Hantzsch synthesis of 2,6-dimethyl-3,5-dimethoxycarbonyl-4-(o-methoxyphenyl)-1,4-dihydropyridine; a novel cyclisation leading to an unusual formation of 1-amino-2-methoxy-carbonyl-3,5-bis(o-methoxyphenyl)-4-oxa-cyclohexan-1-ene.
Hantzsch condensation of two equivalents of methyl-3-aminocrotonate with (m- and p)-methoxybenzaldehyde afforded the expected products 2,6-dimethyl-3,5-dimethoxycarbonyl-4-(m-methoxyphenyl)-1,4-dihydropyridine and 2,6-dimethyl-3,5-dimethoxycarbonyl-4-(p-methoxyphenyl)-1,4-dihydropyridine, whereas o-methoxy-benzaldehyde produced mainly 1-amino-2-methoxycarbonyl-3,5-bis(o-methoxy-phenyl)-4-oxa-cyclohexan-1-ene. The structure of the product, not previously reported in the literature, was determined by 1D and 2D NMR spectra and its MS fragmentation. This is the first example of cyclisation leading to a substituted pyran rather than 1,4-DHP under typical Hantzsch reaction conditions. A plausible mechanism for its formation is postulated.
Filipan-Litvić
Mirela
M
BELUPO Pharmaceuticals, Inc. R&D, Danica 5, 48000 Koprivnica, Croatia. mirela.filipan-litvic@belupo.hr
Litvić
Mladen
M
Cepanec
Ivica
I
Vinković
Vladimir
V
D003460:Crystallization; D003500:Cyclization; D003510:Cyclohexanes / Q000138:chemical synthesis / Q000737:chemistry; D004095:Dihydropyridines / Q000138:chemical synthesis / Q000737:chemistry; D015394:Molecular Structure
D003510:Cyclohexanes; D004095:Dihydropyridines; C038806:1,4-dihydropyridine