A monochloromethyl compound was obtained by the chloromethylation of 3-bromo and 3-chlorobenzanthrone in conc. sulfuric acid with syrn-dichlorodi methyl ether. The position of entered chloromethyl group was confirmed to be the 9th. The dyeing ability of these pyridinium and isothiuronium salts derived from it was investigated Similarly, chloromethylation of 3-, 9- and 10-methylbenzanthrones were carried out, and then bis-chloromethyl compounds from 3- and 10-methylbenzanthrones, and a monochloromethyl compound from 9-methylbenzanthrone were obtained.By the decomposition of these chloromethylated compounds with chromic acid, the positions of chloromethyl groups were investigated. Also, the methods of synthsesis of 3-bromobenzanthrone were investigated.
For the synthesis of acedianthrone, in the first place, I investigated the method to get its intermediate, dianthrone-ethane, from anthrone and glyoxal sulfate and succeeded to find the optimum condition. Chloromethylation of acedianthrone was carried out in conc. sulfuric acid with sym-dichlorodimethyl ether, the conditions for chloromethylation were investigated and a bischloromethyl compound was isolated. By the decomposition of this product with chromic acid anthraquinonecarboxylic acid was obtained. The position of chloromethyl group was identified thus. Pyridinium and isothiuronium salts were obtained from the chloromethylated compound, and these dyeing abilities investigated.
Oxidation of hexamethylbenzene (1) with diluted nitric acid gave tetramethyl phthalic acid (2), trimethyl trimesic acid (3) and 1, 2, 4-trimethylbenzene-3, 5, 6-tricarboxylic acid (4), the structure of which were determined on the basis of the formation of mellophanic acid, trimesic acid and trimellitic acid, respectively, by decarboxylation followed by potassium permanganate oxidation . The carb oxylic acids (2) and (4) readily dehydrated to the corresponding acid anhydrides. The two tricarboxylic acids (3) and (4) have not been reported yet and their esters also.
Reactive dyes of halobenzene type having activated halogen atom were synthsized. Acid dyes of azo-, anthraquinone, and. phthalocyanine type having amino group capable of acylation, were acylated with halonitrobenzenesulfonyl chloride and halonitrobenzoyl chloride, such asand new reactive dyes of next general formulas were obtained.Where D=color component, -NHSO2- or -NHCO- and -NO2 are in o- or p-position to halogen.Those dyes which contain activated fluorine atom, such as (1), (2) and (3) type-especially (1) and (2)-, dye cotton, wool, silk and nylon in the presence of alkali by chemical combination. Dyed fabrics thus obtained were very fast against washing and soaping.
By refluxing the mixture (molar ratio 1: 2) of melamine (M) and acetylsalicylic anhydride (A) for 3.4 hrs. in dioxane was yielded mono-ο-acetoxybenzoyl-M (1), mp 216-7°c. Saponification by refluxing (1) in a 10% aqueous solution of pyridine (P) for 15 mins. gave mono-ο-hydroxybenzoyl-M (2), mp 263°c (d). Crude di-ο-acetoxybenzoyl-M (4), obtained by ref luxing the mixture of (1) and (A) (molar ratio 1: 2) in dioxane for 15 hrs., was saponified by ref luxing for 15 mins. in (P) to give di-ο-hydroxybenzoyl-M (3), mp 304°c (d). Crude tri-ο-acetoxy-benzoyl-M (6), obtained by ref luxing a mixture of (4) and (A) in a molar ratio of 1: 2 for 30 hrs. in dioxane, was saponified by heating for 10 mins. in 5% aq. ammonia to give tri-ο-hydroxybenzoyl-M (5), mp 246-8°c (d). A pure (4), (mp 190-1°c) and a pure (6), (mp 172-4°c (d)) were obtained by acetylation of (3) and (5) with acetic anhydride, respectively. The products (1)-(6) are new compounds. The following azo dyes were synthesized from (2) ; sulf anilic acid→(2), p-nitroaniline-ο-sulfonic acid→(2), orthanilic acid alkali→J acid→(2), orthanilic acid alkali→γ acid→(2) and 2-aminophenol-4-sulfonic acid alkali→J acid→ (2), and the dyeing abilities of their methylol compounds for cotton andrayon investigated.