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Volume 30, Issue 4
Displaying 1-50 of 67 articles from this issue
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KENICHI FUKUHARA, ASAO NAKAMURA, MASAMICHI TSUBOI1982 Volume 30 Issue 4 Pages 1121-1125
Published: April 25, 1982
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESSHigh performance liquid chromatography of aldohexoses, the corresponding 6-deoxy derivatives, and several malto-oligosaccharides has been examined with a Hitachi #3013-N column, and with aqueous CH3CN eluents, at various temperatures. It has been shown that when the concentration of CH3CN in the eluent is higher than 30%, the system works as a partition chromatography, whereas with pure phosphate buffer eluent (H2O) it works as a gel filtration column. Some of the values of the free energy ΔG°and enthalpy ΔH°, assignable to the glucose residue and the 6-OH group in some particular states have been estimated. A possible use of such thermodynamic functions in medicinal chemistry is suggested.View full abstractDownload PDF (506K) -
YOSHINOBU GOTO, TOKIHIRO NIIYA, NORIKO HONJO, TAKAO SAKAMOTO, HIROSHI ...1982 Volume 30 Issue 4 Pages 1126-1133
Published: April 25, 1982
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESSThe experimental data on the relative reactivity of active methyl groups in a given molecule for various pyridines, pyrimidines, and their N-oxide and oxo derivatives were compared with the charge transfer ability (CTA) values calculated by the CNDO/2 method. The reactivity of active methyl groups of these compounds was examined in nitrosation and deuterium exchange reactions, and the CTA values were calculated in the deprotonation step of these reactions. The calculated values were in good accord with the experimental results. In particular, the experimental values for the N-oxides could be well interpreted in terms of the CTA values only when the calculations were performed in the conformation in which a 1 : 1 complex of sodium ion with the N-oxides was formed.View full abstractDownload PDF (732K) -
MASATOSHI TOGAMI, IKUE TAKEUCHI, FUMITAKE IMAIZUMI, MASATO KAWAKAMI1982 Volume 30 Issue 4 Pages 1134-1140
Published: April 25, 1982
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESSFrom bagasse medium on which mycelia of Lentinus edodes (BERK.) SING. had been grown, an acidic polysaccharide (fraction C-1-2) was isolated by deproteinization, removal of nucleic acid, fractionation with barium hydroxide and DEAE-cellulose column chromatography. The purified polysaccharide consisted mainly of xylose, arabinose, mannose, galactose, glucose and uronic acid in a molar ratio of 1.4 : 0.7 : 2.0 : 0.9 : 1.0 : 1.5. The tumor inhibition ratio of the polysaccharide against solid sarcoma 180 was 87.9% in mice given doses of 100 mg/kg×10 d by intraperitoneal administration and the tumors in 5 of 10 mice completely regressed.View full abstractDownload PDF (762K) -
MASAAKI MATSUO, KIYOSHI TANIGUCHI, IKUO UEDA1982 Volume 30 Issue 4 Pages 1141-1150
Published: April 25, 1982
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESSThe synthesis and pharmacological properties of 7-chloro-5-(2-chlorophenyl)-2-(2-dimethylaminoethylthio)-3H-1, 4-benzodiazepine (III-1) and related compounds are described. Compound III-1 was prepared from the thiolactam (II-1) by treatment with 2-dimethylaminoethyl chloride in the presence of base in aqueous methanol and 7-chloro-5-(2-ohlorophenyl)-2-methoxy-3H-1, 4-benzodiazepine (IV) was obtained as a by-product. The latter (IV) was hydrolyzed in acid medium to give methyl (E)-[2-amino-5-chloro-α-(2-chlorophenyl) benzylidene] aminoacetate (syn-form) (XIX), which was converted into the 1, 4-benzodiazepine (I-1) by further acid treatment. Compound XIX isomerized to the corresponding anti-form (XXII) on heating. Most of the compounds prepared had an effect similar to that of diazepam in causing taming and anticonvulsant effects in mice.View full abstractDownload PDF (954K) -
MASAO FUJITA, MASAHIRO NAGAI, TAKAO INOUE1982 Volume 30 Issue 4 Pages 1151-1156
Published: April 25, 1982
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESSThe O-methylation effect on the carbon-13 nuclear magnetic resonance (13C-NMR) chemical shifts of aryl carbons of the ortho-monosubstituted phenols has been investigated. In phenols with nonconjugated substituents (2-11), O-methylation caused an upfield shift by an average of 4.1 ppm for the ortho-methine carbon (C-6), whereas it caused a downfield shift by an average of 1.1 ppm for the substituted ortho-carbon (C-2). This regularity is very useful for the spectral interpretation of some natural products with an ortho-substituted phenol group, such as flavonoids (16-20 and 22). The O-methylation effect of phenols 12-15 with conjugated ortho-substituents on the aryl carbons, especially C-1, C-2 and C-5, differed significantly from that observed in 2-11. On the basis of a limited number of examples, the O-ethylation effect on aromatic carbons seems similar to the O-methylation effect.View full abstractDownload PDF (683K) -
YOSHIAKI FURUYA, HIROFUMI NOZAWA, TETSURO MORITA, TAKASHI MORITA, YOSH ...1982 Volume 30 Issue 4 Pages 1157-1162
Published: April 25, 1982
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESSA specific type of reaction should have a characteristic isokinetic temperature as long as the individual reactions are carried out in the same solvent and the reactions of substrates with bulky groups are excluded. Two kinds of reactions of tertiary amine with carboxylates, quaternization and aminolysis reactions, were distinguished by isokinetic temperatures of 430 and 256, respectively.View full abstractDownload PDF (581K) -
MASANORI KUROYANAGI, SEIGO FUKUSHIMA1982 Volume 30 Issue 4 Pages 1163-1168
Published: April 25, 1982
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESSNine highly oxygenated flavonoids, having eight oxygen functional groups at C-3, 3', 4', 5, 5', 6, 7 and 8, were isolated from Polygonum orientale. Of these compounds, seven (1, 2, 3a, 4, 5a, 6 and 7a) are new compounds and the structures were determined on the basis of spectral evidence as 3, 3', 5, 6, 7, 8-hexamethoxy-4', 5'-methylenedioxy-(1), 5-hydroxy-3, 3', 6, 7, 8-pentamethoxy-4', 5'-methylenedioxy-(2a), 3'-hydroxy-3, 4', 5, 5', 6, 7, 8-heptamethoxy-(3a), 3, 3', 5, 8-tetramethoxy-4', 5', 6, 7-bis (methylenedioxy)-(4), 3'-hydroxy-3, 4', 5, 5', 8-pentamethoxy-6, 7-methylenedioxy-(5a), 3, 3', 4', 5, 5', 8-hexamethoxy-6, 7-methylenedioxy-(6) and 3', 5-dihydroxy-3, 4', 5', 8-tetramethoxy-6, 7-methylenedioxyflavone (7a).View full abstractDownload PDF (764K) -
