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Six polycyclic pyrimidoazepine derivatives: syntheses, molecular structures and supramolecular assembly
Author(s) -
Acosta Quintero Lina M.,
Palma Alirio,
Cobo Justo,
Glidewell Christopher
Publication year - 2016
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/s2053229616004654
Subject(s) - chemistry , azepine , amine gas treating , dimethylformamide , medicinal chemistry , benzene , nucleophile , nucleophilic substitution , diamine , solvent , stereochemistry , polymer chemistry , organic chemistry , catalysis
A versatile synthetic method has been developed for the formation of variously substituted polycyclic pyrimidoazepine derivatives, formed by nucleophilic substitution reactions on the corresponding chloro‐substituted compounds; the reactions can be promoted either by conventional heating in basic solutions or by microwave heating in solvent‐free systems. Thus, (6 RS )‐6,11‐dimethyl‐3,5,6,11‐tetrahydro‐4 H ‐benzo[ b ]pyrimido[5,4‐ f ]azepin‐4‐one, C 14 H 15 N 3 O, (I), was isolated from a solution containing (6 RS )‐4‐chloro‐8‐hydroxy‐6,11‐dimethyl‐6,11‐dihydro‐5 H ‐benzo[ b ]pyrimido[5,4‐ f ]azepine and benzene‐1,2‐diamine; (6 RS )‐4‐butoxy‐6,11‐dimethyl‐6,11‐dihydro‐5 H ‐benzo[ b ]pyrimido[5,4‐ f ]azepin‐8‐ol, C 18 H 23 N 3 O 2 , (II), was formed by reaction of the corresponding 6‐chloro compound with butanol, and ( RS )‐4‐dimethylamino‐6,11‐dimethyl‐6,11‐dihydro‐5 H ‐benzo[ b ]pyrimido[5,4‐ f ]azepin‐8‐ol, C 16 H 20 N 4 O, (III), was formed by reaction of the chloro analogue with alkaline dimethylformamide. (6 RS )‐ N ‐Benzyl‐8‐methoxy‐6,11‐dimethyl‐6,11‐dihydro‐5 H ‐benzo[ b ]pyrimido[5,4‐ f ]azepin‐4‐amine, C 22 H 24 N 4 O, (IV), (6 RS )‐ N ‐benzyl‐6‐methyl‐1,2,6,7‐tetrahydropyrimido[5′,4′:6,7]azepino[3,2,1‐ hi ]indol‐8‐amine, C 22 H 22 N 4 , (V), and (7 RS )‐ N ‐benzyl‐7‐methyl‐2,3,7,8‐tetrahydro‐1 H ‐pyrimido[5′,4′:6,7]azepino[3,2,1‐ ij ]quinolin‐9‐amine, C 23 H 24 N 4 , (VI), were all formed by reaction of the corresponding chloro compounds with benzylamine under microwave irradiation. In each of compounds (I)–(IV) and (VI), the azepine ring adopts a conformation close to the boat form, with the C‐methyl group in a quasi‐equatorial site, whereas the corresponding ring in (V) adopts a conformation intermediate between the twist‐boat and twist‐chair forms, with the C‐methyl group in a quasi‐axial site. No two of the structures of (I)–(VI) exhibit the same range of intermolecular hydrogen bonds: different types of sheet are formed in each of (I), (II), (V) and (VI), and different types of chain in each of (III) and (IV).