6 Methylquinizarin was synthesized through the Diels-Alder reaction of naphthazarin or 5, 8-diacetoxy-1, 4-naphthoquinone with isoprene. Disperse dyes were prepared from 6-methyl-quinizarin, and their dyeing properties on acetate and Tetoron examined. The .Emax of these dyes in ethyl alcohol shifts to shorter wave length than that of the corresponding 1, 4-disubstituted anthraquinones. The colors of dyed cloth vary from violet to greenish blue. Their dyeabilities on Tetoron were as good as that of the corresponding 1, 4-disubstituted anthraquinones. The light fastness on acetate was better but that on Tetoron was worse than that of the corresponding 1, 4-disubstituted anthraquinones. Their wash fastness on acetate was good. The dyes which have bulky substituents or hydrophilic groups showed good sublimation fastness on Tetoron.
In the Friedel-Crafts reaction of xylenes with either cyanuric chloride or 2, 4-dichloro-6-methoxy-S-triazine (DCMT), the differences in reactivity with xylene isomers and their condensed products were investigated. The initial rates of the reaction with cyanuric chloride were determined to be (-dx/dt)t=o=85, 182 and 30 (mol%)(hr-1) for o-, m-, and p-xylene, respectively. When DCMT was used, the reactivity again decreased in the following order ; m->o->p-xylene. 2, 4, 6-Tris(2', 5'-dimethylphenyl)-s-triazine (mp 112-113.5°C) was obtained from p-xylene and cyanuric chloride in a yield of 6.9%. Upon treatment with DCMT, o- or m-xylene gave 2, 4-his (dimethylphenyl)-s-triazine-6-(1H)-onecorresponding to the original xylene in a yield of 12%. Similar reaction using p-xylene, however, was very difficult.
Studies have been made to synthesize trimellitic acid and triazinyl polycarboxylic acid from the condesed products of xylene with cyanuric chloride. The condensed product of o-xylene was oxidized using sodium dichlomate to give 2, 4, 6-tris(3', 4'-phthalc acid)-s-triazine (TPT) in a yield of 7% which was subsequently dehydrated into its anhydride form. Similar method was also applied for the synthesis of trimellitic acid without success. Through oxidation of the condensed products of o-, m-, and mixed xylenes after hydrolysis, trimellitic acid was obtained in yields of 22.0, 25.5, and 24.8% respectively.
In a previous report, the synthesis of p-hydroxybenzoic acid and salicylic acid from alkali phenoxides and carbon dioxide in aprotic-polar solvents was reported. In the present study, the effects of reaction conditions on the yields and the rule of orientation under atmospheric pressure were examined in a typical aprotic-polar solvent, N, N-dimethylfomamide. Stabilities of the alkali salts of p-hydroxybenzoic acid and salicylic acid in the solvent were also tested. It was found that the potassium and sodium salicylates were rather stable, whereas the salts of p-hydroxybenzoic acid, except its dipotassium salt, were rather unstable and readily decomposed into phenol and carbon dioxide.
Metal sulfates supported on α-alumina were shown to be effective catalysts for the formation of ethyl vinyl ether from acetaldehyde diethylacetal. Eighty seven mol % conversion of the acetal with about 100% selectivity for the desired vinyl ether was effected over MnSO4 catalyst at 250°C. It was also shown that the addition of acidic substances to the α-alumina increased the rate of delacoholation and basic substances induced reverse effects. The alcohol elimination reaction may proceed by an acid catalyzed mechanism. Thermal decomposition of the acetal was negligible under the experimental conditions.