KIMIHIRO YOSHIMOTO, TAKAKO WAKAMIYA, YOSHIHIRO NISHIKAWA1982 Volume 30 Issue 4 Pages 1169-1174
Published: April 25, 1982
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESS2, 3, 2', 3'-Tetra-O-benzyl-α, α-trehalose was synthesized conveniently in improved yield according to the known pathway but under modified reaction conditions : namely, α, α-trehalose was treated with α, α-dimethoxytoluene to give its 4, 6 : 4', 6'-di-O-benzylidene derivative, which was benzylated with benzyl chloride in dimethylsulfoxide in the presence of sodium hydride, and subsequently debenzylidenated by hydrolysis with 80% acetic acid. Selective acylation of the key intermediate by reaction with 1.4 molar equivalents of stearoyl chloride, followed by catalytic hydrogenolysis over palladium black, afforded 6-O-stearoyl-α, α-trehalose, mp 116-122°C, [α]18D+108.2°(c=1.0, chloroform), and 6, 6'-di-O-stearoyl-α, α-trehalose, mp 157-160°C, [α]18D+80.8°(c=1.0, chloroform), in an approximate molar ratio of 1 : 3.8. Similarly, 4, 6, 4', 6'-tetra-O-stearoyl-α, α-trehalose, mp 95-97°C and 108-110°C (double melting point), [α]17D+54.5°(c=1.0, chloroform), was also obtained by the use of 4 molar equivalents of acid chloride. Based on comparison of the carbon-13 nuclear magnetic resonance (13C NMR) spectral data and thin-layer and gas-liquid chromatographic behavior, the major components contained in the monoand diester preparations which had been produced in our previous work by transesterification of α, α-trehalose with methyl stearate and shown to possess interesting biological activities were identified as the 6- and 6, 6'-stearates, respectively.View full abstractDownload PDF (852K) -
TOYOKICHI YOSHIDA, SHUNSUKE NARUTO, HITOSHI UNO, HARUKI NISHIMURA1982 Volume 30 Issue 4 Pages 1175-1182
Published: April 25, 1982
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESSThe reactions of the title free sulfoximide with N-bromosuccinimide (NBS) and N-chlorosuccinimide (NCS) afforded the corresponding α-halogenated"free"sulfoximides in good yields. The α-bromination proceeded via a facile N-bromination followed by a bromine transfer reaction of the resulting N-bromosulfoximide. The NCS chlorination, in contrast, proceeded via direct α-chlorination, not via N-chlorination. However, in the presence of potassium carbonate or silica gel N-chlorination occurred predominantly in the NCS chlorination.View full abstractDownload PDF (908K) -
FUMIKO ABE, TATSUO YAMAUCHI1982 Volume 30 Issue 4 Pages 1183-1193
Published: April 25, 1982
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESSCardenolide glycosides, affinosides A, C, D, E, F, G, H and J, were isolated from the stem and bark of Anodendron affine DRUCE, and their structures were elucidated. They have the same sugar moiety as affinoside B, 4, 6-dideoxy-3-O-methyl-D-glycero-D-glycero-2-hexosulopyranose, which is doubly linked to the 2α- and 3β-hydroxyl groups of the aglycone with 2'-acetal and 1'-anomeric hydroxyl groups, respectively. The aglycone of A was identified as 2α, 3β, 11α, 14-tetrahydroxy-12-oxo-14β-carda-4, 20 (22)-dienolide-7β, 8β-epoxide. The others were found to be 2α, 3β, 14-trihydroxy-11-oxo-, 2α, 3β, 12α, 14-tetrahydroxy-11-oxo-, and 2α, 3β, 5, 12α, 14-pentahydroxy-11-oxo-5β, 14β-card-20 (22)-enolide (C, E, and G, respectively), and 2α, 3β, 12β, 14-tetrahydroxy-11-oxo-14β-carda-4, 20 (22)-dienolide (F). H, D, and J were Δ16-derivatives of A, C, and F, respectively. C was hydrolyzed to the aglycone by preliminary splitting of the 2-O-2'linkage by NaBH4 reduction, followed by treatment with HCl / acetone.View full abstractDownload PDF (1217K) -
MASAYOSHI ITO, AKIKO KODAMA, KIYOSHI TSUKIDA1982 Volume 30 Issue 4 Pages 1194-1197
Published: April 25, 1982
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESSThe structure of a new chromophore in II has been confirmed by the synthesis of the tetraene III containing the tetrahydroindene skeleton.View full abstractDownload PDF (556K) -
KAZUAKI KANO, KOJI HAYASHI, HIROSHI MITSUHASHI1982 Volume 30 Issue 4 Pages 1198-1203
Published: April 25, 1982
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESSSteroids having an α-spiro β-methylene γ-lactone structure, (3R) and (3S)-4'-methylenedihydrospiro-[5α-cholestane-3, 3'(2'H)-furan]-2'-one, were synthesized from 5α-cholestan-3-one by means of the Knoevenagel reaction, conjugated addition of a cyanide ion, reduction of ester groups, hydrolysis and dehydration.View full abstractDownload PDF (833K) -
TAICHI OHMOTO, KAZUO KOIKE1982 Volume 30 Issue 4 Pages 1204-1209
Published: April 25, 1982
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESS1-Acetyl-β-carboline (I), 4, 8-dimethoxy-1-ethyl-β-carboline (II), and three new alkaloids, 4, 8-dimethoxy-1-(2-methoxyethyl)-β-carboline (III), β-carbolin-1-yl 4, 8-dimethoxy-β-carbolin-1-yl-ethyl ketone (IV) and 3-methylcanthin-2, 6-dione (V), were isolated from the root of Picrasma quassioides BENNET (Simaroubaceae). The structures were elucidated on the basis of spectroscopic studies and chemical evidence.View full abstractDownload PDF (668K) -
MASAYUKI ONDA, YAEKO KONDA, KIYOIZUMI HINOTOZAWA, SATOSHI OMURA1982 Volume 30 Issue 4 Pages 1210-1214
Published: April 25, 1982
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESSThe alkaloid AM-6201 (1) has been isolated from culture broths of Streptomyces xanthochromogenus strain AM-6201, and its structure elucidation is described.View full abstractDownload PDF (718K) -
TERUHISA FUJIMAKI, HIROTAKA OTOMASU1982 Volume 30 Issue 4 Pages 1215-1220
Published: April 25, 1982
