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Volume 88, Issue 9
Displaying 1-26 of 26 articles from this issue
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MASATSUGU MATSUMOTO, MICHIHIKO MIYAZAKI, MASABUMI ISHII1968 Volume 88 Issue 9 Pages 1093-1096
Published: September 25, 1968
Released on J-STAGE: May 30, 2008
JOURNAL FREE ACCESSDuring examination of controlled potential electrolytic reduction of pyridoxal oxime, its I-E curve was examined and a characteristic curve showing a maximum was obtained. This fact suggested that it would be possible to effect different electrolytic reactions by selecting the cathode potential suitably. Controlled potential electrolysis was carried out with the cathode potential at -0.8 and -1.4 V vs. S.C.E., and it was found that pyridoxamine dihydrochloride and 4-deoxypyridoxine hydrochloride were formed respectively in approximately quantitative yield. Constant-current electrolytic reduction of pyridoxal oxime at a higher current density than that already reported was found to give 4-deoxypyridoxine hydrochloride in approximately quantitative yield. This product was also obtained almost quantitatively by constant-current electrolytic reduction of pyridoxine and pyridoxal, and the route of this electrolytic reaction was presumed.View full abstractDownload PDF (572K) -
YOSHIKI HAMADA, KUNIHIRO UEDA1968 Volume 88 Issue 9 Pages 1097-1102
Published: September 25, 1968
Released on J-STAGE: May 30, 2008
JOURNAL FREE ACCESSWith 80 kinds of thiocyanic derivatives, having been synthesized so far, the pot test against rice blast disease was examined and the correlation between chemical structures and antibacterial activities was studied. Some of the effective compounds were further examined by the field test and the results were described.View full abstractDownload PDF (495K) -
TEISUKE OKANO, KAZUYUKI TSUJI1968 Volume 88 Issue 9 Pages 1103-1111
Published: September 25, 1968
Released on J-STAGE: May 30, 2008
JOURNAL FREE ACCESSInteraction between carcinogenic 4-nitroquinoline 1-oxide (4-NQO) and thiamine has been investigated. When required, we used a model compound which contained a thiazolium or a pyrimidine as part of the thaimine molecule and we found out that either molecular complexation or substitution reaction between 4-NQO and thiamine took place in acid or alkaline region, respectively. The difference spectra of acid mixtures of 4-NQO and thiamine exhibited an absorption maximum in the vicinity of 400 mμ. Spectrophotometric examinations were made on the effects of pH and polarity of solvents upon the complex formation, the molar ratio (1 : 1) and ε, K, and ΔH values of the complex. It was found that the interaction was best explainable in terms of n-π type charge transfer between thiamine and 4-NQO, wherein the pyrimidine moiety of the former acts as electron donor and the latter as electron acceptor. The substitution reaction between 4-NQO and thiamine in alkaline solution was exhibited by the appearance of a new absorption band around 360 mμ region of the spectrum of the mixture as well as by the liberation of nitrite ion from the reaction mixture. Quantitative examination was made on the nitrite ion liberation reaction, and the involvement of thiol group of thiamine and nitro group of 4-NQO was presumed. A chemical structure is proposed for the reaction product, which was separated by paper chromatography. Non-carcinogenic 4-nitropyridine 1-oxide also formed a molecular complex with thiamine in acid medium, but it gave no detectable reaction with the vitamin in alkaline medium.View full abstractDownload PDF (908K) -
