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Volume 26, Issue 2
Displaying 1-50 of 57 articles from this issue
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SHINZO TANABE, TAKEICHI SAKAGUCHI1978 Volume 26 Issue 2 Pages 337-342
Published: February 25, 1978
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESSMechanism of the fluorescence reaction of monosubstituted guanidines with 9, 10-phenanthraquinone was investigated. Benzylguanidine reacted with 9, 10-phenanthraquinone in an alkaline solution to give 2-benzylideneamino-1H-phenanthro [9, 10-d]-imidazole (II) as an intermediate of the fluorescence reaction. II easily underwent hydrolysis with HCl to give a fluorescent product, 2-amino-1H-phenanthro [9, 10-d] imidazole hydrochloride monohydrate (I), and benzaldehyde. II also underwent partial hydrolysis in an alkaline solution to give the free base of I, and the free base reacted with 1-naphthol and 9, 10-phenanthraquinone to give an indophenol pigment, N-(1H-phenanthro [9, 10-d]-imidazolyl)-1, 4-naphthoquinone monoimine (IV). Amidines also reacted with 9, 10-phenanthraquinone in the presence of alkali to afford 2'-(substituted) spiro[9H-fluorene-9, 4'-[4H] imidazol]-5'(3'H)/5'(1'H)-ones (VI and VII) which underwent an intramolecular rearrangement, as a non-fluorescent product.View full abstractDownload PDF (675K) -
MIYOKO KIUCHI, HISATORA KURODA1978 Volume 26 Issue 2 Pages 343-349
Published: February 25, 1978
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESSThe mycelia of Cochliobolus miyabeanus were treated with hot aqueous phenol and the lipopolysaccharide like substance (LPS-LS) was isolated from aqueous layer. By gel filtration, the LPS-LS was separated to 2 fractions (peak I, peak II) and further investigation was carried out about the peak II fraction and following results were obtained. 1) The molecular weight was about 42000. 2) It consisted of protein (2.0-2.2%), carbohydrate (83-88%), phosphorus (4.5-4.7%), and lipid (6.0-7.5%). 3) Arabinose, mannose, glucose, galactose glucosamine, fatty acids with C14 : 0, C16 : 0, and C18 : 0 were detected in the carbohydrate and lipid moieties, respectively. 4) It indicated low degree of pyrogenicity and antigenicity to rabbits.View full abstractDownload PDF (736K) -
YOSHIKI HAMADA, KENICHI MORISHITA, MINORU HIROTA1978 Volume 26 Issue 2 Pages 350-358
Published: February 25, 1978
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESSReissert compounds (II to XI) were obtained by the application of potassium cyanide and acyl chloride to 4, 6-phenanthroline (I) in dichloromethane and water. Reaction of I with silver cyanide and benzoyl chloride afforded the Reissert compounds (XI to XIII), and XIII had an amino group. Reaction of XI with methanol or ethanol gave the Reissert compound XII or XIV. Reaction of XV, XVI, and XVII with potassium cyanide and benzoyl chloride gave compounds (XVIII to XXII). This Reissert reaction was examined by Huckel's approximation and its results on Reissert compounds obtained agreed approximately with experimental results.View full abstractDownload PDF (830K) -
NORIICHI ODA, TSUTOMU OSAKI, SHINICHI NAGAI, ISOO ITO1978 Volume 26 Issue 2 Pages 359-366
Published: February 25, 1978
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESSThe reactivity of 3-ferrocenyl-pyrazolones was studied. Alkylation of 3-ferrocenyl-2-pyrazolin-5-one (2b) occurred on the pyrazolone ring to give 2 or 4 alkyl or 5 alkoxy derivatives. Vilsmeyer-Haack formylation of 3-ferrocenyl-3-pyrazolin-5-one (5a) occurred on the pyrazolone ring at 4 position. Diazocoupling reaction to 3-ferrocenyl-2-pyrazolin-5-ones (2a, b) occurred on the pyrazolone ring at 4 position as well.View full abstractDownload PDF (828K) -
FUMIO YONEDA, TOMOHISA NAGAMATSU, KAZUKO OGIWARA, MICHIKO KANAHORI, SA ...1978 Volume 26 Issue 2 Pages 367-373
Published: February 25, 1978
