Jozef Hodyl PhD Thesis - Theses - Flinders University

The preparation of this compound was by the same method as for 59 using 70(4.21 g, 17.40 mmol), K 2 CO 3 , (6.01 g, 43.5 mmol), and (2S)-(+)-glycidyl tosylate,58, (3.97 g, 17.39 mmol), to yield 60 as a pale yellow oil, 3.71 g, 74%, rf: 0.21. 1 HNMR (CDCl 3 ): δ 6.82 (4 H, s, Ar-H); 4.14 (1 H, dd, J = 3.2, 11.04 Hz, -HCH-);4.06-4.04 (2 H, m, -OCH 2 -); 3.86 (1 H, dd, J = 5.7, 11.04 Hz, -HCH); 3.82-3.79 (2H, m, -OCH 2 -); 3.71-3.64 (6 H, m, -OCH 2 -); 3.59-3.57 ( 2 H, m, -OCH 2 -); 3.32-3.28(1 H, m, -CH-O-); 2.87 (1 H, t, J = 4.48 Hz, -HCH-O-); 2.71 (1 H, dd, J = 2.68, 4.91Hz, -HCHO-); 2.15 (1 H, br s, OH). 13 C NMR (CDCl 3 ): δ 153.15 (1 C, Ar, ipso);152.75 (1 C, Ar, para); 115.53 (2 C, Ar, meta); 115.48 (2 C, Ar, ortho); 72.39 (1 C,CH 2 -CH 2 OH; 70.66 (1 C, -CH 2 -OCH 2 CH 2 OH); 70.24 (1 C, -CH 2 -OCH 2 CH 2 OAr);69.71 (1 C, -CH 2 CH-); 69.35 (1 C, -CH 2 -CH 2 OAr); 67.87 (1 C, -CH 2 -OAr); 61.61 (1C, -CH 2 -OH); 50.14 (1 C, -CH-); 44.56 (1 C, -CH 2 -OCH 2 -).[α] 25 D = +2.35 o (c 2.13,MeOH).7.9 Synthesis of the mono-protected cyclen synthon1,4,7-triformyl 1,4,7,10-tetraazacyclododecane, 5252This compound was synthesised by a method previously established byBoldrini, 131 and modified by Yoo. 109 To a stirred solution of cyclen, 21, (1.0 g 5.80mmol), in anhydrous ethanol (30 cm 3 ), chloral hydrate, (3.84 g, 23.20 mmol), was132