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Volume 80, Issue 10
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Synthesis of Alkyl 8-Alkoxy- and 8-Acyloxy-6-oxoöctanoate. (2)Shojiro Yurugi, Tomiyoshi Fushimi, Mitsuo Numata1960 Volume 80 Issue 10 Pages 1317-1321
Published: October 25, 1960
Released on J-STAGE: February 19, 2010
JOURNAL FREE ACCESSHeating of alkyl 8-chloro-6-oxoöctanoate (III, IV) with fatty acid results in formation of alkyl 6-oxo-7-octenoate (V, VI) and alkyl 8-acyloxy-6-oxoöctanoate (VII, VIII). Addition of a dehydrochlorination agent in this reaction was found to shorten the reaction time and increase the yield of the product. In the reaction of alkyl 8-chloro-6-oxoöctanoate (III, IV) and alcohols, ester exchange occurs due to the liberated hydrogen chloride and alkyl 8-alkoxy-6-oxoöctanoate (IX, X) is formed. Methyl 8-acetoxy-6-oxoöctanoate (VII:R′=CH3) and methyl 8-methoxy-6-oxoöctanoate (IX:R=CH3) undergo mutual transition in the presence of a suitable catalyst.View full abstractDownload PDF (811K) -
Reduction of Methyl 8-Alkoxy- and 8-Acetoxy-6-oxoöctanoateShojiro Yurugi, Mitsuo Numata, Tomiyoshi Fushimi1960 Volume 80 Issue 10 Pages 1321-1326
Published: October 25, 1960
Released on J-STAGE: February 19, 2010
JOURNAL FREE ACCESSReduction of methyl 8-ethoxy-6-oxoöctanoate (IX) to its 6-hydroxy compound (X) was effected in better yield by high-pressure reduction over Raney nickel than with sodium borohydride. The 6-hydroxy compound was acylated to form (XI) and (XII), while its hydrolysis gave the acid (XVII). Heating of the acid (XVII) resulted in formation of a small amount of the lactone (XVIII).
Reduction of methyl 8-acetoxy-6-oxoöctanoate (XXVII) also afforded the 6-hydroxy compound (XXVIII) in better yield by high-pressure reduction over Raney nickel. (XXVIII) was hydrolyzed to 6, 8-dihydroxyoctanoic acid (XXV) and this was esterified to (XXIV). Acetylation of the dihydroxy compound (XXIV) or 6-hydroxy compound (XXVIII) afforded methyl 6, 8-diacetoxyoctanoate (XXII: R=CH3).
High-pressure reduction of methyl 8-benzyloxy-6-oxoöctanoate (XXIX) resulted in formation of 6-hydroxy (XXX) or 6, 8-dihyclroxy compound (XXIV) according to reduction conditions.View full abstractDownload PDF (1008K) -
New Synthesis of 6, 8-Dihaloöctanoic Acid and its EstersShojiro Yurugi, Mitsuo Numata, Tomiyoshi Fushimi1960 Volume 80 Issue 10 Pages 1326-1332
Published: October 25, 1960
Released on J-STAGE: February 19, 2010
JOURNAL FREE ACCESSMethyl 6-hydroxy-8-ethoxyoctanoate (V) was halogenated under various conditions to afford methyl 6-chloro-8-ethoxy- (VI), 6, 8-dichloro- (III), and 6-bromo-8-ethoxy-octanoate (VII), and alkyl 6-bromo-8-chloroöctanoate (XV, XVI) and 6, 8-dibromoöctanoate (XVIII, II). Reaction of methyl 6-hydroxy-8-acetoxy- (VIII) or 6, 8-dihydroxyoctanoate (XX) with hydrogen bromide gave ethyl 6, 8-dibromoöctanoate (II) in a good yield. Chlorination of 6, 8-dichloro- (IV) or 6, 8-dihydroxyoctanoic acid (XXII) afforded 6, 8-dichloroöctanoyl chloride (XXIII).View full abstractDownload PDF (1216K) -
Isomerization and Isomers of Engelitin. (2)Toshio Tominaga, Kazunari Yoshimura1960 Volume 80 Issue 10 Pages 1332-1337
Published: October 25, 1960
Released on J-STAGE: February 19, 2010
JOURNAL FREE ACCESSThe trunk bark of Engelhardtia formosana HAY, collected during 1956-1957, was treated as shown in Chart 1, avoiding heating as much as possible. From this extract, 0.540-0.552% of (+)-dihydrokaempferol 3-L-rhamnoside (I), 0.461-1.261% of afzelin, 0.052-0.112% of astilbin, and 0.029-0.092% of quercitrin were isolated. Hydrolysis of (I) afforded one mole each of L-rhamnose and an aglycone which was identified with (+)-dihydrokaempferol (aromadendrin). The previously reported aglycone B (3, 4′, 5, 7-tetrahydroxyflavanone) and katuranin were found to be a mixed crystal of (+)-dihydrokaempferol and a small amount of dihydroquercetin.View full abstractDownload PDF (1104K) -
Isomerization and Isomers of Engelitin. (3)Toshio Tominaga, Kazunari Yoshimura1960 Volume 80 Issue 10 Pages 1337-1340
Published: October 25, 1960
Released on J-STAGE: February 19, 2010
JOURNAL FREE ACCESSHeating of (+)-dihydrokaempferol 3-L-rhamnoside (I) with 10% pyridine water gives a substance (III) of m. p. 301-302° (decomp.), neoengelitin (II), and neoisoengelitin (IV). In the present series of work, it was established that the previously reported engelitin contained a small amount of astilbin besides (I) and that isoengelitin was (III) contaminated with a small amount of isoastilbin. Therefore, (I) is hereafter corrected to engelitin and (III) as isoengelitin. Hydrolysis of (I), (II), (III), and (IV) afforded L-rhamnose as the sugar (cf. Table II) and dihydrokaempferol as the aglycone (cf. Table III).View full abstractDownload PDF (606K) -
