Sodium Hydroxide → Ethyl acetate methanol ammonia

Participants

Reaction Steps

In more detail, to provide N1-[4-(5-Azobenzotriazoyl)phenyl]-ethane-1,2-diamine (=Compound 1), 5-Aminobenzotriazole (0.854 g, 1.1 eq, 6.37 mmol) was dissolved in HCl (5ml, 50% v/v) and diazotised by dropwise addition of sodium nitrite (0.484 g, 1.2 eq, in 5 ml H2O) at 0° C. An excess of sodium nitrite was detected using starch iodide paper. A dark blue colour indicated excess nitrous acid which inferred the formation of the diazonium salt. Separately N-(1-Naphthyl) ethylenediamine dihydrochloride (1.500 g, 5.79 mmol) was dissolved in sodium acetate buffer (1.0M, 60 ml, pH 6.0) and acetone (80 ml). Diazotised aminobenzotriazole (1.1 eq) was added to this solution dropwise at 0° C. with stirring over 1 hour after which the solution was neutralised by addition of sodium hydroxide (2M). The solid produced was isolated by filtration and washed with sat. KCl (3×50 ml) prior to purification by trituration using methanol and diethyl ether to produce the title compound as an orange solid in 66% yield Rf (EtOAc/CH3OH/NH3 5/1/1) 0.14; dH (270 MHz, CD3OH) 3.00 (2H, t, CH2) 3.48 (2H, t, CH2) 6.69 (1H, dd, arH) 7.51 (1H, t, arH) 7.63 (1H, t, arH) 7.87 (1H, d, arH) 7.94 (2H, m, arHs) 8.13 (1H, d, arH) 8.34 (1H, s, arH) 9.02 (1H, d, arH); dc(270 MHz, CD3OD) 41.40 (CH2) 47.01 (CH2) 104.26 (CH) 114.93 (CH) 115.13 (CH) 116.67 (CH) 117.47 (CH) 122.20 (CH) 124.26 (C) 124.73 (CH) 126.03 (CH) 127.91 (CH) 134.62 (C) 139.91 (C) 146.12 (C) 146.76 (C) 148.98 (C) 151 28 (C); FAB ms m/z 332.1621 [C18H18N7 (M+1) <0.1 ppm].

Provenance & Evidence