UNSATURATED HETERO CHAINS .6. OMEGA-ALKOXY-SUBSTITUTED AND OMEGA-AMINO-SUBSTITUTED OLIGONITRILES - SYNTHESIS, STRUCTURES, AND REACTIVITY

omega-Alkoxy-substituted 1-oxa-3,5-diazahexatrienes (5), 1-oxa-3,5,7-t riazaoctatetraenes (7), and 1-oxa-3,5,7,9-tetraazadecapentaenes (9) we re synthesized by condensation of 1,5-dialkoxy-2-azapropenylium salts (3) or 1,5-dialkoxy-2,4-diazapentadienylium salts (8) with N-acyl- and N-alkoxycarbonylamidines (4). It is the nature of the leaving group w hich mainly determines the chain length of the products obtained. - Co mpounds 7 show ring-chain tautomerism involving the cyclic form 6 in d ependence of the substitution pattern. All omega-alkoxy substituted ol igonitriles 5, 7, and 9 may easily converted to the corresponding omeg a-amino compounds 11, 14, and 15 by reaction with secondary amines 10. Reaction of 5a, b with the primary amine 12 leads to the triazinone 1 3. The Lithiated ketimine 16 converts 5b and 7d to the corresponding 1 -oxa-3,5,7-triazaoctatetraenes 17 and 1-oxa-3,5,7,9-tetraazadecapentae nes 18. Helical geometries dominate the structures of the new oligonit riles in the crystalline state as derived from X-ray analyses effects, which should be strong in the amino derivatives 11, 14, and 15, have no significant influence on the structure of the oligonitriles.