JOURNAL OF THE SOCIETY OF COSMETIC CHEMISTS Table XIV Reactivity of Commonly Used Couplers Towards p-Benzoquinone Diimine at 3OøC and pH 9.5 Coupler Experimental Second Order k • Resorcinol 1.5 X 105 m-Aminophenol 5.5 X 104 2,d-Diaminoanisole 6.0 X 104 1-Naphthol 7.4 X 105 p-Phenylenediamine 34.7 •For d [ dye] /dr ---- k [diimine] [coupler]. high humidity has a marked accelerating effect both on this type of fading and on the intramolecular cyclization of aminoindamines which results in fading to red shades. The conclusions are summarized in Fig. 16. ACKNOWLEDCMENT Thanks are due to Dr. E. P. Camson, Mrs. S. Schumacker, and Messrs. G. W. Arecry and A. G. Fooks for their contributions to the experimental work. (Received May 5, 1972) i•EFERENCES (1) Cotbert, J. F., Benzoquinone imines, Part I, J. Chem. Soc., B, 1969, 207. (2) Corbett, J. F., p-Benzoquinonediimine-A vital intermediate in oxidative hair dyeing, J. $oc. Cosmet. Chem., 20, 253 (1969). (3) Bandrowski, E., Ueber die Oxydation des Paraphenylenediamins, Monatsh. Chem., 10, 127 (1889). (4) Bandrowski, E., Ueber die Oxydation des Paraphenylenediamins, Chem. Bet., 27, 480 (1894). (5) Corbett, J. F., Benzoquinone imine, Part IV, I. Chem. Soc., B., 1969, 818. (6) yon Auwers, K., and Dienes, G., Oxydation des Orthoaminophenols, Fortsch. Chem. Phys., 18, 41 (1924-26). (7) Nagasawa, H. T., Morgan, M. A., and Gutman, N., The enzymic oxidation of o- aminophenols, Biochim. Biophgs. Acta, 28, 665 (1958). (8) Fischer, O., and Hepp, E., Oxidation des Orthophenylenediamins, Chem. Ber., 22, 355 (1889). (9) Yembrick, C., The oxidative condensation of ortho-aminophenols to form aminophe- noxazones, Diss. Abstr., 22, 3862 (1962). (10) Dolinsky, M., Wilson, C. H., Wisneski, H. H., and Demers, F. X., Oxidation products of p-phenylenediamine in hair dyes, J. Soc. Cosmet. Chem., 19, 411 (1968). (11) Kass, G. S., Technology of modern oxidation hair dyes, Amer. Perirum. Aromat., 71, 25, 47 (1956). (12) Kass, G. S., and Hoehm, L., Color reactions of oxidative dye intermediates, J. Soc. Cosmet. Chem., 12, 146 (1961). (13) Tucker, H. H., Hair coloring with oxidation dye intermediates, Ibid., 18, 609 (1967).

OXIDATIVE HAIR DYEING 133 I#TER•EDIATE DYES IN THe- HAll/ •!•enta Hydroxyindoani line v I ( l ) i•-Dlamine (li) Ox, O•'een I TriDn•: lear\• nuclear, I amine B•'own I Polyme•'lc I Indoani line Oxe FADII•G •lagent, a Aminoindoani line '• Blue Indamine • I (i) p-Diaminox. (li) Bluish B•own Trlnuelea• T•inuelear Dye Dye Higher polymer •' Red Diamin•o•_ Higher polymer and/or phenazine and/or Hydro lyric C leav- and/or Hydro lytic C leav- age Products Magenta Amino- age Products (brown) indoaniline (brown) Figure 16. Role of meta difunctional benzenes in oxidative hair dyeing (14) Corbett, J. F., Intermediates and products in oxidative hair dyeing, Proc. Joint Conf. Cosmet. Sci., Washington, D.C., 159 (1968). (15) Corbett, J. F., Benzoquinone imines, Part II, J. Chem. Soc., B., 1969, 213. (16) Corbett, J. F., Benzoquinone imines, Part VIII, Ibid., 1970, 1502. (17) Corbett, J. F., Benzoquinone imines, Part VI, Ibid., 1969, 827. (18) Shah, M. J., Tolgyesi, W., and Britt, A.D., Cooxidation of p-phenylenediamine and resorcinol in hair dyes, J. Soc. Co met. Chem., 23, 853 (1972). (19) Shah, M. J., Chromatographic and spectroscopic studies of the oxidation products of p-phenylenediamine and resorcinol, Ph.D. thesis, George Washington University, 1970.