TEISUKE OKANO, SHUJIRO GOYA, TAKEO TAKAHASHI1968 Volume 88 Issue 9 Pages 1112-1117
Published: September 25, 1968
Released on J-STAGE: May 30, 2008
JOURNAL FREE ACCESSStudies have been carried on the syntheses of 1-cyclohexyl derivatives of uracil, 5-bromouracil, thymine, cytosine, 4-thiouracil, and 2, 4-dithiouracil. 1-Cyclohexyluracil (V) was synthesized through dehydrogenation of 1-cyclohexyl-5, 6-dihydrouracil (III) which was obtained by treating ethyl N-cyclohexyl-β-alaninate with potassium cyanate in acid medium. 1-Cyclohexyl-5-bromouracil (VII) was prepared by dehydrobromination of 5, 5-dibromo derivative of III. 1-Cyclohexylthymine (XII) was synthesized by dehydrogenation of 1-cyclohexyl-5, 6-dihydrothymine (X) obtained through cyclization of methyl N-cyclohexyl-β-aminoisobutylate (IX). Thiation of V gave 1-cyclohexyl-4-thiouracil (XIII), which was treated further with alcoholic ammonia in a sealed tube to yield 1-cyclohexylcytosine (XIV). XIII was also obtained by dehydrogenation of 1-cyclohexyl-5, 6-dihydrothiouracil (XVI) derived from III. We describe then the ultraviolet spectrophotometric properties of 1-cyclohexylsubstituted pyrimidines thus obtained.View full abstractDownload PDF (662K) -
TOZABURO KURIHARA, HIDEO TAKEDA, HIDEO ITO, KEIKO SAGAWA1968 Volume 88 Issue 9 Pages 1118-1122
Published: September 25, 1968
Released on J-STAGE: May 30, 2008
JOURNAL FREE ACCESSA new method of synthesizing 3-substituted-3, 4-dihydro-2H-1, 4 -benzoxazine from o-nitrophenylglycidylether (I) was investigated. The dehydration, with Al2O3 or sulfuric acid, of 3-dialkylamino-1-(o-aminophenoxy)-2-propanol (II) which was prepared from I after undergoing amine cleavage and reduction, afforded 3-dialkylamino-3, 4-dihydro-2H-1, 4-benzoxazine (III) in good yields. III was also synthesized from chlorinated compound of II, 3-dialkylamino-1-(o-aminophenoxy)-2-chloropropane hydrochloride, when it was warmed with dilate alkaline solution. This ring formation can be applied to synthesizing 4-alkyl-3-dialkylaminomethyl-, (or 3-alkoxy-)3, 4-dihydro-2H-1, 4-benzoxazine from the corresponding phenoxy-propanold erivatives. 3-Substituted-3, 4-dihydro-2H-1, 4-benzothiazine was also synthesized by the same reaction from 3-dialkylamino-1-(o-aminophenylthio)-2- propanol with a satisfactory yield. 3-Dialkylamino-1-(o-aminophenoxy)-2-propanone obtained from II, when closed, afforded 3-dialkylamino-2H-benzoxazine. This compound, after being hydrogenated, was identified with III.View full abstractDownload PDF (646K) -
TETSUJI KAMETANI, SEIICHI TAKANO, SATOSHI HIBINO1968 Volume 88 Issue 9 Pages 1123-1127
Published: September 25, 1968
Released on J-STAGE: May 30, 2008
JOURNAL FREE ACCESSFor the purpose of accomplishing the total syntheses of ochotensine (I) and ochotensimine (II), an interesting synthetic route was carried out successfully as shown in chart 3. After protection of the hydroxyl and amino groups in 1-benzyl-1-isoquinoline-carboxylic acid derivative (XI), obtained by phenolic cyclization of 3-hydroxy-4-methoxyphenethylamine with (3, 4-methylenedioxyphenyl) pyruvic acid (X), to ethoxycarbonyloxy derivative (XV), this was cyclized with polyphosphoric acid ester to give the compound (XVI) having a spiro ring similar to ochotensine (I).View full abstractDownload PDF (563K) -
MASAYUKI NAKAGAKI, MASAO KOBAYASHI1968 Volume 88 Issue 9 Pages 1128-1134
Published: September 25, 1968
Released on J-STAGE: May 30, 2008