Isomerization and Isomers of Engelitin. (4)Toshio Tominaga, Kazunari Yoshimura1960 Volume 80 Issue 10 Pages 1340-1344
Published: October 25, 1960
Released on J-STAGE: February 19, 2010
JOURNAL FREE ACCESSFrom the action of hot pyridine water and ethanolic sodium acetate solution, ultraviolet absorption spectra, and rotatory dispersion curves of engelitin (I), neoengelitin (II), isoengelitin (III), and neoisoengelitin (IV), it seemed more appropriate to consider that the aglycone portions in (III) and (IV) before hydrolysis are in cis-form. It is thereby assumed that (I) is (+)-dihydrokaempferol 3-L-rhamnoside, (II) is (-)-dihydrokaempferol 3-L-rhamnoside, (III) is probably (-)-epi- or -cis-dihydrokaempferol 3-L-rhamnoside, and (IV) is probably (+)-epi- or -cis-dihydrokaempferol 3-L-rhamnoside.View full abstractDownload PDF (732K) -
Constituents of the Hot Alcoholic ExtractToshio Tominaga, Kazunari Yoshimura1960 Volume 80 Issue 10 Pages 1345-1347
Published: October 25, 1960
Released on J-STAGE: February 19, 2010
JOURNAL FREE ACCESSHot 70% ethanolic extract of Engelhardtia formosana HAY was treated as shown in Chart 1 and afzelin, quercitrin, engelitin, and astilbin, as well as isoengelitin, isoastllbin, and neoastilbin were isolated. Paper chromatography of the extract solution resulted in detection of neoengelitin, neoisoengelitin, and neoisoastilbin. It is known, therefore, that extraction with cold ethyl acetate, avoiding application of heat, results in extraction of engelitin and astilbin per se, and isolation of their isomers is difficult, while extraction with hot 70% ethanol, as in the present work, results in isomerization of engelitin and astilbin during the extraction procedures, and these secondarily formed isomers are isolated.View full abstractDownload PDF (446K) -
Kenmotsu Mitsuhashi, Shunsaku Shiotani1960 Volume 80 Issue 10 Pages 1348-1353
Published: October 25, 1960
Released on J-STAGE: February 19, 2010
JOURNAL FREE ACCESSReaction of γ-keto acids with monoalkylhydrazines gave 2-alkyl-4, 5-dihydropyrida-zinones or hydrocinnolinones, while corresponding phenylhydrazonecarboxylic acids were obtained with phenylhydrazine, and on heating at 150-170°, the latter converted to 2-phenyl-4, 5-dihydropyridazinones or hydrocinnolinones. Analysis of the ultraviolet spectra of the two series of compounds is discussed.
Reduction of 2-methyl-4a-phenyl-4, 4a, 5, 6, 7, 8-hexahydro-3(2H)-cinnolinone (II′b) with lithium aluminium hydride gave 2-methyl-4a-phenyl-2, 3, 4, 4a, 5, 6, 7, 8-octahydrocinnoline (V), while hydrogenation over the Adams catalyst afforded 2-methyl-4a-phenyldecahydro-3-cinnolinone (VI).
Catalytic hydrogenation of (V) over palladium-carbon or reduction of (VI) with lithium aluminium hydride gave 2-methyl-4a-phenyldecahydrocinnoline (IX). Structure and chemical properties of (V), (VI), and (IX) were examined.
Treatment of 1-benzoyl-2-methyl-4a-phenyldecahydro-3-cinnolinone (VIII) with lithium aluminium hydride afforded (II′b) liberating benzaldehyde.View full abstractDownload PDF (963K) -
On the Preparation of Nitro Derivatives of 6-Hydroxycoumarin-3-carboxylic AcidMasataka Ichikawa, Hisashi Ichibagase1960 Volume 80 Issue 10 Pages 1354-1357
Published: October 25, 1960
Released on J-STAGE: February 19, 2010
JOURNAL FREE ACCESSNitration of ethyl 6-hydroxycoumarin-3-carboxylate (I) with mixed acid gives ethyl 6-hydroxy-5, 7-dinitrocoumarin-3-carboxylate (II), m.p. 160.5°, while nitration in glacial acetic acid gives ethyl 6-hydroxy-7-nitrocoumarin-3-carboxylate (V), m.p. 182-183°, and ethyl 6-hydroxy-5-nitrocoumarin-3-carboxylate (IV), m.p. 182°. Hydrolysis of these two ethyl esters with hydrochloric acid affords 6-hydroxy-7-nitro-coumarin-3-carboxylic acid (VII), m.p. 245-246°, and 5-nitro-6-hydroxycoumarin-3-carboxylic acid (VI), m.p. 203-204°.
The Elbs persulfate oxidation of coumarin-3-carboxylic acid gave 6-hydroxycoumarin-3-carboxylic acid. Application of the same reaction to 7-nitro- (X) and 5-vitro-coumarin-3-carboxylic acid (XI) showed that the hydroxyl group is introduced into 6-position in both acids. The position of the nitro group in the foregoing (V) and (IV) was determined by the use of this reaction.
