All issues
Predecessor
Volume 79, Issue 6
Displaying 1-50 of 55 articles from this issue
-
Takeo Higashino1959 Volume 79 Issue 6 Pages 699-702
Published: June 25, 1959
Released on J-STAGE: February 19, 2010
JOURNAL FREE ACCESSIn the anticipation that the 2-position in 4-alkoxyquinazoline 1-oxide would be active to anionoid reagents, Reissert reaction was carried out on 4-methoxy- (I), 4-ethoxy- (II), 4-butoxy- (III), 4-phenoxy- (IV), and 4-benzyloxy-quinazoline 1-oxide (V) and they afforded the corresponding quinazoline-2-carbonitriles (VI to X). Reaction of (I) and (II) with p-toluenesulfonyl chloride gave 4-methoxy- (XIII) and 4-ethoxy-2-quinazolone (XIV), while their reaction with sulfuryl chloride produced 4-methoxy- (XV) and 4-ethoxy-2-chloroquinazoline (XVI). (I) and (II) were derived to (XIII) and (XIV) on heating in acetic anhydride. These experiments have proved that the 2-position of 4-alkoxyquinazoline 1-oxide is very active to anionoid reagents.View full abstractDownload PDF (560K) -
Takeo Higashino1959 Volume 79 Issue 6 Pages 702-705
Published: June 25, 1959
Released on J-STAGE: February 19, 2010
JOURNAL FREE ACCESSRadziszewski reaction of 4-methoxy- (I), 4-ethoxy- (III), 4-butoxy- (V), and 4-benzyloxy-quinazoline-2-carbonitrile (VII) affords 4-methoxy- (II), 4-ethoxy- (IV), 4-butoxy- (VI), and 4-benzyloxy-quinazoline-2-carbonamide (VIII) in a good yield. Alcoholysis of (III), (V), quinoline-2-carbonitrile (IX), quinoline-4-carbonitrile (XII), and benzonitrile (XX) was carried out. The nitrile was dissolved in dry ethanol, dry hydrogen chloride was saturated in this solution, and the hygroscopic crystals thereby obtained were treated with acid or alkali. Treatment with acid afforded acid amide in the majority, with a minute amount of ester, while treatment with alkali resulted in larger formation of the ester. It was also found that the nitriles of quinazoline and quinoline series tended to form acid amide.View full abstractDownload PDF (580K) -
Quantitative Determination of Saccharin and Dulcin in a Mixture by Potassium Bromide Pellet MethodYuzo Nagase, Shigeo Baba, Michio Suzuki1959 Volume 79 Issue 6 Pages 705-708
Published: June 25, 1959
Released on J-STAGE: February 19, 2010
JOURNAL FREE ACCESSSeparatory determination of saccharin and Dulcin in their mixture was carried out with KBr-pellet method. The key bands of saccharin and Dulcin were 970 and 820cm-1. The sample was prepared with 20 volumes of KBr for infrared use. The limit of detection of each component was about 50γ. Determination error of each component in a mixture was examined by Youden's assay method and standard deviation was within 1.62% in both cases.View full abstractDownload PDF (486K) -
An Improved Synthesis of 1-Phenyl-2-methyl-3-(2-aminoethyl)-5-pyrazoloneIsoo Ito1959 Volume 79 Issue 6 Pages 709-711
Published: June 25, 1959
Released on J-STAGE: February 19, 2010
JOURNAL FREE ACCESSThe carbon in 4-position of the pyrazolone ring is very active that it was brominated to form 1-phenyl-2-methyl-3-bromomethyl-4-bromo-5-pyrazolone which was condensed with diethyl ethoxymagnesiummalonate to afford 1-phenyl-2-methyl-3-(2, 2-bisethoxycarbonylethyl)-4-bromo-5-pyrazolone in 92.5% yield. Starting from this compound, 1-phenyl-2-methyl-3-(2-aminoethyl)-5-pyrazolone synthesized by Sugasawa, et al. and the dimethylamine derivatives were obtained in a good yield.View full abstractDownload PDF (586K) -
Synthesis of Proline Derivatives. (2)Torizo Takahashi, Kazuo Kariyone1959 Volume 79 Issue 6 Pages 711-716
Published: June 25, 1959
Released on J-STAGE: February 19, 2010
JOURNAL FREE ACCESS4-Methyl-2-piperidone (VIII), ethyl 2-oxo-4-piperidineacetate (IX), and 5-phenyl-2-piperidone (XIV) were derived to 3, 3-dichloro-2-piperidone derivatives (XV to XX) by the action of phosphorus pentachloride and sulfuryl chloride or bromine and their reduction with Raney nickel catalyst, in the presence of equimolar amount of triethylamine, at ordinary pressure and temperature, afforded 3-halo-2-piperidone derivatives (XXI to XXIV). Hydrolysis and recyclization products of these derivatives finally gave 3-methylproline (XXV), 2-carboxy-3-pyrrolidineacetic acid (XXVI), and 4-phenylproline (XXVII). (VIII) and (IX) were obtained by the Cope reaction of ethyl cyanoacetate and ethyl acetoacetate or diethyl acetonedicarboxylate, reduction of their products (I and II) to diethyl 2-cyanoglutarate derivatives (III and IV), their partial saponification and decarboxylation, and finally reduction over Raney cobalt. It was also found that (VIII) and (IX) can be obtained easily by catalytic reduction over Raney nickel of ethyl 4-cyano-3-butenoate derivatives (XI and XII) obtained by the Cope reaction of free cyanoacetic acid and ethyl acetoacetate or diethyl acetonedicarboxylate.View full abstractDownload PDF (938K) -
