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Volume 30, Issue 12
Displaying 1-50 of 61 articles from this issue
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TOSHIMASA ISHIDA, MITSUNOBU DOI, TOSHIKAZU OKUNO, MASATOSHI INOUE1982 Volume 30 Issue 12 Pages 4249-4257
Published: December 25, 1982
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESSThe crystal structure of a 1 : 1 complex of adenin-9-ylethylamine and phenylacetic acid, C7H10N6·C8H8O2, has been determined by the X-ray method. The crystal is orthorhombic, space group P212121, with unit-cell dimensions of a=7.050 (2), b=11.835 (4) and c=18.711 (7) A. The structure was solved by the direct method and refined by the blockdiagonal least-squares method to give a final R value of 0.037. In this complex, a salt bridge exists between the anionic carboxyl group of phenylacetic acid and the cationic amino group of adenin-9-ylethylamine. No specific interaction between the adenine and benzene rings was observed. The component molecules are held together by a three-dimensional framework of hydrogen bonds around the twofold screw axis to form an infinite helical array in the a direction.View full abstractDownload PDF (710K) -
JUNICHI YAMASHITA, ICHIRO YAMAWAKI, SHUICHI UEDA, MITSUGI YASUMOTO, NO ...1982 Volume 30 Issue 12 Pages 4258-4267
Published: December 25, 1982
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESSSix types of 5-fluorouracil (5-FU) derivatives were synthesized ; namely, 2, 4-di-O-substituted, 2-O-substituted, 4-O-substituted, 1, 3-disubstituted, 1-substituted and 3-substituted compounds. After oral administration of these compounds to rats, the blood levels of 5-FU were determined. Among O-substituted derivatives, a 4-O-substituted derivative was most easily activated to 5-FU and 2-O-substituted derivatives were next most easily activated. Among N-substituted derivatives, acyl and sulfonyl derivatives showed the highest 5-FU releasing abilities and 1-alkoxymethyl substituted derivatives showed low ability. N-Alkyl substituted derivatives were not activated to 5-FU. Several compounds which gave higher blood levels of 5-FU than that obtained with 1-(tetrahydro-2-furyl)-5-fluorouracil (Thf-FU), as well as same related compounds, were selected and their antitumor activities were examined. The 2-O-substituted derivatives, 2-butoxy-5-fluoro-4 (1H)-pyrimidone (11) and 2-benzyloxy-5-fluoro-4 (1H)-pyrimidone (19), were as effective as Thf-FU. The activities of 2, 4-di-O-substituted derivatives, 2, 4-dibutoxy-5-fluoropyrimidine (1) and 2, 4-dibenzyloxy-5-fluoropyrimidine (6), against Ehrlich carcinoma and against sarcoma 180, respectively, were the same as those of Thf-FU. The 1-substituted derivatives, 1-ethoxymethyl-5-fluorouracil (49) and 1-(1-ethoxy-1-phenylmethyl)-5-fluorouracil (50), were found to be as effective as Thf-FU.View full abstractDownload PDF (942K) -
GENICHIRO NONAKA, ITSUO NISHIOKA1982 Volume 30 Issue 12 Pages 4268-4276
Published: December 25, 1982
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESSAs a result of an investigation of the relatively lower-molecular-weight phenolics in the bark of Cinchona succirubra (Rubiaceae), cinchonains Ia (1), Ib (2), Ic (3) and Id (4), a new class of flavan-3-ols substituted at the A-ring with a C6-C3 unit, have been isolated, together with caffeic acid (5) and (-)-epicatechin (6). The structures of these compounds have been established on the basis of chemical and spectroscopic evidence. A direct coupling of caffeic acid and (-)-epicatechin leading to the formation of cinchonains has also been achieved.View full abstractDownload PDF (910K) -
GENICHIRO NONAKA, OSAMU KAWAHARA, ITSUO NISHIOKA1982 Volume 30 Issue 12 Pages 4277-4282
Published: December 25, 1982
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESSTogether with known proanthocyanidins B-2 (7), B-5 (8), A-2 (9) and C-1 (10), consisting exclusively of (-)-epicatechin (C2, C3 : cis) units, cinchonains IIa and IIb were isolated from red cinchona, the bark of Cinchona succirubra (Rubiaceae). They have been established on the basis of degradative studies, and 1H- and 13C-NMR evidence to be novel proanthocyanidin dimers containing a phenylpropanoid substituent.View full abstractDownload PDF (637K) -
JUNICHI KUNITOMO, MEGUMI OSHIKATA, KAYOKO NAKAYAMA, KIYOKO SUWA, YOSHI ...1982 Volume 30 Issue 12 Pages 4283-4287
Published: December 25, 1982
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESSThe synthesis of dl-steporphine (1), an aporphine-type alkaloid having a hydroxyl group at the 4-position, is described. The acetophenone derivative (4), prepared from 2 and 3 by Friedel-Crafts reaction, was condensed with aminoacetaldehyde diethyl acetal to afford the ketimine derivative (5). The product (6), from the sodium borohydride reduction of 5 or its N-methyl derivative (7) was subjected to hydrolytic cyclization in concentrated hydrochloric acid to afford stereospecifically 1-(2-bromobenzyl)-4-hydroxy-6, 7-methylenedioxy-1, 2, 3, 4-tetrahydroisoquinoline (8) or its N-methyl derivative (9), respectively, with a cis relationship between C1-H and C4-H. The stereospecificity is presumed to be due to intramolecular hydrogen bonding between the alcoholic hydroxyl group and the bromo atom. Irradiation of 9 in dilute hydrochloric acid afforded dl-steporphine (1). This is the first stereospecific synthesis of 4-hydroxyaporphine-type alkaloids, and the method should be adaptable to the synthesis of other alkaloids of this type.View full abstractDownload PDF (663K) -
KENICHI HARADA, SUSUMU ITO, MAKOTO SUZUKI1982 Volume 30 Issue 12 Pages 4288-4296
