The thermal rearrangement of alkali salts of hydroxy benzoic acids in various organic solvents under carbon dioxide pressure was investigated in order to get some information about the effect of solvents on carboxylation of alkali phenoxides with CO2 in solution. Potassium salts of p-hydroxybenzoic acid (POB) and salicylic acid (SA) were stable at 180°C and no isomerization from o-isomer to p-isomer and very little decarboxylation were observed. At 240°C, the recovery of the original acids was much less especially with monosalts of POB and SA. Some solvents were found to affect the stability of the salts. However, the yields of acids and the ratio of p-isomer/o-isomer were not so easily related with the properties of the solvents. The behavior of sodium salts was found to be quite similar to that with the potassium salts at low temperature.
Benzoic acids and sulfur were allowed to react under the initial hydrogen pressure 100 kg/cm2 at 250°C in the presence of MoS3. Toluene and a little amount of α-toluenethiol were obtained. Similar results were also obtained from substituted benzoic acids, but in the case of benzoic acids containing electron-donating group the corresponding thiols were not obtained, the resulting compounds were mainly products of decarboxylation. In the case of phthalic anhydride, thiophthalide was obtained in good yield under the same reaction conditions. Depending on the conditions, thiophthalic anhydride and o-xylene sulfide were obtained in good yield respectively.
The reactions of indazolone with dialkylaminoalkyl halides have been studied under various reaction conditions, using several kinds of solvents and condensing agents. It has been found that the C-3-O of indazolone is substituted by a dialkylaminoalkyl group selectively. The reaction of indazolone with dimethylaminopropyl chloride has been studied in detail in this reaction, 3- (γ-dimethylaminopropoxy) -1H-indazole was found to be mainly produced together with minor formations of the 1, 3-disubstituted derivative of the enol-form and the 1, 2-disubstituted derivative of the keto-form.