Since the nitration of (V) and (IV) afforded (II) in both cases, the two nitro groups in (II) were found to be in 5- and 7-positions.View full abstractDownload PDF (836K) -
Double Molecular Structure of Serpentinine. (1)Hidehiko Kaneko1960 Volume 80 Issue 10 Pages 1357-1361
Published: October 25, 1960
Released on J-STAGE: February 19, 2010
JOURNAL FREE ACCESSIt was concluded that serpentinine, isolated from Rauwolfia serpentina BENTH., is not an inseparable mixture of two bases but a homogeneous substance which has a double molecular formula, C42H44O6N4, rather than C21H22O3N2, and contains two chromophores of tetrahydro-β-carboline and quaternary β-carboline.View full abstractDownload PDF (847K) -
Double Molecular Structure of Serpentinine. (2)Hidehiko Kaneko1960 Volume 80 Issue 10 Pages 1362-1364
Published: October 25, 1960
Released on J-STAGE: February 19, 2010
JOURNAL FREE ACCESSHydrolysis of serpentinine with sodium hydroxide in ethanol-acetone afforded an acid, characterized as the hydrochloride of m. p. 273°(decomp.), [α]D +181°(EtOH). The acid reverted to serpentinine on treatment with diazomethane. Hydrolysis of the alkaloid with 20% sodium hydroxide in methanol-acetone (3:2) at room temperature afforded a half-ester (methyl hydrogenmethoxydihydroserpentininate) as needles, m. p. 253°(decomp.), [α]D-65°(EtOH). Treatment of the half-ester with diazomethane gave methoxydihydroserpentinine as yellow needles, m. p. 252°, [α]D-14°(EtOH).View full abstractDownload PDF (565K) -
Palladium Dehydrogenation of Serpentinine. (1)Hidehiko Kaneko1960 Volume 80 Issue 10 Pages 1365-1369
Published: October 25, 1960
Released on J-STAGE: February 19, 2010
JOURNAL FREE ACCESSDehydrogenation of serpentinine with freshly prepared 30% palladium-carbon in boiling p-cymene gave the following three products: Compound A, which was also obtained by dehydrogenation of serpentinine over palladium-carbon at 280°, was identical with deethylalstyrine. Compound B, which has two anhydronium chromophores, was considered to have a double molecular structure. Compound C, which was named flavoserpentinine, was identical with an authentic sample of flavopereirine.View full abstractDownload PDF (708K) -
Palladium Dehydrogenation of Serpentinine. (2)Hidehiko Kaneko1960 Volume 80 Issue 10 Pages 1370-1374
Published: October 25, 1960
Released on J-STAGE: February 19, 2010
JOURNAL FREE ACCESSDehydrogenation of serpentinine in boiling p-cymene in the presence of 30% palladium-carbon, which has been kept in a desiccator for 1 week, gave the following three products: Compound D was shown to be identical with dihydroflavopereirine prepared synthetically. Compound E was proved to be the half-ester of Compound B. Compound F, which was also obtained by dehydrogenation of serpentinine at 100° over palladium-maleic acid, contained two chromophores of quaternary β-carboline and 6, 7-dihydroindolo[2, 3-α]quinolizinium and was inferred to have a double molecular structure (VI).View full abstractDownload PDF (724K) -
Synthesis of Compound C (Flavopereirine) and Compound D (Dihydroflavopereirine), and the Probable Structure of SerpentinineHidehiko Kaneko1960 Volume 80 Issue 10 Pages 1374-1378
Published: October 25, 1960
Released on J-STAGE: February 19, 2010
JOURNAL FREE ACCESSCompound C (flavopereirine) and Compound D (dihydroflavopereirine), isolated from the products of dehydrogenation of serpentinine, were synthesized and proved to be 3-ethylindolo [2, 3-a] quinolizinium base and 3-ethyl-6, 7-dihydroindolo [2, 3-a] quinolizinium base, respectively. All the findings described in the present and the preceding papers are in good agreement with the bimolecular formula (X) for serpentinine.View full abstractDownload PDF (755K) -
Palladium Dehydrogenation of Serpentine. (1)Hidehiko Kaneko1960 Volume 80 Issue 10 Pages 1378-1382
Published: October 25, 1960
Released on J-STAGE: February 19, 2010
JOURNAL FREE ACCESSDehydrogenation of serpentine over palladium-carbon at 280° or in boiling p-cymene yielded flavoserpentine, m. p. 200-202°, C18H16N2. This was shown to be identical with the product obtained by palladium-malefic acid dehydrogenation of ajmalicine, and was proved synthetically to have a structure of 2-methyl-3-ethylindolo[2, 3-a]-quinolizinium base.View full abstractDownload PDF (847K) -
Palladium Dehydrogenation of Serpentine. (2)Hidehiko Kaneko1960 Volume 80 Issue 10 Pages 1382-1386
Published: October 25, 1960
Released on J-STAGE: February 19, 2010
JOURNAL FREE ACCESSThe structure of some pyridine derivatives which were important intermediates for the synthesis of flavoserpentine were discussed, based on their infrared spectra.View full abstractDownload PDF (746K) -
Oxidation of AldosesToshiaki Komatsu1960 Volume 80 Issue 10 Pages 1387-1391
Published: October 25, 1960
Released on J-STAGE: February 19, 2010
JOURNAL FREE ACCESSStructural specificity requirement of a substrate in aldose oxidation by Acetobacter suboxydans was examined with intact cells. Among the various aldoses tested, D-xylose, D-glucose, D-gulose, and D-glycero-D-gulo-heptose were oxidized to the corresponding aldonic acids. It was found that in the oxidation of D-glucose, D-gluco-pyranose is first oxidized to D-glucono-δ-lactone which is then hydrolyzed to D-gluconic acid. Considering the structural requirement for aldose oxidation of this bacteria, with reference to the pyranose structure, it is found that the rule of cyclitol oxidation is not applicable and that the C-1 hydroxyl is oxidized when the C-3 and C-4 positions bear equatorial-equatorial or axial-axial hydroxyls, and there are no axial-equatorial or equatorial-axial hydroxyls in C-2 and C-5 positions.View full abstractDownload PDF (703K) -