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESSThe reaction of 2-methylphthalonimide (1) with malononitrile gave 4-dicyanomethylene-2-methylhomophthalimide (2) in 95% yield. The Michael reaction of 2 with compounds having an active methylene or methyl group (3a-d) afforded the corresponding spiro [2-methylhomophthalimide-4, 4'-(4'H-pyran)] compounds (4a-d). In contrast, the reaction of 2 with other active methylene compounds (3e-h) afforded only the same product, spiro [2-methylhomophthalimide-4, 1'-(3'-amino-2'-cyano-5', 6'-dihydro-5'-methyl-1'H-pyrano [2, 3-c] isoquinolin-6'-one)] (5), which was found to be produced by the reaction of 2 with homophthalimide in quantitative yield. All the latter reactions can be regarded as the results of retrograde Michael reactions between the reactants 2 and active methylenes (3e-h). By refluxing a methanol solution of 2 in the presence of a basic catalyst, the ringtrasformation product, methyl 1-dicyanomethyl-2-methyl-3-oxo-isoindoline-1-carboxylate (8) was obtained in 80% yield.View full abstractDownload PDF (611K) -
YASUMITSU TAMURA, HIROYUKI IKEDA, IWAO MORITA, HIDETSUGU TSUBOUCHI, MA ...1982 Volume 30 Issue 4 Pages 1221-1224
Published: April 25, 1982
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESSO-(p-Toluenesulfonyl)-N-methyl-, -N-ethyl-, and -N-isopropyl-hydroxylamines and O-mesitylenesulfonyl-N-methylhydroxylamine were prepared. The N-methyl and N-ethyl derivatives were found to react with tertiary amines and triphenylphosphine to give the corresponding N-(alkylamino) ammonium salts and P-(alkylamino) phosphonium salts, but the N-isopropyl derivative was less reactive, probably due to steric effects. These reagents also reacted with tri-n-butylborane to give the corresponding alkyl-n-butylamines.View full abstractDownload PDF (549K) -
TADASHI OKAWARA, TAKASHI MATSUDA, MITSURU FURUKAWA1982 Volume 30 Issue 4 Pages 1225-1233
Published: April 25, 1982
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESSPiperazine-2, 5-diones (2) were prepared by N-alkylation between two molecules of α-halocarboxamides (1) in the presence of a phase transfer catalyst in yields of 64-88%. β, γ, δ and ε-Lactams (6, 9 and 13) were similarly synthesized by intramolecular N-alkylation of the corresponding halocarboxamides (5, 8 and 12) under phase transfer conditions in 53-99% yields.View full abstractDownload PDF (865K) -
MASAICHIRO MASUI, YOSHIYUKI KAMADA, ETUKO SASAKI, SHIGEKO OZAKI1982 Volume 30 Issue 4 Pages 1234-1243
Published: April 25, 1982
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESSThe anodic oxidation of several different types of β-alkanolamines, R1R2C (OH) CR3R4NR5R6, was studied by cyclic voltammetry and controlled potential electrolysis in an aqueous carbonate buffer of pH 10 at a glassy carbon electrode. Upon oxidation, both the (α) C-(β) C and the C-N bonds are cleaved. Substituents R1-R4 affect the first oxidation potential and product distribution. The relative rates of the bond cleavages were estimated from the oxidation products. It was found that most of the amine cleaves through the (α) C-(β) C bond when at least one of the R groups is phenyl, nearly half cleaves through this bond when R is alkyl, and only about a tenth does so when R1-R4 are all hydrogen. The stability of the transient intermediates at the e-c step of the e-c-e process seems to affect the oxidation potentials and to govern the relative rates of the (α) C-(β) C bond cleavage. A scheme for the reaction processes is proposed.View full abstractDownload PDF (1005K) -
YOSHIHIRO HARIGAYA, SEIKO TAKAMATSU, HIROKO YAMAGUCHI, MASAYUKI ONDA1982 Volume 30 Issue 4 Pages 1244-1250
Published: April 25, 1982
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESSChiral benzo [c] phenanthridines have been synthesized. Aminolysis of the (-)-epoxyhydroxy lactone (3) with methylamine stereospecifically gives the (+)-trihydroxy lactam (5), from which the (+)-10b-hydroxychelidonine (7) and (+)-11-epichelidonine analogs (10) are derived. The absolute configurations of the compounds obtained are assigned on the basis of that of (-)-3 and the results obtained from the subsequent stereocontrolled reactions. The absolute configurations of (+)-7 and (+)-10 are confirmed by Horeau's method.View full abstractDownload PDF (828K) -
TAMIO MORIKAWA, KENJI TSUJIHARA, MIKIO TAKEDA1982 Volume 30 Issue 4 Pages 1251-1256
Published: April 25, 1982
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESSStructural determination of the isomeric L-arabinosylureas (1a, 2a, and 3a) and their facile isomerization into the thermodynamically stable isomer (3a) by acid are described. The reaction of L-arabinose with 3-methoxy-n-propylamine followed by treatment with 2-chloroethyl isocyanate gave a mixture of the ureas (1a, 2a, and 3a) in a ratio of 3 : 2 : 1. They were determined to be the β anomer (1a) and the α anomer (3a) of 3-(L-arabinopyranosyl)-1-(2-chloroethyl)-3-(3-methoxy-n-propyl) urea and the β anomer (2a) of the corresponding L-arabinofuranosyl derivative, respectively. Isomerization of these ureas was examined in formic acid solution by monitoring their thin layer chromatography. Complete isomerization of both 1a and 2a into 3a was observed, while 1a isomerized into 3a via 2a. Consequently, the selective isomerization of a mixture of these ureas into 3a could readily be effected by formic acid treatment. The nitrosation of these ureas by the use of dinitrogen tetroxide gave the corresponding nitrosoureas (4a, 5a, and 6a), and their structures are discussed.View full abstractDownload PDF (636K) -
YASUMITSU TAMURA, LINGCHING CHEN, MASANOBU FUJITA, YASUYUKI KITA1982 Volume 30 Issue 4 Pages 1257-1262
Published: April 25, 1982
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESS3, 4-Dihydro-5-hydroxycarbostyril (3), a key intermediate for a clinically used β-receptor blocking agent (1), and its 7-aza analog (4) were prepared by an acid-catalyzed cyclization of the N-pivaloylamino-esters (17 and 19), which were obtained by using organolithiation of 3-methoxy-5-(pivaloylamino) pyridine and m-pivaloylanisidine, followed by Wittig and catalytic hydrogenation reactions. Some related pyridine derivatives (15 and 24) were also prepared.View full abstractDownload PDF (675K) -
YASUHIKO SATO, HIDEO NAKAI, TOMISHIGE MIZOGUCHI, MASAZUMI KAWANISHI, Y ...1982 Volume 30 Issue 4 Pages 1263-1270
Published: April 25, 1982
