Reductive debenzylation of 2,6,8,12-tetraacetyl-2,4,6,8,10,12-hexaazatetracyclo5,5,0,0~(5,9),0~(3,11)dodecane derivatives

摘要

The composition of products from catalytic hydrogenolysis of 4,10-dibenzyl-2,6,8,12-tetraacetyl-2,4,6,8,10,12-hexaazateiracyclo[5,5,0,0~(3,11),0~(5,9)]dodecane in acid solutions is studied by HPLC method. In a mixture of formic acid with acetic, propionic and isobutyric acids there is formed a mixture of two main products: 4,10-diformyl-2,6,8,12-tetraacetyl-2,4,6,8,10,12-hexaazatetracyclo[5,5,0,0~(3,11), 0~(5,9)]dodecane and 4-formyl-2,6,8,12-tetraacetyl-2,4,6,8,10,12-hexaazatetracyclo[5,5,0,0~(3,11),0~(5,9)]dodecane. In aqueous solutions of formic acid there is formed a mixture of the same products, but the process becomes complicated due to hydrolysis of amide groups. A part of the hydrolysis products preserve the structure of 2,4,6,8,10,12-hexaazatetracyclo[5,5,0,0~(3,11),0~(5,9)]dodecane. The alkaline hydrolysis of 4,10-diformyl-2,6,8,12-tetraacetyl-2,4,6,8,10,12-hexaazatetracyclo[5,5,0,0~(3,11),0~(5,9)]dodecane leads to 2,6,8,12-tetraacetyl-2,4,6,9,10,12-hexaazatetracyclo[5,5,0,0~(3,11), 0~(5,9)]dodecane.