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Synthesis 2003(9): 1377-1382
DOI: 10.1055/s-2003-40209
PAPER
© Georg Thieme Verlag Stuttgart ˙ New York

Synthesis of Novel Thieno- and Pyrrolo[2,3-d]pyrimidines peri-Fused with Pyrimidine­, 1,4-Diazepine and 1,4-Thiazepine Rings

Sigitas Tumkevicius*, Zivile Sarakauskaite, Viktoras Masevicius
Department of Organic Chemistry, Faculty of Chemistry, Vilnius University, Naugarduko 24, 2006 Vilnius, Lithuania
Fax: +37(5)2330987; e-Mail: sigitas.tumkevicius@chf.vu.lt;
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Publication History

Received 25 February 2003
Publication Date:
24 June 2003 (online)

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Abstract

An easy and efficient synthesis of the versatile, hitherto unreported alkyl 4-chloro- or 4-(alkoxycarbonylmethyl)amino(thio)-5-amino-2-methylthiothieno[2,3-d]- and pyrrolo[2,3-d]pyrimidine-6-carboxylates 3,5,6,8, from 6-chloro-4-(alkoxycarbonylmethylamino)-2-methylthiopyrimidine-5-carbonitriles 2a,b is described. Reaction of 5-amino-4-chloropyrrolo[2,3-d]pyrimidine 6 with sarcosine methyl ester gave the novel 2,3,5,6,9-pentaazabenz[cd]azulene 7. Heating 5-amino-4-(ethoxycarbonylmethylthio)pyrrolo[2,3-d]pyrimidine 5 in DMSO in the presence of potassium carbonate afforded the first representative of 6-thia-2,3,5,9-tetraazabenz[cd]azulene 9. Reaction of 5-amino-4-(alkoxycarbonylmethylamino)thieno- and pyrrolopyrimidines 3 and 8 with ethyl orthoformate or formalin in the presence of acids furnished the new 1-thia-3,5,6,8-tetraaza-, 1,3,5,6,8-pentaazaacenaphthylenes 10a,b and their 3,4-dihydro derivatives 11a,b. Acylation of 3 and 8 with chloroacetyl chloride gave the 5-chloroacetylamino intermediates 12a,b, which on heating in DMF in the presence of potassium carbonate cyclised to give the 2-thia-3,5,6,8-tetraaza- and 2,3,5,6,9-pentaazabenz[cd]azulene derivatives 13a,b.

Key words

cyclisations - heterocycles - amino acids - 2,3,5,6,9-pentaazabenz[cd]azulenes - 1-thia-3,5,6,9-tetraazabenz[cd]azulenes - 6-thia-1,3,5,9-tetraazabenz[cd]azulene - azaacenaphthylenes