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESSN-Phthaloylglycine (1a) was irradiated with a high pressure mercury lamp to give N-methylphthalimide (2a) in an excellent yield. N-Phthaloyl derivatives 1b-k of other α-amino acids also afforded the decarboxylated products 2b-k. In the cases of N-phthaloylserine (1l) and di-phthaloylcystine (1m), N-vinylphthalimide (3) was isolated as a major product. On the other hand, N-phthaloylmethionine (11a) and methyl N-phthaloylmethionate (11b) were treated in the same manner to give the aza-thiacycloheptanol derivatives 12a-b having a new ring system. Solvent effects and possible pathways of these reactions were examined.View full abstractDownload PDF (852K) -
HIROTAKA SHIBUYA, HIROMICHI FUJIOKA, AKIHARU KAJIWARA, YOSHIO YAMAMOTO ...1982 Volume 30 Issue 4 Pages 1271-1279
Published: April 25, 1982
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESSAs a continuation of our transformation studies on terpenoids, three optically active 5-methoxy-1, 2, 2-trimethylcyclopentane derivatives, i.e., (+)-(1R, 3R, 5S)-3-acetoxymethyl-5-methoxy-1, 2, 2-trimethyl-1-vinylcyclopentane (7), (+)-(1R, 3R, 5S)-3-acetoxymethyl-1-(3'-hydroxypropenyl)-5-methoxy-1, 2, 2-trimethylcyclopentane (8), and (-)-(1R, 3R, 5S, 1'R)-3-acetoxymethyl-1-(1', 2'-epoxyethyl)-5-methoxy-1, 2, 2-trimethylcyclopentane (9), were synthesized from d-camphor (1) via 5-oxo-d-bornyl acetate (6). All three compounds (7, 8, 9) retain the C-4 configuration of d-camphor at their C-3 positions.View full abstractDownload PDF (1036K) -
HIROTAKA SHIBUYA, HIROMICHI FUJIOKA, YOSHIO YAMAMOTO, KENJI SUZUKI, IS ...1982 Volume 30 Issue 4 Pages 1280-1288
Published: April 25, 1982
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESSThree 5-methoxy-1, 2, 2-trimethylcyclopentane derivatives, i.e., (+)-(1R, 3R, 5S)-3-acetoxymethyl-5-methoxy-1, 2, 2-trimethyl-1-vinylcyclopentane (3), (+)-(1R, 3R, 5S)-3-acetoxymethyl-1-(3'-hydroxypropenyl)-5-methoxy-1, 2, 2-trimethylcyclopentane (4), and (-)-(1R, 3R, 5S, 1'R)-3-acetoxymethyl-1-(1', 2'-epoxyethyl)-5-methoxy-1, 2, 2-trimethylcyclopentane (5), which were synthesized from d-camphor (1) via 5-oxo-d-bornyl acetate (2), were subjected to acid treatment. It was found that i) treatment of 3 with 2, 4, 4, 6-tetrabromocyclohexa-2, 5-dienone yielded a 4-bromo-2-oxabicyclo [3.3.0] octane derivative (8), ii) BF3-etherate treatment of 4 resulted in a ring-enlargement reaction giving two cyclohexane derivatives (13, 14), and iii) BF3-etherate treatment of 5 furnished a 2-oxabicyclo [3.3.0] octane derivative (15) which was derivable through successive migrations of the methyl residues.View full abstractDownload PDF (999K) -
TAKUSHI KURIHARA, KEIKO NASU, JUNKO BYAKUNO, TSUTOMU TANI1982 Volume 30 Issue 4 Pages 1289-1299
Published: April 25, 1982
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESSThe reactions of the 6-acetyl-5-ethoxycarbonyl- or 5, 6-diethoxycarbonylimidazo-[1, 2-a] pyrimidine derivatives (7a, b), which were prepared by condensation of 2-amino-4, 5-diphenylimidazole (4) with ethyl 3-ethoxymethylene-2, 4-dioxovalerate (5a) or ethyl ethoxymethyleneoxaloacetate (5b), with diazomethane are described. Thus, reaction of 7a with diazomethane at room temperature afforded three products whose structures were assigned as ethyl 5a-acetyl-4a, 5a-dihydro-2, 3-diphenyl-5H-cyclopropa [e] imidazo [1, 2-a] pyrimidine-4a-carboxylate (9), ethyl 5a-acetyl-2, 3-diphenyl-4a, 5a, 5b, 7-tetrahydro-6H-aziridino [c]-5H-cyclopropa [e] imidazo [1, 2-a] pyrimidine-4a-carboxylate (10), and the 6-methyl analog (11) of 9. When reacted with diazomethane under ice cooling, 7a afforded only 9 in 73.0% yield. Reaction of 7b with diazomethane at room temperature gave four products whose structures were assigned as diethyl 4a, 5a-dihydro-2, 3-diphenyl-5H-cyclopropa [e] imidazo [1, 2-a] pyrimidine-4a, 5a-dicarboxylate (14), diethyl 2, 3-diphenyl-4a, 5a, 5b, 7-tetrahydro-6H-aziridino [c]-5H-cyclopropa [e] imidazo [1, 2-a] pyrimidine-4a, 5a-dicarboxylate (15), diethyl 7, 8-diphenyl-3a, 3b, 5, 9a-tetrahydro-4H-aziridino [c]-3H-pyrazolo [3, 4-e] imidazo [1, 2-a] pyrimidine-3a, 9a-dicarboxylate (16), and diethyl 3a, 9a-dihydro-7, 8-diphenyl-4-methyl-3H-pyrazolo [3, 4-e] imidazo [1, 2-a] pyrimidine-3a, 9a-dicarboxylate (17). The chemical properties of 9 were also investigated. For example, 9 reacted with hydrochloric acid to give the 5, 8-dihydro-5-chloromethylimidazo [1, 2-a] pyrimidine (19) in excellent yield. When heated with acetic acid, 9 yielded the 5, 8-dihydro-5-acetoxymethylimidazo [1, 2-a] pyrimidine (25) in 12.7% yield, in addition to 40.0% yield of the 5-acetoxy-5, 6-dihydro-9H-imidazo [1, 2-a] [1, 3] diazepine (26), which was transformed into the N-imidazolylpyridone (27) by treatment with potassium hydroxide. On catalytic hydrogenation over 5% palladium charcoal, 9 gave the 5, 6-dihydro-9H-imidazo [1, 2-a] [1, 3] diazepine (32), which was then derived to the 9H-imidazo [1, 2-a] [1, 3] diazepine (36) by bromination followed by dehydrobromination.View full abstractDownload PDF (1325K) -
KATSUHIDE MATOBA, AKIKO FUKUSHIMA, HIROKI TAKAHATA, YOSHIRO HIRAI, TAK ...1982 Volume 30 Issue 4 Pages 1300-1306
Published: April 25, 1982
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESSA 9, 17-diazasteroid system, I, was synthesized from an aminoester, III, and cyclohexanone. Unfortunately the yield was poor. Another 9, 17-diazasteroid system, II, was prepared from the condensation product, XVa, of quinoline N-oxide with an active methine compound, IV. Thus, XVa was hydrolyzed, followed by decarboxylation, reduction and cyclization. The yield in each step to II was moderate.View full abstractDownload PDF (905K) -
EIKO OHTSUKA, SUSUMU SHIBAHARA, MORIO IKEHARA1982 Volume 30 Issue 4 Pages 1307-1314
Published: April 25, 1982
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESSAn octanucleotide dACCCGGGT and decanucleotide dCGACCCGGGT have been synthesized by an improved phosphotriester method. The octanucleotide has a selfcomplementary sequence and the decanucleotide has two protruding nucleotides when it forms a duplex. Thermal properties and circular dichroism spectra of these oligonucleotides have been investigated under various conditions to find differences in the stabilities of these oligonucleotides. A possible concatemer structure of the decanucleotide duplex is suggested on the basis of its circular dichroism spectra in concentrated solution.View full abstractDownload PDF (906K) -
