β-Hydroxy-γ-chioropropyl 2-formly-6-allylphenyl ether was prepared from 3-allylsalicyl aldehyde to which diethylamine was applied and β-hydroxy-γ-diethylaminopropyl 2-formly-6-allylphenyl ether was obtained. The latter can also be obtained by the condensation of 3-allylsalicylic acid and β-hydroxy-γ-diethylaminopropyl chloride. Application of symm.-bis-diethylamino-iso-propyl chloride on 3-allylsalicyl aldehyde gave symm.-bis-diethylamino-iso-propyl 2-formyl-6-allylphenyl ether.
A crude, free sterol was extracted, by an ordinary method, from a dried powder of Patiria pectinifera Müller and Troscher, a kind of starfish collected in the Hokkaido, Japan. Purification by fractional recrystallization and formation of m-dinitrobenzoate, a specific sterol, m.p. 144-6°, [α]D12=+4.4°, was isolated and designated as “patiriasterol”. This substance easily gives digitonide and absorbs 1mol. H2 by catalytic reduction. By the application of the relationship between steroid structure and the optical rotation developed by Bernstein et al. (J. Org. Chem. 6, 319 ), the following structure, yet unknown in literature, is forwarded.
1) Chui-koe (Rana tigerina and R. rugulosa) sometimes are found to have their heart beating even 30minutes after injection which has a tendency to increase with the lowering of temperature (at 10% danger rate, it was 63.82-33.46% in Summer, and 79.92-52.08% in Autumn). The limit of confidence in the mother group obtained from average values of the sample in static examples, also is so small that they cannot be used for Focke's test method (at 5% danger rate by the use of F5 leaves, it was 2.16-1.60 in the Summer and 2.14-1.45 in the Autumn). 2) Plancy frogs (Rana plancyi Lataste) of ordinary weight (15-45g) showed no effect on Focke's values by the difference in weight both in Summer and Autumn, female and male, and at 5% danger rate. It is unnecessary to observe effects by dividing the animals into male and female if the total number is around 100. Use of this animal for Focke's method in Formosa was found to be suitable (potency, with F5-leaves, were 4.62-3.86 in the Summer and 3.16-2.56 in the Autumn: with F4.5-leaves, it was 4.42-3.52 in the Summer and 3.58-2.74 in the Autumn). 3) The difference in the potency of commercial F5-leaves (Sankyo) and F4.5-leaves (Fujisawa) is not great at 5% danger rate, no definite difference being observed (Plancy frogs). 4) Average sample values for F5- and F4.5-leaves are lower in the Summer than in Autumn, the difference being significant at 5% danger rate (Plancy frogs). 5) The digitalis leaves grown in Formosa give variable results against male and female Plancy frogs and such samples sometimes show different potency values. However, it has been shown that digitalis could be cultivated in Formosa to give leaves which would pass the rules set in Japanese Pharma-copoeae. (September 1939)
Studies were made of the oil obtained from the adipose tissues of Chúi-koe, a kind of frogs (Rana tigerina Daudin and R. rugulosa Wiegmann or R. tigerina Anderson) caught in the suburbs of Taipei, Formosa, between October and November in 1942. These fatty substances were obtained from male and female frogs separately and results of observations were as follows: 1) Oil: (a) That from females contained a remarkable amount of carotinoids but no great difference existed in general properties. (b) Solid fatty acids, from both sexes, were palmitic and stearic acids while liquid acid included unsaturated acid of C18 series and a higher unsaturated acid. (c) Unsaponifiable substances, from that of both sexes, were mostly steroid, especially, cholesterol, with the addition of a small amount of carotinoid. 2) Fat: This was dipalmitostearin from both sexes.
Studies were made on the fatty substances obtained from the adipose tissue of 1606 male and female toads (Bufo melanostictus Schneider) caught during June in the suburbs of Taipei, Formosa. Although the experiments had to be given up, following points were learned: 1) The amount of fatty oil obtained was ca. 83% of the weight of adipose tissues. 2) This fatty oil contained 0.22% non-saponifiable substances, 1.49% free fatty acids and 98.29% triglycerides. 3) Of the total fatty acid, the solid acid (41%) was chiefly composed of palmitic and stearic acids and the liquid acid (59%) contained unsaturated acids of C18 series and those of still greater molecule. 4) The non-saponifiable substance contained orange dyestuff and colorless, platelet crystals.
