Jozef Hodyl PhD Thesis - Theses - Flinders University

7.10 Synthesis of macrocyclic receptor ligands1-(benzyloxycarbonyl)-4,7,10-tris-((S)-2-hydroxy-3-phenoxypropyl)-1,4,7,10-tetraazacyclododecane, 71OHHOOONNNNHOHOOHHO71This compound was synthesised by an established method modified fromSmith. 94 A solution of 56 (638 mg, 4.25 mmol), in anhydrous ethanol (10 cm 3 ) wasadded drop-wise to a refluxing solution of 50 (424 mg, 1.40 mmol), dissolved inanhydrous ethanol (10 cm 3 ). The reaction was monitored for the disappearance of thestarting epoxide by TLC on silica (eluent 10% hexane/DCM rf: 0.39) for thedisappearance of 56, 10 days. Evaporation of the solvent in vacuo gave 71 as aviscous yellow oil; yield 1.0 g, quantitative. 13 C NMR (CDCl 3 ): δ 158.48 (3 C, Ph,ipso); 156.35 (1 C, C=O); 136.45 (1 C, Bn, ipso); 129.28 (6 C, Ph); 129.25 (1 C,Bn); 128.34 (2 C, Bn); 127.88 (2 C, Bn); 120.72 (3 C, Ph); 114.38 (6 C, Ph); 69.62(2 C, OCH 2 ); 68.82 (1 C, OCH 2 ); 67.10 (1 C, OCH 2 Bn); 66.70 (2 C, CH); 65.93 (1C, CH); 59.10 (2 C, CH 2 N); 57.89 (1 C, CH 2 N); 54.06 (2 C, cyclen -CH 2 ); 53.31 (2C, cyclen -CH 2 ); 50.40 (2 C, cyclen -CH 2 ); 47.42 (2 C, cyclen -CH 2 ).136