MASAYUKI SATO, NORIO KANUMA, TETSUZO KATO1982 Volume 30 Issue 4 Pages 1315-1321
Published: April 25, 1982
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESSDiketene-acetone adduct (2, 2, 6-trimethyl-1, 3-dioxin-4-one) 1 reacts with amide NH to give the corresponding N-acetoacetates 2. Formamide and basic amides such as picolinamide, on treatment with the adduct, are transformed to the N-acyl-2, 6-dimethyl-4-oxo-4H-pyran-3-carboxamide (4a and 4p) together with the corresponding N-acetoacetates.View full abstractDownload PDF (686K) -
JUN TODA, TAKEHIRO SANO, YOSHISUKE TSUDA, YOSHITAKA ITATANI1982 Volume 30 Issue 4 Pages 1322-1332
Published: April 25, 1982
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESSDiacetyllycorine, an Amaryllidaceae alkaloid, was transformed stereoselectively to the more heavily oxygenated congener, O-demethylungiminorine, by a route similar to that suggested for the biosynthesis of narcissidine. Similarly, acetylhippamine was converted to ungiminorine. A method of high yield conversion of lycorine to hippamine is also described. The above transformations constitute a formal total synthesis of ungiminorine.View full abstractDownload PDF (1114K) -
MOTOI YOGO, KOSAKU HIROTA, SHIGEO SENDA1982 Volume 30 Issue 4 Pages 1333-1337
Published: April 25, 1982
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESSThe mechanism of the ring transformation of 6-chloro-1, 3-oxazine-2, 4-diones (1) into barbituric acids (2) in the presence of primary aliphatic amines was studied. It has been elucidated that the mechanism involves initial attack on the 2-position of 1 by an amine and subsequent intramolecular cyclization of the ureide intermediate (5).View full abstractDownload PDF (528K) -
MASAO HATTORI, GAKUSEN KIM, SAYURI MOTOIKE, KYOICHI KOBASHI, TSUNEO NA ...1982 Volume 30 Issue 4 Pages 1338-1346
Published: April 25, 1982
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESSThrough investigation of the metabolism of sennosides by intestinal contents and feces of the rat, the main metabolic pathways were elucidated and found to be quite different from those previously proposed on the basis of the metabolites produced by individual strains isolated from the human intestine. Sennoside A was hydrolyzed in a stepwise fashion to produce sennidin A via sennidin A-8-monoglucoside by β-glucosidase present in the intestinal contents and feces, and sennoside B to sennidin B via sennidin B-8-monoglucosides in a similar way. The resulting metabolites, sennidins A and B, were interconvertible under the experimental conditions used, and were further reduced to give rheinanthrone, a purgative active principle of Rhei Rhizoma and senna, possibly by reductase bound to cell membranes of intestinal bacteria.View full abstractDownload PDF (915K) -
TOHORU TATSUHARA, FUMIE TABUCHI, ITSUKO NISHIMURA, HIDEKI MURO, FUMIYO ...1982 Volume 30 Issue 4 Pages 1347-1351
Published: April 25, 1982
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESSA rapid and precise method for the determination of sulfite ion by isotachophoresis was developed. The leading electrolyte used was 0.01 M L-histidine hydrochloride in 30% aqueous acetone (pH 4.0) and the terminating electrolyte was 0.01 M hexanoic acid (pH 3.5). This method also successfully detected sulfate, the oxidation product of sulfite, which may be formed in various pharmaceutical procedures including sterilization. The limits of detection were 0.2 mM as sulfite and 0.1 mM as sulfate. No pretreatment of the sample was required. This procedure could be applied to the simultaneous determination of sulfite and sulfate and should be useful in pharmaceutical analysis.View full abstractDownload PDF (596K) -
AKIRA SHIRAHATA, MASANORI YOSHIOKA, ZENZO TAMURA1982 Volume 30 Issue 4 Pages 1352-1357
Published: April 25, 1982
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESSDegradation of 3H-epinephrine during incubation for 14 h at 37°C in a phosphate buffer, pH 7.0, containing ascorbic acid was observed in a study on the radioimmunoassay of epinephrine. Chromatographic separations of the products were carried out on a large scale. They were identified as 1, 2, 3, 4-tetrahydro-4, 6, 7-trihydroxy-2-methylisoquinoline (1) and 1, 2, 3, 4-tetrahydro-4, 7, 8-trihydroxy-2-methylisoquinoline (2). These products were synthesized from epinephrine and formaldehyde for the first time. Our results suggested that 3H-epinephrine reacted with formaldehyde generated through the oxidation of ascorbic acid by oxygen from air under the incubation conditions used above to yield 1 or 2. Care is clearly required in using ascorbic acid as an antioxidant in catecholamine studies.View full abstractDownload PDF (752K) -
YOUICHI KOMIYAMA, TETSUO ADACHI, YOSHIMASA ITO, KAZUYUKI HIRANO, MAMOR ...1982 Volume 30 Issue 4 Pages 1358-1362
Published: April 25, 1982
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESSA method for the analysis of androsterone sulfate in serum by means of an enzymatic cycling reaction was developed. Androsterone sulfate was solvolyzed, extracted and purified on Sephadex LH-20, then androsterone was oxidized by 3α-hydroxysteroid dehydrogenase from Pseudomonas tetstosteroni and the resulting NADH was determined by an enzymatic cycling method. The cycling system consisted of two enzyme, alcohol dehydrogenase from yeast and diaphorase from Clostridium kluyverii, and resazurin was used as an electron acceptor for diaphorase. Subsequently, resorfin formed from the resazurin was determined by the rate assay method at Ex560, Em580 and 25°C. A linear relationship was obtained between the amount of androsterone and ΔF/min in the range from 0.035 to 3.5 μg/ml. The recovery, the reproducibility and the correlation between the proposed method and the conventional method using gas-liquid chromatography were also good. It appears that this simple and sensitive method could be useful as a clinical diagnostic test.View full abstractDownload PDF (610K) -
SHUJIRO GOYA, AKIRA TAKADATE, HIROYUKI FUJINO, MASAKI OTAGIRI, KANETO ...1982 Volume 30 Issue 4 Pages 1363-1369
Published: April 25, 1982
