Cyclocondensation of the disodium salt of [RNH(CH2)2]2NR (R = 4-MeC6H4SO2) with [Cl(CH2)2]2NH in DMF at room temp. for 3 days gave 17% macrocycle I (R as before). Condensation of I with (ClCO)2 in CH2Cl2 gave 91% of the bridged bicyclic compd. II (R as before, R12 = O) which was reduced by LiAlH4 in THF to give 17% II (R as before, R1 = H) (III). III was also prepd. in 16% yield by condensation of I with (p-MeC6H4SO3CH2)2 in refluxing MeCN contg. Na2CO3 for 4 days. Deprotection of III by 96% H2SO4 at 100° gave 43% of the title compd. II (R = R1 = H) (IV). IV behaves as a dinucleating ligand forming a 2Cu2+ complex, in which there is a weak ferromagnatic interaction between the Cu atoms.
Synthesis of 1,2-bis(1,4,7,10-tetraazadodecanyl)ethane, a double-ring fully saturated macrocycle containing 12-membered tetraaza subunits
BUTTAFAVA, ARMANDO;FABBRIZZI, LUIGI;PEROTTI, ANGELO
1984-01-01
Abstract
Cyclocondensation of the disodium salt of [RNH(CH2)2]2NR (R = 4-MeC6H4SO2) with [Cl(CH2)2]2NH in DMF at room temp. for 3 days gave 17% macrocycle I (R as before). Condensation of I with (ClCO)2 in CH2Cl2 gave 91% of the bridged bicyclic compd. II (R as before, R12 = O) which was reduced by LiAlH4 in THF to give 17% II (R as before, R1 = H) (III). III was also prepd. in 16% yield by condensation of I with (p-MeC6H4SO3CH2)2 in refluxing MeCN contg. Na2CO3 for 4 days. Deprotection of III by 96% H2SO4 at 100° gave 43% of the title compd. II (R = R1 = H) (IV). IV behaves as a dinucleating ligand forming a 2Cu2+ complex, in which there is a weak ferromagnatic interaction between the Cu atoms.I documenti in IRIS sono protetti da copyright e tutti i diritti sono riservati, salvo diversa indicazione.
