Examinations were made of the nitration of diethlene- and triethylene-glycol by the use of acid mixtures of various conditions in the ranges of dehydration values of 1.61 to 5.00. The melting and boiling points, and specific gravity of diethylene-glycol dinitrate were determined. At a low pressure following equation can be given: logt=0.096logp+2.0534 where t is the boiling point in °C and p, vapor pressure in mm. Properties, specific gravity and boiling point of triethylene-glycol dinitrate were determined.
5-Halogen compounds of 6-methoxy-8-nitroquinoline obtained by the direct chlorination or bromination of the latter were methoxylated and reduced, by which 5, 6-dimethoxy-8-aminoquinoline was obtained. Condensation of this with α-diethylamino-δ-pentanone-diethylacetal to Schiff's base and subsequent reduction gave the objected compound listed in the subtitle. This gives crystalline salt by condensation with 2-hydroxycinchonic acid.
Quercetin was isolated from the alcohlic extract of the leaves of Euphoria Longana Lam., and was proved by mixed fusion as pentacetyl-quercetin. A glucoside assumed to be quercitrin was isolated from crude tannin but values did not coincide with the published facts. This was thoroughly methylated by diazomethane, decomposed by dil. H2SO4, and pale-yellow, methylated aglycone, m.p. 191-2°, was obtained. This was proved by mixed fusion to be 3-hydroxy-5, 7, 3′, 4′-tetramethoxyflavone, m.p. 192°, which was prepared from rutin obtained from the flowers of Sophora japonica L. This proved that the bonding of sugar was at 3-position so that the glucoside must inevitably be quercetin-3-rhamnoside, i.e. quercitrin. Although there is a slight differences in the melting point from that found in literature it must be quercitrin as was earlier found by Mr Ohta (J. Pharm. Soc., Formosa. 53 (1942)).
A glucoside was isolated from the alcoholic extract of the leaves of Leucaena glauca Benth. The yield, about 0.0% of the leaves. The aglycone of this glucoside is quercetin and the sugar, rhamnose, and quantitative determination proved this to be quercetin-monorhamnoside. Thorough methylation of this glucoside with an excess of diazomethane and subsequent hydrolysis gave 3-hydroxy-5, 7, 3′, 4′-tetramethoxy-flavone Which proves that the original glucoside was quercetin-3-rhamnoside, i.e. quercitrin.
Syntheses of the derivatives of 2-amino-5-p-chlorobenzene-mercapto- or -sulfone-thiazole from p-chloropheny-mercapto-ketone, -sulfone-ketone or -mercapto-acetal are explained. The latter 3 compounds are obtained by the condensation of p-chlorothiophenol or p-chlorobenzenesulfinic acid and chloro-acetone, chloro-acetophenone or bromacetal, respectively.
1) Mechanisms of alkaline decomposition were observed of arylmercapto- and arylsulfone-ketones. 2) Halogenation of arylmercapto-acetone results in the substitution of halogen atom in the methylene radical situated next to S-atom. In the case of arylsulfone-acetone, however, halogen goes in the methylene radical next to -SO2- group which, under the presence of hydrogen halides, transits in majority of cases to the methyl radical at the end. 3) Halogen compounds of arylmercapto-ketone are generally unstable and decomposes upon heating with alcohol.
Condensation of the Na-salt of p-thiocresol and 2-phenylamino-4-chloromethylthiazole, obtained from phenylthiourea and dichloro-acetone, results in 2-phenylamino-4-p-toylmercaptomethylthiazole. Oxidation of the latter gives 2-phenylamino-4-p-tolylsulfonemethyl-thiazole, m.p. 158-9°, which coincides with a compound obtained by the condensation of phenylthiourea and α-bromo-α′-p-tolyl-sulfone-acetone. From these facts, it is clear that the substance obtained generally by the condensation of α-bromo-α′-arylsulfone-acetone and thiourea is a compound of 4-arylsulfonemethylthiazole.
In order to observe the reaction of Grignard reagents on pyridine-N-oxide and its derivatives, the author re-examined the studies made by Colonna (C. A. 30, 3420) on pyridine-N-oxide. Ethereal solution of phenyl-MgBr was added to the anhydrous benzene solution of pyridine-N-oxide. Treatment of reaction products revealed formations of α-phenylpyridine and diphenyl-dipyridyl, the latter being assumed as γ, γ′-dipyridyl. These results show that the reaction of pyridine-N-oxide and phenyl-MgBr proceeds as in (A) (Cf. Figure in the original text) forming α-phenylpyridine. Polymerization from (II) is difficult to realize, for the formation of diphenyldipyridyl and it is assumed that the reaction proceeds as in (B) through (III). Yields of α-phenylpyridine and diphenyldipyridyl are comparatively low and the ratio of their formation is about 8:5.