N-(1-Methyl-2-thiocyano-4-hydroxy-1-butenyl)-N-[(2-methyl-4-amino-5-pyrimidinyl)methyl]formamide (Cyanothiamine) and its Derivatives. (6)Haruo Yonemoto1959 Volume 79 Issue 6 Pages 717-720
Published: June 25, 1959
Released on J-STAGE: February 19, 2010
JOURNAL FREE ACCESSThe formation of thiamine methyl sulfide from cyanothiamine by reaction with potassium hydroxide in methanol was examined and it was found that thiocyanates were able to methylate thiamine and thiophenol by the action of alkali. It was thereby assumed that in this reaction, methylation agent was formed which attacked the thiol group, which was comparatively resistant to oxidation, in thiamine and thiophenol, and the methylation agent here formed was presumed as methyl cyanate.View full abstractDownload PDF (623K) -
Syntheses of Riboflavin 5′-Phosphite and Pyridoxine 5-Phosphite by Use of Diphenyl ChlorophosphiteTeruo Tanaka1959 Volume 79 Issue 6 Pages 721-722
Published: June 25, 1959
Released on J-STAGE: February 19, 2010
JOURNAL FREE ACCESSReaction of diphenyl chlorophosphite and alcohols, in the presence of a base, and hydrolysis of the product gives the monoester of phosphorous acid. Using this reaction, isobutyl, sec-butyl, cyclohexyl, and benzyl esters were obtained in 60-80% yield from the corresponding alcohols. By a similar process, riboflavin 5′-phosphite was prepared from riboflavin and pyridoxine 5-phosphite from isopropylidenepyridoxine.View full abstractDownload PDF (348K) -
Masao Tomita, Kentaro Hirai1959 Volume 79 Issue 6 Pages 723-728
Published: June 25, 1959
Released on J-STAGE: February 19, 2010
JOURNAL FREE ACCESSThe ultraviolet spectra of stephanine (I) and crebanine (II), the aporphine-type bases of Menispermaceae alkaloids, show a rather characteristic absorptions compared to other known aporphine bases (Fig. 1). dl-1, 2, 8-Trimethoxyaporphine (III) and dl-1, 2, 8, 9-tetramethoxyaporphine (IV), similar to but possessing dimethoxyl group in place of methylenedioxy group in (I) and (II), were prepared and their ultraviolet absorption spectra were examined. The two substances showed similar absorptions in the ultraviolet region but the broad shoulder in the region of 300mμ seen in (I) and (II) was so weakened as to be hardly seen, although the absorption curves were similar to those of (I) and (II) (Fig. 2).View full abstractDownload PDF (962K) -
Constitution of Nupharamine. (1)Tsutomu Ohashi1959 Volume 79 Issue 6 Pages 729-734
Published: June 25, 1959
Released on J-STAGE: February 19, 2010
JOURNAL FREE ACCESSReduction of nupharamine (I) with palladium-carbon catalyst afforded tetrahydronupharamine (II) possessing a tetrahydrofuran ring. Reduction of (I) over palladiumcarbon in hydrochloric acidity resulted in liberation of hydroxyl to form desoxynupharamine (III) and its further reduction over palladium-carbon gave tetrahydrodesoxynupharamine (IV). Application of thionyl chloride to the des-N compound (XI), C15H30O2, obtained by repeated exhaustive methylation and reduction of (II), afforded an anhydro compound (XII) and the infrared spectrum of its dihydro compound (XIII) agreed with that of anhydronupharanediol (A) derived from desoxynupharidine. Ozonolysis of the anhydro compound (XII) afforded 1-(3-tetrahydrofuryl)-4-methyl-8-nonanone (XIV) (B), formaldehyde, and a monobasic acid (XV). These facts have revealed that (XII) is a mixture of (C) and (D). Since application of methylmagnesium iodide to (XIV) reverted it back to (XI), formula (F) was given to (XI).
Heating of (I) with hydrochloric acid resulted in substitution of the hydroxyl with chlorine to form (XVI), C15H25ONCl⋅HCl, which easily underwent dehydrochlorination by alkali hydrogen carbonate to form (XVII), and ozonolysis of (XVII) gave acetone. These facts revealed that the carbon skeleton of nupharamine (I) takes the straightchain sesquiterpene-type configuration indicated by formula (D) and therefore, the partial structure indicated by (G) is proposed for nupharamine (I).View full abstractDownload PDF (1122K) -
Constitution of Nupharamine. (2)Tsutomu Ohashi1959 Volume 79 Issue 6 Pages 734-737
Published: June 25, 1959
Released on J-STAGE: February 19, 2010
JOURNAL FREE ACCESSIt had been revealed in the preceding paper that the carbon skeleton in nuphar-amine takes the acyclic sesquiterpenoid configuration similar to desoxynuphar-idine (A) and a partial structure (B) was assigned to (I). In the present series of work, the nitrogen-containing ring in (I) clarified.
