1-Amino-2-hydroxyanthraquinone was synthesized from ammonolysis of 1-chloro-2-hydroxyanthraquinone. 1-Chloro-2-aminoanthraquinone in conc. sulfuric acid was diazotized with sodium nitrite and decomposition by heating for 30min. at 150°C yielded 87% of theory of 1-chloro-2-hydroxyanthraquinone, mp 226.9-7.6°C. Ammonolysis of 1-chloro-2-hydroxyanthraquinone was completed by heating for 6 hrs. at 100°C in 15 times of its weight of 28% aqueous ammonia and 0.1 mole copper sulfate catalyst. Alkali insoluble portion and aqueous barium hydroxide solution insoluble portion were removed and recrystallization of the product from 50% aqueous solution of ethanol gave red needles. However, this was not a pure 1-amino-2-hydroxyanthraquinone but contained yellow colored 1-chloro-2-hydroxyanthraquinone and others as impurities from the result of examinations by alumina column chromatography, paper chromatography, and spectrometric analysis. The purity was found to be 93% by spectrometric analysis and this can be utilizable for synthesis of intermediate of anthraquinone-oxazole dyes.
For synthesis of 2, 5-dianilinoterephthalic acid (2) as an intermediate for synthesis of organic red pigment, a linear type quinacridone (1), synthesis of (2) through diketene (3) ?A-haloacetoacetic acid ester (4), diethyl succinylsu ccinate (5), and diethyl dianilinoterephthalate (6) has been investigated from industrial point of view. It was found that no solvent was necessary for synthesis of (4) from (3), and using of a small amount of hydrochloric acid and 10% excess of aniline than the theory for synthesis of (6) from (5) gave yield of (6) 95% of theory.
In this report, the properties of polymer have been clarified and the experiments on properties of polymer have been carried out in order to find its value for practical using. Also, a comparison of PCA and PMA has been made in this study. Superior elongation strength was shown by PCA than PMA and it gave superior heat-resistant property in elongation test. There was no great difference from PMA in impact test but the hardness was much higher than PMA. There was no great difference between these two in abrasion resistance. An average thermal deformation of PCA was 136.4°c and that of PMA was 93.9°c. The behavior of PCA against the elevation of temperature indicated that the hardness remain unchanged until it reached to 2-3°c lower than the deformation temperature but its bending was increased rapidly thereafter. These facts gave an indication that the molding treatment of PCA can be made easier than PMA. The refractive index of PCA was 1.5194. There was no great difference in the transmittance of light between them. The result of weathering test indicated that no difference was shown for practical using. Resistance to chemicals was slightly superior in PCA than PMA.
The method of synthesis of α, β-bis[5-methylbenzolyl-(2)]-ethylene, a principal constituent of well known fluorescent dye for polyester type synthetic fibers under the trade name UviteX ER Conc., has been investigated. Also, a few derivatives of α, ?β-bis[be nzoxazolyl-(2)]-ethyle ne were synthesized and the properties of those which were effective for increasing the whiteness of Tetlon have been compared. The results of syntheses of these objective compounds indicated that a method of synthesis with good yield and purity of product was found. Tests on syntheses and dyeing of the derivatives of this type of compound indicated that the property of inereasing of whiteness was effected considerably by the substituent on benzene ring attached to the oxazole ring.
