:3). After pouring the reaction mixture into the crushed ice it was neutralized with 5% aqueous HCl. The solid separated out was filtered off, dried, and recrystallized from alcohol. White solid (0.22 g, 70%), mp 200-201 oC. IR (KBr) νmax/ cm-1: 2200 cm-1 (CN), 805 cm-1 (striazine) 774 cm-1 (C-Cl); 1H NMR (400 MHz, DMSO-d6, δ, ppm); 7.05 (2H, d, J 7.5 Hz, phenoxyl), 7.40 (2H, d, J 7.5 Hz, phenoxyl); 13C NMR (100 MHz, DMSO-d6, δ, ppm): 109.18, 119, 124.07, 132.12, 150.48, 168.03, 178.33; Anal. calcd. for C10H4Cl2N4O: C, 44.97, H, 1.51, N, 20.98. Found: C, 44.80, H, 1.60, N, 20.86 %. Synthesis of 4-[4,6-Bis(cyclopropylamino)-1,3,5-triazin-2-yloxy]benzonitrile (7). A solution of 6 (5.34 g, 0.02 mole) in dry THF (10 mL) and cyclopropylamine (1.08 g, 0.019 mole) in dry THF (10 mL) was mixed with anhydrous K2CO3 (2.76 g, 0.02 mole) and stirred at room temperature for 2 h. The reaction was monitored by TLC (toluene: acetone 6:4). To the reaction mixture again a solution of cyclopropylamine (1.08 g, 0.019 mole) in dry THF (10 mL) and anhydrous K2CO3 (2.76 g, 0.02 mole) were added and refluxed for 6 h. The reaction was monitored by TLC (in toluene: acetone 6:4). The reaction mixture was then poured into crushed ice and neutralized with dil HCl. The solid separated out was filtered off, washed with water and recrystallized from alcohol. White solid (5.62 g, 75%), mp 192-193 oC. IR (KBr) νmax/ cm-1: 3335 cm-1 (NH str.), 2210 cm-1 (CN), 1345 cm-1 (C-O-C), 806 (s-triazine); 1H NMR (400 MHz, DMSO-d6, δ, ppm); 0.44 – 0.59 (4H, m, CH2, cyclopropyl), 2.40 (1H, m, CH, cyclopropyl), 3.50 (1H, m, NH, cyclopropylamino), 7.06 (2H, d, J 7.5 Hz, phenoxyl), 7.44 (2H, d, J 7.5 Hz, phenoxyl); 13C NMR (100 MHz, DMSO-
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