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESSA new synthesis of 1, 3-dimethyl-6-azalumazines (isofervenulins) is described. The reaction of 6-amino-1, 3-dimethyl-5-nitrosouracil (I) with acid hydrazides in refluxing aprotic solvents such as dimethylformamide (DMF), dimethyl sulfoxide (DMSO) or sulfolane affords the corresponding 1, 3-dimethyl-6-azalumazines (II) along with byproducts, 2, 4, 9, 11-tetramethyl-8-azapurino [7, 8-f]-6-azapteridine-1, 3, 10, 12 (2H, 4H, 9H, -11H)-tetrones (III). These 8-azapurino [7, 8-f]-6-azapteridines were alternatively prepared by the condensation of II with 6-amino-1, 3-dimethyluracil in refluxing DMF. Compounds II were converted into 8-substituted theophyllines (V) by reductive ring contraction with sodium dithionite in formic acid.View full abstractDownload PDF (672K) -
YOSHIO NAKAGAWA, MIEKO IKAWA, KOGO HIRAGA1978 Volume 26 Issue 2 Pages 374-378
Published: February 25, 1978
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESSBiological fate of 14C-labeled butylated hydroxytoluene (14C-BHT) in rat liver was investigated. After a single oral dose of 14C-BHT, the radioactivity was reached a maximum concentration in the liver after 6 hr and in the serum after 6-12 hr. A bulk of radioactivity was found in the supernatant fraction, although the amount of radioactivity and specific radioactivity increased in the microsomal fraction with time. The radioactivity which was incorporated into the microsomal fraction was mainly located in the smooth ER 3-6 hr after the administration. These results suggest that the radioactivity, which was incorporated into the supernatant fraction, migrated to the microsomal fraction.View full abstractDownload PDF (676K) -
TERUHIKO MESHI, HAJIME TAMAKI1978 Volume 26 Issue 2 Pages 379-386
Published: February 25, 1978
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESSVarious factors influencing intestinal absorption of a quaternary anticholinergic agent, timepidium bromide (TB), were studied in rats using in situ intestinal loop technique. Bile, mucin and intestinal mucous material significantly decreased the amount of TB absorbed from intestinal loops. This decrease was assumed to be due to bonding of TB cation to anionic groups of bile constituents, mucin and intestinal mucous membranes. Gastric juice and hydrochloric acid significantly increased the absorption of TB. Organic acids, such as citric, malic and acetic acid, also increased the absorption of TB. The greatest increase in absorption of TB was observed in the presence of citric acid. Citric acid had this facilitatory effect only when added to the medium in relatively high concentrations (0.05M) and at relatively low pH. However, this increased absorption was shown not to be simply the result of an acidic intestinal environment or irreversible changes in the gut wall.View full abstractDownload PDF (937K) -
HAJIME TAMAKI, TERUHIKO MESHI1978 Volume 26 Issue 2 Pages 387-393
Published: February 25, 1978
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESSEnhancement of absorption of a quaternary anticholinergic agent, timepidium bromide (TB), was studied in vivo and in situ in rats. Intraduodenally administered citric acid markedly increased the amount of TB absorbed, but orally administered citric acid did only slightly. The difference in absorption of TB between oral and duodenal administration of citric acid was assumed to be due to the fact that citric acid delayed gastric emptying. It was found that the absorption of TB from in situ intestinal loop varied with drug concentration, the greater the concentration the greater the absorption. In the presence of high concentrated solution of tertiary amine of TB, diphemanil methylsulfate or prifinium bromide, which are structural analogues of TB, the absorption of TB was markedly enhanced. This increased absorption of TB was unrelated to the activity of the additives as an anticholinergic agent.View full abstractDownload PDF (851K) -
HIROSADA SUGIHARA, KIYOSHI UKAWA, AKIO MIYAKE, KATSUMI ITOH, YASUSHI S ...1978 Volume 26 Issue 2 Pages 394-404
Published: February 25, 1978
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESSA method for preparing 5-substituted 2-tertiary-alkylamino-6-hydroxy-1, 2, 3, 4-tetrahydro-1-naphthalenols was described. The method involves the preparation of 1-alkylamino-2-hydroxy-1, 2, 3, 4-tetrahydronaphthalenes from 2-bromo-1-hydroxy derivatives via 1, 2-epoxides followed by the transposition of 1-alkylamino and 2-hydroxy groups via the ring closure to 1, 2-aziridines. Formation of the epoxides and aziridines and the reaction of epoxides with amines were examined in detail. The ring-opening reaction of epoxides was regioselective and the attacking position of a nucleophile was not affected by the electronic effects of substituents on the benzene ring. Cyclization into aziridine rings was best accomplished by the Wenker method using a sulfur trioxide-triethylamine adduct as the sulfating agent. Using our process, trans-2-tert-butylamino-6-hydroxy-5-hydroxymethyl-1, 2, 3, 4-tetrahydro-1-naphthalenol (70) was synthesized as conformationally fixed analog of salbutamol.View full abstractDownload PDF (1106K) -