Published: December 25, 1982
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESSThe structural assignment of each of five sugar components from a basic antibiotic, sporaviridin, is described : two are neutral monosacharides, D-quinovose and D-glucose, and the remaining three are amino sugars, D-viosamine, D-acosamine and L-vancosamine. D-Acosamine is only the second example of a 3-amino-2, 3, 6-trideoxyhexose having D-configuration to be isolated from nature (D-angolosamine was the first).View full abstractDownload PDF (840K) -
YOSHIRO KOBAYASHI, TAKEO TAGUCHI, SATOSHI MITSUHASHI, TADASHI EGUCHI, ...1982 Volume 30 Issue 12 Pages 4297-4303
Published: December 25, 1982
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESS1α, 25-Dihydroxy-26, 26, 26, 27, 27, 27-hexafluorocholesterol was synthesized by two procedures. Cholenic acid was converted to the 1α-hydroxy-24-sulfone derivative and hexafluoroacetone was reacted with the lithiated 24-sulfone. Subsequent removal of the sulfonyl group afforded the hexafluoro-1α, 25-dihydroxy compound. An alternative process consists of construction of the hexafluoro-25-hydroxy part on the side chain followed by the introduction of a hydroxy group at the 1α-position. The hexafluoro derivative was converted to the vitamin D form, 1α, 25-dihydroxyhexafluorovitamin D3, via the corresponding 5, 7-diene.View full abstractDownload PDF (811K) -
KIYOSHI TOMIOKA, HIDEMICHI MIZUGUCHI, KENJI KOGA1982 Volume 30 Issue 12 Pages 4304-4313
Published: December 25, 1982
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESSA novel method for the asymmetric synthesis of both enantiomers of 2, 3-disubstituted-butanolides (8) was devised using a readily available (S)-4-hydroxymethyl-4-butanolide 4-derivative (6) as a chiral source in the asymmetric induction and as the carbon framework of 8. Application of this method to the asymmetric total synthesis of podorhizon (23) and deoxypodorhizon (4) is described.View full abstractDownload PDF (1054K) -
YASUSHI HONMA, YASUO SEKINE, TOMIKI HASHIYAMA, MIKIO TAKEDA, YASUTOSHI ...1982 Volume 30 Issue 12 Pages 4314-4324
Published: December 25, 1982
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESSA series of phenyl-substituted pyrones, pyridines, and pyrimidines bearing a 5-tetrazolyl or N-(5-tetrazolyl) carbamoyl group as an acidic moiety was synthesized. The compounds were tested for antiallergic activity by passive cutaneous anaphylaxis (PCA) assay in rats after oral administration. Among the compounds synthesized. N-(5-tetrazolyl)-6-phenylpyridine-2-carboxamides (53, 54 and 55) were found to display remarkably high potency.View full abstractDownload PDF (1054K) -
ITSUO YOSHIZAWA, KYOKO NAGATA, SHINJI ITOH1982 Volume 30 Issue 12 Pages 4325-4333
Published: December 25, 1982
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESSThe formation of a C20-carbonium cation during the hot acid hydrolysis of pregnanediol disulfate (1b) and the role of this cation in the rearrangement reactions were examined. Hydrolysis of 1b in boiling 3N hydrochloric acid in oxygen-18 water gave 17α-ethyl-17β-methyl-18-nor-5β-androst-13-en-3α-ol (2) as the main product, together with pregnanediol (1a), 17α-methyl-D-homo-5β-androstane-3α, 17aβ-diol (3), 17α-methyl-17aβ-chloro-D-homo-5β-androstan-3α-ol (4), 5β-pregn-20-en-3α-ol (5a), 5β-pregnane-3α, 20β-diol (10), and other minor degradation products. The isotope content of these products was determined by gas chromatography-mass spectrometry. Among then, 3 and 10 were quantitatively labeled with 18O at 17aβ- and 20β-ol, respectively, and 1a was 74% labeled at 20α-ol. No uptake of 18O into 3α-ol of the products was observed. These results confirm the formation of the C20-carbonium cation from 1b. Hydrolysis of 5β-pregn-20-en-3α-ol sulfate (5b), which is considered to be the conjugated base of the C20-cation, gave 2 as the main product accompanied with 1a, 3, 4, 5a, and 10. This result suggests that the C20-carbonium cation plays an important role as an intermediate to D-homosteroids as well as to the Δ15-olefin 2.View full abstractDownload PDF (819K) -
HIKARU OKABE, YUMI MIYAHARA, TATSUO YAMAUCHI1982 Volume 30 Issue 12 Pages 4334-4340
Published: December 25, 1982
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESSThe structures of momordicosides K and L, bitter principles in the fruits of Momordica charantia L. (Cucurbitaceae), were elucidated as 7-O-β-D-glucopyranosides of 3β, 7β-dihydroxy-25-methoxy-cucurbita-5, 23-dien-19-al and 3β, 7β, 25-trihydroxy-cucurbita-5, 23-dien-19-al, respectively, from spectral and chemical evidence.View full abstractDownload PDF (822K) -
TOSHINOBU MORITA, RYOJI KASAI, OSAMU TANAKA, JUN ZHOU, TSUNGREN YANG, ...1982 Volume 30 Issue 12 Pages 4341-4345
Published: December 25, 1982
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESSFrom rhizomes of Panax japonicus var. major (Chinese name : Zu-Tziseng) collected in Yunnan, China, two known oleanolic acid-saponins, chikusetsusaponin-IVa (6) and-V (1), two dammarane-saponins, ginsenoside-Rd (3) and notoginsenoside-R2 (2), and two new dammarane-saponins named majonoside-R1 (7) and-R2 (13) were isolated. By means of 13C-nuclear magnetic resonance (NMR) and mass spectrometry, the common aglycone of both new saponins was proved to be 3β, 6α, 12β, 25-tetrahydroxy-(20S, 24S)-epoxy-dammarane (11) (ocotillol-type triterpene) and the structures of 13 and 7 were elucidated to be 6-O-β-xylopyranosyl (1→2)-β-glucopyranoside and 6-O-β-sophoroside of 11, respectively.View full abstractDownload PDF (585K) -
