OXIDATION PRODUCTS IN HAIR DYES 417 ø.ø I .60 .70 1.0 INFRACOIID ,Jll• • 3 4 5 6 7 8 9 10 11 12 13 14 15 WAVELENGTH (MICRONS) Infrared spectrum of Bandrowski's base, crystallized acetone-H20, KBr disc Figure Figure I.O- a, 0,5- o drogens attached to nitrogen at 4.15 and 5.20r. The latter two singlets broadened greatly on addition of a trace of gaseous HC1 and one of them, 5.20r, was removed easily by deuterium exchange. These data are con- sistent only with structure D. The infrared and visible spectra of Band- rowski's base are shown in Figs. 4 and 5.

418 JOURNAL OF THE SOCIETY OF COSMETIC CHEMISTS 3 4 Figure 6. 5 6 7 8 9 10 11 12 13 14 WAVELENGTH (MICRONS) Infrared spectrum of DMF-soluble materiol from band V, crystallized DMF-I-I,,O, KBr disc Band V This band does not move in the TLC system used and may correspond with the insoluble "azine" fraction of Cox. It can be partially removed from the "chromatostick" with dimethyl formamide and precipitated with water to give a material with the following elemental analysis: C, 46.12% H, 4.25% N, 14.34% and 0, 35.29% (by difference). Based on this analysis and its infrared spectrum (Fig. 6), band V appears to be a high molecular weight oxygenated material or a mixture of such ma- terials rather than an azine. An attempt at molecular weight determi- nation by mass spectrometry was unsuccessful. The largest fragment observed was m/e 108, corresponding to phenylenediamine or quinone. OXIDATION IN DILUTE H202 Several 4.0-g samples of phenylenediamine were oxidized at room temperature in dilute ammoniacal peroxide, using a molar ratio of perox- ide to phenylenediamine of 2.5 to 1 with an over-all peroxide concentra- tion of approximately 0.65% (total volume 460 ml). The individual samples were filtered at various intervals, and the insoluble material was analyzed by TLC plus spectrophotometry of the separated bands. The rate of formation of insoluble material is shown in Fig. 7. All precipi- tates were found to have practically the same composition regardless of reaction time (24 to 310 hours). The tiltrates were examined by UV and visible spectrophotometry and were found to contain mainly unreacted phenylenediamine plus small amounts of bands I, II, III, and IV. The amount of unreacted phenylenediamine decreased with time. However, the amounts of bands I, II, III, and IV in solution remained practically constant regard- less of reaction time.