REACTIONS OF VANILLIN AND ITS DERIVED COMPOUNDS. XI.¹ CINNAMIC ACIDS DERIVED FROM VANILLIN AND ITS RELATED COMPOUNDS^{2, 3}

Abstract

In continuing our studies on the toxicities and ultraviolet absorption characteristics of esters of vanillic and related acids, it was desired to investigate the substituted cinnamic acids related to vanillin. These cinnamic acids are easilyprepared by condensation of the desired aldehyde with malonic acid in the presence of a trace of piperidine with pyridine as a solvent, in accordance with the Doebner modification of the Perkin reaction. The actual procedure employed in this study is an adaptation of the above reaction made by Vorsatz (1) for the preparation of cinnamic acids having a free phenolic group, and is recommended by Johnson (2) for the preparation of ferulic acid. The Vorsatz adaptation employs long standing at room temperature instead of the short boiling originally used by Doebner (3). We have found this modification to be equally satisfactory for the preparation of nonphenolic cinnamic acids. In this study cinnamic acids were prepared from the following aldehydes: vanillin, veratraldehyde, 5-nitrovaniIlin, 5-chlorovanilIin, o-benzylvanillin, piperonal, and orthovanillin. Only in the case of the 5-nitrovanillin was heating necessary to obtain reaction. The reaction of orthovanillin with malonic acid in the Vorsatz procedure yielded a crystalline compound melting at 119-120°, the structure of which was not ascertained, but which yielded orthoferulic acid when boiled with alkali or when allowed to stand for an extended period. No trace of a coumarin or coumarincarboxylic acid was obtained.These acids were esterified with anhydrous ethanol in the presence of sulfuric acid to give good yields of the ethyl esters. Data for the acid and the ester preparations are found in Table I (references to earlier preparations are included). The inhibiting concentrations of the esters were determined for the four representative aerobic microorganisms-namely, non-sporeforming-(Aerobacter aerogenes) and sporeforming-(Bacillus mycoides) bacteria and molds (Aspergillus

Biosynthesis of podophyllotoxin in Linum album cell cultures

“…After 5 h 30 min of stirring at 85°C, the reaction was quenched by a mixture of icecold water and concentrated HCl (6 ml; 1:1, v/v). The white precipitate obtained was washed with cold water (5 ml (Pearl and Beyer 1951). For ESI-MS, 1 H and 13 C NMR data, see electronic supplementary material.…”

Developmental Expression and Substrate Specificities of Alfalfa Caffeic Acid 3-O-Methyltransferase and Caffeoyl Coenzyme A 3-O-Methyltransferase in Relation to Lignification1

“…The remaining portion was freeze dried for lignin analyses. Chemicals 5-Hydroxyferulic acid was synthesized via 5-hydroxyvanillin by the methods of Banerjee et al (1962) and Pearl and Beyer (1951). Its structure was confirmed by 1 Hand 13 C-NMR analysis.…”

An alternative methylation pathway in lignin biosynthesis in Zinnia.

“…5-Hydroxyvanillin was synthesized from 5-iodovanillin according to Banerjee et al (1962). 5-Hydroxyferulic acid was prepared by condensation with malonic acid (Pearl and Beyer, 1951). tran~-2-~%-Ferulic acid and hans-4-2-%coumaric acid were synthesized by condensation reaction of vanillin and Qhydroxybenzaldehyde, respectively, with 2-14C-malonic acid.…”