Abstract
Acylation of (1,3-dihydro-1,3-dimethyl-2H -benzimidazol-2-ylidene)acetonitrile
with mixed anhydrides of N -Boc proline and
4-thiazolidinecarboxylic acid was found to proceed at the exocyclic
carbon atom yielding the corresponding C -acyl
derivatives. Removal of the protecting group with equimolar amount
of hydrochloric acid effected simultaneous cyclization affording
2-(3-amino-5,6,7,7a-tetrahydro-1-oxo-1H -pyrrolizin-2-yl)-
and 2-(5-amino-7,7a-dihydro-7-oxo-1H ,3H -pyrrolo[1,2-c ]thiazol-6-yl)-1,3-dimethylbenzimidazolium
chlorides. Reduction of the prepared salts with sodium borohydride
resulted in 3-amino-2-(2,3-dihydro-1,3-dimethyl-1H -benzimidazol-2-yl)-5,6,7,7a-tetrahydro-1H -pyrrolizin-1-one and 5-amino-6-(2,3-dihydro-1,3-dimethyl-1H -benzimidazol-2-yl)-1,7a-dihydro-3H ,7H -pyrrolo[1,2-c ]thiazol-7-one, respectively. These
compounds were shown to be masked aldehydes. Their reactions with
phenylhydrazine and hydroxylamine yielded corresponding hydrazones
and oximes, whereas condensation with malononitrile furnished 2-amino-5a,6,7,8-tetrahydro-5-oxo-5H -pyrido[3,2-b ]pyrrolizine-3-carbonitrile
and 2-amino-5a,6-dihydro-5H ,8H -thiazolo[3′,4′:1,5]pyrrolo[2,3-b ]pyridine-3-carbonitrile.
Key words
acylations - amino aldehydes - heterocycles - nitriles - reduction
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Full crystallographic parameters have
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