SHIGERU AONUMA, MASARU OKABE, YUICHI KAWAI, MAKOTO KAWAGUCHI1978 Volume 26 Issue 2 Pages 405-410
Published: February 25, 1978
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESSZona solubility properties to proteases were found to be different depending on the surroundings in which the treatments were done. The authors found that not all mouse ova which ovulated after the usual superovulation treatment were susceptible to zona removal by proteases in modified Krebs Ringer bicarbonate medium, that this susceptibility diminished as the time between ovulation and recovery increased, and that the proportion of fertilizable ova in vitro was the same order and the same pattern as the changes of zona solubility properties. The additional treatment of the mice with PMS abolished the decline in susceptibility and fertilizability. When ova were recovered at 12 hr after HCG injection and held in culture for a further 12 hr, there was no significant decline in either variable. If ova were placed for 2 hr in sperm suspension, dissolution of the zona by protease was completely prevented but this effect was not produced by sperm-free supernatants of sperm suspension. The effect was induced sooner by in vitro capacitated spermatozoa (15 min) than by epididymal spermatozoa (45 min). The loss of dissolution susceptibility in these treatments with sperm suspension was associated with the time of sperm penetration reported in previous paper.View full abstractDownload PDF (776K) -
HIROSADA SUGIHARA, KIYOSHI UKAWA, AKIO MIYAKE, YASUSHI SANNO1978 Volume 26 Issue 2 Pages 411-422
Published: February 25, 1978
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESS5- or 7-Substituted cis- and trans-2-tert-butylamino-6-hydroxy-1, 2, 3, 4-tetrahydro-1-naphthalenols (cis-29-cis-32) and (trans-30-trans-35) were synthesized from 1, 2-N-tertbutylimino derivatives. Acid-catalyzed ring opening of 1, 2-alkylimino-1, 2, 3, 4-tetrahydronaphthalene derivatives (1-11) produced a mixture of cis- and trans-2-alkylamino-1, 2, 3, 4-tetrahydro-1-naphthalenol derivatives whose ratio was markedly affected by substituents on the benzene ring. Stereoselective ring opening of the aziridines and interconversion of cis- and trans-2-alkylamino-1-tetralols via 1-hydroxysulfonyloxy intermediates were described. The reaction mechanism of acid-catalyzed ring opening of the aziridines and hydrolysis of 2-alkylamino-1-hydroxysulfonyloxy-1, 2, 3, 4-tetrahydronaphthalene derivatives is also discussed.View full abstractDownload PDF (1270K) -
SHINZO TANABE, TAKEICHI SAKAGUCHI1978 Volume 26 Issue 2 Pages 423-428
Published: February 25, 1978
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESSThe structures of the fluorescent products produced by the reaction of butylbiguanide, β-phenethylbiguanide, and N, N-dimethylbiguanide with 9, 10-phenanthraquinone in the presence of alkali were investigated. These biguanides gave a free base (IIIb) or ethanol adducts (IVb and Vb) of 2-alkylguanidino-1H-phenanthro [9, 10-d] imidazoles from alkaline solution and their hydrochloride monohydrates (IIIa and IVa) or dihydrochloride (Va) from acidic solution. The structure of these products was determined from their elemental analyses and nuclear magnetic resonance, mass, and high-resolution mass data.View full abstractDownload PDF (651K) -
MITSUZI YOSHIDA, KAZUO KURETANI, AKIO HOSHI1978 Volume 26 Issue 2 Pages 429-434
Published: February 25, 1978