Two exhaustive methylation and partial reduction of tetrahydrodesoxynuphar-amine (II) affords a des-N compound (V) whose ozonolysis gives 1-(3-tetrahydro-furyl) pentan-4-one (VI) (semicarbazone: m.p. 142.5°). Based on these facts, formula (D) was given to (V), and (E) or (F) to (IV). The dehydrogenated compound (VII), obtained by heating (I) with palladium, produced pyridinetricarboxylic acid (VIII) by permanganate oxidation and its trimethyl ester (IX), m.p. 59.5°, was found to be identical with trimethyl 2, 3, 6-pyridinetricarboxylate obtained by permanganate oxidation of quinaldine. In the face of these reaction results, formula (G) is proposed for nupharamine (I).View full abstractDownload PDF (743K) -
Zinc-Casein. (3). Synthesis of Zinc-Histidine ChelateKentaro Tanaka1959 Volume 79 Issue 6 Pages 737-743
Published: June 25, 1959
Released on J-STAGE: February 19, 2010
JOURNAL FREE ACCESSPreparation of three kinds of zinc-histidine chelate was carried out. A mixture of 10-2M zinc sulfate and 10-2M histidine is acid and does not show any characteristic absorption but the mixture allowed to stand for a long time in alkaline state shows absorption maximum at 262mμ. A solution of 10-2M histidine in alkaline state shows absorption maximum at 258mμ but addition of 10-2M zinc sulfate to it results in the formation of a zinc-histidine chelate with absorption maximum at 262mμ (Fig. 1). Zinc-histidine chelate with absorption maximum at 266mμ (Fig. 2) is obtained by electrolytic formation described by Minato and Tanaka and this chelate is the same as the substance isolated by these workers from zinc-casein complex. When pH of the solution is raised above 9.0 during electrolysis, the absorption maximum shifts to 262mμ (Fig. 3). The ratio of zinc to histidine in the zinc-histidine chelates with absorption maxima at 266mμ and at 262mμ was determined as 1:2 by the use of radioactive 65Zn (Fig. 4). Even the chelates not showing characteristic absorption spectra were found to form chelates, probably with combination ratio of 1:2, by determination by polarography (Fig. 6) and potentiometric titration (Fig. 7). According to examinations of absorption spectra and polarogram, the chelates devoid of absorption spectra is stable at below pH 6.0, that with absorption maximum at 266mμ is stable at pH 3.0-8.5, and that with absorption at 262mμ is stable at pH 5.5-9.8. Of these three, the one showing no characteristic spectrum is the least stable, while the other two are about the same, though the one with absorption at 262mμ is the most stable (Figs. 5 and 8).View full abstractDownload PDF (1009K) -
Zinc-Casein. (4). Structures of Zinc-Histidine ChelateKentaro Tanaka1959 Volume 79 Issue 6 Pages 744-748
Published: June 25, 1959
Released on J-STAGE: February 19, 2010
JOURNAL FREE ACCESSAssumed structure for zinc-histidine chelate may be represented by the formulae (I), (II), (III), (IV), (V), and (VI). The three kinds of zinc-histidine chelate obtained by the present writer (s) and described in the preceeding paper all are positive to the Pauli reaction, showing the presence of =NH group in the structure, and the ratio of zinc to histidine is 1:2. Therefore, the structures (I), (II), and (III) seem most probable. Compounds having the chelate ring of (I) were prepared of zinc-glycine chelate (B) and zinc-alanine chelate (C), and their absorption spectra were measured (Fig. 2). Since this chelate ring has no characteristic absorption spectrum, the chelate showing no such spectrum was assumed to have this structure (I). Histidine methyl ester was led to the zinc-histidine methyl ester chelate (D) and its absorption spectrum was measured (Fig. 2), from which it was learned that the chelate ring of (II) had a characteristic absorption maximum at 262mμ, and the zinc-histidine complex with absorption at 262mμ was found to have this structure (II). The histidine derivative with inactivated amino group, α-mono-DNP-histidine (E) was led to its zinc chelate (F) and its spectrum with absorption maximum at 266mμ (Fig. 3) indicated that the zinc-histidine chelate with absorption maximum at 266mμ has this structure (III).View full abstractDownload PDF (745K) -
Application of Robinson-Mannich Reaction to Benzocycloheptenone. (1). Synthesis of 2-Oxo-2, 3, 4, 4a, 6, 7-hexahydro-5H-dibenzo[a, c]cycloheptatrieneTadashi Fujita1959 Volume 79 Issue 6 Pages 748-751
Published: June 25, 1959
Released on J-STAGE: February 19, 2010
JOURNAL FREE ACCESSPlans were made for the syntheses of compounds possessing a dibenzocycloheptene ring, the skeleton of colchinol methyl ether obtained on decomposition of colchicine. Application of the Robinson-Mannich reaction to benzocycloheptenone afforded 2-oxo-2, 3, 4, 4a, 6, 7-hexahydro-5H-dibenzo[a, c]cycloheptatriene (IV) whose dehydrogenation produced 2-hydroxy-6, 7-dihydro-5H-dibenzo[a, c]cycloheptatriene (VIII).View full abstractDownload PDF (614K) -
