RI 2969 The 1, 3-Dimethyl-5-Phenoxyacetic Acid And The 1, 2-Dimethyl-3-Phenoxyacetic Acid

In view of the current interest in the constituents of low-temperature tar, the Synthesis of three known xylenols and their hydroxyacetic acid derivatives has been undertaken by the U. S. Bureau of Mines. One of these xylenols, the 1,3,2 derivative first reported by Steinkopf and Höpner,4 has been described by Brown and Branting.5 The other two derivatives, the 1,3,5 first reported by Schütz6 and the 1,2,3 reported by Steinkopf and Höpner, have now been studied in greater detail. In the present work the synthesis of 1,2,3-xylenol and 1,3,5-xylenol was repeated, with some improvements in the former. The hydroxyacetic acid derivatives were also prepared, and it was found that while the melting point of the 1,2,3 derivative agreed with that of Steinkopf and Höpner. that of the 1,3,5 derivative was found to be 111° instead of 85 to 86° as reported by Schütz, by Steinkopf, and later by Bruckner. The discrepancy between the melting-point figures is doubtless due to differences in the purity of the xylenols used in the synthesis of the acids. Schütz obtained his 1,3,5 acid by recrystallizing an impure sample obtained from a mixture of xylenols. The difficulty of obtaining a pure acid by starting with a mixture is demonstrated by Bruckner, who despite painstaking efforts was unable to obtain the pure 162.5° melting 1,2,4 isomer from a mixture that persistently melted at 138° C. Steinkopf did not repeat Schütz's work but merely used the latter's figures in compiling a table. Bruckner, on the other hand. apparently also made the acid (by an improved method), and it is difficult to explain his checking Schütz's figure, unless it is that he, too used a symmetrical xylenol obtained from a tar and not prepared synthetically, as was the one reported in this paper.