From the bark of Magnolia Kobus DC., belonging to the Magnoliaceae, a quaternary base was isolated. This base was obtained as a chloride, crystallized in colorless plates or prisms, m. p. 260-261° (decomp.), and has the composition of C12H20O2NCl. This base was proved to be identical with salicifoline chloride [β-(3-hydroxy-4-methoxyphenyl)-ethyl-trimethylammonium chloride], an alkaloid found in the bark of Magnolia salicifolia Maxim. Furthermore, the remaining alkaloids in the mother liquor obtained after removing this base, were isolated as the Reineckate. Chromatographic analysis of the Reineckate in acetone solution on alumina showed that only salicifoline was present and no alkaloids other than salicif olive could be recognized.
Es wurde festgestellt, dass die bei der Oxydation des Tetrahydropirolatins (oder Tetrahydropirolagenins) erhaltene Säure mit der 4, 8-Dimethylnonansäure-(1) identisch ist. Auf Grund dieses Nachweises dürfte man von nun an über die Konstitution des Tetrahydropirolatins als (VII) im Klaren sein.
The authors identified from domestic Mahonia japonica DC. isotetrandrine (I, R=CH3) and berbamine (I, R=H) as the tertiary bases; berberine, palmatine and jatror-rhizine as the quaternary bases, and in addition a nitrogen-free neutral substance, m. p. 211-212.5°, in minute quantities. Although the Indian Mahonia usually yielded oxyacanthine, the authors showed that oxyacanthine was not to be found in the Japanese Mahonia, isotetrandrine being contained in large quantities instead. This is the first evidence of the occurrence of isotetrandrine in families other than the Menispermaceae.
(1) Thioacetanilides with electron-attracting groups in the benzene nucleus (thioacet-anilide, m-nitro-, p-methylsulfonyl-, p-nitro-, o-nitro-, and 2-nitro-4-methoxy-thioacet-anilides) were subjected to benzothiazole ring-formation. Among them, m-nitrothio-acetanilide (33%), p-cyanothioacetanilide (32%), and 2-methoxy-4-nitrothioacetanilide (24%) underwent cyclization in a fair yield. p-Methylsulfonylthioacetanilide is on the borderline between cyclizable and non-cyclizable thioacetanilides. p-Nitro- and o-nitro-thioacetanilides did not undergo ring-closure under the conditions examined. (2) The cyclized product obtained from m-nitrothioacetanilide was found to be 2-methyl-7-nitrobenzothiazole instead of the expected 2-methyl-5-nitrobenzothiazole.
(1) Nitration of 2-methyl-4-chlorobenzothiazole gave 2-methyl-4-chloro-7-nitrobenzothiazole, m. p. 163-164°, in 70% yield. (2) Nitration of 2-methyl-4, 7-dichlorobenzothiazole gave 2-methyl-4, 7-dichloro-6-nitrobenzothiazole, m. p. 167-168°, in 84% yield, along with a small quantity of other mononitro derivative, m. p. 119-120°. (3) Nitration of 2-methyl-4, 6-dichlorobenzothiazole gave 2-methyl-4, 6-dichloro-7-nitrobenzothiazole, m. p. 188-189°, in 20% yield.
(1) Nitration of 2-methylbenzothiazole gave 6-nitro-2-methylbenzothiazole, m. p. 165° (yield, 83%), along with a small amount of other mononitrobenzothiazole, m. p. 117° (yield, 3.7%). The product of m. p. 117° melted at 96-116° when mixed with 7-nitro-2-methylbenzothiazole, m. p. 120°. (2) Nitration of 2-methyl-6-acetylaminobenzothiazole gave 7-nitro-6-acetylamino-2-methylbenzothiazole in practically a qantitative yield. No other isomers, especially 5-nitro-6-acetylamino-2-methylbenzothiazole, were obtained.
Using various metallic complex salts, the precipitation of protein was studied of casein and egg-albumin. The results obtained are summarized as follows: 1. In an acid range of the isoelectric point of protein, the precipitation occurs by complex salts containing complex anion, while in an alkaline range, most of the complex salts containing complex cation cause the precipitation. Neither complex of low valency, such as [Co(NH3)4C2O4]Cl, [Co(NH3)4(NO2)2]Cl and [Co(NH3)4CO3]2SO4⋅3H2O, nor non-electric complex, such as [Co(NH3) (NO2)3], cause any precipitation in the whole pH range. 2. Of complex salts used, the capacity of precipitating protein depends on the valency. 3. In the range of concentration under examination, the equivalence of complex ion combined with a given protein remains almost constant independent of the variety, valency and the concentrations of complex salt added. 4. The effect of the time of standing hardly influences the equivalence of complex ion. 5. While the equivalence of cation complex salt increases with the increase of pH, that of anion complex increases with the decrease of pH. 6. These results support the facts that the precipitation appears in stoichiometrxc ratio and that each complex salts have the capacity for combining with acid or basic radicals in protein.
