ORTHOAMIDES - LI - PUSH-PULL-BUTADIENES AND HETEROCYCLES FROM ALKYNE CARBOXYLIC-ACID ORTHOAMIDES AND CH2-ACIDIC COMPOUNDS

The acetylides 4b, 4f react with N,N,N',N',N '',N ''-hexamethylguanidi niumchloride (5) to give the orthoamides 6b, 6f, resp. From CH2-acidic compounds and the orthoamides 6a, c, e can be obtained the push-pull- substituted butadienes 8a-8aj. The 2,3,5-trimethyl-thiadiazolium salt 9 does not condense with 6e, as other CH2-acidic compounds do, instead the vinylogous guanidinium salt 10a is produced. On healing, the kete naminals 8d, aa cyclize to give the pyridone-carbonitriles 11a, b, res p. From di-amino-coumarins 12 and the ortho-carboxylic acid amideaceta ls 13a, b and the ketenaminal 16 resp., the amidines 14a-c and the het erocyclic compounds 15a-c resp., are formed. The enamines 17a-c, 19a, b react with the orthoamides 6a-f to give the pyridine derivatives 18a -l, 20a-h and 21a, b, resp. Analogously, from 6-amino-uracil 22 and 6a , b, e, fare formed the pure 7-dimethylaminopyrido[2,3-d] pyrimidines 23a, b or mixtures of compounds 23c, d and the isomeric 4-dimethylamin o-pyrido[2,3d]pyrimidines 24a, b resp., which can be separated via the ir salts 25a,b/26a,b. The heterocyclic compounds 30a-d, 32a,16 can be prepared from the pyrazole derivatives 28, 31 resp. and the orthoamide s 6a-f.