Application of Robinson-Mannich reaction to Benzocycloheptenone (2). Synthesis of 2-Oxo-9, 10-dimethoxy- and 2-Oxo-9, 10, 11-trimethoxy-2, 3, 4, 4a, 6, 7-hexahydro-5H-dibenzo[a, c]Tadashi Fujita1959 Volume 79 Issue 6 Pages 752-756
Published: June 25, 1959
Released on J-STAGE: February 19, 2010
JOURNAL FREE ACCESSIn connection with the syntheses of compounds possessing a dibenzocycloheptene ring, Robinson-Mannich reaction was applied to benzocycloheptenones and 6-(3-oxobutyl)-6, 7, 8, 9-tetrahydro-5H-cycloheptabenzen-5-one was obtained as an intermediate. Cyclization and dehydration of this compound afforded 2-oxo-9, 10-dimethoxy-and 2-oxo-9, 10, 11-trimethoxy-2, 3, 4, 4a, 6, 7-hexahydro-5H-dibenzo[a, c]cycloheptatriene. 6-(3-Oxobutyl)-2, 3, 4-trimethoxy-6, 7, 8, 9-tetrahydro-5H-cycloheptabenzen-5-one showed some resistance to cyclization and dehydration and this was assumed to be due to the effect of methoxyl in 4-position.View full abstractDownload PDF (862K) -
Studies on the Constituents of Japanese and Chinese Crude Drugs. IShoji Shibata, Takao Murakami, Yoshihiro Nishikawa1959 Volume 79 Issue 6 Pages 757-760
Published: June 25, 1959
Released on J-STAGE: February 19, 2010
JOURNAL FREE ACCESSMethanolic extract of the root of Pueraria Thunbergiana BENTH. (Japanese origin), and of P. pseudo-hirsuta TANG et WANG, and P. Thomsonii BENTH. (Chinese origin) was treated by the lead salt method and the portion precipitating with basic lead acetate afforded daidzein, m. p. 320° (decomp.), daidzin, m. p. 215-217° (decomp.), substance-e as needles, m. p. 187° (decomp.), C21H20O9, and substance-f as hygroscopic prisms. Substances e and f were assumed to be hitherto unknown isoflavone derivatives from their coloration characteristics and ultraviolet spectral examinations.View full abstractDownload PDF (729K) -
Syntheses of Nitro-aminodiphenyl Ether Derivatives. (1)Kenji Ikawa1959 Volume 79 Issue 6 Pages 760-764
Published: June 25, 1959
Released on J-STAGE: February 19, 2010
JOURNAL FREE ACCESSMononitrodiphenyl ether-monocarboxylic acids, possessing a nitro and a carboxyl groups in each benzene ring, were submitted to the Curtius and Hofmann reactions, as indicated in Chart 1, and a series of corresponding nitro-aminodiphenyl ethers were prepared. In general, the Curtius reaction gave a comparatively better yield than the Hofmann method.View full abstractDownload PDF (1068K) -
Syntheses of Nitro-aminodiphenyl Ether Derivatives. (2)Kenji Ikawa1959 Volume 79 Issue 6 Pages 764-768
Published: June 25, 1959
Released on J-STAGE: February 19, 2010
JOURNAL FREE ACCESSA series of dinitrodiphenyl ether derivatives, possessing one nitro group in each benzene ring and in different positions were submitted to partial reduction with hydrogen sulfide in ammonia and ethanol. It was thereby found that the compounds possessing nitro groups in symmetric positions produced only one kind of monoamino derivatives while those with nitro groups in non-symmetric positions also produced one kind of monoamino compounds but the nitro group in meta-position was preferentially reduced when the nitro is in position meta to the phenoxyl, irrespective of the position of the other nitro group, and in the absence of a nitro group in meta-position, that in ortho-position was preferentially attacked over that in para-position (Chart 1). Partial reduction of such diphenyl ethers by catalytic reduction over palladium-carbon afforded a mixture of monoamino and diamino compounds as well as other intermediate products (azoxy compounds). The Ullmann condensation of 4-, 3-, and 2-acetamidophenol as a potassium salt with 4-, 3-, and 2-nitrobromobenzene afforded the corresponding acetamido-nitrodiphenyl ether derivatives and their saponification gave 9 kinds of nitro-aminodiphenyl ether derivatives.View full abstractDownload PDF (931K) -
Cleavage of Diphenyl Ether Derivatives by Hydrazine Hydrate. (6)Kenji Ikawa1959 Volume 79 Issue 6 Pages 769-772
Published: June 25, 1959
Released on J-STAGE: February 19, 2010
JOURNAL FREE ACCESSHydrazinolysis with hydrazine hydrate was examined with mononitro-monoamino-diphenyl ethers possessing one each nitro and amino group in each benzene ring. In compounds with nitro group in the position ortho to phenoxyl group, hydrazine hydrate effected cleavage of ether oxygen to form o-nitrophenylhydrazine (II) and the corresponding aminophenol derivative (III). (II) easily underwent dehydration to form 1-hydroxybenzotriazole (IIa).
