No abstract

The stereochemistry of 3-arylideneflavanones has been established by the preparation of both cis (3a-c) and trans (2a-c) isomers. Configurations and conformations are assigned on the basis of nmr spectra. The products obtained by the acid-catalyzed condensation of flavanones and aromatic aldehydes have the trans configuration.Ultraviolet irradiation produces the cis isomers. Allylic coupling constants show that the trans isomers exist in the conformation with the 2-phenyl group axial. The cis isomers appear to exist in both conformations. In 2,2-diphenylchromanone (4) the steric effect of the second phenyl group causes formation of the cis product 2,2diphenyl-3-benzylidenechromanone (5). o-Hydroxybenzaldehyde with flavanone does not give the benzylidene derivative but forms o-hydroxybenzylflavone.Flavanones have been condensed with a number of aromatic aldehydes to form 3-arylideneflavanones (termed flavindogenides) in high yield.1 Flavindogenides have also been isolated as coproducts during the preparation of flavanones by the acid-catalyzed condensation of aromatic aldehydes and substituted o-hydroxyacetophenones.2 Interest in 6-nitro-3-benzylideneflavanones as bacteriostats led Széll and Zarandy to reinvestigate methods for their preparation.3 Recently two natural products, eucomin and eucomol, related in structure to flavindogenides, were isolated.4 Eucomin is the first member of the arylidenechromanone family to be found in nature. Two geometrical isomers are possible for the product from the condensation of aromatic aldehydes and flavanones since the /3-aryl groups of the flavindogenide may be either cis or trans to the carbonyl group. In the reported cases only one of the two possible geometrical isomers was obtained. The condensation of aryl aldehydes with methylene compounds normally yields unsaturated products which have the carbonyl function trans to the larger group at the /3-carbon atom.6•6 However, as shown below, there was some evidence to suggest that 3-(2-nitrobenzylidene)flavanone prepared in the normal way had the cis configuration. Cromwell and coworkers7 prepared ¿rans-2-(2-aminobenzylidene) -4,4-dimethyltetralone by the reduction of the corresponding nitro compound with iron and acetic(1) (a) A.

The configurations of 2-arylmethylene-2,3-dihydro-5-methylbenzo[b] thiophen-3-ones, prepared by the condensation of 2,3-dihydro-5-methylbenzo[b]thiophen-3-ones with aromatic aldehydes, and of their photoisomers are assigned on the basis of n.m.r. spectroscopic and chemical evidence. 4, Ireland 2-ARYLMETHYLENE-2,3-DIHYDROBENZO[b]THIOPHEN-3 -0 ~~s (thioaurones) t are generally prepared by the acid-catalysed condensation of aromatic aldehydes with 2,3-dihydrobenzo[b]thiophen-3-ones.

No abstract

2'-Tosyloxychalcon.e epoxide (6a) on reaction with alkali gave flavonol (4a) while similar treatment of 6'-methoxy-2'-tosyloxychalcone•epoxide (6b), both at room temperature and. at the boiling point of the reaction medium, afforded 5-methoxyaurone (Sb). The latter result indicates that an epoxide is not an intermediate in the production of flavanols from 2'-hydroxy-6'-methoxychalcone epoxides on treatment with alkaline hydrogen peroxide (AFO Reaction) at the higher temperature. Epoxide 6a on treatment with boron trifluoride etherate gave a mixture of flavanonol and flavonol while epoxide 6b gave.formyldesoxybenzoin ( 9) under similar conditions.