HAIR COLORING WITH OXIDATION DYE INTERMEDIATES 627 desirability of having the small P.P.D. molecule penetrate into the cor- tex of the fiber before it is changed into the larger Bandrowski's base, an efficiency of 5 to 10% for the dyeing operation is certainly less than de- sired. This procedure can be used as an experimental method for studying practical ways for improving the yield of colored procucts. The formation of Bandrowski's base has also been used to determine what happens when P.P.D., and resorcinol are used together. By using 0.10 M P.P.D. alone a yield of 5.03% Bandrowski's base was obtained. However, when the solution was 0.10 M in both P.P.D. and resorcinol, there was no visual evidence of a precipitate but an insoluble residue of 0.10%, based on the concentration of P.P.D., was obtained. It is evident that the presence of resorcinol prevented the formation of Ban- drowski's base. This agrees with the results obtained by Cox (26). SUMMARY A survey of oxidation hair coloring has been presented along with data and suggestions that should be useful to those working in this field. In- cluded are 33 primary intermediates and 20 color modifiers of the ben- zene-naphthalene series and the 5 main members of the recently an- nounced pyridine series. The important effect of the color modifiers on fading and color has been demonstrated, and areas and possible methods for additional fruitful research in improving oxidation hair coloring have been suggested. ACKNOWLEDGMENTS The author expresses his appreciation to Lowenstein Dyes and Cos- roetics Inc., and its officers and laboratory staff for assistance and en- couragement and for permission to make public the contents of this paper. (Received January 25, 1967) REFERENCES (1) Heald, R. C., Methods of dyeing hair without the use of an oxidizing agent, Am. Per- ruiner, 78, 40 (1963). (2) Wilmsmann, H., Beziehungen zwischen der Molekfilgr6sse aromafischer verbindungen und ihrem Penetrations-verm6gen ffir das menschliche Haar, J. Soc. Cosmetic Chemists, 12,490 (1961). (3) Erdmann, E., Monnet et Cie., French Patent 158,558 (1883). (4) Kass, G., and Hoehm, L., Color reactions of oxidation dye intermediates, J. Soc. Cos- metic Chemists, 12, 148 (1961). (5) Forster, R. D., and Soyka, C., Fur dyes oxidation and identification, J. Soc. Dyers Colourists, 47, 108 (1931).

628 JOURNAL OF THE SOCIETY OF COSMETIC CHEMISTS (6) Austin, W. E., The chemistry of oxidation fur dyeing, J. Tech. Assoc. Fur Industry, 1, 140 (1930) 2, 63, 68, 69, 73 (1931) 3, 17 (1932). (7) Color (ndex, The Society of Dyers and Colourists, The American Association of Textile Chemists and Colorists, second edition, 3, 3759-3762 (1956). (8) Heiling6tter, R., Constitution, coloring power, and toxicity of hair dyes, Am. Per- fumer, 63,345-348 (1954). (9) 10) 11) 12) 13) 14) 15) (16) (17) (18) (19) (20) (21) (22) (23) (24) (25) (26) Wilmsmann, H., et al., U.S. Patent 3,128,232 (April 7, 1964). Lange, F. W., U.S. Patent 3,200,040 (Aug. 10, 1965). International Critical Tables, McGraw-Hill Book Company, New York, N.Y. (1928), 4, 137, 138, 139, 143, 144. Cook, M. K., Base for permanent hair dyes, Drug Cosmetic Ind., 82,316 (Sept. 1960). Lange, F. W., Pyridine derivatives a new class of oxidativc hair dyes, Am. Perfumer, 80, 33-37 (1965). Lange, F. W., U.S. Patent 3,231,471 (Jan. 25, 1966). Cook, M. K., Private communication (Oct. 14, 1966). Tschitschibabin, A. E., and Kirsanow, A. W., Diamino-pyridin, Ber., 60, 768 (1927). Bandrowski, E., Ueber die Oxidation des Paraphenylendiamins, Ber., 27, 480, 486 (1894). Erdmann, E., Oxidationsprodukte des p-Phenylendiamins, Ber., 37, 2906-2913 (1904). Ritter, J. J., and Schmitz, G. H., The constitution of Bandrowski's base, J. Am. Chem. Soc., 51, 1587-1589 (1929). Green, Arthur G., g)uinonoid addition as the mechanism of dyestuff formation, J. Chem. Soc., 103,933 (1913). Lauer, W. M., and Sunde, C. J.. The structure and mechanism of formation of the Bandrowski's base, J. Org. Chem., 3,261 (1938) 17,609 (1952). Austin, W. E., Fur dyes and their oxidation products, J. Soc. Dyers Colourists, 72• 574- 576 (1956). Heiduschka, A., and Goldstein, E., Ueber das Oxydationsprodukt des p-Phenylen- diamins dutch Wasserstoffsuperoxyd, Arch. Pharm., 254, 584-625 (1916). Cox, H. E., The chemical examination of furs in relation to dermatitis, Analyst, 59• 3-11 (1934). Goldemberg, R. L., Hair coloring and bleaching, Drug Cosmetic Ind., 89• 530 (1961). Cox, H. E., Hair dyes the functions and reactions of phenols, Analyst, 65• 395 (1940)