1-Anilinoanthraquinones (2a-2c) having anthraquinone-oxazole ring in paraposition were synthesized, visible absorption spectra of these were compared with 1-anilino- and 1-(4-R-substituted-anilino)anthraquinones (R=NH2 or NO2), and clarified that anthraquinone-oxazole ring had electron-attractive property and its intesity was in order of nitro ≥ anthraquinone (2 : 1) oxazole > anthraquinone (1 : 2) oxazole a> anthraquinone (2 : 3) oxazole. These three kinds of dye (2a-2c) were synthesized by Ullmann condensation of 1-aminoanthraquinone and corresponding 2-(4-bromophenyl) anthraquinoneoxazole (3a-3c), respectively. 2-(4-Bromophenyl) anthraquinone-oxazoles (3a-3c) were synthesized as follows: (1). 2-Amino-3-hydroxyanthraquinone or2-amino-3-bromoanthraquinone was benzoylated with 4-bromobenzoyl chloride and each was treated for oxazole ring formation to obtain the same 2-(4-br.omophenyl) anthraquinone (2 : 3) oxazole (3a). (2). Similarly, the reaction of 1-amino-2-hydroxyanthraquinone and 4-bromobenzoyl chloride caused benzoylation and oxazole ring formation at the same time and gave 2-(4-bromophenyl) anthraquinone (1 : 2) oxazole (3b). This extraordinary reactive property was explained by intramolecular hydrogen bonding. Also, (3b) was obtainable by benzoylation of 1-amino-2-bromoanthraquinone with 4-bromobenzoyl chloride and its oxazole ring formation but the yield was low. (3). Benzoylation of 1-hydroxy-2-aminoanthraquinone with 4-bromobenzoyl chloride and its oxazole ring formation gave 2-(4-bromophenyl) anthraquinone (2 : 1)-oxazole (3c). The dyes (2a-2c), synthesized by condensation of 2-(4-bromophenyl) anthraquinone-oxazoles and 1-aminoanthraquinone, were used for dyeing of cotton by 2% IW method and following results were obtained on vat dyeing, color, and light fastness: (2a): red brown, greenish red brown, 4-5 th grade. (2b) red, red brown, 5 th grade. (2c): orange red, brownish red, 45th grade.
Radical reaction product from 1, 1, 1, 3-tetrachloropropane and 1, 1, 1, 5-tetrachloropentane with ethylene was white wax-like product and its structure was considered to be a graft telomer from infrared absorption spectrum. As this product was considered to be a side reaction product on telomerizaton of ethylene with carbon tetrachloride, comparison of the reactivity with chaint ransfer agents indicated that the reaction was in order of CCl4 >> Cl(CH2CH2)2-CCl3 > ClCH2CH2CC13. Especially, using of greater mole ratio of C2H4/Cl(CH2-CH2)nCCl3 or highly concentrated initiator gave fairly high reactivity for side reaction. However, there was almost no such reaction by using lower concentration of initiator and relatively lower concentration of ethylene. The numerical av. degree of polymerization of graft telomer was changeable in wide range (4-23), especially, the graft telomer from 1, 1, 1, 3-tetrachloropropane was much influenced by the relative concentration of ethylene.
Oxidation of methylnaphthalenes with aqueous sodium bichromate under pressure was carried out to obtain naphthoic acids. β-naphthoic acid obtained from β-methylnaphthalene was extremely pure. The yield was about 900% and independent on the reaction temperatures between 230°c and 270deg;c when the reaction was carried out under 20 atm CO2 pressure. But without CO2 addition the yield was depressed to 70-80%. As the Oxidizing ability of bichromate is considerably lowered in strong alkaline solution, carbon dioxide was used to neutralize the sodium hydroxide produced during the reaction, thus keeping the reaction medium nearly neutral. Molar ratio of bichromate to methylnaphthalene above 1.2 was necessary to obtain the high yield. The concentration of bichromate above 25% gave poor result, especially when the reaction was carried out at low bichromate ratio without CO2. Oxidation of crude methylnaphthalene oil gave the mixture of naphthoic acids, and the molar ratio of β- to α-naphthoic acid was established as about 2 from the melting point curve.
There are practically no detailed investigations on the relation between the concentration of metal naphthenates and their activities for liquid phase oxidation of p-xylene. The author has been investigated on this reaction by use of manganese, nickel, copper, chromium, and cobalt naphthenate catalysts. The results indicated that manganese, nickel, and copper naphthenate catalysts showed considerable difference in activity by the difference in concentration of catalyst. In case of using the same catalyst, the formation of p-toluic acid is increased with an increase in the concentration of catalyst to a certain extent, but the formation of p-toluic acid is rapidly decreased above a certain concentration of the catalyst and finally there is no formation of p-toluic acid. This kind of conversion of catalyst activity from positive to negative value with an increase of catalyst concentration has been recognized in case of copper catalyst as an exception, but such phenomenon has not been considered to happen in other metal-sailt catalysts. Cobalt and chromium naphthenates catalysts showed no such unusual effect of high concentration of catalyst.