1) The interaction between testosterone and estrone could be regarded as a synergistic action in respect to the weight of seminal vesicles, prostate anterior and intramedial lobes (SVP) of golden hamsters, but not in respect to that of their prostate posterior lobes (PP), while the correlation between the weight of SVP and PP was certified as being significant and positive. 2) The weight of thymus was clearly reduced by the administration of testosterone. 3) The weight of adrenal gland was found not to be clearly influenced by any treatment in this experiment. 4) The increase of the weight of the seminal vesicle was explained histologically.
The authors obtained from Menispermum dauricum DC. growing in Japan, dauricine and a new base, m. p. 147-150°, which crystallized in yellow needles, but the content of the latter was very minute. The authors carried out the cleavage reaction of O-methyldauricine (II) by metallic sodium in liquid ammonia, and as a result of the investigation of the bisected bases, obtained l-1-(4′-methoxybenzyl)-6, 7-dimethoxy-N-methyl-1, 2, 3, 4-tetrahydroisoquinoline (III) and l-1-(4′-hydroxybenzyl)-6, 7-dimethoxy-N-methyl-1, 2, 3, 4-tetrahydroisoquinoline (l-armepavine) (IV). Thus, it has been proved that dauricine is represented by the formula (I), and the configuration of the two asymmetric centers in the molecule of dauricine are both in l-form.
Salicifoline chloride has been isolated from the bark of Magnolia stellata Maxim., belonging to the family Magnoliaceae, which grows in Japan. It has been found that the bark of this plant furnishes as high a percentage (0.3%) of salicifoline as that of Magnolia Kobus DC. Besides, a nitrogen-free substance with the melting point of 206 to 207°, was obtained in small quantities.
4-Oxychinolin-N-oxyd gibt bei der Nltrierung mit konz. Salpetersäure in Essigsäureanhydrid-Lösung das 3-Nitroderivat. Beim Erhitzen von 4-Nitrochinolin-N-oxyd mit Essigsäureanhydrid wurden eine kleine Menge von 3-Nitro-4-oxychinolin, N-Acetoxy-3-nitro-4-chinolonbetain und 4-Oxychinolin-N-oxyd erhalten. Die Entstehung von 3-Ni-troderivaten wurde durch Hinzufügen von Dimethylanilin unterdruckt, wobei nur das 4-Oxychinolin-N-oxyd mit guter Ausbeute entsteht.
Tetrodotoxin, which had previously been purified through chromatographic column of starch and active charcoal, was further purified through chromatopile and recrystallization by which crystalline pure tetrodotoxin, possessing a potency of MLD 0.012γ/g. body wt. of mouse, was obtained as prismatic crystals.
As a result of the investigation of alkaloids in the Japanese Mahonia Fortunei Fedde, the authors identified oxyacanthine, berbamine, jatrorrhizine, berberine and palmatine, and confirmed that it furnishes almost the same alkaloids as the Indian Mahonia. It has also been clarified that the Japanese Mahonia japonica DC. contains isotetrandrine and berbamine as the tertiary bases, whereas Mahonia Fortunei Fedde furnishes oxyacanthine and berbamine. Furthermore, it has been found that in Mahonia japonica DC. the root contains quite the same alkaloids as the trunk.
Bei der Druckhydrierung des Matrins wurde ein stereoisomeres Matrin erhalten, welches man als Allomatrin bezeichnete. Das bisher in der Literatur beschriebene Matridin ist das Desoxydihydroderivat des Allomatrins. Das letztere wurde also als das Allomatridin korrigiert. Das dem Matrin entsprechende Desoxydihydroderivat wurde durch Reduktion des Matrins mit Liciumaluminiumhydrid erhalten, welches man aufs neue als das Matridin benannte. Dem Allomatrin entsprechende Allomatrinsäure wurde hergestellt.
By periodic oxidation of α-methyl-D-glycopyranoside, D′-methoxy-D-hydroxymethyldiglycolic aldehyde p-nitrophenylhydrazone, m.p. 125° (decomp.), is obtaind. This hydrazone is decomposed in acid solution to glyoxal p-nitrophenylosazone, free glyoxal, glyceraldehyde and methanol.
The hot plate method for analgesic test was examined. The jump reaction, which is exhibited at 70° within 10 sec., is always prolonged by hypnotics, although other pain reactions remain unchanged. The analgetic action of barbiturates can be assayed by the hot plate method, when the prolongation of jump reaction time is assumed to be an indication of their analgetic activity.
The authors have prepared dl-O, O-dimethylcoclaurine (II) and dl-O, O-dimethyl-N-methylcoclaurine, viz., dl-1-(4′-methoxybenzyl)-6, 7-dimethoxy-N-methyl-1, 2, 3, 4-tetrahydroisoquinoline (III), starting with natural dl-coclaurine (I), and some comments have been made on their data. From these results, it has been clarified that the d-, l- and dl-form of the substance (III) all show the same melting point of 62°.
The mixture of bicyclic sesquiterpene lactones obtained from the rhizome of Inula Helenium was reduced by aluminum amalgam and the reduction product was separated into dihydro-isoalantolactone and dihydro-alantolactone in a pure state. The dihydro-alantolactone was converted into 1, 2-dihydroxytetrahydro-alantolactone.