In compounds with the nitro group meta to phenoxyl group, (IV) resisted hydrazinolysis, either at ordinary or higher pressure, and only reduction of the nitro group occured to produce a diamino derivative (V). In the case of compounds with a nitro group para to phenoxyl group, (VI) resisted hydrazinolysis at ordinary pressure but submitted to hydrazinolysis at higher pressure to form p-nitrophenylhydrazine (VII) and the corresponding aminophenol derivative (VIII), with a minute amount of the reduction product as diamino derivative (IX). Under some reaction conditions, the substance (VIII) further underwent autoreduction to form nitroaniline (VIIb) and nitrobenzene (VIIa).View full abstractDownload PDF (694K) -
Syntheses of 2-(ω-Dialkylaminoalkyl)-5, 6-methylenedioxyisoindoline DerivativesTomokichiro Fujisawa, Kozo Okada1959 Volume 79 Issue 6 Pages 772-774
Published: June 25, 1959
Released on J-STAGE: February 19, 2010
JOURNAL FREE ACCESSHydrastic acid (V) was prepared from safrole by a slightly modified Ichikawa method and hydrastimide obtained from the anhydride of (V) and ω-dialkylamino-alkylamines was submitted to the Tafel reduction to form 2-(ω-dialkylaminoalkyl)-isoindolines (X). Hypotensive action of the dimethiodide of (X) was examined.View full abstractDownload PDF (483K) -
Syntheses of 4-Benzylisoquinoline DerivativesTomokichiro Fujisawa1959 Volume 79 Issue 6 Pages 775-777
Published: June 25, 1959
Released on J-STAGE: February 19, 2010
JOURNAL FREE ACCESS4-Benzylisoquinolines and their 3, 4-dihydro compounds were prepared from 3, 4-methylenedioxybenzyl methyl ketone obtained from safrole. Examination of antispasmodic action of these compounds showed that they all had papaverine-like activity.View full abstractDownload PDF (698K) -
Syntheses of Indole DerivativesTomokichiro Fujisawa1959 Volume 79 Issue 6 Pages 778-783
Published: June 25, 1959
Released on J-STAGE: February 19, 2010
JOURNAL FREE ACCESS1, 2-Dimethyl-5, 6-methylenedioxyindole was obtained in a good yield from 3, 4-methylenedioxybenzyl methyl ketone. Attempts to derive the indole compound to pyrroloisoquinoline (XVI) was unsuccessful. A few condensation reactions were attempted on the 3-formyl derivative (Va).View full abstractDownload PDF (1137K) -
Syntheses of Phenanthridine DerivativesTomokichiro Fujisawa1959 Volume 79 Issue 6 Pages 783-785
Published: June 25, 1959
Released on J-STAGE: February 19, 2010
JOURNAL FREE ACCESS3-Methyl-8, 9-methylenedioxy-1, 2, 3, 4, 4a, 10b-hexahydrophenanthridine (VIII) was prepared from 3, 4-methylenedioxybenzyl methyl ketone.View full abstractDownload PDF (478K) -
Pharmacological Activities of the Extracts. (1)Yukio Ishida1959 Volume 79 Issue 6 Pages 785-788
Published: June 25, 1959
Released on J-STAGE: February 19, 2010
JOURNAL FREE ACCESSAqueous digest solution of the root nodule of horse bean (Vicia Faba L.) and soy bean (Glycine Max MERRIL) was found to have vasoconstricting activity, as tested by the Krawkow-Pissemski method with rabbit. Chromatographic fractionation of the methanolic extract using activated alumina gave E-fraction which showed contraction of uterus and intestines. Coon test on blood pressure of fowl showed initial lowering, followed by elevation of pressure. The effective principle is dialyzed by cellophane membrane and is comparatively stable to heat.View full abstractDownload PDF (633K) -
On the Amino Acids and Triterpenoid in the Root Nodule of Horse BeanYukio Ishida1959 Volume 79 Issue 6 Pages 788-790
Published: June 25, 1959
Released on J-STAGE: February 19, 2010
JOURNAL FREE ACCESSMethanolic extract of the root nodule of horse bean (Vicia Faba L.) was fractionated by activated alumina and the Ac-and E-fractions so obtained were submitted to two-dimentional paper partition chromatography. The Ac-fraction contained aspartic and glutamic acids, and the E-fraction was composed of glycine, threonine, arginine, proline, valine, phenylalanine, leucine, and isoleucine, as well as three unidentified substances (A, B, and D) positive to ninhydrin reaction. A crystalline triterpenoid (yield, 0.17%) mp 250-251.5°, was obtained from the T-fraction. This substance formed an acetate of m.p. 217-218.2° and these were found to be identical by mixed fusion with betulin, obtained from the trunk of silver birch (Betula platyphylla var. japonica), and from the various properties of betulin diacetate.View full abstractDownload PDF (560K) -
A Compound Colored with Ninhydrin from the Root Nodule of Horse Bean. (1)Yukio Ishida1959 Volume 79 Issue 6 Pages 790-793
Published: June 25, 1959
Released on J-STAGE: February 19, 2010
JOURNAL FREE ACCESSA substance positive (brownish yellow) to ninhydrin reaction was obtained from the root nodule of horse bean (Vicia Faba L.). This substance came in hexagonal plates, decomposing gradually from around 250° and blackening at around 300°, failing to show any clear melting point. Its isoelectric point is 4.5 by the paper electrophoretic test. It is insoluble in organic solvents sparingly soluble in cold water, but soluble in hot water. Its heating with hydrochloric acid results in reddish purple coloration to ninhydrin. Examination of this substance and its hydrochloric acid hydrolyzate by paper chromatography indicated that it is positive to Morgan's amino sugar reaction and reaction for sugar by p-anisidine. This substance was named legnodulic acid. Melting point of DNP-legnodulic acid was 178-180° (decomp.).View full abstractDownload PDF (1025K) -
Infrared Spectra of Protein-bound SteroidsHiroo Takikawa1959 Volume 79 Issue 6 Pages 794-799
Published: June 25, 1959
Released on J-STAGE: February 19, 2010
JOURNAL FREE ACCESSInfrared absorption spectra of 14 kinds of steroidal hormones bonded to bovine serum albumin or globulin were analyzed. With albumin, hydrogen bonding had been formed between the hydroxyl at C-3 and carbonyl in protein (I) as =C-OH→O=C-NH or hydroxyl at C-17 and carbonyl in protein (II) as =C-OH→O=C-NH, while in globulin, there was a hydrogen bonding between carbonyl at C-3 in steroid and imino in protein (III) as =C=O←HN-C=O and carbonyl in C-17 with imino in protein (IV) as =C=O←HN-C=O, besides (I) and (II) types. Therefore, types of bonding between methylandrostenediol, ethynylestradiol, estradiol, and estriol with albumin and globulin are (I) and (II), that of estrone, androsterone, dehydroepi-androsterone with albumin is (I) and with globulin (I) and (IV), that of testosterone, cortisone, hydrocortisone, Δ1-dehydrocortisone, and Δ1-dehydrohydrocortisone with albumin is (II), and that with globulin are (II) and (III), while that of progesterone and desoxycorticosterone with globulin is (III) type. The ratio of bonding is 1 mole of albumin to 1-3 moles of the steroid, or 1 mole glubulin to 6-9 moles of the steroid.View full abstractDownload PDF (1046K) -