Oxidation of Aldonic AcidsToshiaki Komatsu1960 Volume 80 Issue 10 Pages 1392-1395
Published: October 25, 1960
Released on J-STAGE: February 19, 2010
JOURNAL FREE ACCESSStructural requirement of a substrate in oxidation of aldonic acids by Acetobacter suboxydans was examined using intact cells. Of the various aldonic acids examined, the secondary alcohol adjacent to the primary alcohol was oxidized in D-gluconic acid, D-glycero-D-gulo-heptonic acid, and D-erythro-L-talo-octonic acid. It was thereby found that the rule of polyol oxidation was not applicable for aldonic acid oxidation by this bacteria and it was assumed that the secondary alcohol adjacent to the primary alcohol is oxidized when the acid possesses D-gluco-type structure in the molecular terminal, as viewed from the primary alcohol, and does not possess trans-hydroxyl between its D-gluco-type structure and carboxyl group.View full abstractDownload PDF (690K) -
On the Constitutions of Oxidation Products of D-Glycero-D-gulo-heptonic Acid and D-Erythro-L-talo-octonic Acid by Acetobacter suboxydansToshiaki Komatsu1960 Volume 80 Issue 10 Pages 1395-1398
Published: October 25, 1960
Released on J-STAGE: February 19, 2010
JOURNAL FREE ACCESSStructural studies were made on the oxidation products of D-glycero-D-gulo-heptonic acid and D-erythro-L-talo-octonic acid by Acetobacter suboxydans. The former product was found to be 6-oxo-D-glycero-D-gulo-heptonic acid and the latter was assumed to be 7-oxo-D-erythro-L-talo-octonic acid.View full abstractDownload PDF (807K) -
On the Reaction of 3-Trimethylsilylphenol with Electrophilic ReagentsTadashi Hashimoto1960 Volume 80 Issue 10 Pages 1399-1404
Published: October 25, 1960
Released on J-STAGE: February 19, 2010
JOURNAL FREE ACCESSVarious kinds of cationoid reagent were reacted with 3-trimethylsilylphenol (II). Reaction with bromine resulted in primary and secondary substitutions in 4- and 6-positions to afford 3-trimethylsilyl-4-bromophenol and 2, 4-dibromo-5-trimethylsilylphenol. The third substitution occured at either 2- or 3-position and further bromination gave 2, 3, 4, 6-tetrabromophenol. Diazo coupling took place in 4-position and reduction of the azo compound so obtained afforded 3-trimethylsilyl-4-aminophenol. Nitration of the acetate of (II) with acetyl nitrate was difficult. Friedel-Crafts reaction of (II) by application of anhydrous aluminium chloride and acetic anhydride to its methyl ether afforded p-methoxyacetophenone. Fries reaction of (II) by application of anhydrous aluminium chloride to its acetate gave o- and p-hydroxyacetophenone, while Reimer-Tiemann reaction by application of chloroform and potassium hydroxide gave 4-trimethylsilylsalicylaldehyde. Nitrosation with nitrous acid gave 3-trimethylsilyl-4-nitrosophenol and its catalytic reduction afforded the corresponding amine.View full abstractDownload PDF (1110K) -
Takeo Higashino1960 Volume 80 Issue 10 Pages 1404-1407
Published: October 25, 1960
Released on J-STAGE: February 19, 2010
JOURNAL FREE ACCESSSeveral kinds of anionoid reagent were reacted with 4-quinazolinecarbonitrile (II). Reaction of (II) with 10% potassium hydroxide or 2N hydrochloric acid at room temperature afforded 4-quinazolinone (IV), reaction with sodium methoxide or ethoxide afforded 4-methoxy- (Va) or 4-ethoxy-quinazoline (Vb), with sodium phenoxide gave 4-phenoxyquinazoline (VIII), reaction with hydrazine gave 4-hydrazinoquinazoline (X), and reaction with butylamine, piperidine, or aniline gave 4-butylamino- (XII), 4-piperi-dino- (XIII), or 4-anilino-quinazoline (XIV). The foregoing experiments showed that the 4-position in (II) was very reactive to anionoid reagents.View full abstractDownload PDF (558K) -
Arsenic TestMasanobu Iguchi, Atsuko Nishiyama, Yuzo Nagase1960 Volume 80 Issue 10 Pages 1408-1410
Published: October 25, 1960
Released on J-STAGE: February 19, 2010
JOURNAL FREE ACCESSBy treatment of arsenous acid with dilute sulfuric acid and zinc, hydrogen arsenide evolved with a large quantity of hydrogen was detected by using D. O. P. and P. E. G. as an adsorbent, eluting with hydrogen. Limit of detection was 0.001mg. of As2O3 and the limit of determination was 0.004mg.View full abstractDownload PDF (410K) -
Studies on Direct Reading Coulometer for Constant Current Coulometry and its ApplicationsYoshihiro Maekawa, Yoshiko Okazaki1960 Volume 80 Issue 10 Pages 1411-1414
Published: October 25, 1960
Released on J-STAGE: February 19, 2010
JOURNAL FREE ACCESSAn apparatus for constant-current coulometry and result of titrations using this apparatus are described. This newly devised apparatus is provided with a constant-current power supply using a double-negative feedback circuit in which several levels of constant current is always obtained accurately by only switching and a counter which indicates the quantity of electricity used irrespective of the current value and a counter working in conjunction with this switching of the current and which counts the different frequency pulse and indicates the quantity of electricity used, irrespective of the current value. By the use of such an apparatus, constant-current coulometry, which was not generally adopted due to inconvenience of handling, can be put to practical use by ease of handling and a high precision can be obtained. Moreover, time required for titration is shortened since it is possible to change electrolytic current during titration.