JOURNAL FREE ACCESSSolubility of magnesium hydrogen l-aspartate was examined. This salt is very easily soluble in water but hardly dissolves in organic solvents. In a mixture of water and organic solvents miscible with water, such as methanol, ethanol, propanol, and acetone, the salt distributes between the two layers, forming a dilute solution of the salt in the upper layer and a concentrated solution in the lower layer. The solubility of the slat in the upper layer increases exponentially with the molar fraction of water in the upper layer and the solubility is not affected by temperature. Analysis was carried out on the propanol-water-aspartate system in the upper and lower layers, three-componental phase diagram was prepared, and the Plait point, at which the upper and lower layers agreed, was calculated. It was also found that the exponential function established between the solubility in the upper layer and molar fraction of water thereof is also applicable to the lower layer.View full abstractDownload PDF (718K) -
SEIGO FUKUSHIMA, TADATAKA NORO, YASUHISA SAIKI, AKIRA UENO, YUKIO AKAH ...1968 Volume 88 Issue 9 Pages 1135-1142
Published: September 25, 1968
Released on J-STAGE: May 30, 2008
JOURNAL FREE ACCESSThree sorts of new compounds have been isolated from Leptorumohra miqueliana H. ITO (=Polystichopsis miqueliana TAGAWA) (Aspidiaceae) and they have been named leptorumolin, leptorumol and protofarrenol. Their melting points and molecular formula are as follows : leptorumolin (I), mp 218°, C18H22O8 ; leptorumol (II), mp 254°, C11H10O4 ; and protofarrerol, mp 210°, C17H18O6. In this report, by means of the nuclear magnetic resonance, ultraviolet, infrared and mass spectrum analyses, as well as degradation reactions, the structure of II was determined to be 5, 7-dihydroxy-6, 8-dimethylchromone, and I is also confirmed to be 4-methoxy-D-glucoside of II, whose binding site is at 7-position of chromone ring. On the other hand, from the starting material of 3, 4-dimethylphoroacetophenone, 5, 7-dihydroxy-6, 8-dimethylchromone (II) was synthesized successfully.View full abstractDownload PDF (826K) -
MASAO TOMITA, SHENG-TEH LU, SAN-JYI WANG, CHI-HO LEE, HSUEH-TSAN SHIH1968 Volume 88 Issue 9 Pages 1143-1147
Published: September 25, 1968
Released on J-STAGE: May 30, 2008
JOURNAL FREE ACCESSFrom the duramen of Magnolia hachirachirai DANDY, which was maintained for 7 years after the collection, bases shown in Table I have been isolated. Among them, base C, orange yellow needle crystals, mp 225-226° (decomp.), [α]D ±0° (CHCl3), C20H17O5N, has been identified to be 1, 2, 9, 10-tetramethoxy-7H-dibenzo[de, g]quinoline-7-one (V). Base D, whose HBr salt, being colorless columnar crystals, mp 248-250°, [α]D +102° (MeOH), has been certified to be d-N-norglaucine (II), which is coincident with N-methyl derivatives of d-glaucine (II). As it is previously reported, immediate treatment after the collection of Magnolia kachirachirai DANDY afforded d-glaucine (I) as a main base, however, 7 years after the collection, the main base was to be 1, 2, 9, 10-tetramethoxy-7H-dibenzo[de, g]quinoline-7-one (V), besides a trace of d-glaucine (I).View full abstractDownload PDF (599K) -
SAN-JYI WANG, SHOU-HO CHENG1968 Volume 88 Issue 9 Pages 1148-1150
Published: September 25, 1968
Released on J-STAGE: May 30, 2008
JOURNAL FREE ACCESSBy the investigation of alkaloid components in stems and roots of Illigera luzonensis (PERSL) MERR. (Hernandiaceae) (Japanese name "tengunohana"), actinodaphnine (VIII) was isolated and certified.View full abstractDownload PDF (400K) -