Biological Properties of Protein-bound SteroidsHiroo Takikawa1959 Volume 79 Issue 6 Pages 799-802
Published: June 25, 1959
Released on J-STAGE: February 19, 2010
JOURNAL FREE ACCESSTestosterone and estrone were each incubated with bovine serum albumin or globulin in a phosphate buffer (pH 8.0) and biological action of the steroid-serum protein complex so obtained was examined. Testosterone-globulin complex has the action of increasing the weight of seminal vesicle and prostate gland of mice, in about the same degree as that by crystalline testosterone, but the action of testosterone-albumin complex was somewhat weaker. Estrone-albumin complex showed about the same effect on rat vaginal smear as that of crystalline esterone but that of estrone-globulin complex was slow in the appearance of effect. Incubation of these compleces with bovine liver homogenate in phosphate buffer rapidly liberated the steroid from testosterone-albumin and estrone-globulin compleces, resulting in liberation of 50% of testosterone and 90% of estrone 8 hours later. This liberation was comparatively slower in testosterone-globulin and esterone-albumin compleces, resulting in liberation of 18% of testosterone and 44% of estrone after 8 hours.View full abstractDownload PDF (618K) -
Eiichi Suenaga1959 Volume 79 Issue 6 Pages 803-808
Published: June 25, 1959
Released on J-STAGE: February 19, 2010
JOURNAL FREE ACCESSExaminations were made of heterocyclic formazyl derivatives as a reagent for colorimetry of copper and zinc. Using a spectrometer, composition of the complex salt in solution and optimum pH for the formation of complex salts were determined spectrochemically. It was thereby found that o-{2-[α-(2′-carboxyphenylazo)benzylidene]hydrazino} pyridine is the most suitable as the colorimetric reagent and that, by adjusting the pH, it would be possible to make separatory determination of the two ions.View full abstractDownload PDF (614K) -
Determination of Blood SugarKiyoshi Takiura, Kyoko Koizumi1959 Volume 79 Issue 6 Pages 809-814
Published: June 25, 1959
Released on J-STAGE: February 19, 2010
JOURNAL FREE ACCESSIt has been clarified that the KIO4-polarography described in the preceding paper could be applied to the determination of blood sugar and gives a better result than the existing method. In the process elaborated by the present authors, there is no necessity for deproteinization procedure and the reaction is stoichiometric so that there is no necessity for an empirical factor in calculating the found values. In this process, the plasma solution obtained by addition of isotonic or slightly hypertonic phosphate buffer (pH 7.0) to blood and centrifuging the blood corpuscles was used as the sample solution. A small amount of monosaccharides is present in the blood corpuscles but its amount does not vary physiologically and the use of plasma for measurement of blood-sugar value is rational. A mixture of 1cc. of the plasma solution (corresponding to 0.1cc. of blood) and 10cc. of the KIO4-Sφrensen buffer solution (10-3M, pH 7.0) is maintained at 25°±0.1° for a definite length of time (0.5-2 hrs.) and the wave-height of the first wave of IO4- is measured by polarography. A blind test is carried out at the same time and the amount of the reagent consumed is calculated from the difference in two values. Comparative examination of this method, Hagedorn-Jensen method, and anthrone method was made by measuring the normal value of blood sugar and blood sugar levels in rabbits after administration of glucose, insulin, or epinephrine. All three methods were found to give similar values and it was proved that they could be interchanged.View full abstractDownload PDF (973K) -
Syntheses of β-Substituted Acetals of Propionitrile DerivativesKanji Tokuyama1959 Volume 79 Issue 6 Pages 814-819
Published: June 25, 1959
Released on J-STAGE: February 19, 2010
JOURNAL FREE ACCESS2-Substituted 2-dialkoxymethylpropionitriles and their enol ether derivatives with phenoxy and naphthyloxyl in their 2-position were prepared. Condensation of these compounds with acetamidine was carried out. It was concluded from this and previously obtained results that the pyrimidine compounds are formed in a good yield when the substituent in 2-position, either in 2-alkoxymethylene- or 2-dialkoxymethyl-propionitriles, is alkoxyl or amino, but that the yield is poor when the said substituent is aryl or acetamido group. The yield of pyrimidines from 2-hydrogenated compounds is intermediate of the former two. On the other hand, reaction of 2-diethoxymethylacrylonitrile (I) with p-nitroaniline or 2, 4-dinitroaniline was found to be specific in the formation of 2-p-nitroanilinomethylene-3-p-nitroanilinopropionitrile (XX) or 2-o, p-dinitroanilinomethylene-3-o, p-dinitroanilinopropionitrile (XXII).View full abstractDownload PDF (1040K) -
Synthesis of 2-Ethoxymethylene-3-acetoxypropionitrileKanji Tokuyama1959 Volume 79 Issue 6 Pages 819-824
Published: June 25, 1959
Released on J-STAGE: February 19, 2010
JOURNAL FREE ACCESSReaction of 2-ethoxymethylene-3-acetoxypropionitrile (VII) and acetamidine was carried out. The reaction in methanol afforded the anticipated 2, 7-dimethyl-5, 6-dihydropyrimido[4, 5-d]pyrimidine (V), while the same in ethanol unexpectedly afforded 2-methyl-4-amino-5-acetamidomethylpyrimidine (VI) and 2, 7-dimethyl-5, 6-dihydropyrimido[4, 5-d]pyrimidine (V), besides 2-methyl-4-amino-5-hydroxymethyl-pyrimidine (X). This reaction in ethanol, when carried out under a more drastic reaction conditions, produces only (VI).View full abstractDownload PDF (932K) -
On the Structure of GitorinYoshio Sasakawa1959 Volume 79 Issue 6 Pages 825-829
Published: June 25, 1959
Released on J-STAGE: February 19, 2010
JOURNAL FREE ACCESSThe structure of gitorin was established as gitoxigenin monoglucoside by Tschesche and his co-workers. Gitorin was subjected to the action of the enzyme of a snail and then chromatographed (benzene·ethylacetate·water (8:5:4), ascending method), whereupon only one spot (Rf 0.485) appeared at a place different from those of gitorin (Rf 0.00) and gitoxigenin (Rf 0.68). From the reaction mixture, the product was isolated and it was proved to be gitoroside. On the other hand, hydrolysis of gitorin under mild conditions (0.05N HCl in 50% methanol, for 45mins., heated) afforded digilanidobiose as sugar and from these facts, gitorin must be considered as gitoxigenin digilanidobioside.