A good precision was obtained by titration of 0.1-10mg. of arsenic trioxide by electrolytic generation of bromine, with coefficient of variation of 0.1%.View full abstractDownload PDF (766K) -
Synthesis of 2, 3, 4, 4a, 5, 6-Hexahydro-1H-pyrimido[3, 4-a]quinolineMasanori Nagata1960 Volume 80 Issue 10 Pages 1414-1417
Published: October 25, 1960
Released on J-STAGE: February 19, 2010
JOURNAL FREE ACCESS2-(2-Aminoethyl) quinoline (V), obtained by selective catalytic reduction of 2-quinolineacetonitrile (I) over Raney nickel catalyst under high pressure, was reacted with ethyl chlorocarbonate and gave the corresponding urethan (VIII). 1, 2, 3, 4-Tetra-hydro compound (IX), obtained by the reduction of (VIII) over platinum oxide catalyst, was cyclized by fusion at 200° to 2, 3, 4, 4a, 5, 6-hexahydro-1H-pyrimido[3, 4-a]quinolin-1-one (X), which was reduced by lithium aluminium hydride to 2, 3, 4, 4a, 5, 6-hexahydro-1H-pyrimido[3, 4-a]quinoline (XI). (XI) was readily hydrolyzed by mineral acid to 2-(2-aminoethyl)-1, 2, 3, 4-tetrahydroquinoline (VI) and formaldehyde.View full abstractDownload PDF (696K) -
Hideo Tani1960 Volume 80 Issue 10 Pages 1418-1424
Published: October 25, 1960
Released on J-STAGE: February 19, 2010
JOURNAL FREE ACCESS1-Oxides of substituted pyridine derivatives easily form their N-methoxylated quaternary salts by reacting with dimethyl sulfate. Potassium cyanide was added to the solution of the resulting salts in water or water containing other solvents, by which the reaction took place immediately at temperatures between 15° and 30°. After stirring for 15-45 minutes the product was extracted with chloroform and separated by alumina chromatography or vacuum distillation. Thus, corresponding 2- and 4-cyanopyridine were obtained. However, N-alkoxylated quaternary salts of 4-dimethylaminopyridine and 2-ethoxycarbonylaminopyridine did not react with potassium cyanide. The methoxyl group of 1, 4- or 1, 2-dimethoxypyridinium methylsulfate was found to undergo substituted with cyano group and 2, 4- or 2, 6-dicyanopyridine was isolated in considerable amount.View full abstractDownload PDF (1425K) -
Alkaloids of Berberis Tschonoskiana REGEL. (3). The Structure of ObaberineTakehiko Kugo, Michio Tanaka, Takuo Sagae1960 Volume 80 Issue 10 Pages 1425-1428
Published: October 25, 1960
Released on J-STAGE: February 19, 2010
JOURNAL FREE ACCESSA new base named obaberine was isolated as the tertiary, non-phenolic base from Berberis Tschonoskiana REGEL (Japanese name ‘Ohba-megi’) as needle crystals of m. p. 139-140°, and other crystalline new bases of m. p. 57-58° and m. p. 105-107° were also found to be present.
Obaberine is a non-phenolic base indicated by the molecular and empirical formulae of C38H42O6N2=C32O24(OCH3)4(-O-)2(NCH3)2. Various reactions of this base such as the Hofmann degradation of its methiodide, oxidation of its methine base with potassium permanganate, and cleavage reaction with sodium in liquid ammonia revealed that this base is an oxyacanthine type of biscoclaurine bases and its data were very similar to those of O-methyloxyacanthine (III) (cf. Table I). Whereas obaberine forms crystals melting at 139-140°, O-methyloxyacanthine is derived by methylation with diazomethane of oxyacanthine, which had been known for scores of years as an amorphous base. Attempted crystallization of O-methyl-oxyacanthine in the present series of experiments successfully afforded it as needle crystals of m. p. 139-140°. Obaberine and O-methyloxyacanthine (III) were proved to be the same substances by comparative identification through admixture and infrared absorption spectra (in Nujol) of the free bases as well as their picrates. Oxyacanthine (II) is known to be distributed widely in Berberis sp. plants and its methyl ether, obaberine (O-methyloxyacanthine) (III), has now been found for the first time in nature, in Berberis Tschonoskiana REGEL.View full abstractDownload PDF (835K) -
Kentaro Hirai, Kinji Harada1960 Volume 80 Issue 10 Pages 1429-1432
Published: October 25, 1960
Released on J-STAGE: February 19, 2010
JOURNAL FREE ACCESSdl-1, 2-Methylenedioxy-9, 10, 11-trimethoxyaporphine (I) was synthesized by the route shown in Chart 1. The ultraviolet spectrum of (I), as shown in Fig. 1, showed a specific absorptions for an aporphine-type bases in general, similar to those of stephanine, crebanine, and allied bases prepared to date. In the Pschorr reaction for phenanthrene cyclization during this synthesis, a by-product was obtained besides the objective (I). This by-product was 2-methyl-6, 7-methylenedioxy-1, 2, 3, 4-tetrahydroisoquinoline (XV) which is assumed to have been formed by cleavage of the aminobenzyl-tetrahydroisoquinoline compound (XIV) into upper and lower fragments. The usual by-product of this Pschorr reaction, the further deaminated benzyltetra-hydroisoquinoline compound, was not obtained.View full abstractDownload PDF (723K) -
Morizo Ishidate, Sakahiko Owari, Toshio Kinoshita1960 Volume 80 Issue 10 Pages 1433-1436
Published: October 25, 1960
Released on J-STAGE: February 19, 2010
JOURNAL FREE ACCESSA modified method was established for the determination of glucuronic acid utilizing generation of furfural. In the modified method, distillation of furfural is substituted by benzene extraction. Its sensitivity and reproducibility are high, procedures are simple, reagents are stable, and the method is adapted for determination of glucuronic acid and conjugated glucuronic acid in biological materials (Fig. 2).