ATSUSHI NUMATA, KOSEI OHNO, HIROSHI IRIE, SHOJIRO UYEO1968 Volume 88 Issue 9 Pages 1151-1162
Published: September 25, 1968
Released on J-STAGE: May 30, 2008
JOURNAL FREE ACCESSIn the course of an investigation on the structure of enmein (I), isolated from Isodon trichocarpus, five well-characterized products (IV-VIII) were obtained by pyrolysis of bisdehydrodihydroenmein (II). In the present paper, synthesis of two (V and VI) of those compounds which obviously originated from ring A of compound (II) is reported. The former compound, 6-hydroxy-7-methylphthalide (V), was prepared in the following way. Chloromethylation of m-methoxybenzoic acid under the forcing conditions gave a mixture of compounds consisting of X, XI, and XII which were separated by fractional crystallization. Hydrogenation of XI followed by treatment with hydriodic acid yielded V, identical with one of the pyrolysis products mentioned above. The latter compound (VI) was synthesized by two alternative methods. First, compound (XXII) was treated with thionyl chloride to give XXIII which was then subjected to bromination, followed by sodium borohydride reduction, giving XXXI. The resulting XXXI was subsequently dehydrobrominated to give XXXII, which on oxidation, followed by C-methylation, gave a compound which was identical with VI. The other method used to produce VI involves first the addition of dimethyl acetylenedicarboxylate to butadiene. The resulting diester (XLVII) was converted to the anhydride (XLVIII) and then reduced with lithium aluminum hydride, giving XLIX. Treatment of this with NBS yielded LII which was debrominated by treatment with Raney Ni. The resulting hydroxy-lactone (LIII) was oxidized and then C-dimethylated to yield VI.View full abstractDownload PDF (1354K) -
TETSUJI KAMETANI, KUNIYOSHI SAKURAI, HIDEO IIDA1968 Volume 88 Issue 9 Pages 1163-1167
Published: September 25, 1968
Released on J-STAGE: May 30, 2008
JOURNAL FREE ACCESSHydrolysis of O, O, O-tribenzylberbamunine type compounds, which were obtained by Ullmann reaction of l-7, 4'-O, O-dibenzyl-3'-bromo-N-methylcoclaurine (VI) with d-7-benzyl-N-methylcoclaurine (VII) and l-VII, gave berbamunine (I) and the compound (IX), respectively. Methylation of the latter compound (IX) with diazomethane gave O-methyldauricine. On the other hand, the same methylation of the former optically active berbamunine (I) afforded O, O, O-trimethylberbamunine (III).View full abstractDownload PDF (553K) -
AYA NITTA, HIROSHI IRIE1968 Volume 88 Issue 9 Pages 1168-1169
Published: September 25, 1968
Released on J-STAGE: May 30, 2008
JOURNAL FREE ACCESSBy application of Horeau's method and the benzoate rule to hamaudol mono methyl ether (II), the absolute configuration of hamaudol (I) has been established to be represented by formula (IV).View full abstractDownload PDF (370K) -
TEISUKE OKANO, KAZUO OHIRA1968 Volume 88 Issue 9 Pages 1170-1178
Published: September 25, 1968
Released on J-STAGE: May 30, 2008
JOURNAL FREE ACCESSPolarographic behaviors of pyrazine (I), 2, 5-dimethylpyrazine (II), 2, 3, 5, 6-tetramethylpyrazine (III), 3-hydroxy-2, 5-dimethylpyrazine (IV), 3-methoxy-2, 5-dimethyl-pyrazine (V), 3-chloro-2, 5-dimethylpyrazine (VI), 1-oxides and 1, 4-dioxides of I, II, and III, and 1-oxides of IV, V, and VI at various pH values have been investigated. Whereas in acid region the polarographic waves of N-oxide groups were characteristic of diffusion as well as kinetic currents, in alkaline region they were characteristic exclusively of kinetic current, and it was presumed that at lower pH-values N-oxide group is reduced in its