[In addition, it must be mentioned Prof. Dr. R. Tschesche has kindlly given support to this work by a personal communication.]View full abstractDownload PDF (1569K) -
Studies on the Product of the Cyclization of Bis[4-(1-methyl-3-carboxypropylidene)hydrazinophenyl] SulfoneTakao Takubo, Tomonori Tadaoka, Toshi Sawai1959 Volume 79 Issue 6 Pages 830-831
Published: June 25, 1959
Released on J-STAGE: February 19, 2010
JOURNAL FREE ACCESSIt has been found by direct heating of bis[4-(1-methyl-3-carboxypropylidene)hydrazinophenyl] sulfone at 160° resulted in the cyclization to form bis[4-(3-methyl-6-oxo-1, 4, 5, 6-tetrahydropyridazino)phenyl] sulfone. The reaction took a different course when heated at 180-190° in the presence of zinc chloride as a catalyst and formed bis(2-methyl-3-carboxymethyl-5-indolyl) sulfone.View full abstractDownload PDF (341K) -
Takeo Higashino1959 Volume 79 Issue 6 Pages 831-833
Published: June 25, 1959
Released on J-STAGE: February 19, 2010
JOURNAL FREE ACCESSCatalytic reduction of 4-benzyloxyquinazoline 1-oxide (IX) in methanol over palladium-carbon catalyst, at ordinary temperature and pressure, results in the formation of 4-quinazolone (XI) via 4-hydroxyquinazoline 1-oxide (X). The use of Raney nickel in the same reduction results in a different course of reaction and (IX) is reduced to (XI) through 4-benzyloxyquinazoline (XII).View full abstractDownload PDF (485K) -
Growth-Curve of Zygosaccharomyces salsus in Fluid Media and Effect of Some Compounds on itFukujiro Fujikawa, Yuhei Hitosa, Yoshiko Yagi1959 Volume 79 Issue 6 Pages 834-836
Published: June 25, 1959
Released on J-STAGE: February 19, 2010
JOURNAL FREE ACCESSThe growth curve of Zygosaccharomyces salsus, one of the yeast that produces membranous mold on soy sauce, was measured in liquid medium with electrophotometer and the curve was found to be almost identical with that of Zygosaccharomyces japonicus reported earlier, the lag phase taking the first 18 hours, going into the increased logarithmic growth phase from about 24th hour and continuing for 60th hour, and beginning the stationary phase from about 72nd hour. Propyl and butyl p-hydroxybenzoate, in 3.33×10-4M concentration, completely inhibited the lag and logarithmic-growth phases, while propyl and butyl orsellate showed the same phenomenon in 2.5×10-4M concentration. Butyl orsellate showed complete inhibition of growth in 1.25×10-4M and above concentration, and growth was stopped when its 1.25×10-4M was added at the beginning of lag phase or during logarithmic growth phase. Culture tests showed that this compound acted in bactericidal manner.View full abstractDownload PDF (417K) -
Structure of Isoxazole Compound derived from Ethyl 2-FormylacetoacetateHiroyuki Yasuda1959 Volume 79 Issue 6 Pages 836-838
Published: June 25, 1959
Released on J-STAGE: February 19, 2010
JOURNAL FREE ACCESSReaction of ethyl α-formylacetoacetate and hydroxylamine hydrochloride in ethanol results in the formation of ethyl methylisoxazolecarboxylate. Its cleavage with sodium ethoxide produces ethyl 1-cyanoacetoacetate which shows that the ester produced is ethyl 5-methylisoxazole-4-carboxylate. Reëxamination of the report (D. R. P. 634, 286) that the reaction of ethyl α-ethoxymethyleneacetoacetate and hydroxylamine produces ethyl 3-or 5-methylisoxazole-4-carboxylate revealed that this product is also ethyl 5-methylisoxazole-4-carboxylate.View full abstractDownload PDF (446K) -
Cleavage of 1, 6-Dimethoxydibenzo-p-dioxinYasuo Inubushi, Keiichi Nomura1959 Volume 79 Issue 6 Pages 838-842
Published: June 25, 1959
Released on J-STAGE: February 19, 2010
JOURNAL FREE ACCESSCleavage reaction of 1, 6-dimethoxydibenzo-p-dioxin (I) with metallic sodium in liquid ammonia was examined and the two compounds produced from this reaction were clarified as 2-hydroxy-6, 3′-dimethoxydiphenyl ether (II) and 2, 2′-dimethoxy-6, 6′-dihydroxybiphenyl (III). The yield of (II), considered to be the normal product in this reaction, was found to become large by lowering the reaction temperature and addition of ammonium chloride during the reaction.View full abstractDownload PDF (717K) -
The Separatory Determination of Glucuronic Acid and Glucuronide by Ion Exchange ResinMorizo Ishidate, Shoji Takitani, Terumi Nakajima1959 Volume 79 Issue 6 Pages 843-845