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESSSome new and known coumarincarboxylic acids were synthesized for use as fluorescence probes. The fluorescence properties of these compounds were examined in various solvents and albumin solutions. The fluorescence of 7-anilinocoumarin-4-acetic acid (I) was significantly enhanced in nonpolar solvents and in the presence of human serum albumin (HSA). The binding parameters of I were estimated from the fluorescence enhancement and spectral change of I bound to HSA. The Scatchard plots and the continuous variation plots indicated that only the primary site was capable of enhancing the fluorescence and causing the spectral changes of I. Digitoxin displaced I from its primary site on HSA, but site 1 and site 2 drugs on the basis of Sudlow's classification did not significantly displace the probe. The present data indicate that I may be useful as a third site marker.View full abstractDownload PDF (739K) -
KENJI SHIMADA, TAKEICHI SAKAGUCHI, MITSUO IKEDA1982 Volume 30 Issue 4 Pages 1370-1376
Published: April 25, 1982
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESSThe mechanisms of protein separation by high-performance liquid chromatography (HPLC) using a Shodex OH pak B-804 column were examined, and an attempt was made to relate the separation behavior of some proteins to their molecular weight, isoelectric point and/or molecular size. HPLC elution was carried out with several kinds of buffer solutions at different pH values to cover the range of protein isoelectric points, and the effect of the addition of salts on the elution time was tested. Elution was not necessarily in order of molecular weight or molecular size, and also varied according to whether or not protein-protein, protein-solute and/or protein-column packing interactions occurred in the buffer solutions used.View full abstractDownload PDF (686K) -
YOSHIHIRO NISHIKAWA, RYOUTA TATEZAKI, HIROMITSU OHNO1982 Volume 30 Issue 4 Pages 1377-1380
Published: April 25, 1982
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESSThe effects of twenty-three disaccharide esters of fatty acids on the phagocytic response of the reticuloendothelial system (RES) were examined by measuring the intravascular clearance of colloidal carbon 24 h after a single intraperitoneal injection into ddY mice. A marked increase in the phagocytic activity was demonstrated with the following samples : i) nine lots of industrially produced sucrose-tallowates containing the mono- and higher esters of stearic and palmitic acids (ca. 2-4 : 1) in various ratios ranging from 3 : 7 to 7 : 3, and ii) three laboratory-prepared samples, that is, sucrose-(di)- and -(poly)-stearates and trehalose-(di)-stearate. The phagocytic indexes shown by these agents at doses of 100 and 50 mg/kg, and, in some cases, even at 25 mg/kg were higher than, or comparable to, that obtained with 50 mg/kg of zymosan. Such a significant RES-stimulation could not be observed with other samples, i.e., a lot of commercial sucrose-tallowate consisting almost entirely of monoesters and a commercial sucrose-palmitate containing the mono-, di- and polyesters, ii) laboratory-prepared samples such as sucrose- and trehalose-(mono)-stearates, and -(mono)-myristates, maltose-(mono)-, -(di)-, and -(poly)-stearates and maltose-(mono)- and -(poly)-palmitates, and iii) sucrose and stearic acid in the free form.View full abstractDownload PDF (633K) -
TSUTOMU MIMURA, KAZUHIRO MAEDA, HISAYO HARIYAMA, SHIGERU AONUMA, MIKIO ...1982 Volume 30 Issue 4 Pages 1381-1386
Published: April 25, 1982
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESSCrude squid melanin obtained from ink bags of Ommastrephes bartrami LESUEL was found to exhibit a strong inhibitory effect on gastric secretion in rats. The crude melanin was separated into high molecular fraction SM I (mol. wt.>160000) and low molecular fraction SM II (average mol. wt. ca. 39000) by gel filtration on a Sephadex G-100 column, and Fr. SM II showed a stronger biological activity. Fr. SM II contained a melanoprotein composed of melanin pigment 90%, protein 5.8% and carbohydrate 0.8%, and significantly decreased gastric secretion at the dosage of 1 mg/kg, i.p. or i.v. Fr. SM II also prevented ulcer formation in pylorus-ligated rats and aspirin-induced ulcer.View full abstractDownload PDF (708K) -
KAZUYUKI HIRANO, YUICHI IIIZUMI, MAMORU SUGIURA, JUN MIYAZAKI, KAZUMAS ...1982 Volume 30 Issue 4 Pages 1387-1392
Published: April 25, 1982
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESSAmong various tissue-specific alkaline phosphatases, sialic acid was detected in liver, placental and meconial alkaline phosphatases, but not in the intestinal one. The content of acidic amino acids was larger than that of basic amino acids in the purified enzymes. Placental, intestinal and liver alkaline phosphatases contained 4 g-atoms of zinc/mol of enzyme, but the meconial alkaline phosphatase contained 2 g-atoms of zinc / mol of enzyme. N-Terminal amino acid residues of the intestinal and meconical alkaline phosphatases were both phenylalanine, whereas that of placental enzyme was isoleucine and that of liver enzyme was leucine. The tryptic peptide patterns of human placental, intestinal, meconial and liver alkaline phosphatases were similar to one another in part. The activecenter-containing peptides labelled with 33PO4 from human placental, intestinal, meconial and liver alkaline phosphatases had the same mobility on a thin layer chromatogram.View full abstractDownload PDF (1056K) -
NOBUYA TAMURA, KAZUHIKO TAKAHASHI, NAOHIRO SHIRAI, YUTAKA KAWAZOE1982 Volume 30 Issue 4 Pages 1393-1400
Published: April 25, 1982
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESSThe quantitative structure-mutagenicity relationship among 8 substituted styrene oxides, p-methyl-, p-butyl, p-phenyl, p-chloro, m-chloro, p-cyano, p-nitro, and the parent styrene oxide, was examined. Mutagenic and cytocidal activities were correlated with the reactivity of the epoxide (Hammett's σ), the van der Waals volume of the molecule (VW), and/or the partition parameter (π). Multiple regression analyses revealed that mutagenic capacity could be well described by a linear combination of σ and log VW and that cytocidal capacity depended only on π of the derivatives, as already reported by Sugiura et al.View full abstractDownload PDF (855K) -