protonated form. In acid media, 1-oxides of I, II, and III exhibited double waves, the first of which being attributable to reduction of N-oxide groups and the second to that of the pyrazine nucleus (production of 1, 4-dihydro compounds). Reduction of the two N-oxide groups of 1, 4-dioxide of I proceeded simultaneously. In the case of 1-oxides of IV and V' N-oxide group and pyrazine nucleus were reduced simultaneously ; V was reduced further to piperazine compound. The cause of the different polarographic reductivities of IV and V was ascribed to a difference in their tautomeric forms. The first wave of 1-oxide of VI was attributable to reduction of the N-oxide group, and the second wave to reduction which involves hydrogenation of the nitrogen atoms of the ring and, at the same time, detachment of the chloro radical from the ring. The detachment of chlorine was confirmed further through controlled-potential electrolysis. The proposed sequences of reduction were given in charts.View full abstractDownload PDF (883K) -
TEISUKE OKANO, AKIRA TAKADATE1968 Volume 88 Issue 9 Pages 1179-1184
Published: September 25, 1968
Released on J-STAGE: May 30, 2008
JOURNAL FREE ACCESSFluorine nuclear magnetic resonance (NMR) spectra of the following derivatives of pyrimidine (Py) at 60 Mcps in dimethyl sulfoxide, with trifluoroacetic acid as internal standard, have been obtained and examined : 2, 4, 6-trifluoro-Py (I), 4-amino-2, 6-difluoro-Py (II), 4-amino-2, 6-difluoro-5-methyl-Py (III), 4-amine-2-fluoro-6-methyl-Py (IV), 4-amino-2-fluoro-5, 6-dimethyl-Py (V), 6-fluoro-4-hydroxy-5-methyl-Py (VI), 4-amino-6-fluoro-5-methyl-Py (VII), 2-amino-4-fluoro-6-methyl-Py (VIII), 2-amino-4, 6-difluoro-Py(IX), 2-amino-4, 6-difluoro-5-methyl-Py(X), 6-fluoro-4-hydroxy-2-methyl-Py (XI), 4-amino-6-fluoro-2-methyl-Py (XII), 6-fluoro-4-hydroxy-2, 5-dimethyl-Py (XIII), 4-amino-6-fluoro-2, 5-dimethyl-Py(XIV), 4, 6-difluoro-2-phenyl-Py(XV), 4, 6-difluoro-5-phenyl-Py(XVI), 4-amino-6-fluoro-2-phenyl-Py(XVII), and 4-amino-6-fluoro-5-phenyl-Py(XVIII). 19F signals of these compounds were rather broadened by 14N quadrupolar relaxation. The NMR signals of 2-position fluorines occurred in lower magnetic field (for I-V, δ=-20.05--31.97 ppm) than those of 4-or 6-position fluorines (for VI-XVIII, δ=-0.50-21.79ppm). Discussion was made on the influence of substituents on the 2- as well as 4(6)-fluorine chemical shifts. It was revealed that substituent effects were expressed more markedly in the 19F NMR spectra than in the 1H NMR spectra of the corresponding non-fluorinated compounds. Smaller spin-spin coupling constants were obtained for J4(6)F-5H (I, II, VIII, IX, and XII, J=1.3-3.3 cps) than for J2F-5H(IV, J=4.7 cps). An approximate parallelism was found to exist between 19F chemical shifts and electron densities at the carbon atoms adjacent to fluorines.View full abstractDownload PDF (727K) -
TETSUJI KAMETANI, HIDEO IIDA, TOYOHIKO KIKUCHI1968 Volume 88 Issue 9 Pages 1185-1188
Published: September 25, 1968
Released on J-STAGE: May 30, 2008
JOURNAL FREE ACCESSMannich reaction of 1-(3-hydroxy-4, 5-dimethoxybenzyl)-6, 7-dimethoxy-1, 2, 3, 4-tetrahydroisoquinoline (VII) hydrochloride with formalin afforded compound (Ia), which was cyclized in the ortho position of the hydroxyl group. On the other hand, Mannich reaction of O-benzyl derivative (VI) in 98% acetic acid and 37% formalin afforded both compounds (VIIIa and VIIIb), which were debenzylated with ethanolic hydrochloric acid to give stepharotine (I) and protoberberine (Ia), respectively. This fact reveals that the cyclization of VI was taken place in both positions of the ortho and para orientation against benzyloxy group.View full abstractDownload PDF (479K) -