In this modified method, 10cc. of a sample is placed in a glass-stoppered test tube, 10cc. of 32% hydrochloric acid is added, and the tube is heated in a boiling water bath for 2 hours. The tube is then cooled with water, 10cc. of benzene is added, and the mixture is shaken thoroughly. To 5cc. of the benzene layer, 5cc. of aniline-acetic acid reagent (10cc. of aniline and 35cc. of water diluted to 500cc. with glacial acetic acid) is added, and optical density is measured at 517mμ after 30 to 70 minutes, using an equivolume mixture of benzene and aniline-acetic acid reagent solution as the reference
This determination is interfered by the presence of pentose and ascorbic acid but pentose can be eliminated by treatment with ion exchange resin and ascorbic acid will not affect the determination if the sample is heated in a water bath for 20 minutes.View full abstractDownload PDF (640K) -
Masauobu Iguchi, Atsuko Nishiyama, Yuzo Nagase1960 Volume 80 Issue 10 Pages 1437-1440
Published: October 25, 1960
Released on J-STAGE: February 19, 2010
JOURNAL FREE ACCESSPhenylmercuric acetate was found to form a stable complex compound with diphenylcarbazone in alkaline state. This complex compound showed absorption maximum at 580mμ in chloroform solution and the complex compound was found to be a unity with 1:2 ratio of phenylmercuric acetate to diphenylcarbazone by the continuous variation method. Phenylmercuric acetate in one tablet (containing 1% of phenylmercuric acetate) was determined by shaking its 1% solution in sodium acetate with 5×10-4M chloroform solution of diphenylcarbazone and measurement of optical density of this chloroform layer at 570mμ. Presence of halogen ion was found to interfere in this reaction.View full abstractDownload PDF (558K) -
Aminocyclopentane Derivatives. (3)Torizo Takahashi, Akira Kato, Noriyasu Hirose1960 Volume 80 Issue 10 Pages 1440-1443
Published: October 25, 1960
Released on J-STAGE: February 19, 2010
JOURNAL FREE ACCESSEthyl 1-ethyl-2-oxocyclopentanecarboxylate oxime was catalytically reduced to the amine (III), which was condensed with benzaldehyde, and the Schiff base so formed was reduced to the amine (IX) over palladium-carbon. Similar treatment of ethyl 2-anilinocy-clopent-1-enecarboxylate by reduction over Raney nickel or palladium-carbon afforded the amine (XIX). Condensation of ethyl 2-oxocyclopentanecarboxylate and ethyl bromide, with sodium ethoxide as the condensation agent afforded ethyl ethyladipate and its Dieckmann reaction gave ethyl 2-oxo-3-ethylcyclopentanecarboxylate, whose oxime was catalytically reduced to form the amine (XXX). These amines (III, IX, XIX, and XXX) were reacted with various acyl halides and 21 kinds of N-acylated compounds were prepared. Further, five kinds of related compounds were also prepared.View full abstractDownload PDF (630K) -
Effects of Argininosuccinic Acid and Canavaninosuccinic Acid on the Growth of Lactobacillus arabinosus 17-5Saburo Muraoka1960 Volume 80 Issue 10 Pages 1444-1448
Published: October 25, 1960
Released on J-STAGE: February 19, 2010
JOURNAL FREE ACCESSLactobacillus arabinosus, strain 17-5, requires arginine or pyridoxal in the Henderson-Snell medium. This lactobacillus grows in a pyridoxal-free medium by the addition of ornithine or citrulline in place of arginine and, therefore, arginine acitivity of argininosuccinic acid was examined under this medium condition. Argininosuccinic acid was hardly utilized when pH of the medium was 4.5-7.0 but 5-8% of L-arginine, based on molar concentration, was utilized at pH 7.5-8.0. Under the same condition, citrulline-utilizable Lactobacillus casei, SK 3-3, also utilized argininosuccinic acid but not Streptococcus faecalis R. Canavaninosuccinic acid, structurally related to argininosuccinic acid, inhibited the growth of Lact. arabinosus and this inhibition was recovered by addition of citrulline, arginine, or argininosuccinic acid. The antagonism of arginino- and canavanino-succinic acid was non-competitive.View full abstractDownload PDF (858K) -
Studies on the Lipotropic Agents. (1). Examination of Several Factors affecting the Development of Fatty Liver and its Characters, and Assay of the Lipotropic Effect of a few DrugsTadayuki Kobayashi1960 Volume 80 Issue 10 Pages 1448-1455
Published: October 25, 1960
Released on J-STAGE: February 19, 2010
JOURNAL FREE ACCESSAssay method for anti-fatty liver pharmaceutics was examined and a simple method of determination was devised. Male rats of pure strain, 3-weeks old, are bred on low-protein diet for 10-20 days. Excised fresh liver is ground with anhydrous sodium sulfate, extracted with ether, and the residue left after evaporation of ether extract is weighed. This gives the quantity of crude fats in the liver. Some examinations were also made on biological action of rats fed on low-protein diet. In the fatty liver caused by low-protein diet added with cholesterol, increase of fatty acid in liver fat is far greater than that of cholesterol, and the increase of ester cholesterol was marked. Dietary fatty liver causes lowering of hepatic functions. Anti-fatty liver action of several pharmaceutics was examined by this assay method and such action was found in choline, vitamin B12, and N-benzyloxycarbonyl-L-glutamylcholine. The latter compound was found to have anti-fatty liver activity in much smaller quantity than the amount of choline contained in its molecule.View full abstractDownload PDF (1210K) -
Manufacture of Lipotropic Substance from Alisma plantago L. (“Takusha”)Tadayuki Kobayashi1960 Volume 80 Issue 10 Pages 1456-1459
Published: October 25, 1960
Released on J-STAGE: February 19, 2010
JOURNAL FREE ACCESSThe benzene-insoluble portion of the methanolic extract of Alisma plantago L. contained choline and sugar, and benzene-soluble portion contained a lipid containing phosphorus, choline, and unsaturated fatty acid in its molecule and differing from lecithin, choline, methionine, citrovorum factor, vitamin B12, or biotin. It is a new substance which has anti-fatty liver activity. Chemical and physiological properties of these fractions were examined.View full abstractDownload PDF (733K) -
Lipotropic Effect of Alisma plantago L. (“Takusha”) ExtractTadayuki Kobayashi1960 Volume 80 Issue 10 Pages 1460-1465
Published: October 25, 1960
Released on J-STAGE: February 19, 2010
JOURNAL FREE ACCESSThe extract obtained from Alisma plantago L. was examined for anti-fatty liver activity on rat fatty liver caused by low-protein diet. It was found that the more purified (1⋅1⋅1⋅1) fraction had stronger effect than the extracted component (1) and that the fraction (1⋅1⋅1⋅1) + choline corresponding to the amount of component (1) had anti-fatty liver effect equal to that of (1). Comparative examination on the standard sample of the component (1⋅1⋅1⋅1) with choline and lecithin showed that they had approximately equal anti-fatty liver activity. Component (1⋅1⋅1⋅1) and lecithin showed stronger anti-fatty liver activity when added with a small quantity of choline (in 0.01% dose which in itself showed no activity) than when used alone. The effect of component (1⋅1⋅1⋅1) on the amount of cholesterol, ratio of free and total cholesterol, phospholipid, and cholesterol lipid ratio in the serum and liver during examination of anti-fatty liver activity was examined in comparison with those of choline and lecithin, and it was found that the component (1⋅1⋅1⋅1) is a new substance, different in biological activity from choline or lecithin.View full abstractDownload PDF (831K) -
Several Biological Criteria of Alisma plantago L. (“Takusha”) ExtractTadayuki Kobayashi1960 Volume 80 Issue 10 Pages 1465-1468
Published: October 25, 1960
Released on J-STAGE: February 19, 2010
JOURNAL FREE ACCESSSome examinations were made on the biological activity of the component (1⋅1⋅1⋅1) from Alisma plantago L. and following facts were found:
1) Acute toxicity, LD50, is 780mg./kg. by intravenous injection and 1270mg./kg. by intraperitoneal injection in mice, but no death occurred on oral administration of 4000mg./kg.