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESS5-Fluorouridine and 1-β-D-arabinofuranosylcytosine are active against various tumors as antimetabolites. Antitumor activity and mode of action of their nucleotides, 5-fluorouridine 5'-phosphate and 1-β-D-arabinofuranosylcytosine 5'-phosphate, were examined. 5-Fluorouridine 5'-phosphate was active similar to the nucleoside against L1210 leukemia, but the nucleotide showed higher therapeutic ratio than 5-fluorouracil and 5-fluorouridine. The mode of action of these nucleotides was examined by the incorporation of labeled precursors into acid-insoluble fraction of the cells for 30 min. Inhibition patterns of these nucleotides were the same as those of the nucleosides, but the potency of the nucleotides was very weak, and increased with time. Analysis showed that these nucleotides were dephosphorylated on the cell surface and the dephosphorylation was greater than that of phenolphthalein monophosphate. 5-Fluorouridine 5'-phosphate was considered to be a good candidate for an antitumor agent.View full abstractDownload PDF (633K) -
YOSHITERU IDA, NAOKI NODA, SHIRO KUBO, TETSUYA KOMORI, TOSHIO KAWASAKI1978 Volume 26 Issue 2 Pages 435-439
Published: February 25, 1978
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESSTwo kinds of furanoid norditerpene glucosides, named diosbulbinosides D (I), mp 169-173°(dec.), [α] D-31°, and F (II), mp 193-195°(dec.), [α]350-25°, were isolated from the fresh root tubers of Dioscorea bulbifera L. forma spontanea MAKINO et NEMOTO. On the basis of chemical and spectral evidences I and II were assigned the structures, 6-O-β-D-glucopyranosides of the enol forms, 5-en-6-ols, of coexisting diosbulbins D (IV) and F (V), respectively. They are noted as the non-conjugated enol glucosides.View full abstractDownload PDF (635K) -
NAKAO KOJIMA, YUKIO SUGIURA, HISASHI TANAKA1978 Volume 26 Issue 2 Pages 440-447
Published: February 25, 1978
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESSSolution equilibria of the In (III) and Ga (III) complex species of 2, 3-dimercaptopropionylglycine (DMPG) and 2-mercaptopropionyl-L-cysteine (MPC) have been investigated by potentiometry in aqueous solution. The formation constants of various species and their distribution as a function of pH were evaluated with a non-linear leastsquares treatment of the potentiometric data. The structural features and the complexation mechanisms were proposed through the interpretation of the results of the potentiometric and infrared spectral (in D2O) studies. In the various protonated species formed in the In (III) solutions of DMPG and MPC, the carboxyl and sulfhydryl groups are protonated, respectively. In the 1 : 1 DMPG-In (III) system, the stable In (OH) L species formed even in the alkaline solution. Ga (III) resists complexation with monosulfhydrylcontaining ligands in contrast to In (III), but forms the complex with disulfhydryl-containing ligands in spite of the occurrence of the hydrolytic precipitation during part of the titration of the MPC-Ga (III) solution. Once formed Ga (III) complex is stable as well as In (III). Two sulfhydryl groups of peptides were required for complexation, even in the In (III) case. In all cases, no deprotonation of the peptide-amide proton was observed. The potentiometric calculations gave the large values of the equilibrium constants of the complexes, indicating that the disulfhydryl-containing peptides are remarkably effective towards the formation of the complexes of In (III) and Ga (III) in aqueous solution.View full abstractDownload PDF (804K) -
SADAO OIDA, AKIRA YOSHIDA, EIJI OHKI1978 Volume 26 Issue 2 Pages 448-455
Published: February 25, 1978
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESSPhotolysis of N-diazoacetyloxazolidine compounds, 7c and 8c, afforded oxapenams, 9 and 10, respectively. The physical data of 9 and 10 along with their behavior on thinlayer chromatograms were consistent with that of the samples derived from clavulanic acid (1), a β-lactamase inhibitor, confirming their structures. Further, a methylene oxapenam 18 was obtained from an oxapenam 17 having a phenylseleno group by selenoxide elimination reaction.View full abstractDownload PDF (1059K) -
TOSHIRO IBUKA, YUJI MORI, TOSHITAKA AOYAMA, YASUO INUBUSHI1978 Volume 26 Issue 2 Pages 456-465
Published: February 25, 1978