TOYOKICHI YOSHIDA, SHUNSUKE NARUTO, HITOSHI UNO, HARUKI NISHIMURA1982 Volume 30 Issue 12 Pages 4346-4351
Published: December 25, 1982
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESSThe reactions of S-benzyl-and S-(p-nitrobenzyl) sulfoximides 1a, b with N-bromosuccinimide or tert-butyl hypochlorite gave the corresponding N-halosulfoximides 2a, b or 3a, b, respectively, in good yields. The N-bromo-S-(p-nitrobenzyl) sulfoximide 2b decomposed in the presence of a light source to give the corresponding α-bromosulfoximide 4b, whereas the other N-halosulfoximides 2a and 3a, b did not give the corresponding α-halosulfoximides 4a and 5a, b. On treatment with N-chlorosuccinimide, the p-nitrobenzyl-sulfoximide 1b underwent both N- and α-chlorinations, while the benzylsufoximide 1a underwent only N-chlorination. The halosulfoximides 2-5 underwent base-induced rearrangements under various conditions to give the corresponding N-sulfinylimines 6 via the same three-membered cyclic sulfoximide intermediate, a thiazirine S-oxide 8.View full abstractDownload PDF (668K) -
AKIO OHSAWA, TAKAYUKI KAWAGUCHI, HIROSHI IGETA1982 Volume 30 Issue 12 Pages 4352-4358
Published: December 25, 1982
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESSFlash vacuum pyrolysis (FVP) of benzaldoximes and aryl ketoximes afforded nitriles and additional aromatic compounds which were presumably generated from intermediary iminyl radicals. The FVP also gave benzoxazoles, which were presumably formed from iminoxyl radicals. Benzyl ketoximes afforded indoles together with fragmentation products of the iminyl radicals.View full abstractDownload PDF (596K) -
MASAYUKI SATO, NORIO KANUMA, TETSUZO KATO1982 Volume 30 Issue 12 Pages 4359-4364
Published: December 25, 1982
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESSThe reactions of diketene-acetone adduct (2, 2, 6-trimethyl-1, 3-dioxin-4-one) (1) with heteroxyclic ylides were investigated. Heating of the adduct with isoquinolinium bis (ethoxycarbonyl) methylide (3a) gave ethyl 1-acetyl-2-hydroxypyrrolo [2, 1-a] isoquinoline-3-carboxylate (6a). Under similar conditions, isoquinolinium cyano (ethoxycarbonyl)-methylide (3b) and phenacylide (3d) gave 1-acetyl-2-ethoxycarbonyloxypyrrolo [2, 1-a]-isoquinoline-3-carbonitrile (7) and 1-acetyl-3-benzoyl-2-hydroxypyrrolo [2, 1-a] isoquinoline (6d), respectively. Isoquinolinium dicyanomethylide (3e) reacted with the adduct in a different manner to give bis (6-methyl-4-oxo-4H-1, 3-oxazin-2-yl) methylide (8). Pyridinium ylides similarly reacted with the adduct to give indolizines and oxazinylmethylides.View full abstractDownload PDF (589K) -
TAMIO MORIKAWA, KENJI TSUJIHARA, MIKIO TAKEDA, YOSHIHISA ARAI1982 Volume 30 Issue 12 Pages 4365-4372
Published: December 25, 1982
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESSA series of five 3, 3-disubstituted nitrosoureas having the nitrosoureido group at the C-3 position of methyl glucoside were prepared and tested for antitumor activities. Heating of methyl 2, 3-anhydro-α-D-allopyranoside (I) with various alkylamines followed by reaction with 2-chloroethyl isocyanate gave two regioisomers (II and III). The major product (II) and the minor product (III) were determined to be the ureido derivatives of methyl glucoside and methyl altroside, respectively. Nitrosation of II with dinitrogen tetroxide gave 3-substituted 1-(2-chloroethyl)-3-(methyl α-D-glucopyranosid-3-yl)-1-nitrosoureas (VI) in good yields. All the nitrosoureas obtained were remarkably active against leukemia L-1210 and Ehrlich ascites carcinoma. The structure-activity relationships of positional isomers with respect to the nitrosoureido group are discussed.View full abstractDownload PDF (835K) -
HIROKO KIMATA, RYOJI KASAI, OSAMU TANAKA1982 Volume 30 Issue 12 Pages 4373-4377
Published: December 25, 1982
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESSIn connection with our studies on the chemical evaluation of commercial Bupleuri Radix, isolation and identification of saponins of Juk-Siho (a Korean Bupleuri Radix) and roots of Bupleurum longeradiatum, the source plant of this crude drug, were carried out. From Juk-Siho, five saponins 1-5 were isolated. The saponins 1-3 were identified as saikosaponins-a (1), -c (2) and -d (3), respectively, all of which have already been isolated from roots of Bupleurum falcatum. The structures of the new saponins, named chikusaikosides-I (4) and -II (5), were estabished as 3-O-β-xylopyranosyl (1→2)-β-glucopyranosyl-(1→3)-β-fucopyranoside of saikogenin F (6) and 3-O-β-glucopyranosyl (1→6)-(α-rhamnopyranosyl (1→4)-β-glucopyranoside of 6, respectively. From roots of B. longeradiatum, saponins 1-4 were isolated and identified. During the course of the structure study of 4 by 13C-nuclear magnetic resonance (13C-NMR), an anomalous glycosylation shift for the 1, 2-linked glycoside was encountered.View full abstractDownload PDF (609K) -
KIMIO KATSUURA, MASAO OHTA, KEMMOTSU MITSUHASHI1982 Volume 30 Issue 12 Pages 4378-4383
Published: December 25, 1982
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESSThe synthesis and analgesic properties of thiazolo [4, 5-f] morphans (XIIa-c) are described. Monothiazolization of ethyl 2-methyl-1, 3-dioxo-2-cyclohexaneacetate (I) afforded the 2-aminothiazole derivative (II), which was deaminated to ethyl 4, 5, 6, 7-tetrahydro-4-methyl-5-oxo-4-benzothiazoleacetate (V) by means of the Sandmeyer reaction and subsequent hydrogenolysis of the resulting chloride (IVa). In several steps, V was converted to 2, 5-dimethyl-9-oxothiazolo [4, 5-f] morphan (X). Thiazolo [4, 5-f] morphan derivatives (XIIa-c) were synthesized from this key intermediate (X).View full abstractDownload PDF (757K) -