HIROSHI NAKAGAWA1982 Volume 30 Issue 4 Pages 1401-1407
Published: April 25, 1982
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESSThe effects of tableting procedures on the preferred orientation of phenacetin and aspirin crystals in a tablet were investigated. Among aspects of tableting procedures which might affect the preferred crystal orientation, the granulation process, the shape of the punch and the addition of magnesium stearate were investigated. A wet granulation method decreased the mobility of crystals during compression, and thus reduced the degree of preferred orientation. This phenomenon was considered to be one of reasons for the improved lamination properties seen with the granulation method. The shape of the punch affected the preferred orientation ; a concave punch caused a more complex preferred orientation pattern than a flat punch. The preferred orientation was considered to correspond to the stress distribution in a tablet. Magnesium stearate reduced the interparticle friction and facilitated the attainmnet of preferred orientation. The characteristic preferred orientation of crystals in the neighborhood of the upper surface and side surface of a tablet was investigated. The broadest faces of crystals were aligned in parallel to the upper punch face and the die wall.View full abstractDownload PDF (754K) -
TOSHIO YOSHIOKA, KYOKO IKEUCHI, MITSURU HASHIDA, SHOZO MURANISHI, HITO ...1982 Volume 30 Issue 4 Pages 1408-1415
Published: April 25, 1982
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESSA gelatin sphere-in-oil-in-water (S/O/W) multiple emulsion was prepared by dispersing primary sphere-in-oil (S/O) emulsion into an external aqueous phase and its potential for prolonging parenteral absorption of bleomycin was studied in rats and rabbits. Intramuscular injection of bleomycin in an S/O/W emulsion formulation provided a sustained plasma concentration which was almost equal to those obtained after injeotion of S/O emulsion and oily suspension, while immediate appearance of bleomycin in plasma and subsequent rapid clearance were observed following intravenous or intramuscular injection of aqueous drug solution. The prolonged release of bleomycin from the multiple emulsion was confirmed by observation of the retarded disappearance of the drug from the injection site. S/O/W emulsion also exhibited enhanced lymphatic transfer of bleomycin following injection into the appendix of rabbits. These results show the potential of S/O/W emulsion as a parenteral dosage form in addition to its superior injectability. The possibility that the instability of multiple emulsions during storage could be at least partly overcome by employing lyophilization processing was demonstrated.View full abstractDownload PDF (1004K) -
REIKO IWAOKU, KAZUHIKO ARIMORI, MASAHIRO NAKANO, KANETO UEKAMA1982 Volume 30 Issue 4 Pages 1416-1421
Published: April 25, 1982
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESSPhenobarbital was dissolved faster from a β-cyclodextrin complex than from phenobarbital powder, and it was released faster from suppositories containing its β-cyclodextrin complex than from those containing phenobarbital powder. After rectal administration of the suppository containing the β-cyclodextrin complex to rabbits, the blood concentration of the drug was higher than that following administration of the phenobarbital suppository. Since β-cyclodextrin tended to retard absorption of the drug in solution from the rectum, enhanced absorption of the drug from the complex was attributed to fast release from the suppository due to rapid dissolution.View full abstractDownload PDF (635K) -
KIKUO IWAMOTO, JUN WATANABE, KATSUAKI IMAI, MASAHIKO SHIBATA, JUNJI HI ...1982 Volume 30 Issue 4 Pages 1422-1429
Published: April 25, 1982
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESSTo evaluate the distribution, metabolism and excretion of urea in normal rats, plasma concentration profiles, whole-body autoradiograms and urinary, fecal and expiratory excretions following intravenous administration of 14C-urea were investigated. High (1000 mg/kg) and low (0.0675 or 0.117 mg/kg) doses of urea were employed to examine dose-induced differences in the plasma levels and in the whole-body autoradiograms. Plasma radioactivity-time curves were analyzed according to a two-compartment open model. There were no significant differences in almost all of the pharmacokinetic parameters for these two doses. Even in the case of parameters with significant differences (α, β and k10), the dose dependency was considered to be rather small. When these parameters are compared with those for creatinine, k12 and k21 (which are both transfer rate constants for urea between plasma and tissue compartments) were significantly larger than those for creatinine, while (Vd')extrap for urea was about one-third of that for creatinine. There was also no significant dose dependency in the whole-body autoradiograms. The distribution pattern of urea radioactivity was almost uniform except in the kidney and urinary bladder even at an early stage (at 5 and 20 min). Following the intravenous doses, urea was regarded as being eliminated predominantly via the renal route, since more than 80% of the dose was excreted into the urine in 24 h. However, expiratory excretion of the radioactivity was about 12% in 24 h following i.v. administration of 14C-urea, while that after p.o. administration was approximately 37%.View full abstractDownload PDF (1131K) -
HIROSHI FUJIWARA, SUSUMU KAWASHIMA, MASAKO OHHASHI1982 Volume 30 Issue 4 Pages 1430-1436
Published: April 25, 1982
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESSThe interaction of ampicillin and benzaldehyde in aqueous solution was investigated. A modified iodine colorimetry (I2-colorimetry) was used for the assay of ampicillin in solutions containing ampicillin and benzaldehyde. Thus, total ampicill n including bioactive ampicillin-like substances which are present in aqueous solution could be determined by I2-colorimetry after diluting the solution and adjusting it to pH 3.5-4.0. The time courses of degradation of ampicillin with benzaldehyde in phosphate buffer (pH 8.00) at 35°C were followed by this method, and the reaction was found to be pseudo-first-order. Further, it was found that benzaldehyde inhibited the degradation of ampicillin under these conditions. In view of the above results and the changes in the ultraviolet spectra of the solution, it is concluded that ampicillin and benzaldehyde form a complex.View full abstractDownload PDF (776K) -
