Coupled Processes of Methoxycarbonylation and Cyclization of N,haloanilines.-Methoxycarbonylation of the title diynes (I) yields the usual acyclic diesters (IV) and/or the pyridine derivatives (V). The latter are formed by further addition of a methoxycarbonyl group to the diesters and subsequent cyclization. The ratios depend on the substitution pattern of the aryl moiety. -(ABDULGANIEVA, S. A.; MANCHUK, Z. N.; ZHAPAROVA, Z. M.; ERZHANOV, K. B.; Zh.
The catalytic oxidative methoxycarbonylation reaction of N,N-dipropargylarylamines has been investigated. PdCl 2 -CuCl 2 has been studied as a catalytic system. Consecutive reactions of substitutive and additive methoxycarbonylation have been going in this process, which has been complicated by dimerisation, polymerization and cyclization processes. Apparently the results of process are determined by stability of intermediate reactionary complexes with participation of catalytic system PdCl 2 -CuCl 2 . The structures of synthesized cyclic amino triesters are established by analysis of experimental spectra NMR 1 H and 13 C, comparison with calculated spectra of possible hypothetic structures and estimation of thermodynamics properties by Joback fragmentation and MOPAC Semi-empirical PM3 methods.
ChemInform Abstract Aroylation as well as chloroacetylation of the title compound (I) proceeds regiospecifically to afford mixtures of the isomeric N-acyl derivatives (III) and (IV). The mixtures (IIIa)/(IVa) or (IIIb)/(IVb), on prolonged storage in CCl4 at room temperature, afford the pure isomers (IVa) or (IVb). This is confirmed by 1H NMR spectroscopy. The isomers (IIIa) and (IIIb) are, hence, the products of kineticly controlled reactions, whereas (IVa) and (IVb) are the thermodynamically more stable isomers. The chloroacetyl derivatives (IIIc)/(IVc) or (IIId)/(IVd), on prolonged storage in CDCl3 at room temperature, form equilibrium mixtures. The isomers (IIIc) and (IIId) are found to be the main components. This is probably due to the enhanced electron accepting character of the chloroacetyl substituents as compared to their aroyl analogues.
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