2) Subacute toxicity was tested by feeding the rats on a diet added with 0.1% or 1.0% of the component (1⋅1⋅1⋅1) but there was no marked change in body weight increase, weight of various organs, or amount of liver fats after 2.5 months.
3) This component (1⋅1⋅1⋅1) of Alisma plantago L. was found to alleviate lipemia caused by fat administration but it was not possible to prove the presence of a clearing factor in the plasma.View full abstractDownload PDF (551K) -
Alkaloids of Cocculus lauriforius DC. (Suppl. 16). Synthesis of dl-4′-Methyl-6-demethylcoclaurineHideo Yamaguchi, Kenji Senpuku, Eiko Morokuma1960 Volume 80 Issue 10 Pages 1469-1471
Published: October 25, 1960
Released on J-STAGE: February 19, 2010
JOURNAL FREE ACCESSOne of the allied compounds of coclaurine (I), dl-4′-methyl-6-demethylcoclaurine (XIII) (1-(4-methoxybenzyl)-6, 7-dihydroxy-1, 2, 3, 4-tetrahydroisoquinoline), was prepared by the route shown in Chart 1.View full abstractDownload PDF (434K) -
Yoshio Fukui, Yoshiro Kuwahara, Kazumi Saheki, Masamichi Mori1960 Volume 80 Issue 10 Pages 1472
Published: October 25, 1960
Released on J-STAGE: February 19, 2010
JOURNAL FREE ACCESSSynthetic process for 2, 4, 6-trimethoxyaniline was examined. The objective aniline derivative was obtained in a high yield by nitration of 1, 3, 5-trimethoxybenzene with nitric acid in a mixed solution of acetic and sulfuric acids, and reduction of its product with active iron.View full abstractDownload PDF (133K) -
Flavonoids of the Leaves of Castanea pubinervis SCHNEID., Hydrocotyle Wilfordi MAXIM., Sanguisorba hakusanensis MAKINO., Euptelaea polyandra SIEB. et ZUCC.Tashichiro Nakaoki, Naokata Morita1960 Volume 80 Issue 10 Pages 1473-1475
Published: October 25, 1960
Released on J-STAGE: February 19, 2010
JOURNAL FREE ACCESSPale yellow microneedles, m. p. 231-232°, and m. p. 232-233°, were respectively obtained in 0.02% and 0.025% yield from the leaves of Castanea pubinervis SCHNEID. and Hydrocotyle Wilfordi MAXIM., and both were identified as hyperin (quercetin 3-galactoside). Pale yellow microneedles, m. p. 176-177°, were obtained in 0.5% yield from the leaves of Sanguisorba hakusanensis MAKINO and it was identified as isoquercitrin (quercetin 3-glucoside). The pale yellow microneedles, m. p. 242-243°, m. p. 240-241°, and m. p. 240-241°, obtained in respective yields of 0.3%, 0.7%, and 0.01% from the leaves of Lactuca repens MAXIM., Carthamus tinctoria L., and Daucus Carota L. var. sativa DC., were all identified with luteolin 7-glucoside. The pale yellow microneedles, m. p. 175-176°, m. p. 174-175°, and m. p. 174-175°, obtained in respective yields of 0.02%, 0.01%, and 0.01% from the leaves of Ilex integra THUNB., Smilax china, and Smilax medica SCHL. et CHAM., were identified as rutin.View full abstractDownload PDF (671K) -
Tamotsu Danno, Yoshio Kowa1960 Volume 80 Issue 10 Pages 1476-1479
Published: October 25, 1960
Released on J-STAGE: February 19, 2010
JOURNAL FREE ACCESSMamushi venom, lysolecithin, and three kinds of stressors were used as fragility factor for vascular wall. Protective effect of various pharmaceutics against vascular fragility factor was judged by area of hemorrhagic spot, the area of dye infiltration, and the presence or absence of hemorrhage in the stomach wall. Acute toxicity (LD50) of the crude Mamushi venom used was 33mg./kg. by subcutaneous and 21mg./kg. by intravenous injection in mice. Effect of pharmaceutics against subcutaneous hemorrhage in mice by Mamushi venom was judged by the size of hemorrhagic spot after subcutaneous injection of 1 γ of venom per mouse, the effect being positive when the spot was larger than 5mm. in diameter and negative when smaller. As a result, relative potency of various pharmaceutics, with AC-17 as 1, was 0.47 for ACS, 0.77 for vitamin C, 0.59 for hesperidin, and 0.66 for rutin. Inhibitory effect of various pharmaceutics against accelerated vascular infiltration of lysolecithin was also examined, using Mamushi venom similarly. The relative potency of the pharma ceutics, with AC-17 as 1 was 0.68 for ACS. 0.79 for rutin, and 0.99 for hesperidin. In experimental peptic ulcer test, hemorrhage of stomach wall was inhibited by vascular strengthening pharmaceutics possessing hemostatic action.View full abstractDownload PDF (811K) -
Yuzo Nagase, Masanobu Iguchi1960 Volume 80 Issue 10 Pages 1480-1482
Published: October 25, 1960
Released on J-STAGE: February 19, 2010