Published: June 25, 1959
Released on J-STAGE: February 19, 2010
JOURNAL FREE ACCESSSeparatory determination of glucuronic acid and various glucuronides by chromatography with anion exchange resin was examined. Phenylglucosiduronic acid, menthylglucosiduronic acid, and sodium anilino-N-glucosiduronate were used as the sample of glucuronide. The mixture was passed through a column (7×150mm.) packed with ca. 5cc. of Amberlite IRA-411 (R-Cl type) in weakly alkaline state, and elution of the column with N hydrochloric acid afforded glucuronic acid and N-glucuronides labile to acid. Further elution of the column with a mixture of hydrochloric acid and methanol (44:500) separated the 0-glucuronides. Determination was made through carbazole method. The use of this procedure with urine sample added with known amounts of test substances resulted in recovery rate of 93.9-101.5%.View full abstractDownload PDF (433K) -
Tozaburo Kurihara, Kenji Suzuki1959 Volume 79 Issue 6 Pages 845-847
Published: June 25, 1959
Released on J-STAGE: February 19, 2010
JOURNAL FREE ACCESSAcylcysteamines were prepared by the reaction of cysteamine and carboxylic acid esters or cysteamine and N, S-diacylcysteamine. N-Acylcysteamine was found capable of acylating sulfanilamides at around pH7, at room temperature, and this acylation mechanism was presumed. Aliphatic acyl compounds of these N-acyl-cysteamines showed hypotensive activity.View full abstractDownload PDF (448K) -
Syntheses of Piperidine and Quinoline DerivativesTomokichiro Fujisawa1959 Volume 79 Issue 6 Pages 848-849
Published: June 25, 1959
Released on J-STAGE: February 19, 2010
JOURNAL FREE ACCESS3, 4-Methylenedioxybenzyl methyl ketone (II) was led to 1-methyl-4-(3, 4-methylenedioxyphenyl)-4-piperidyl methyl ketone (IV). Pfitzinger reaction of (II) afforded 2-methyl-3-(3, 4-methylendioxyphenyl) cinchoninic acid (VIII).View full abstractDownload PDF (257K) -
Eiichi Suenaga1959 Volume 79 Issue 6 Pages 850-852
Published: June 25, 1959
Released on J-STAGE: February 19, 2010
JOURNAL FREE ACCESSOf the heterocyclic formazyl derivatives, {2-[2-Pyridyl(2-carboxyphenylazo)methylene]hydrazino} benzene was prepared by Sehan, who reported that it formed a coördinated, unsaturated cobalt complex salt. In the present series of work, a heterocyclic formazyl compound, in which the pyridine and benzene rings are interchanged, was synthesized in order to find if the complex salt formed by reaction with a metal ion is an abnormal complex as obtained by Sehan and others.View full abstractDownload PDF (590K) -
Joji Yamada1959 Volume 79 Issue 6 Pages 852-853
Published: June 25, 1959
Released on J-STAGE: February 19, 2010
JOURNAL FREE ACCESSFor the purpose of finding progestational substances of long duration, several esters of 17α-methyl-19-nortestosterone and 17α-ethynyltestosterone were prepared and their follicular hormonal activity was examined by the modified method of Clauberg and of Allen-Corner methods. No increase in efficacy or its duration was found by the esterification of these compounds, in oral administration.View full abstractDownload PDF (331K) -
Hideo Matsumaru1959 Volume 79 Issue 6 Pages 854-855
Published: June 25, 1959
Released on J-STAGE: February 19, 2010
JOURNAL FREE ACCESSDownload PDF (251K) -
1959 Volume 79 Issue 6 Pages e1a
Published: 1959
Released on J-STAGE: February 19, 2010
JOURNAL FREE ACCESSDownload PDF (109K) -
1959 Volume 79 Issue 6 Pages e1b
Published: 1959
Released on J-STAGE: February 19, 2010
JOURNAL FREE ACCESSDownload PDF (109K) -
1959 Volume 79 Issue 6 Pages e1c
Published: 1959
Released on J-STAGE: February 19, 2010
JOURNAL FREE ACCESSDownload PDF (109K) -
1959 Volume 79 Issue 6 Pages e1d
Published: 1959
Released on J-STAGE: February 19, 2010
JOURNAL FREE ACCESSDownload PDF (109K) -
1959 Volume 79 Issue 6 Pages e1e
Published: 1959
Released on J-STAGE: February 19, 2010
JOURNAL FREE ACCESSDownload PDF (109K) -
1959 Volume 79 Issue 6 Pages e1f
Published: 1959
Released on J-STAGE: February 19, 2010
JOURNAL FREE ACCESSDownload PDF (109K) -
1959 Volume 79 Issue 6 Pages e1g
Published: 1959
Released on J-STAGE: February 19, 2010
JOURNAL FREE ACCESSDownload PDF (109K)