416 JOURNAL OF THE SOCIETY OF COSMETIC CHEMISTS mol) of fiamino ethyl morpholine, and 60 ml pyridine is heated for 7 hours at 135 ø . After cooling of the reaction mixture and centrifuging off the unreacted material, the pyridine is removed in vacuum. The residue obtained is warmed with 500 ml of M/1 HC1, and the insoluble impurities are filtered off. The flitrate obtained after cooling is adjusted to a pH of 7.5 with NaOH. The crude product precipitates, and is isolated by filtration. It is then purified by passing a solution in a benzene-hexane mixture, through an alumina column. Two adsorbed zones are obtained, the lower orange band being the desired product. It is sufficient to cut the aluminia column, and recover the product by warm alcohol extraction of the aluminia. After cooling the alcoholic solution, 2-(/•morpholino-ethyl) amino- anthraquinone is obtained with a yield of about 250/0 . This product is obtained in the form of yellow crystals melting at 190 ø . Table I Calculated as Analysis C20 H20 N• O a Found C% 71-43 71.39 71.30 H% 5.95 6.11 6.04 N% 8.33 8.22 8.27 The tertiary base thus obtained, dissolved in chlorobenzene by heat, is quaternized by the action of methyl sulphate at a temperature of 110-115 ø (contact period about 30 minutes). After cooling, the quaternary thus formed--methyl [2-timethyl morpholinium/ethalyamine anthraquinonel sul- phate-is dried. Yield: 91%. In the same way, the following two dyes were prepared from 2-chloro- anthraquinone, with a yield always below 30•o, despite numerous variations in the methods: (a) Methyl [2-(fitrimethylammonium)propylamino-anthraquinonel sulphate, by condensation with N,Ndimethyl 7 propylene diamine. (b) Methyl [2-(fimethyldiethylammonium) ethylamino-anthraquinone] sul- phate, by condensation with N,Ndiethyl fi ethylene diamine. Methyl [2- (fimethyldiethylammonium) ethylamino- anthraquinone was prepared with very good yields from 2-amino-anthraquinone, in accordance with the process described below. A mixture of 165 g (0-74 mol) of 2-amino-anthraquinone, 485 g (3.54 mol) of N,Ndiethylamino ethyl chloride, 1600 ml of nitrobenzene is heated for 2 hours at 180 ø.

SYNTHESIS OF SOME NEW QUATERNARY DYES 417 The crude hydrochloride of the product which precipitates on cooling, is separated, washed in hexane, and dried. For purification it is dissolved in warm water, the impurities are filtered off and the tertiary base is precipi- tated by 10M NaOH. The precipitated product is separated. We obtained 175 g of 2-(•.N,Ndiethylamino-ethyl)amino-anthraquinone, practically pure, with a yield of 73%. After recrystallization in hexane, the product melts at 123 ø . Table II Calculated as Analysis Cs0 Hs0 N s O s Found C% 74.52 74.50 74.33 H% 6.84 6.61 6-72 N% 8.69 8.68 8.74 To a refluxing solution of 165 g of 2-(•.N,Ndiethylamino-ethyl) amino- anthraquinone in 1600 ml of benzene, 77.5 g of methyl sulphate is added. After maintaining the reflux for one hour, the methyl [2-(• methyl diethyl ammonium) ethylamino anthraquinone] sulphate thus formed is cooled and drained, with a yield of 93%. Left in the air, this product in due course becomes a monohydrate. Series II* Methyl [1-hydroxy 4-(7, methyl piperidinium)propylamino-anthraquinone] sul- phate. A mixture of 36 g (0'15 mol) of quinizarin, 24.2 g (0.165 mol) of 7'amino propyl piperidine (97ø/0), and 225 ml toluene is refluxed for 7 hours. The tertiary base is isolated in the form of an oxalate by adding 24g of oxalic acid dissolved in ether to the cooled reaction mixture. The oxalate is air dried (61 g), and then dissolved in water. The corresponding base is liberated by adjusting to a pH of 8.5 with NaOH, and extracting with ether. The ethereal extracts are evaporated, and the residue recrystallized from hexane. An 82% yield of 1-hydroxy 4-7, piperidine propyl) amino-anthra- quinone (98 g) is obtained. After two recrystallizations from hexane, the product melts at 105 ø. Table III Calculated as Analysis C2 s Hs 40a lg s Found C% 72.53 72.43 72.35 H% 6.59 6.72 6.83 lg% 7.69 7.81 7.75 *While this work was in progress we became aware of Ichikawa's work (9). He synthesized compounds similar to those mentioned here, but not involving heterocyclic substitutions, and studied them in connection with the dyeing of synthetic textiles.