878 JOURNAL OF THE SOCIETY OF COSMETIC CHEMISTS The oxidation pigment under study is, therefore, a linear unbranched polyindophenol. There is no evidence of cyclization to oxazines. This result demonstrates that the early oxidation steps, leading from PPD to polyindophenol, occur with relative ease. The later steps, cyclization to oxazines, occur much more slowly if at all, and it is doubtful if they occur in the presence of much unreacted PPD and resorcinol. In this case, with only a 31% yield of pigment, considerable unreacted PPD remained, and this is also true of most hair dyeing operations. By using the analytical methods described here or similar ones it should be possible to examine other pairs of intermediates and other conditions, as well as the more complicated mixtures used in hair dyeing. It would be interesting to see whether azines of any kind are formed in some cases. CONCLUSIONS Both quinonediimine (QDI) and Bandrowski's base (BB) are formed when p-phenylenediamine alone is oxidized under hair dyeing conditions. However, when PPD is co-oxidized with other dye intermediates in equal amounts, especially resorcinol, neither QDI nor BB appears. Either a different reaction path is followed, excluding both of these, or the QDI reacts as fast as it is formed to give the final colored products. For this reason PPD should never be used alone in patch tests to predict sensitivity to hair dyes, but only in combination with peroxide and other dye intermediates. An oxidation pigment prepared from PPD and resorcinol (1: 1) proved to be a mixture of polymeric indophenols, straight-chain and unbranched, with no significant ring-closure to oxazines. ACKNOWLEDGMENT The authors would like to acknowledge the contribution of Dr. Franz J. Pure in the early stages of this work. (_Received October 11, 1967) _REFERENCES (1) Cox, H. E., The functions and reactions of phenols, Analyst, 65, 893 (1940) The chemical examination of furs in relation to dermatitis, Part IV, Ibid., 59, 8 (1934). (2) Erdmann, E., Oxydations product des p-phenylendiamins, Ber. Deut. Chem. Ges., 37, 2776, 2906 (1904). (3) Austin, W. E., The chemistry of oxidation fur dyeing, J. Tech. Assoc. Fur Ind., 6, 127 (1935).

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