The Synthesis of Hydroxyphenyl- and the Hydroxymethylphenyldihydrochaulmoogric Acids¹

Disobutylphenol Synthesis-Structure-Properties-Derivatives

“…of systematic investigations concerning the addition of phenols to various unsaturated compounds (31)(32)(33)(34)(35)(36)(37)(38)(39)(40)(41)(42)(43)(44)(45)(46)(47), is now manufactured on an industrial scale.1 For this reason investigations in regard to its structure and its physical, chemical, and physiological properties, as well as to the preparation of a large number of derivatives (35) became desirable. The results of these investigations are given here.…”

“…It has been shown that the major components of commercial diisobutylene obtained in the polymerization of isobutylene (the latter a by-product in the petroleum cracking process and hence easily available) are 1 Róhm and Haas Company, Philadelphia, Pa. 2,4,4-trimethyl-l-pentene and 2,4,4-trimethyl-2-pentene (6,10,15,20,27,28,(56)(57)(58). Nevertheless, it has been repeatedly observed that upon addition of hydrogen bromide, only one product is formed-namely, 2-bromo-2,4,4-trimethylpentane with bromine adding to the tertiary carbon atom (6,26,49), as follows: Since phenol always adds to a double bond in a manner similar to that of halogen acids (39,44,46), and since there is no reason why addition should take place differently in this case, it appears certain that the phenyl group is in the same position as would be occupied by the bromine-namely, at the tertiary carbon atom. Thus the analogous 2-(p-hydroxyphenyl)-2,4…”

“…A new and rather unique additional structure proof was effected as follows: The diisobutylphenol was hydrogenated and the resulting p-diisobutylcyclohexanol was oxidized to the corresponding cyclohexanone (45). The oxime of this ketone was not identical with the oxime of a-diisobutylcyclohexanone, the latter having been prepared by the interaction of diisobutyl hydrobromide with the sodium salt of cyclohexenol (46). Further oxidation of both cyclic ketones yielded in the first case the new ß-diisobutyladipic acid (45), and in the latter, adipic acid itself ( 46 Still another structure proof included the treatment of molar mixtures of diisobutylphenol and carbolic acid with aluminum chloride, forming p-ieri-butylphenol (54,55).…”