SYNTHESIS OF SOME NEW QUATERNARY DYES 419 recrystallized from chlorobenzene. Thus, with a yield of 80%, 1-oxy 2,4-(pN,Ndimethylaminophenyl)amino-anthraquinone which melts at 245 ø is obtained. The product, recrystallized three times from chlorobenzene, melts at 255 ø . Table V Calculated as Analysis %0 H2• N40a Found C% 73.17 73.65 73-37 Hø/o 5.69 5'85 5-92 N % 11.38 11-56 11-22 This tertiary amine is quaternized at a temperature of 80 ø for half an hour, using a chlorobenzene solution of methyl sulphate. After cooling and air drying, 2-methyl [1-hydroxy 2,4-(ptrimethylammonium) phenylamino- anthraquinone I sulphate, with an 88•o yield is obtained. In the same way, using methyl iodide, we obtained 2-[1-hydroxy 2,4- (ptrimethylammonium) phenylamino-anthraquinonel iodide. (Received: 11th February 1964.) REFERENCES {1) R. L. Goldemberg Am. Perfumer Aromat. 74 48 {November 1050). (2) French Pat. 1,138,055 Supplement 70,067. (3) French Pat. 1,137,020. (4) Belgian Pat. 576,014. (5) Patent pending. (6) J. Soc. Dyers Colourists 69 410 (1053). (7) Code of European Continental Study Group, 2nd Edn. 31 (1058). {8) R. Sidi and R. Longueville Les accidents par produits capillaires 16 (1058) (Edition Medicales Flammarion, Paris). {0) M. Ichikawa Tokyo Kdgyd Daigaku Gakuhd Ser. B 127 (1050) Chem Zentr. 12648 (1962). Introduction by Mrs. A. Bugaut The violet, purple and grey dyes described in this communication constitute merely a part of the experiments carried out in our laboratories, on quaternary salts derived from anthraquinone. All these substances may be considered as interesting material for hair tinting, and with their help, the development laboratory can achieve any required shade. Of the three new series mentioned, we have studied particularly the violet and purple dyes obtained when substituting only one of the two hydroxy groups of quinizarine by an aliphatic N,Ndialkyl diamine or by

420 JOURNAL OF THE SOCIETY OF COSMETIC CHEMISTS /•amino ethyl morpholine or fiamino propyl piperidine. The substitution is followed by quaternization of the tertiary amine. A grey dye has been synthesized by substituting only the hydroxy groups in the 2- and 4-positions of the 1,2,4-trihydroxy anthraquinone by N,Ndimethyl pphenylene diamine, and by subsequent quaternization. We have also widened the range of shades obtained up to now with this type of quaternary compounds, by synthesizing new yellow dyes. These may be obtained from the 2-chloro anthraquinone and diamines mentioned above. Nevertheless, the yields are rather low as the fichlorine atom in the anthraquinone ring is not so mobile as that in a position. It is more advantageous to start with •amino anthraquinone for instance, the reaction of •amino anthraquinone with N,N-diethyl amino ethyl chloride gives an excellent yield. In our opinion these dyes possess the following advantages: Good solubility, possibility of dyeing over a wide pH range, good resistance to sunlight, no dermatological action. It should also be emphasized that solutions of these dyes--in which quaternary amino groups form part of an heterocyclic nucleus such as morpholine or piperidine--have the great advantage of never developing unpleasant odours on storage. This was the main reason for studying these types of dyes. DISCUSSION MR. A. J. M. VERHAAR: The hydroxy anthraquinones which you use as starting materials remind me of two well known hair dyes: Lawsone and Juglone, 2- and 5-hydroxy naphtoquinones, respectively. Have you ever tried to make quaternary ammonium derivatives from these compounds ? (As these molecules are smaller, one would expect a better penetration into the hair shafts than with anthraquinone derivatives). THE LECTURER: No. MR. A. J. M. VERHAAH: Most quaternary surface active substances are rather strong eye irritants. Do you have any data on eye irritating effects of your quaternary dyes ? THE LECTURER: Tests on rabbits' eyes using the Draize method proved these dyes to be completely innocuous. MR. A. J. M. VERHAAR: It is one of the great advantages of oxidation hair dyes that the hair is bleached while it is dyed. This is not only necessary when the hair is to be tinted in a lighter shade, but also when another shade of the same depth is wanted. Are the quaternary anthra- quinone dyes resistant to bleaching conditions, particularly to an alkaline medium and hydrogen peroxide ?