Some New Aromatic Orthoformates

Abstract

Vol. 46 drolysis products, while phosphotungstic acid, as might be expected, leaves practically no peptides in solution. The large quantity of free amino nitrogen in the filtrate from the latter precipitation indicates the existence of amino acids in solution. This indication was verified by the isolation of glutamic acid. A more extended examination will doubtless show the presence of other amino acids in the free state. SummaryIn the fermentation of corn mash B. grnnulobacter pectinovorum brings about a rapid hydrolysis of the proteins. From 50 to 75% of the total protein is converted into soluble products during the fermentation which is approximately complete in from 3 to 4 days. One-half of the total soluble products may be formed in 24 hours.The hydrolysis results chiefly in the formation of simple peptides and amino acids. Due to these buffers and to acids of low dissociation, a high titratable acidity rhay be produced without causing much change in the hydrogen-ion concentration.Although numerous alkyl orthoformates have been described, the phenyl ester is the only simple aromatic compound of this type known.' It has been obtained by Tiemann2 and by Auwers3 as a by-product of the Reimer-Tiemann reaction. Tiemann stated that attempts were being made to prepare similar compounds from other phenols, but nothing else was published on the subject.It has recently been shown4 that phenyl orthoformate can be conveniently prepared by the action of chloroform on dry potassium phenolate a t a fairly high temperature. This method has now been employed for the preparation of the 0 -, m-and p-tolyl esters from the corresponding cresols. The yields of these compounds are poor, and their purification is rendered difficult by the fact that they are accompanied by comparatively large quantities of dark, viscous, alkali-insoluble glues. The 1 Since the completion of this work, the author finds that Keil [Ann., 352, 273 (1907)] records, in a footnote, the formation of the p-tolyl ester as a by-product of the action of chloroform on p-cresol in alkaline solution.

The Reimer-Tiemann Reaction.

“…1. Orthoformic esters O-alkylation by chloroform instead of nuclear Calkylation gives rise to orthoformic esters (17, 18, 46,120,135,144). Two types of "abnormal" products may result from the reaction between phenolic compounds and chloroform in alkaline medium.…”