In order to obtain terephthalic acid by oxidation of cyclooctatetrane, oxidation reactions with chromic acid, hypochlorite, chlorate, and selenium dioxide have been investigated and the yield of terephthalic acid was found to be extremely poor in each case. In case of using of selenium dioxide, o-phthalal dehyde, phenylglyoxal, and cyclooctatrienone were obtained.
Electrolytic oxidation of cyclooctatetraene by use of mercury and lead electrodes has been investigated. Mercury electrode gave phenylacetaldehyde in high yield, while lead electrode gave large amount of resinous substance and carbon dioxide, with a small amount of terephthalic acid, and others.
dl-α-Piperonylidene-β-piperonyl-γ-butyrolactone (dl-Hibalactone) was synthe sized by condensation of piperonal and β-piperonyl-γ-butyrolactone . γ-Lactoneincluded in the latter was synthesized by reductive hydrogenolysis of methyl thiolbenzyl diester of piperonylsuccinic acid.
A direct synthetic method of perchloethylene with tetrachloroethane and oxygen, applying Deacon reaction, has been investigated. At first the catalyst to be used for Deacon reaction was studied, and it was found that copper chloride and potassium chloride on silica gel is suitable. As reaction condition, temperature of above 400°c and hydrogen chloride : oxygen mole proportion of 4:1 (same as theoretical) were preferable. Secondly the reaction between tetrachloroethane and oxygen, using this copper chloride-potassium chloride silica gel catalyst, has been investigated. Perchloroethylene was formed in this reaction, and the velocity of its formation was about the same as that of the thermal reaction of tetrachloroethane and chlorine. The rate of Deacon reaction, taking place simultaneously in the tetrachloroethane-oxygen reaction, is much faster than that of singl Deacon reaction. However, the rate-determining step of tetrachloroethane-oxygen reaction is found to be existed in the step of Deacon reaction. The catalyst accelerates substitution chlorination of trichloroetylene, but is no use in the reaction of tetrachloroethane itself. Oxygen is consumed mainly in Deacon reaction.
An addition reaction of alcohol on dicyandiamide in the presence of copper salt catalyst has been investigated. Guanyl-o-alkylisourea copper complex salt was synthesized with quantitative yield. By removing the copper from this complex copper salt, its salt was prepared with good yield. A high yield of guanyl-o-alkylisourea salt, which could not have been obtained when the acid catalyst was used, was investigated. Some guanyl-o-alkylisourea salts were newly prepared. By using of any desired copper salt and alcohol in the copper catalyst method, it is possible to obtain corresponding guanyl-o-alkylisourea salteasily. Therefore this method is considered to be a very convenient method for general synthesis of guanyl-o-alkylisourea salt, The mechanism of the formation of guanyl-o-alkylisourea copper complex salt was proposed by assuming of the formation of dicyandiamide coppr complex salt as the inital intermediate of this reaction.
Although linear type quinacridone (1) has red or rd purple coloration and is used as an organic pigment, the values of linear type quinacridone derivatives having various substituent groups as the pigment are not known. Twenty two kinds pf derivatives having substituent groups, chloro-, methyl- and methoxygroups, were synthesized by the author, their colors and the properties of crystal transition by immersion in dimethylformamide have been investigated with an object of finding valuable pigment. The results obtained are as follows: (1) Twenty kinds of diethyl 3, 6-dihydro-2, 5-diarylaminoterephthalate were newly prepared and their m.p. were given. (2) In the 4, 8- and 2, 6-substituents, blue coloration was increased in the order of chloro, methyl and methoxy group; also, the blue coloration was stronger in 2, 6- than 4, 8-substituent when the substituent groups were the same. (3) In case of immersion in boiling dimethylformamide, methyl substituent showed crystal transition easily but some of chloro and methoxy substituents were difficult to show crystal transition, especially those having chloro or methoxy group in 2-, 3-, 6-, and 7-position. (4) 3, 4, 7, 8-Tetrachloro derivative (orange color), 1, 2, 5, 6-tetrachloro derivative (red color), and 2, 6-dimethoxy derivative (purple color) were found to be valuable as the pigment from their coloration and difficulty of crystal ansition. Also, their syntheses by Friedel-Crafts reaction were established.
Advantage or disadvantage of using of catalyst for synthesis of arylaminoanthraquinone from 1-chloroanthraquinone has been investigated. Also, the conditions for reaction of formation of 1, 4-bis(arylamino)anthraquinone and 1-hydroly-4-arylaminoanthraquinone from quinizarin were clarified. Twentyfive kinds of arylaminoanthraquinones were obtained from aniline, o-, m-, and p-toluidines, and mesidine, and 1-chloro-, 1, 5-dichloro- and 1, 8-dichloroanthraquinones and quinizarin and their properties were clarified.
Chloromethylation of 1-p-toluidinoanthraquinone, a simplest structure in arylaminoanthraquinones, with sym-dichlorodimethylether in conc. sulfuric acid gave mono- and bis (chloromethyl) compounds. The chioromethyl group was introduced into ortho-position to methyl group in 1-p-toluidinoanthraquinone and this fact was confirmed by the identif iati of reduction product froofm monochloromethyl compound with LiA1H4. Several derivatives from chloromethyl compound, and its isothiuronium salt and pyridinium salt were prepared and their properties were clarified.