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESSThe Diels-Alder reaction of the novel 1, 3-bis (trimethylsiloxy) cyclohexa-1, 3-dienes (3a-3c) with acrylonitrile followed by hydrolysis afforded the exo-2-cyano-1-hydroxybicyclo [2. 2. 2] octanes (4a-4c) and the endo-2-cyano-1-hydroxybicyclo [2. 2. 2] octanes (5a-5c) as the major and the minor adducts, respectively. The configuration of the cyano group of the adducts were inferred from the nuclear magnetic resonance spectral inspections of the appropriate derivatives obtained from the adducts and these assignments of the adducts (4a, 4b, 5a, and 5b) were supported by chemical evidence.View full abstractDownload PDF (1298K) -
HIROSHI TAKAHASHI, HIROTAKA OTOMASU1978 Volume 26 Issue 2 Pages 466-471
Published: February 25, 1978
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESSUnconjugated chiral azomethines, N-isobutylidene derivatives of (S)-α-amino acid esters (I-VI) were synthesized. The structures of these compounds were confirmed by the infrared, mass spectrum and nuclear magnetic resonance (NMR) spectra. The conformations were discussed by the NMR spectra. The characteristic absorption band for the unconjugated chiral azomethine compounds were observed nearly at 240 nm by the circular dichroism spectra.View full abstractDownload PDF (651K) -
SHIGERU GOTO, HIRONORI YOSHITOMI, MASAKO NAKASE1978 Volume 26 Issue 2 Pages 472-480
Published: February 25, 1978
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESSThirteen sulfonylurea derivatives were synthesized and their binding with bovine serum albumin was investigated, using an equilibrium dialysis technique. The Scatchard plots for data of 11 sulfonylurea derivatives indicated the presence of more than two classes of a binding site. The binding parameters, k1, k2, n1, and n2 were computed by the principle of least squares method. Physicochemical properties such as the dissociation constant in water and partition coefficient with octanol-water system were obtained. With the use of Hansh analysis, BSA binding constants could be represented as follows : For the binding constant at the primary site, log k1=0.512 log P+3.754, binding constant at the secondary site, log k2=0.334 log P+0.240 pKa+1.480. An important role of hydrophobicity must be considered for binding at the primary site, but electrostatic force as well as hydrophobic force must also be included for binding at the secondary site.View full abstractDownload PDF (820K) -
ZENICHI HORII, CHUZO IWATA, YOSHIHIKO NAKASHITA1978 Volume 26 Issue 2 Pages 481-483
Published: February 25, 1978
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESSdl-Pronuciferine has been synthesized via photochemical cyclization of 8-bromo-1, 2, 3, 4-tetrahydro-6, 7-dimethoxy-1-(4-hydroxybenzyl)-2-methylisoquinoline.View full abstractDownload PDF (445K) -
ISAO KITAGAWA, MASAYUKI YOSHIKAWA, AKIKO KADOTA1978 Volume 26 Issue 2 Pages 484-496
Published: February 25, 1978
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESSIn a continuing study on the selective cleavage method for the β-D-glucuronide linkage contained in oligoglycoside, the behavior of methyl β-D- and α-D-glucuronides and methyl β-D- and α-D-galacturonides has been examined towards lead tetraacetate oxidation followed by alkali treatment. It has been found that the lead tetraacetate degradation method is a useful tool for cleavage of the α-D-glucuronide and β-D-galacturonide linkages as well as the β-D-glucuronide linkage. The α-D-galacturonide has been found to show considerable resistance for lead tetraacetate oxidation. In addition, the dialdehyde intermediate (23) in the reaction sequence has been shown to be a promissing species which is readily convertible to nitrocyclitols.View full abstractDownload PDF (1469K) -
YASUHIRO YAMANE, KAZUO SAKAI, IKUO MORITA1978 Volume 26 Issue 2 Pages 497-503
Published: February 25, 1978
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESSEffect of molybdenum on 4-hydroxyaminoquinoline 1-oxide (4-HAQO) reductase activity was examined in the liver of mice. 4-Nitroquinoline 1-oxide reductase in the mouse liver hardly showed decrease in the activity by the administration of tungsten. 4-HAQO reductase activity showed 40-50% decrease of the control by the administration of tungsten to mice as in xanthine oxidase and sulfite oxidase, molybdenum-containing enzymes. The 4-HAQO reductase activity decreased by the administration of tungsten was recovered by the administration of molybdenum.View full abstractDownload PDF (800K) -