HARUO SAIKACHI, KEIJI TAKAI1968 Volume 88 Issue 9 Pages 1189-1196
Published: September 25, 1968
Released on J-STAGE: May 30, 2008
JOURNAL FREE ACCESSCurtius degradation was attempted with new compounds, 5-nitro-2-furoyl azide and (5-nitro-2-furyl) acryloyl azide, and the amount of the corresponding products of unstable 5-nitro-2-furyl isocyanate and (5-nitro-2-furyl) vinyl isocyanate has been confirmed by the IR analysis. Among the isocyanates, the 5-nitro-2-furyl compound was reacted with 16 amines, 5 alcohols and 5 thiols to give carbamoylamines, carbamates and thiocarbamates, respectively. (5-nitro-2-furyl) vinyl compound was reacted with 14 amines, alcohols and p-methoxyphenol to afford corresponding carbamoylamine and carbamates respectively.View full abstractDownload PDF (743K) -
YOSHIHISA ARAI, KINGO ENOMOTO1968 Volume 88 Issue 9 Pages 1197-1207
Published: September 25, 1968
Released on J-STAGE: May 30, 2008
JOURNAL FREE ACCESSIsoquinoline derivatives were classified into five types according to the substituents at 1-position and the relationship between chemical structures and toxicities was investigated. LD50 tended to become lower with increasing degrees of hydrogenation of the isoquinoline ring. In 1-alkyl substituted isoquinoline derivatives LD50 became higher as the number of carbon branches of the 1-alkyl residue increased. Pathological changes were caused by almost all 1-alkyl substituted compounds, especially the ones possessing a tertiary alkyl residue at 1-position. In the cases of 1-aryl and 1-aralkyl substituted compounds, the swelling of liver depended on the simultaneous presence of the methylenedioxy residues at 3', 4'-position of the terminal phenyl residue of the 1-substituent and at 6, 7-position of the isoquinoline ring. However, no pathological change was observed with 1-(2-methylbutyl)-3-methyl-6, 7-methylenedioxyisoquinoline·HCl (B-15) and 1-neopentyl-3-methyl-6, 7-methylenedioxyisoquinoline·HCl (B-33). These compounds showed marked inhibitory action on the experimental tumors as described in a previous paper. From the above observation, it was suggested that the compounds possessing a methylene residue between 1-carbon of the isoquinoline ring and a secondary-or tertiary-alkyl residue in the 1-alkyl substituent would have an anti-tumor activity and little side effect.View full abstractDownload PDF (1093K) -
TATSUO OZAWA, SATOSHI NAGAOKA, NAOHIDE KINAE1968 Volume 88 Issue 9 Pages 1208-1213
Published: September 25, 1968
Released on J-STAGE: May 30, 2008
JOURNAL FREE ACCESSWhen an ethanol solution, in which were dissolved N-aryl-glucosylamine (I) (1 mole) and arylamine (1-1.5 mole) was allowed to stand at room temperature, N, N'-diarylform-amidine salt of D-arabonic acid (III) was initially precipitated (after 1-2 weeks). Secondly 1-aryl-benzimidazol (VI) (VIa, 4' : CH3, 6 : CH3 VIb, 4' : OCH3, 6 : OCH3) and N, N'-diaryloxalamide (VII) were precipitated after a lapse of 30 to 60 days. Finally N, N'-diarylurea (VIII) and azobenzene derivative (IX) were deposited after 40 to 80 days' keep standing. Deposits were all seperated from the residual solution, ethanol being evaporated. The remaining non-volatile residue was extracted with boiling water, and N-aryl-D-arabonamide (IV) was obtained as a water soluble fraction. Similarly, by allowing to stand at room temperature, III, IV, VI and VII were also obtained from the ethanol