ENKOU NAGASHIMA, KUNIO SUZUKI, MINORU SEKIYA1982 Volume 30 Issue 12 Pages 4384-4395
Published: December 25, 1982
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESSThermal rearrangements of allyl perchlorovinyl sulfides, such as 2, 2-dichloro-, 1, 2-dichloro- and 1, 2, 2-trichloro-substituted vinyl sulfides, are shown to involve unique rearrangements of the carbon skeletons with migration of the chlorines.View full abstractDownload PDF (916K) -
KENJI YAMAGATA, YUKIHIKO TOMIOKA, MOTOYOSHI YAMAZAKI, TAKUMI MATSUDA, ...1982 Volume 30 Issue 12 Pages 4396-4401
Published: December 25, 1982
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESSThirane reacted with malononitrile and sodium hydride to give 2-amino-3-cyano-4, 5-dihydrothiophene (IIa) in 57% yield. Similarly, 2-methyl (or 2-phenyl) thirane reacted with malononitrile to form 2-amino-3-cyano-5-methyl (or 4-phenyl)-4, 5-dihydrothiophene (IIb or IIc). The reactions of the 2-benzamido (or 2-acetamido) derivatives of (IIa or c) with N-bromosuccinimide (NBS) in the presence of 2, 2'-azobisisobutyronitrile gave the corresponding 5-bromothiophenes. On the other hand, the 2-benzamido (or 2-acetamido) derivative of IIb reacted with NBS to yield 2-benzamido (or 2-acetamido)-3-cyano-5-methylthiophene.View full abstractDownload PDF (674K) -
MICHIKO MIYAHARA, MASAHIRO NAKADATE, SHOKO SUEYOSHI, MASAYUKI TANNO, M ...1982 Volume 30 Issue 12 Pages 4402-4406
Published: December 25, 1982
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESS2-Nitrosoureido-1, 3, 4-thiadiazoles were effective against both mouse lymphoid leukemia L1210 and rat ascites hepatoma AH13. Some 2-acylamino-1, 3, 4-thiadiazoles were also effective against L1210. The anti-L1210 action of these 2-acylamino-1, 3, 4-thiadiazoles was blocked by administration of nicotinamide. Among these compounds, 2-propanoylamino-1, 3, 4-thiadiazole was the most effective against L1210, with a maximum T/C% of 166.View full abstractDownload PDF (564K) -
FUMIHIKO YOSHIZAKI, SHUJI HISAMICHI, YOSHIKAZU KONDO, YURIE SATO, SHIG ...1982 Volume 30 Issue 12 Pages 4407-4411
Published: December 25, 1982
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESSFive new furylhydroquinone derivatives, named shikonofurans A, B, C, D and E, were found in the root of Lithospermum erythrorhizon SIEB. et ZUCC. (Boraginaceae). Shikonofuran A was proved to have the structure I, shown in Chart 1, by direct comparison of the spectral data of its diacetate with those of echinofuran leucoacetate. The structures of the other compounds were established on the basis of spectral and chemical evidence as II, III, IV and V, shown in Chart 1.View full abstractDownload PDF (613K) -
YOSHIHITO WATANABE, TETSUO ADACHI, YOSHIMASA ITO, KAZUYUKI HIRANO, MAM ...1982 Volume 30 Issue 12 Pages 4412-4416
Published: December 25, 1982
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESSWe have developed a competitive enzyme immunoassay to determine serum α-fetoprotein for use in clinical diagnosis. β-Galactosidase is employed as a label enzyme with anti-human α-fetoprotein antibody-coated polystyrene beads. By the proposed method, human α-fetoprotein could be determined in the range of 0.1 to 100μg/ml within 2h. Recovery of α-fetoprotein from various serum samples was good. The correlation coefficient between the proposed method and the sandwich enzyme immunoassay, which is commercially available, was 0.969. Coefficients of variation in the within- and between-assays were 7.7 to 9.3% and 6.6 to 20.7%, respectively. This method is rapid, simple and accurate, and is eminently suitable for use as a screening procedure for hepatoma and neural tube defects.View full abstractDownload PDF (601K) -
KAZUTAKI SHIMADA, HISASHI SHINKAI, TOSHIO NAMBARA1982 Volume 30 Issue 12 Pages 4417-4421
Published: December 25, 1982
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESS4-Hydroxyestrone 3- and 4-monoglucuronides were synthesized from catechol estrogens by means of the Koenigs-Knorr reaction with methyl α-acetobromoglucuronate. The position of the glucuronyl residue introduced was unequivocally elucidated by leading the products to the known 4-hydroxyestrone monomethyl ethers. Sulfation of 4-hydroxy-estrone with sulfur trioxide-pyridine complex followed by fractional crystallization provided 4-hydroxyestrone 3-sulfate. The isomeric 4-sulfate was prepared from 4-hydroxyestrone 3-benzyl ether by sulfation and subsequent hydrogenolysis. 4-Hydroxyestradiol monoglucuronides and monosulfates were also obtained from the corresponding 17-ketones by borohydride reduction. The preparation of guaiacol estrogen monoglucuronides and monosulfates is also described.View full abstractDownload PDF (686K) -
JUNICHI GOTO, KAZUHIKO SUZAKI, TOSHIO NAMBARA1982 Volume 30 Issue 12 Pages 4422-4428
Published: December 25, 1982
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESSThe 3-glucuronides of unconjugated and glyco- and tauro-conjugated bile acids having a 7- or 12-oxo group have been synthesized. Introduction of a glucuronyl residue at the C-3 position was achieved by the Koenigs-Knorr reaction using cadmium carbonate as a catalyst. The 3-glucuronides of conjugated bile acids were prepared by three sequential reactions : esterification with p-nitrophenol, glucuronidation at C-3, and amide formation with ethyl glycinate or taurine. The nuclear magnetic resonance spectral properties of 3-glucuronides of oxo bile acids and related compounds are briefly discussed.View full abstractDownload PDF (729K) -