1) Several 4-hydroxycoumarins substituted with unsaturated aromatic acyl groups in their 3-positions, e.g. 3-cinnamoyl-, 3-(p-acetylaminocinnamoyl)-, 3-(3′, 4′-methylene-dioxycinnamoyl)-, 3-cinnamylidene-acetyl-, 3-(α-naphthalacetyl)-, 3-(9-anthralacetyl)-, 3-furfuralacetyl-, and 3-(p-hydroxy-m-methoxycinnamoyl)-4-hydroxycoumarins, were synthesized. 2) The antibacterial activities of the compounds synthesized were tested againstStaphylococcus aureus and Escherichia coli for their antibacterial activities and it was found that of the new compounds tested 4-hydroxycoumarins having polycyclic aromatic nucleus in the side-chains on 3-position were most active, and that the side-chains on. this position are not restricted to long-chained aliphatic acyl groups in order to display high antibacterial activities of 4-hydroxycoumarins.
Synthesis of 4′, 5′-methylenedioxy-3, 4, 5, 6, 7, 8-hexahydro-6-amino-(2′, 1′:1, 2-benzoquinolizine) and some of its derivatives, starting from β-(3, 4-methylenedioxyphenyl)-ethyl bromide and ethyl nicotinate, is described. Their amoebicidal activities are now being examined.
A pigment produced by Penicillium multicolor G. M. P. was identified with sclerotio-rine obtained from Penicillium sclerotiorum van Beyma. On alkaline decomposition, it yielded an acid, C10H16O2, and on oxidation with chromic acid, it gave a ketone, C16H13O6Cl, along with methylethylacetic acid. The structure of the C10-acid was established as C2H5-CH(CH3)-CH=C(CH3)-CH=CH-COOH, and a partial formula of sclerotiorine was proposed.
On the reactions of aromatic aldehydes and α-amino acids, further evidences were obtained by paper chromatography. It is proved that the reaction of Type 1 gave four color spots of amines with ninhydrin, two yellow spots, which changed to purple after a few hours, and two purple spots, whereas the reaction of Type 2 gave two purple spots. The four spots of the former reaction were assumed to correspond to the types of amines: type A(A′) (independent of the structure of α-amino acids), 1, 2-diphenyl ethanolamine-type (Y→P); type B(B′), (independent of the structure of α-amino acids), benzylamine-type (Y→P), type C(C′) (dependent on the structure of α-amino acids), norephedrine-type (P), and type D(D′) (dependent on the structure of α-amino acids), lower aliphatic amines (P), respectively. The two spots of the latter reaction were assumed to correspond to the types of amines: type C(C′), ephedrine-type (P), and type D(D′), lower aliphatic amines (P), respectively. It is proved that the amines of type A(A′) and B(B′) are essential to the reaction of Type 1.
Die Alkaloide der Wurzelknollen von Aconitum sanyoense Nakai var. typicum Nakai wurden chromatographisch analysiert. Als kristallinische Komponente wurde ausser den schon bekannten Alkaloiden, Aconitin, Hypaconitin und Mesacontin ein neues Alkaloid von der Zusammensetzung C27H31NO6 und vom Schmp. 172-174° entdeckt. Das letztere wurde wegen seiner geringeren Toxität als Ignavin genannt. Ignavin enthält weder die Methoxyl- noch N-Methylgruppe und bildet ein Jodmethylat, welches ein mol Wasser weniger enthält. Ignavin reagiert mit keinem der üblichen Ketonreagenzien und geht bei katalytischer Reduktion in Dihydroignavin über. Ignavin gibt bei der Hydrolyse mit methanolischer Kali-Lösung ein mol Benzoësäure und ein Alkamin C20H25NO4, das als Anhydroignavinol genannt wurde. Anhydroignavinol ist ein α-Glykol, und eine Hydroxylgruppe des letzteren ist beim Ignavin benzoyliert vorhanden.
Since the proof given in earlier works is doubtful, the structure of ethyl acetusnetate was discussed again in the present paper. On alkaline decomposition of ethyl C-methylacetusnetate, usnetic acid was obtained along with methylacetusnetol. By this result, the structure of ethyl acetusnetate was established as having a γ-substituted acetoacetic ester form of side-chain. Infrared absorption spectra of the condensation product of ethyl acetusnetate with resorcinol and the oxidative degradation product of diacetylusnic acid previously reported by us were measured, showing the former to be a coumarin derivative and obtaining a further evidence of the presence of coumaran-2-one structure in the latter compound.
Hyposantonin and isohyposantonin do not undergo conversion such as that seen with desmotroposantonin by treatment with sulfuric acid, but yield dihydrosantinic acid. Those two compounds also undergo racemization by alkali fusion and yield optically inactive dihydrosantinic acid. It is assumed from the formation of dihydrosantinic acid that the steric difference between hypo- and isohypo-santonin is the difference in the position of the hydrogen atom attached to C5. Crystallographic measurements were made of optically active and inactive dihydrosantinic acids.