HAIR COLORING WITH OXIDATION DYE INTERMEDIATES {•11 of 9.7 and hydrogen peroxide at a concentration of 3• as applied to the hair. In the tables data are listed for each intermediate on patents, fade- ometer readings, solubility, and color produced. Patent information was obtained from the patent literature, from publications by Forster and Soyka (5) and Austin (6), and the Color Index (7). Additional data on toxicity may be found by consulting Heiling6tter (8). All fastness- to-light tests were run on a standard fadeometer. Most of the solubil- ities in water were determined by dissolving a weighed excess of the in- termediate in deionized water at 35 øC, adjusting the pH to 9.7 + 0.2 by the dropwise addition of ammonium hydroxide, and bringing the total volume to 100 cc. After the temperature had fallen to 25 øC, the solu- tion was filtered through a Gooch crucible and the solubility determined by difference. In a few cases where the solubility given in the literature far exceeded that used in hair dyeing this figure was used in the tables but always with the temperature recorded beside the solubility figure. In all cases the purest intermediates available were used. All dyeings were performed by immersion for forty-five minutes at room temperature, using natural white hair at a hair/liquor ratio of 1 to 50. For the primary intermediates, with the exception of the diphenyl- amine derivatives, 0.025 3//solutions of each dye were used. With the diphenylamine derivatives dye concentrations of 0.005 3//were used be- cause of their limited solubility and intense coloring power. For the mixtures of color modifiers and primary intermediates the concentration of each was 0.01 3//. In addition to the intermediates the solutions con- tained deionized water, 10% isopropyl alcohol, hydrogen peroxide at a concentration of 3% and sufficient ammonium hydroxide to adjust the pH to 9.7 q- 0.2 after the addition of the peroxide. After immersion for forty-five minutes the hair was rinsed in running water and dried. Dyeing with Primary Intermediates The effect of constitution on color, depth of shade, solubility, and light fastness of p-phenylenediamine derivatives is shown in Table I. Table II summarizes the results with o-phenylenediamine and its deriva- tives. The results with p-aminophenol and its derivatives are given in Table III. It was expected that the addition of an amino-group in the ortho- position of p-aminophenol would increase the depth o[ shade, as was the case with p-phenylenediamine. However, the opposite effect was ob-

612 JOURNAL OF THE SOCIETY OF COSMETIC CHEMISTS Table I Para-Phenylenediamine Derivatives Color Compound Patent on Hair a Depth of Shade Solubility Fades (Darkest at pH 9.7 After to (g/100 (in Lightest) ml) hours) p-Phenylenediamine F.P. 158,558 Black with red 3 cast p-Toluylenediamine G.P. 47,349 Medium brown 6 sulfate Chloro-p-phenylene U.S.P. 1,434,449 Red brown 5 diamine sulfate Nitro-p-phenylene G.P. 211,567 Dark red ... diamine 1,2,4-Triaminobenzene G.P. 514,003 Deep black 1 dihydrochloride p-Aminodimethylaniline G.P. 47,349 Oxford grey 4 p-Aminodiphenylamine G.P. 92,006 Blue black 2 p-Aminoacetanilide ... No color 7 4.27 6 11.9 6 7.75 38 0.23 30 9.78 30 1.97 8 0.10 24 ...... Derivative used at a concentration of 0.025 moles/1. Table II Ortho-Phenylenediamine Derivatives Depth Color Compound Patent on Hair a of Shade Solubility Fades (Darkest at pH 9.7 After to (g/100 (in Lightest) ml) hours) o-Phenylenediamine 3,4-Toluylenediamine o-Toluylenediamine 4-Chloro-o-phenylene diamine 4- Nitro-o-phenylene diamine 5-Chloro, 3-nitro o-phenylencdiamine G.P. 213,581 Yellow G.P. 213,581 Golden brown G.P. 213,581 Golden grey brown U.S.P. 1,536,725 Brown gold G.P. 190,622 Red orange Orange 3.56 4 2.49 6 2.29 10 0.91 6 0.03 42 0.03 14 Derivative used at a concentration of 0.025 moles/1.