MASATO SHINODA, YASUNORI KUSHI, MOTOYUKI SHIMIZU, SHIZUO NAKAJIN, SABU ...1982 Volume 30 Issue 12 Pages 4429-4434
Published: December 25, 1982
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESSA leukocytosis promotion-inhibiting factor (LPIF) was isolated and purified from crude bovine bile. The purified LPIF was homogeneous on 15% polyacrylamide gel electrophoresis. It inhibits the effects of leukocytosis-promoting substance in rabbits. The molecular weight of LPIF was estimated to be 1.2×104, and the isoelectric point was at pH 8.2. The active component dissociated into two subcomponents with molecular weights of 9000 and 3000 on sodium dodecyl sulfate (SDS) polyacrylamide electrophoresis.View full abstractDownload PDF (581K) -
YUSUKE SASAKI, YASUYUKI AKUTSU, MICHIKO MATSUI, KENJI SUZUKI, SHINOBU ...1982 Volume 30 Issue 12 Pages 4435-4443
Published: December 25, 1982
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESSThirty diketopiperazines were synthesized as analogs of cyclo (-Tyr-Arg-). The analgesic activities of these analogs were evaluated after intracerebral administration in mice. In the cyclo (-X-Arg-) series of analogs, cyclo [-Tyr (Et)-Arg-] showed the most potent activity. In the cyclo (-Tyr-Y-) series of analogs, the activity decreased in the order Y=homoarginine, p-guanidinophenylalanine, 2-amino-4-guanidinobutyric acid, Lys, Orn, His, α, γ-diaminobutyric acid and Pro. Among the analogs synthesized, cyclo-[-Tyr (Et)-Har-], which was designed on the basis of the above results, exhibited remarkably potent analgesic activity, being 17 times more potent than cyclo (-Tyr-Arg-) and nearly as potent as morphine on a molar basis. The structure-activity relation of cyclo(-Tyr-Arg-) is discussed in the light of these results.View full abstractDownload PDF (978K) -
YOSHIYUKI KIMURA, HIROMICHI OKUDA, SHIGERU ARICHI1982 Volume 30 Issue 12 Pages 4444-4447
Published: December 25, 1982
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESSThe effects of geniposide isolated from Gardeniae Fructus ("San-shi-shi"in Japanese) on metabolic alterations in high sugar diet-fed rats were investigated. It was found that the oral administration of the high sugar diet caused hyperlipemia, liver injury with elevation of glutamic pyruvic transaminase (GPT) in the serum, and the accumulation of lipid peroxide in the liver. Geniposide reduced the serum triglyceride, lipid peroxide, phospholipid, glucose, insulin and GPT in the high sugar diet-fed rats. It was found that the administration of geniposide reduced the sucrase activity in the small intestine and the deposition of lipid peroxide in the liver.View full abstractDownload PDF (507K) -
TAKASHI ABIKO, HIROSHI SEKINO1982 Volume 30 Issue 12 Pages 4448-4456
Published: December 25, 1982
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESSTwo new analogues of serum thymic factor (STF), [Dab3]- and [Asn5, Gln9]-STF and four thymic factor fragments, H-Lys-Ser-Gln-OH, H-Lys-Ser-Gln-Gly-OH, H-Lys-Ser-Gln-Gly-OH and H-Lys-Ser-Gln-Gly-Gly-Ser-OH, were synthesized by the solution method, and were tested to determine their effects on the low E-rosette forming cells in patients with chronic renal failure. The analogue [Dab3]-STF and three fragments, H-Lys-Ser-Gln-Gly-OH, H-Lys-Ser-Gln-Gly-Gly-OH and H-Lys-Ser-Gln-Gly-Gly-Ser-OH, increased E-rosette forming capacity when incubated in vitro with patient's blood, but [Asn5, Gln9]-STF and the tripeptide, H-Lys-Ser-Gln-OH, had no effect.View full abstractDownload PDF (966K) -
YOSHIAKI KAWASHIMA, TAKETOSHI KESHIKAWA, HIDEO TAKENAKA, HISAKAZU SUNA ...1982 Volume 30 Issue 12 Pages 4457-4463
Published: December 25, 1982
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESSComputer simulation of closely packed agglomeration of heterogeneous binary circles on a two-dimensional plane was conducted by the use of a random addition model to investigate the mechanism of agglomeration of dispersed particles in a liquid suspension. Under centripetal force, a new coarse or fine circle approached a coarse circle placed on the origin from a random direction. The production of approaching circles was regulated by the probability coefficient of collision (Pc), defined as nf/nf0. The diameter of agglomerate (Dm) was defined as the square root of the area of the 360-gon inscribed in the periphery of the agglomerate. The growth rate of agglomerate was described by equation (3) in the text. log Dm=C3 log t+C4 (λ) (3) The constant C3 reached a maximum at 50 to 60% coarse circle fraction in the agglomerate. The value of Dm (=10C4 (λ) at t=1) increased with increasing coarse circle fraction and the diameter ratio of circles in the agglomerate. The kinetics of agglomeration simulated by the present model followed the first-order rate equation (5) in the text. [numerical formula] The porosity of the agglomerate reached a maximum at 50-60% coarse circle fraction in the agglomerate. The coordination number of the agglomerate increased with increasing coarse circle fraction in the agglomerate. This finding was explained by the fact that the coordination number of coarse circles was larger than that of fine circles in the agglomerate.View full abstractDownload PDF (709K) -
YOICHI SAWAYANAGI, NAOKI NAMBU, TSUNEJI NAGAI1982 Volume 30 Issue 12 Pages 4464-4467
Published: December 25, 1982
