1,3-DIAZA-1,S-BUTADIENES - SYNTHESIS AND CONVERSION INTO PYRIMIDINES BY [4-PI-PI] CYCLOADDITION WITH ELECTRON-DEFICIENT ACETYLENES - SYNTHETIC UTILITY OF 2-(TRICHLOROMETHYL)PYRIMIDINES(2)

Methods have been devised to generate 1H-1,3-diaza-1,3-butadienes bear ing a leaving group at position-4 in latent, masked, and unprotected f orms. A hallmark of these azadienes is that they undergo thermal [4 pi + 2 pi] cycloaddition reactions with electron deficient acetylenes to give adducts which are aromatized to pyrimidine derivatives under the reaction conditions. Thus, 1-(methoxycarbonyl)-3-acylamidines 17 on b eating in solution are converted in situ into the 1,3-diaza-1,3-dienes 18 and/or 19 which react with dimethyl acetylenedicarboxylate (DMAD) to produce the pyrimidines 20. The 1-Boc-1,3-diaza-1,3-dienes 24 are m asked forms of the LH-dienes inasmuch as they react with DMAD under re latively mild conditions to give the dihydropyrimidine adducts 25, whi ch are easily detectable by H-1 NMR spectroscopy, and which aromatize to pyrimidines 26 at higher temperatures. The 4-methylthio compounds 3 1 and 33, and the 2-(trichloromethyl) compounds 37, are isolable, rela tively stable, 1H-1,3-diaza-1,3-butadienes, These easily prepared comp ounds react with electron deficient acetylenes under mild conditions t o provide the pyrimidines 20, 34, and 38, respectively, in fair to exc ellent yields. The 2-(trichloromethyl)pyrimidines 38 are very useful p recursors of a wide variety of other 2-substituted pyrimidines 46-52.