solution of arylamine and 1-deoxy-1-arylamino-D-fructose (II), Amadori rearranged compound, derived from I. Carbon chain of glucose is decomposed fragmentally at the bond C1-C2 to give arabonic acid formed from the bond C2-C6. By the reaction of arylamine with the fragment C1 separated from the bond C1-C6 of glucose, V, VI, VII and VIII are formed by autoxidation free radically. In the basic ethanol solution of arylamine, the reaction of II with arylamine may possibly proceed in the reverse course to Amadori rearrangement, and the hydrogen at C3 of enaminol (Chart 3), which appears in both courses, is pulled out to form free radical X1. By the intramolecular rearrangement, X is formed from X1. Thus the peroxide begins to initiate the decomposition between C1-C2 of X.View full abstractDownload PDF (684K) -
NAOKATA MORITA, MINEO SHIMIZU, MUNEHISA ARISAWA1968 Volume 88 Issue 9 Pages 1214-1217
Published: September 25, 1968
Released on J-STAGE: May 30, 2008
JOURNAL FREE ACCESSIn continuation of previous studies, components of the plants of Fagara genus were examined. Pale yelloy prisms, mp 110-112°, were isolated in 0.03% yield from the fresh leaves of Fagara okinawensis NAKAI, This substance was identified as 2-hydroxy-3, 4, 6-trimethoxyacetophenone by comparison with synthesized sample and was named xanthoxylone. Diosmin (0.01%) and hesperidin (0.03%) were also isolated from its leaves, and skimmianine (0.1%) and hesperidin (0.48%) from the tree bark. From Fagara cuspidata ENGL, linarin-like substance was isolated from the fruit rind in 0.66% yield, poncirin (0.05%) from the leaves, and hesperidine from the tree bark and root bark in respective yield of 0.05 and 0.66%. Ethyl acetate extract of the root bark of Fagara nitida ROXB. yielded 0.03% of vitexin, and the etheral extract of the root bark of Fagara ailanthoides var. yakumontana SUGIMOTO yielded 0.21% of xanthyletin and the methanolic extract yielded 0.2% of hesperidin.View full abstractDownload PDF (531K) -
JUTARO OKADA, SHUSHI MORITA, YOSHIHISA MIWA1968 Volume 88 Issue 9 Pages 1218-1226
Published: September 25, 1968
Released on J-STAGE: May 30, 2008
JOURNAL FREE ACCESSAmmoxidation of benzaldehyde by using oxygen gas as an oxidant was examined in methanolic solution at 30°, in the presence of cupric chloride and sodium methylate catalysts, and kinetics of the reaction was studied. The reaction is a complex one, which proceeds summarily according to the following scheme : [chemical formula] The order and the rate constant of each reaction were determined (Table I). It was found that the rate constants, k1, k-1, k2, k-2, are affected by the concentration of catalysts (Table I, II, III), and that the activity of cupric chloride decreases during reaction (Fig.4, 5). The rate of reaction of benzaldehyde, the rate of formation of benzylidenimine and benzonitrile were determined as the equations, (19), (20) and (10), respectively.View full abstractDownload PDF (782K) -
SHOJI HARA1968 Volume 88 Issue 9 Pages 1227-1234
Published: September 25, 1968
Released on J-STAGE: May 30, 2008