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESSThe dissolution step of practically insoluble drugs plays an important role in the drug absorption. In this study, with a view to an application of chitin and chitosan to pharmaceutical preparations, the dissolution behavior of ground mixtures of griseofulvin with chitin and chitosan was investigated. Ground mixtures of griseofulvin with chitin, chitosan and crystalline cellulose were prepared by grinding in a ball mill. The X-ray diffraction patterns and results of differential scanning calorimetry suggested a relative decrease in the size of the crystals of griseofulvin in the ground mixtures. The dissolution rate of griseofulvin from the ground mixtures was significantly greater than that from the physical mixture or from intact griseofulvin powder. The ground mixture with chitosan showed fastest dissolution. These results indicate that chitin and chitosan can improve the dissolution properties of griseofulvin.View full abstractDownload PDF (480K) -
MASAO KOBAYASHI, SHIGEYUKI ISHIKAWA, MASAYOSHI SAMEJIMA1982 Volume 30 Issue 12 Pages 4468-4478
Published: December 25, 1982
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESSSeveral kinds of ointments in the Japanese pharmacopeia were tested in an oscillation rheometer and the results were analyzed by the nonlinear method proposed by Onogi. The stress (σ) curve obtained by application of sinusoidal strain (γ=γ0sinωt) was approximated by a Fourier series, and the first order function (σ1st) was regarded as the linear part. A nonlinearity parameter Dnl was defined as the difference between observed σ and σ1st. Dnl showed different ω dependency for each ointment, and seemed to be related to the pattern of the rheogram. Ordinal viscoelastic parameters such as storage modulus (G'), loss modulus (G"), loss tangent (tan δ), and so on were calculated from the 1st function. The ω dependencies of these parameters were also different for each ointment. The influence of the weight fraction of solid (f8) or liquid component (1-f8) on these parameters was examined for simple ointment and macrogol ointment. A bending point was observed on the log G' vs. f8 plot, which might correspond to the occurrence of stiff bridge structures in the vehicles. Tan δ of the simple ointment was found to increase, in spite of the increase of solid component. This was presumed to be due to a greater increase of G" than of G'. This example shows that the increase of fs does not always result in a relative increase of rheological elasticity. Continuous shear measurement was performed with a Ferranti-Shirley viscometer and several parameters were compared with those obtained by the oscillation method. The correlation seemed to be closer when the shear rate was smaller.View full abstractDownload PDF (957K) -
ISAO SUGIMOTO, KOUZO SASAKI, AKIRA KUCHIKI, TOSHIHIRO ISHIHARA, HIROSH ...1982 Volume 30 Issue 12 Pages 4479-4488
Published: December 25, 1982
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESSIn order to develop preparations of nifedipine with good bioavailability and stability, especially in relation to humidity, various fine granules were prepared by coating lactose surfaces with a dispersion system of nifedipine and water-soluble polymer. The system using polyvinylpyrrolidone (PVP) or hydroxypropylmethylcellulose (HPMC) showed good dissolution properties and bioavailability of nifedipine. It was found that nifedipine in these preparations was chemically stable for 3 months at 75% relative humidity and 40°C. An X-ray diffraction study suggested that nifedipine was present in its amorphous form in the preparations using HPMC or PVP. Amorphous nifedipine in fine granules using HPMC was found to be stable under humid conditions, although crystallization occurred in the granules using PVP. The fine granules using HPMC and PVP both showed good bioavailabilities after oral administrations in dogs, and no significant difference was observed in bioavailability parameters between the fine granules using HPMC and PVP. Preparation of fine granules using HPMC may be a useful means to improve the bioavailabilities and stabilities of poorly water-soluble drugs.View full abstractDownload PDF (971K) -
MOTOHARU IWATSURU, HIDEO NISHIGORI, KAZUO MARUYAMA1982 Volume 30 Issue 12 Pages 4489-4493
Published: December 25, 1982
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESSThe classification of 9 antiinflammatory agents, as well as warfarin and diazepam, on the basis of the binding site on human serum albumin (HSA) was studied by means of competition experiments with bilirubin. The displacement effect was evaluated through kinetic measurements of the free bilirubin concentration by oxidation with hydrogen peroxide and horseradish peroxidase. Bilirubin is a suitable marker for the localization of binding sites, because it has one high-affinity site which is on the loops 3-4 (including Lys-240) in the model of the secondary structure of HSA. Oxyphenbutazone, mefenamic acid and flufenamic acid displaced bilirubin strongly (first group). Sulfinpyrazone, warfarin, ibuprofen, phenylbutazone and aminopyrine showed moderate effects (second group). Ketophenylbutazone, antipyrine and diazepam showed the lowest displacing activity (third group). These results suggest that the binding sites of the first group were the same as or very close to the bilirubin site. The second group may be bound in the neighborhood of the bilirubin site or in the overlapping region of the bilirubin and warfarin sites. The third group may be bound to a different site (s) from bilirubin.View full abstractDownload PDF (562K) -
MORIO KIYOZUMI, MOTOHIRO MISHIMA, SUMIKO NODA, KAZUYO MIYATA, YOSHIHIR ...1982 Volume 30 Issue 12 Pages 4494-4499