MASANORI YONAHA, YUKO OHBAYASHI, TAKAMICHI ICHINOSE, MASARU SAGAI1982 Volume 30 Issue 4 Pages 1437-1442
Published: April 25, 1982
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESSThe toxicity of mercuric chloride (MC) in mice, measured in terms of the single dose lethal to 50 percent of the animals after 12 h, was enhanced by prior exposure to a vitamin E-deficient diet and by pretreatment with diethyl maleate, and was diminished by pretreatment with N, N'-diphenyl-p-phenylenediamine. Lipid peroxidation as determined by measurement of the pentane content in expired gases of rats showed a dose-dependent increase 12 h after the subcutaneous injection of MC. In the kidney of rats 12 h after a 4 mg/kg dose of MC, formation of thiobarbituric acid (TBA)-reactive substances was greatly increased. Slight increases of pentane in expired gases and of TBA-reactive substances in the kidney of rats at earlier times after a 2 mg/kg dose of MC were also seen compared to the control. After injection of MC (2 or 4 mg/kg), glutathione was decreased in the kidney at 12 h. The urinary excretions of alkaline phosphatase (ALP) and leucine aminopeptidase (LAP) were markedly increased 6 h after a 4 mg/kg dose of MC, and at a dose of 2 mg/kg the excretion of LAP, but not that of ALP, was also elevated at 12 h after MC. These results indicate that lipid peroxidation may be partly responsible for the acute-toxic effect of MC, which involves renal damage.View full abstractDownload PDF (637K) -
MACHIKO ONO, SHINZO TAMURA1982 Volume 30 Issue 4 Pages 1443-1452
Published: April 25, 1982
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESSAminolysis and alcoholysis reactions of β-arylaminoacrolein and its N-acyl derivatives were studied. Acid-catalyzed aminolysis of β-(N-benzoyl-p-toluidino) acrolein (III) occurred at the β-position of III, accompaying the reversible interaction of the amine and the formyl group of III. In the reaction of III and amine in methanol under neutral conditions, aminolysis at the β-position of III and alcoholysis of the amide carbonyl group of III proceeded in parallel ; the latter reaction was catalyzed by amine. In either case, no evidence for aminolysis at the amide carbonyl group of III was obtained. The reaction of the formyl group of III proceeded mainly when III and amine were reacted in benzene solution. Thus, 1-(N-benzoyl-p-methylphenylamino)-3-(p-chlorophenylimino)-1-propene (XII) was obtained when III and p-chloroaniline were reacted in benzene. Alkaline hydrolysis of XII afforded 1-(p-methylphenylamino)-3-(p-chlorophenylimino)-1-propene (XIII), an unsymmetrical malonaldehyde dianil. Aminolysis and alcoholysis reactions of 1-arylamino-3-arylimino-1-propene (malonaldehyde dianil) and its N-acyl derivatives were also studied. Alcoholysis occurred at the amide carbonyl group of N-acyl derivatives, while aminolysis occurred at the 1-position except for the case of 1-(N-phenylcarbamoyl-p-methylphenylamino)-3-(p-methylphenylimino)-1-propene (XIV).View full abstractDownload PDF (1024K) -
MACHIKO ONO, SHINZO TAMURA1982 Volume 30 Issue 4 Pages 1453-1462
Published: April 25, 1982
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESSThe reaction sequence of hydrolysis of N-acyl derivatives of malonaldehyde dianil was examined. Hydrochloric acid-catalyzed hydrolysis occurred at the imino group to form arylamine and β-(N-acylarylamino) acrolein ; the latter compound is not stable in acidic solution. In the case of 1-(N-phenylcarbamoyl-p-methylphenylamino)-3-(p-methylphenylimino)-1-propene, hydrolysis occurred at both the imino and carbamoyl groups. Buffer-catalyzed hydrolysis occurred at the imino group, and the resulting β-(N-acylarylamino) acrolein and arylamine reacted to form β-arylaminoacrolein and N-acylarylamine. This aminolysis reaction was suppressed in hydrochloric acid-catalyzed hydrolysis. Alkaline hydrolysis of N-acyl derivatives of malonaldehyde dianil and of β-arylaminoacrolein occurred at the amide carbonyl group except in the case of 1-(N-tosyl-p-methylphenylamino)-3-(p-methylphenylimino)-1-propene. N-Tosyl-p-toluidine was obtained in this case.View full abstractDownload PDF (1040K) -
MACHIKO ONO, SHINZO TAMURA1982 Volume 30 Issue 4 Pages 1463-1472
Published: April 25, 1982
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESSβ-(p-Toluidino) crotonaldehyde (V), a possible reactant of the Combes reaction, was prepared by the alkaline hydrolysis of β-N-(p-chlorobenzoyl)-p-toluidinocrotonaldehyde (XXIV). Compound XXIV was prepared by the hydrochloric acid-catalyzed hydrolysis of 3-[N-(p-chlorobenzoyl)-p-methylphenylamino]-1-(p-methylphenylimino)-2-butene (XXIII). Compound XXIII was prepared by the alkaline hydrolysis of 1, 3-bis [N-(p-chlorobenzoyl)-p-toluidino]-1, 3-butadiene (XXII). The alkaline hydrolysis and alcoholysis of 1, 3-bis (N-acyl-p-toluidino)-1, 3-butadiene (VIII) and the hydrochloric acid-catalyzed hydrolysis of 3-(N-acyl-p-methylphenylamino)-1-(p-methylphenylimino)-2-butene (VI) were examined.View full abstractDownload PDF (1135K) -
TAKAO WATANABE, MASAAKI MATSUO, KIYOSHI TANIGUCHI, IKUO UEDA1982 Volume 30 Issue 4 Pages 1473-1476
Published: April 25, 1982
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESSAn improved method for the synthesis of 7-chloro-5-(2-chlorophenyl)-2-(2-dimethylaminoethylthio)-3H-1, 4-benzodiazepine (IIa) and related compounds is described. IIa was obtained in 75.1% yield by the reaction of the 1, 4-benzodiazepin-2-one (Ia) with 2-dimethylaminoethanethiol in the presence of titanium tetracbloride ; a small amount of 7-chloro-5-(2-chlorophenyl)-2-dimethylamino-3H-1, 4-benzodiazepine (III) was obtained as a byproduct. A mechanistic interpretation of the formation of III is presented.View full abstractDownload PDF (488K)