394 JOURNAL OF THE SOCIETY OF COSMETIC CHEMISTS each of these 10 dyes. These included: (a) li•oToin, (b) ethanol, (c) ethanol to which an equal volume of cold water was added after hot filtra- tion, (d) methanol, (e) methanol to which an equal volume of cold water was added after hot filtration, (f) n-butanol, (g) xylene, (h) propylenegly- col, (i) pyridine, (j) pyridine to which 3 volumes of cold water was added after hot filtration, and (k) water. Even though the 10 dyes that survived the three fastness tests (Table XII) are an insufficient sample upon which to postulate a theory, the ob- servation can be made that in eight of these dyes the position meta to the oxygen or imine group is substituted by a nitro or an amino group. It has been confirmed that substitution in the benzene ring has a definite effect on the stability of the indophenol and indamine dyes. Although nine of the dyes described in this paper might find a useful application in semipermanent hair coloring, it is hoped that a complete range of suit- able colors will be developed by further research with the indophenols and indamines. Table XlI Properties of Dyes that Passed the Three Tests Light Rccrystn. Color of Recryst. Fastness Melting Color of Dye- Dye No. Method Product (hr) Point (øC) ing on Hair A-11 j Black 14 163 Yellow-brown A-13 j Orange 17 220 D Yellow-orange B-11 k Medium brown 16 277 Red-orange B-12 c Black 12 189 Bright yellow B-13 d Orange 23 140 Bright orange C-9 e Black 14 240 Ash brown C-12 e Black 11 165 Yellow-gold C-13 e Dark brown 33 above 290 Red-orange C-14 e Black 13 192 Golden brown D-1 e Light brown 10 112 Red-gray SUMMARY A review has been given of the recent literature on semipermanent hair coloring. A method of application of these colors has been selected from these references and a series of tests proposed for evaluating semi- permanent hair dyes. Three factors led to the selection of indophenols indamines for this research. It had been established that penetration of the fiber can be increased by decreasing the size of the dye molecule. Indophenols and indamines are among the smallest dye molecules known but are of limited stability. It had been reported that their stability can

COLORING WITH SEMIPERMANENT DYES 395 be enhanced by the introduction of halogen or alkyl groups into the dye molecule. Eighty indophenol or indamine dyes were prepared using, where applicable, intermediates that are commonly used in permanent hair dyeing and their halogen or alkyl substitution products. These dyes were evaluated for their substantivity to human hair, their fastness to light, and the stability to storage of the dye solutions. Ten of these dyes passed these fastness tests, but with these a full range of colors could not be obtained. It is hoped that further work with this series of dyes might ultimately lead to the ideal semipermanent hair color. (Received November 16, 1970) SUPPLEMENT NO. 1 Results a of Tests on p-Aminodimethylaniline Plus: Number and Compound Depth of Hours to Shade Fade Ageing Color on Hair 1. Phenol P F-4 2. Catechol P P-10 3. Resorcinol P F-6 4. Pyrogallol P F-4 5. 3,5-Dimethylphenol P F-1 6. 2,6-Dimethylphenol P F-3 7. 2,5-Dimethylphenol P F-7 8. 0-Aminophenol P P-10 9. m-Aminophenol P F-7 10. 2-Hydroxy-4-a•ninotoluene P F-5 11. 2-Amino-4-nitrophenol P P-14 12. 2-Amino-5-nitrophenol P F-5 13. 2-Amino-4,6-nitrophenol P P-17 14. Aniline P P-10 15. 0-Phenylenediamine P F-6 16. m-Phenylenediamine P F-3 17. m-Toluylenediamine P F-3 18. 2,4-Dianfinoanisol P F-4 19. Nitro-m-phenylenediamine P F-3 F Gray-blue F Light ash P Light ash P Dull gray-green F Dull green-gray F Dark blue F Dark bright blue F Yellow-blonde F Dark-gray F Purple-gray P Good yellow-brown P Bright yellow P Good dark orange F Medium blue-gray F Dark gold F Medium dark blue F Dark gray F Dark blue P Dark yellow means passed and F means failed.