Published: December 25, 1982
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESSThe effects of dietary fibers on the gastrointestinal absorption of cadmium were studied. The fibers, such as lignin, cellulose, and sodium carboxymethylcellulose (Na CMC), produced a slight decrease in the contents of cadmium in the tissues of rats following a single oral administration of cadmium. In addition, in rats fed continuously with the experimental diets containing cadmium together with fibers, lignin and Na CMC significantly decreased the contents of cadmium in the tissues. These results show that the fibers depressed the intestinal absorption of cadmium. It is suggested that the inhibitory effects of these fibers on the gastrointestinal absorption of cadmium were due to their intrinsic properties, such as ability to bind cadmium and effect on viscosity, and that the differences of inhibitory effects of the fibers on the intestinal absorption of cadmium were related to differences in such physical properties.View full abstractDownload PDF (624K) -
KAZUHIRO NOJIMA, TAKESHI OHYA, SABURO KANNO, MASAAKI HIROBE1982 Volume 30 Issue 12 Pages 4500-4506
Published: December 25, 1982
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESSUpon irradiation with a xenon lamp through a Pyrex filter (cut-off below 290 nm), olefinic compounds such as trans-stilbene, cyclohexene, 4, 5-dibromocyclohexene and aldrin reacted with nitrogen dioxide, an air pollutant which induces photochemical smog, in air and gave the corresponding epoxides in good yields, while phenanthrene gave 9, 10-phenanthrenequinone and 9-hydroxy-10-nitrophenanthrene. Furthermore, the photochemical and dark reactions of phenanthrene 9, 10-oxide with nitrogen dioxide in air both resulted in the same products as above. Therefore, phenanthrene 9, 10-oxide seems to be an intermediate in the photochemical reaction of phenanthrene with nitrogen dioxide in air.View full abstractDownload PDF (682K) -
JUZIRO NISHIJO, IKUKO YONETANI1982 Volume 30 Issue 12 Pages 4507-4511
Published: December 25, 1982
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESSThe interaction of theophylline with benzylamine in aqueous solution was studied by the solubility method and by proton nuclear magnetic resonance (1H-NMR) spectroscopy. The results show that two types of intearctions, ion pair and stacking, occur between theophylline and benzylamine. Apparent stability constants for the formation of complexes of the ion pair type and stacking type were estimated approximately at 25°C.View full abstractDownload PDF (540K) -
JUNICHI ODO, MAMI UEMATSU, YUTAKA SAITO, YOSHIMASA TANAKA1982 Volume 30 Issue 12 Pages 4512-4515
Published: December 25, 1982
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESSThe infrared spectra of [bis (L-asparaginato) zinc (II)]n and its isotopic complexes containing 64Zn, 68Zn and deuterium have been measured in the region between 4000 and 200 cm-1. By referring to the isotope frequency shifts, three bands at 301, 265 and 244 cm<-1> have been assigned to Zn-ligand stretching vibrations caused from coupling among Zn-O and Zn-N stretching vibrations. The frequency range of the Zn-O stretching vibrations suggests that the Zn-O binding force of zinc-amino acids is probably larger than has been considered.View full abstractDownload PDF (485K) -
TAKAO MORI, HIDEO BANDO, YOSHIO KANAIWA, ETUKO SATO, TAKASHI AMIYA1982 Volume 30 Issue 12 Pages 4516-4517
Published: December 25, 1982
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESSTreatment of 4, 4-dimethyl-5α-cholest-1-en-3-one with nitric acid gave 4, 4-dimethyl-2-nitro-5α-cholest-1-en-3-one. A possible mechanism for the nitration is proposed.View full abstractDownload PDF (322K) -
MASATAKE NIWA, HIROSHI TAKAMIZAWA, HIROSHI TATEMATSU, YOSHIMASA HIRATA1982 Volume 30 Issue 12 Pages 4518-4520
Published: December 25, 1982
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESSFour piscicidal diterpenes have been isolated from the roots of Stellera chamaejasme L. (Thymelaeaceae). These compounds were identified as huratoxin, subtoxin A, simplexin and pimelea factor P2.View full abstractDownload PDF (388K) -
TAKEO HIGASHINO, SHIZUO YOSHIDA, EISAKU HAYASHI1982 Volume 30 Issue 12 Pages 4521-4525
Published: December 25, 1982
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESSThe reaction of 9-phenyl-9H-purine-6-carbonitrile (1) with nucleophilic reagents occurred by addition of the reagent across the C-N triple bond of the cyano group, and substitution of the cyano group was not observed. Thus, the reactions with hydroxylamine, hydrazine, amines, Grignard reagents, and 98% sulfuric acid gave the corresponding amidoxime (2), amidorazone (3), amidines (4), ketones (5), and amide (7), respectively. Alcoholysis of 1 gave the ester (6) and 7 together with the ring fission product of the imidazole portion, alkyl 5-amino-6-anilino-4-pyrimidine-carboxylate (8). Amides (10), the hydroxamic acid (11), and the hydrazide (12) were prepared from the methyl ester (6a).View full abstractDownload PDF (520K) -
KANAME TAKAGI, HIKARI MORITA, KATSUHIKO NAGAHARA, ATSUSHI TAKADA1982 Volume 30 Issue 12 Pages 4526-4528
Published: December 25, 1982
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESSReactions of 3, 4-dibromo-3, 4-dihydrocoumarin (3) with acetamidine and benzamidine gave 6-(2-hydroxyphenyl)-4-oxo-3, 4-dihydropyrimidines (1a and 1b) having in the 2-position the methyl and phenyl substituents, respectively. In these reactions, the coumarin 3 was converted in the first place into 3-bromocoumarin (4) which was then transformed to the pyrimidines 1a and 1b. The coumarin 4 did not undergo the Perkin rearrangement with amidines.View full abstractDownload PDF (417K) -