JOURNAL FREE ACCESSNew methods of synthesis of the 2-oxo-A-norsteroids (1a, b), starting materials for preparation of 2-oxa-3-oxo-steroids (2a, b) by Baeyer-Villiger reaction, were described. (1) 2-Hydroxymethylene-3-oxosteroids (5a, b) were oxidized with ozone and then with hydrogen peroxide to obtain 2, 3-secosteroid-2, 3-dioic acids (6a, b). By heating with acetic anhydride, the hydroxyl groups in the seco acids (6a, b) were protected as the acetates, and the dicarboxylic groups were changed to acid anhydrides (7a, b) simultaneously. The anhydrides (7a, b) were heated and pyrolysed at 160-180° (bath temperature : 180-240°). When a more higher temperature was used, various side reactions occurred and the yield was minimized. (2) 2, 3-Secosteroid-2, 3-dioic acids (6a, b) were esterified by diazomethane or 1-2% hydrogen chloride in methanol. Dimethyl esters (12a, b) or their acetates (13a, b) were heated with sodium hydride and methanol in toluene to produce 3ξ-carbomethoxy-2-oxo-A-norsteroids (14a, b or 15a, b), which were hydrolyzed by dilute alkali at room temperature. Saponification products (16a, b) were decarboxylated by heating in acetic acid or acetic anhydride to produce 2-oxo-A-norsteroids (1a, b or 8a, b) in excellent yields. The characteristics of the second synthetic route were as follows : purification of the intermediates was not necessary and the purity of the end products was very high.View full abstractDownload PDF (812K) -
YOSHIAKI KAMANO, YASUHIDE TACHI, TATEO OTAKE, MANKI KOMATSU1968 Volume 88 Issue 9 Pages 1235-1241
Published: September 25, 1968
Released on J-STAGE: May 30, 2008
JOURNAL FREE ACCESSAqueous extract of the air-dried leaves and branches of Quercus stenophylla MAKINO (Japanes name "Urajirogashi") formed a precipitate on addition of lead acetate and from this precipitate, ellagic acid, succinic acid, catechol, pyrogallol, gallic acid, 3, 3'-di-O-methylellagic acid, quercetin, kaempferol, β-D-glucogallin, and isoquercitrin were isolated and identified. Examination of tannin in this plant showed that the so-called 'Urajirogashi' tannin is a hydrolysable tannin and consists of ellagitannin and gallotannin.View full abstractDownload PDF (682K) -
SHUZO TAKAGI, TOYOSHI KATAGI, KEIKO TAKEBAYASHI1968 Volume 88 Issue 9 Pages 1242-1244
Published: September 25, 1968
Released on J-STAGE: May 30, 2008
JOURNAL FREE ACCESSSeparation of some Aconitum alkaloids by gas chromatography of trimethylsilyl ethers were attempted successively. The stationary liquid phases used were SE-30 (3%), OV-1 (5%), OV-17 (3%), and XE-60(3%). Retention times and chromatograms are shown in Table I and Figure 1 and 2 respectively. With a OV-17 column, kobusine and pseudo-kobusine were not well separated, and with a XE-60 column, in addition, benzoylaconine was not detected. The better chromatograms were obtained using a non-polar column (SE-30 or OV-1).View full abstractDownload PDF (434K) -
YOSHIAKI OHNISHI, MIYOJI HANAOKA1968 Volume 88 Issue 9 Pages 1244-1245
Published: September 25, 1968
Released on J-STAGE: May 30, 2008
JOURNAL FREE ACCESSFriedelin was isolated from the ethyl acetate extract of the leaves of Quercus stenophylla MAKINO by the purification through alumina column chromatography.View full abstractDownload PDF (367K) -
YOSHIAKI KAMANO, YASUHIDE TACHI, TATEO OTAKE, MANKI KOMATSU1968 Volume 88 Issue 9 Pages 1246-1249
Published: September 25, 1968
Released on J-STAGE: May 30, 2008
JOURNAL FREE ACCESSFrom the petr. ether extracts of the air-dried leaves and branches of Quercus stenophylla MAKINO (Japanese name "Urajirogashi"), n-paraffins, friedelin (I), epi-friederanol (II), friedelanol (III) and taraxerol (IV) were isolated by column chromatography on silicagel, and were identified. In addition, the components of n-paraffins were investigated by gas chromatography, and were confirmed to contain pentacosane (V) (3%), heptacosane (VI) (40%), nonacosane (VII) (28%) and hentriacontane (VIII) (20%).View full abstractDownload PDF (447K)
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