An apparatus to measure the radiation pressure of sound was deviced in order to determine the relationship between some chemical reaction and intensity of supersonic waves. In general, the chemical action of supersonic waves show a maximum value at a definite intensity. For example, sodium 2, 6-dichlorophenol-indophenolate solution was discolored best when the intensity of the waves was 166erg/cm3 energy density and discoloration of KMnO4 solution at 177erg/cm3. Liberation of I2 from KI solution and the action of radiated distilled water to liberate I2 from KI have maximum activities at 215erg/cm3.
1) Reduction of bromacetone by Al-ethoxide gives ω-bromo-isopropyl alcohol, application of diethylamine to which gives ω-diethylamino-isopropyl alcohol. 2) Following compounds were synthesized from C-allylguaiacol: symm.-Bis-diethylamino-isopropyl 2-methoxy-6-allylphenyl ether, b.p.12 199°; β-Hydroxy-γ-diethylaminopropyl 2-methoxy-6-allylphenyl ether, b.p.5 160°, β-Methoxy-γ-diethylaminopropyl 2-methoxy-6-allylphenyl ether, b.p.15 213-5°, and β-Allyloxy-γ-diethylaminopropyl 2-methoxy-6-allylpheny ether b.p.9 197°.
Hydroquinine, 6′-acetylamino-and 6′-amino-hydrocinchonidine, isoquinoline and quinoline methiodide were treated with quinine dehydrogenase solution obtained from rabbit liver. Oxidation products obtained were α′-hydroxy compounds from quinine derivatives and isocarbostyril and N-methyl-α-quinoline, respectively, from the last two named. Treatment of quinoline with enzyme solution obtained from canine liver did not give any product.
In order to observe the physiological properties of styryl dyes, a comparatively simply compounds of photosensitive heterocyclic ammonium salt dyes, over 30 kinds of dyes were obtained by the condensation of aromatic aldehydes and aromatic heterocyclic ammonium salts in EtOH solution under the presence of piperidine. Ammonium salts used were synthesized from lepidine, 6-methoxylepidine, quinaldine, 4-aminoquinaldine, 2, 4-dimethylthiazole, α-picoline, γ-picoline, 2, 4-lutidine and 2, 6-lutidine with alkyl halides such as ethyl, propyl, butyl and octyl bromides and methyl iodide. Aldehydes used were benzaldehyde, piperonal, vanillin, furfural, p-dimethylaminobenzaldehyde and anisaldehyde.
Preparative method for anil type dyes obtained by dehydration of nitrosoaryl and heterocyclic ammonium salts possessing active methyl radical is explained together with brief summary of the properties of dyes thus formed. The condensation is brought about by the addition of piperidine as a catalyst in an alcoholic solution of nitrosoaryl and ammonium salt. The yield varies greatly according to the amount of catalyst added and reacting temperature. When the temperature is high, by-product of azo dyes increases due to reduction of nitrosoaryl while a large amount of catalyst works as neutralizing agent on ammonium salt so that the yield of anil dyes also falls. In the latter experiment, the reacting temperature is best around 0°C. Anilino type dyes were synthesized by Ogata but the author also synthesized several of these dyes in order, first, to observe the physiological effects of the dyes themselves and also to utilize them as an intermediate compound for carbocyanine.
Synthesis of aromatic heterocyclic ammonium salt was studied as a material for the syntheses of cyclic ammoninm salt dyes. Several knowledges were obtained as to the difference in the formation rate of salts according to the kinds of alkyl and halogen used for alkyl halides and according to the kind of aromatic heterocyclic bases. The experiments were carried out by reacting the equivalent moles of the base and alkyl halide in MeOH under a definite condition and the amount of salt formed was determined by measuring the specific resistance of the reacting solution. As the number of carbon atoms in the alkyl radical increases, the reaction rate decreases. The reaction rate is increased in the order of Cl<Br<I.
3-Methyl-5-phenyl-2, 4-dione-oxazolidine (I), m.p. 111-111.5°, and 3-methyl-5, 5-diphenyl-2, 4-dione-oxazolidine (II), m.p. 98-98.5°, were synthesized, by the condensation of guanidine and mandelic ester and benzilicester, respectively, saponification of 2-imino-4-oxazolidone compound here formeds and subsequent methylation with diazomethane. (I) can also be obtained by the condensation of mandelic ester and urethane with subsequent methylation. The yield by former method was 43% for (I) and 14% for (II), and that by the latter was 40.6% for (I). 5, 5-Dimethyl-3-diethylaminoethyl-2, 4-dione-oxazoli-dine (III), b.p.1 107-8°, was obtained by the application of diethylaminoeth chloride on 5, 5-dimethyl-2, 4-dione-oxazolidine with an yield on crude product of 65%, on purifiied product of 39%. (III) gives a hydrochloride of m.p. 186°.