MASATO SHIMIZU, MASAYUKI ISHIKAWA, YASUO KOMODA, YUKIMI MATSUBARA, TER ...1982 Volume 30 Issue 12 Pages 4529-4533
Published: December 25, 1982
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESSA new route for the synthesis of (±)-trypargine (I) is described. The Pictet-Spengler reaction of Nb-benzyltryptamine with α-ketoglutaric acid was carried out in aprotic media to afford the key intermediate, 2-benzyl-1, 2, 3, 4-tetrahydro-9H-pyrido [3, 4-b] indole-1-propionic acid (IIa), which was converted into (±)-trypargine (I) in five or six steps.View full abstractDownload PDF (552K) -
HIROMICHI BESSO, RYOJI KASAI, JUNXIAN WEI, JUFEN WANG, YUHICHIRO SARUW ...1982 Volume 30 Issue 12 Pages 4534-4538
Published: December 25, 1982
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESSSeveral Ginseng saponins, ginsenosides-Ro (1), -Rb1 (2), -Rb2 (3), -Rc (4), -Rd (5), and -Re (6), have already been isolated from American Ginseng, roots of Panax quinquefolium L. In the present work, further investigation of minor saponins of this plant drug led to the isolation and identification of ginsenosides-Rg1 (7), -Rg2 (8), -Rb3 (9), and -F2 (11), pseudogin-senoside-F11 (10), and gypenoside-XVII (13). In addition to these known saponins, a new saponin named quinquenoside-R1 (12) was also isolated and its structure was determined as mono-O-acetyl-ginsenoside-Rb1 with the acetyl group located at the 6-hydroxyl group of the terminal glucosyl moiety of the β-sophorosyl group.View full abstractDownload PDF (542K) -
ICHIRO TAKAHASHI, SHIRO TERASHIMA1982 Volume 30 Issue 12 Pages 4539-4544
Published: December 25, 1982
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESSThe title compounds (11-14, 16, 17), which are expected to be valuable in the synthesis of 11-deoxyanthracyclinones, were prepared from readily available 1, 8-dihydroxyan-thracene-9, 10-dione (chrysazin) (3) by employing the Claisen rearrangement or Marschalk reaction as a key synthetic step.View full abstractDownload PDF (791K) -
TETSUJI KAMETANI, HIROYASU SEKINE, TOSHIO HONDA1982 Volume 30 Issue 12 Pages 4545-4547
Published: December 25, 1982
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESSThe synthesis of benzhydryl esters of cephalosporin derivatives (4-6) and removal of the benzhydryl protecting group with formic acid are described.View full abstractDownload PDF (427K) -
SANSEI NISHIBE, KAZUKO OKABE, HIROKI TSUKAMOTO, AKIYO SAKUSHIMA, SUEO ...1982 Volume 30 Issue 12 Pages 4548-4553
Published: December 25, 1982
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESSA new caffeoyl glycoside of β, 3, 4-trihydroxyphenethyl alcohol, designated as suspensaside (1), was isolated from the fruits of Forsythia suspensa VAHL (Oleaceae). The structure of 1 was established as DL-β, 3, 4-trihydroxyphenethyl-O-α-L-rhamnopyranosyl-(1→6)-4-O-caffeoyl-β-D-glucopyranoside on the basis of analysis of the carbon-13 nuclear magnetic resonance spectrum and chemical evidence. Compound 1 exhibited antibacterial activity against Staphylococcus aureus TERASHIMA. with MIC 4.1 mM (2.6 mg/ml).View full abstractDownload PDF (605K) -
HIROYUKI NAKATA, YUTAKA SASHIDA, HIROKO SHIMOMURA1982 Volume 30 Issue 12 Pages 4554-4556
Published: December 25, 1982
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESSA new compound, p-hydroxyphenethyl trans-ferulate, was isolated together with 7-(3-methyl-2-butenyloxy) coumarin from the roots of Heracleum lanatum MICHX. var. nipponicum HARA. Both compounds strongly inhibited the growth of the roots of Brassica rapa L. var. pervidis BAILEY.View full abstractDownload PDF (420K) -
MASATOSHI YAMAGUCHI, NAOTAKA KURODA, YOSUKE OHKURA1982 Volume 30 Issue 12 Pages 4557-4561
Published: December 25, 1982
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESSPhosphorescence derived from 3, 4-dihydroxyphenyl derivatives such as catecholamines in aqueous basic solution and its use for the assay of epinephrine and norepinephrine in urine by high-preformance liquid chromatography are described. Intense phosphorescence is obtained from epinephrine and norepinephrine when the amines are allowed to stand in 0.02 M sodium hydroxide at room temperature for 20 min. The limits of detection for epinephrine and norepinephrine are 2×10-8 and 4×10-8M (1 and 2 pmol in 50 μl of sample required for the phosphorimetric procedure), respectively. As little as 5 and 10 pmol of epinephrine and norepinephrine, respectively, in 2.0 ml of urine can be assayed.View full abstractDownload PDF (553K) -
NOBUHIRO MURAMATSU, YUKIO GOTO, TAMOTSU KONDO1982 Volume 30 Issue 12 Pages 4562-4565
Published: December 25, 1982
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESSMicrocapsules having the same surface composition but different surface potentials were prepared, and the effect of the surface potential of the microcapsules on platelet adhesiveness was studied. It was found that platelet adhesion was facilitated by an increase in the surface potential of the microcapsules, and that coating of the microcapsules with plasma caused no change in this trend of facilitated platelet adhesion, though the difference in surface potential disappeared after plasma coating. Therefore, the surface potential of the microcapsules was concluded not to affect the platelet adhesion directly but to influence the adsorption of plasma components on the microcapsules, thereby producing changes in platelet adhesiveness.View full abstractDownload PDF (426K)