JOURNAL FREE ACCESSPolarography of phenylmercuric acetate exhibits a two-step wave, as has been reported by numerous workers. Phenylmercuric iodide is an extremely soluble compound and precipitates on the addition of potassium iodide to the acetate. This precipitation reaction was utilized for determination by amperometric titration at the potential of -0.5V vs. S. C. E., using potassium iodide standard solution. The result is shown in Fig. 1. Conditions for the titration were as follows: 3×10-4M, sample concentration; potassium iodide standard solution ca. 4×10-3M pH 4.0-8.5; gelatin concentration, 0.02%, ethanol at 10 (v/v)%. The temperature range of 10-30° showed no effect. This method was applied to a commercial tablet (each tablet containing ca. 1mg, of phenylmercuric acetate) and polarographic wave of phenylmercuric acetate was not affected by the bulking agent and foaming agent in the tablet, or rather, they tended to act as maximum suppressor and supporting electrolyte.View full abstractDownload PDF (435K) -
Quantitative Determination of Phenylmercuric AcetateYuzo Nagase, Shigeo Baba, Michio Suzuki1960 Volume 80 Issue 10 Pages 1482-1483
Published: October 25, 1960
Released on J-STAGE: February 19, 2010
JOURNAL FREE ACCESSDetermination of phenylmercuric acetate was carried out by addition of 0.05(w/v)% of potassium iodide[131I]solution to form the insoluble iodide of phenylmercuric acetate and measurement of specific radioactivity of the supernatant by a scintillation counter. Determination of phenylmercuric acetate in the range of 0.25-2.0mg. was possible with standard deviation of below 0.025. Presence of a bulking agent does not interfere in the present determination but the presence of chloride ion was found to cause negative error.View full abstractDownload PDF (273K) -
Toshio Yoshino, Akihiro Seno, Mizuho Sugihara1960 Volume 80 Issue 10 Pages 1484-1486
Published: October 25, 1960
Released on J-STAGE: February 19, 2010
JOURNAL FREE ACCESSDetermination of yohimbine hydrochloride by amperometric titration was examined. Yohimbine hydrochloride undergoes quantitative reaction with silicotungstic acid in 0.1M potassium hydroxide solution to form a 2:1 complex and in hydrochloric acid to form a 4:1 complex. The reaction with phosphotungstic acid in hydrochloric acid gives a complex of 6:1 ratio, and these complexes separate out as a white precipitate. By the use of this reaction, a minute quantity of yohimbine hydrochloride was determined under following conditions: Ec=-0.75V (vs. S. C. E.) when silicotungstic acid was used as the titrant and Ec=-0.40V (vs. Hg pool) when phosphotungstic acid was used as the reagent. Mercury drop electrode was used. Concentration of hydrochloric acid must be over 0.05M when using silicotungstic acid and over 0.5M when using phosphotungstic acid.View full abstractDownload PDF (364K) -
Pechmann's Reaction of Methyl 2-Methyl-4, 5-dihydro-3-furancarboxylateYoshikata Kuwayama1960 Volume 80 Issue 10 Pages 1487-1488
Published: October 25, 1960
Released on J-STAGE: February 19, 2010
JOURNAL FREE ACCESSCondensation of 2-methyl-3-methoxycarbonyl-4, 5-dihydrofuran (II), obtained by the rearrangement reaction of acetobutyrolactone, and phenols in 80% sulfuric acid with phosphoryl chloride was examined and the products obtained were found to be identical with the condensates of acetobutyrolactone by the Pechmann reaction reported in the preceding paper. From this fact, the dihydrofuran ring in (II) reacts as enol-ether in the present reaction and that the cleavage of furan ring precedes in this reaction.View full abstractDownload PDF (300K) -
Distribution of Flavonoids and Stilbenoids of Coniferae LeavesMitsuo Takahashi, Tokuzo Ito, Akihiko Mizutani, Koichiro Isoi1960 Volume 80 Issue 10 Pages 1488-1492
Published: October 25, 1960
Released on J-STAGE: February 19, 2010
JOURNAL FREE ACCESSMethanol extract of over 100 kinds of Coniferae plants was examined by paper chromatography for the presence of flavonoids and stilbenoids, and it was found that quercetin and kaempferol were distributed widely in this family. Myricetin, isorhamnetin, and taxifolin were detected and these were assumed to be present mainly as a glycoside. It was also confirmed that resveratrol is distributed in some of the Picea and Abies spp.View full abstractDownload PDF (659K) -
Supplementary Evidence for the Probable Structure of SerpentinineHidehiko Kaneko1960 Volume 80 Issue 10 Pages 1493-1495
Published: October 25, 1960
Released on J-STAGE: February 19, 2010
JOURNAL FREE ACCESSHydrolysis of ajmalicine with methanolic potassium hydroxide in acetone, followed by methylation with diazomethane gives methoxydihydroajmalicine (VII). From analogy, the structure of methoxydihydroserpentinine obtained by similar treatment of serpentinine was assumed to be as formulated by (III). From the NMR spectrum of serpentinine, the compound was proved to have a dimeric structure.View full abstractDownload PDF (340K)
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