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A concise and efficient synthesis of amino‐substituted (1 H ‐benzo[ d ]imidazol‐1‐yl)pyrimidine hybrids: synthetic sequence and the molecular and supramolecular structures of six examples
Author(s) -
Vicentes Daniel E.,
Rodríguez Ricaurte,
Ochoa Patricia,
Cobo Justo,
Glidewell Christopher
Publication year - 2019
Publication title -
acta crystallographica section c
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.304
H-Index - 17
ISSN - 2053-2296
DOI - 10.1107/s2053229619012087
Subject(s) - diamine , chemistry , pyrimidine , stereochemistry , trifluoroacetic acid , hydrogen bond , molecule , medicinal chemistry , organic chemistry
A concise and efficient synthesis of a series of amino‐substituted benzimidazole–pyrimidine hybrids has been developed, starting from the readily available N 4 ‐(2‐aminophenyl)‐6‐methoxy‐5‐nitrosopyrimidine‐2,4‐diamine. In each of N 5 ‐benzyl‐6‐methoxy‐4‐(2‐phenyl‐1 H ‐benzo[ d ]imidazol‐1‐yl)pyrimidine‐2,5‐diamine, C 25 H 22 N 6 O, (I), 6‐methoxy‐ N 5 ‐(4‐methoxybenzyl)‐4‐[2‐(4‐methoxyphenyl)‐1 H ‐benzo[ d ]imidazol‐1‐yl]pyrimidine‐2,5‐diamine, C 27 H 26 N 6 O 3 , (III), 6‐methoxy‐ N 5 ‐(4‐nitrobenzyl)‐4‐[2‐(4‐nitrophenyl)‐1 H ‐benzo[ d ]imidazol‐1‐yl]pyrimidine‐2,5‐diamine, C 25 H 20 N 8 O 5 , (IV), the molecules are linked into three‐dimensional framework structures, using different combinations of N—H…N, N—H…O, C—H…O, C—H…N and C—H…π hydrogen bonds in each case. Oxidative cleavage of 6‐methoxy‐ N 5 ‐(4‐methylbenzyl)‐4‐[2‐(4‐methylphenyl)‐1 H ‐benzo[ d ]imidazol‐1‐yl]pyrimidine‐2,5‐diamine, (II), with diiodine gave 6‐methoxy‐4‐[2‐(4‐methylphenyl)‐1 H ‐benzo[ d ]imidazol‐1‐yl]pyrimidine‐2,5‐diamine, which crystallized as a monohydrate, C 19 H 18 N 6 O·H 2 O, (V), and reaction of (V) with trifluoroacetic acid gave two isomeric products, namely N ‐{5‐amino‐6‐methoxy‐6‐[2‐(4‐methylphenyl)‐1 H ‐benzo[ d ]imidazol‐1‐yl]pyrimidin‐2‐yl}‐2,2,2‐trifluoroacetamide, which crystallized as an ethyl acetate monosolvate, C 21 H 17 F 3 N 6 O 2 ·C 4 H 8 O 2 , (VI), and N ‐{2‐amino‐6‐methoxy‐4‐[2‐(4‐methylphenyl)‐1 H ‐benzo[ d ]imidazol‐1‐yl]pyrimidin‐5‐yl}‐2,2,2‐trifluoroacetamide, which crystallized as a methanol monosolvate, C 21 H 17 F 3 N 6 O 2 ·CH 4 O, (VII a ). For each of (V), (VI) and (VII a ), the supramolecular assembly is two‐dimensional, based on different combinations of O—H…N, N—H…O, N—H…N, C—H…O and C—H…π hydrogen bonds in each case. Comparisons are made with some related structures.