KATSUMI ITOH, HIROSADA SUGIHARA, AKIO MIYAKE, NORIO TADA, YOSHIKAZU OK ...1978 Volume 26 Issue 2 Pages 504-513
Published: February 25, 1978
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESSInvestigations on the essential conformation of adrenergic catecholamines led us to synthesize 6-amino-1, 2-dihydroxy-6, 7, 8, 9-tetrahydro-5H-benzocyclohepten-5-ol derivatives (1), which are seven-membered rigid analogues of catecholamines. Although catalytic reduction of the amino ketones (9 and 10) leading to the analogues of noradrenaline and isoproterenol (1a and 1c) yielded mixtures of 5, 6-cis and trans isomers, it was found that lithium aluminum hydride reduction of α-hydroxyimino ketone (12) gave exclusively cis-amino alcohol (13a-cis) and that reduction of α-acetamido ketone (14) with sodium borohydride followed by hydrolysis afforded 13a-trans. Several pairs of 5, 6-cis and trans isomers of 1 were prepared by catalytic reduction of 13a-cis and 13a-trans or their Nsubstituted derivatives. N-tert-Butyl derivative (1d-trans) was prepared via 13d-trans which was obtained by hydrolysis of an azirizino compound (24).View full abstractDownload PDF (1143K) -
HISASHI ISHII, TSUTOMU ISHIKAWA, YUHICHIRO ICHIKAWA1978 Volume 26 Issue 2 Pages 514-519
Published: February 25, 1978
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESSEthyl isodecarine (3) was synthesized by Pschorr reaction of (E)-styrene carboxylic acid (13). The structure of decarine (2) was established by chemical evidence that ethyl isodecarine (3) is not identical with the sample of ethyl decarine (15).View full abstractDownload PDF (752K) -
YASUHARU SUGA, YOHKO MARUYAMA, SACHIKO KAWANISHI, JUNZO SHOJI1978 Volume 26 Issue 2 Pages 520-525
Published: February 25, 1978
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESSPhytolaccasaponin B, E and G, the major saponins of Phytolacca americana L. (Phytolaccaceae), have been isolated. The structures of phytolaccasaponin B, E and G have been established to be phytolaccagenin 3-O-[β-D-glucopyranosyl (1→4)-β-D-xylopyranoside]-28-O-β-D-glucopyranoside (4), phytolaccagenin 3-O-β-D-glucopyranosyl (1→4)-β-D-xylopyranoside (5) and phytolaccagenin 3-O-β-D-xylopyranoside (6), respectively. Phytolaccatoxin reported by Stout, et al. was assumed to be a mixture of more than three saponins, but the main saponin was identified as 5 by thin-layer chromatography.View full abstractDownload PDF (810K) -
KOTARO TAKAHASHI, MASAKO TAKANI1978 Volume 26 Issue 2 Pages 526-529
Published: February 25, 1978
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESSThe structure of the degradation product of dihydrousnic acid, obtained by the oxidation with potassium permanganate, followed by the dry distillation was studied and a possible formula was put forward on basis of the chemical and spectral evidences.View full abstractDownload PDF (565K) -
TOKUHIRO WATANABE, FUMIKO HAMAGUCHI, SADAO OHKI1978 Volume 26 Issue 2 Pages 530-538
Published: February 25, 1978
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESSReduction of 3-substituted phthalimides with sodium borohydride in 90% methanol was found to give one kind each of reduction product and solvolysis product. In the case of an electron-withdrawing nitro group, the carbonyl group in 2-position was selectively reduced to the hydroxyl group, whereas in the case of an electron-donating amino, acetamido, hydroxyl, or methoxyl group, the carbonyl group in 1-position was reduced to the methylene group, and the formation of a solvolysis product increased. In the case of 4-substituted compounds, two kinds each of reduction product and solvolysis product were obtained. When the substituent was a nitro group, ratio of the products from reduction of imidocarbonyl in 1- and 2-position was about 5 : 4, while this ratio became about 4 : 5 inversely in the case of electron-donating substituent groups. In the solvolysis products, the position attacked in the imidocarbonyl and the position reduced became the same, and their ratio was the same as in the reduction products.View full abstractDownload PDF (974K) -
MASAHIKO FUJINO, MITSUHIRO WAKIMASU, SUSUMU SHINAGAWA, CHIEKO KITADA, ...1978 Volume 26 Issue 2 Pages 539-548
Published: February 25, 1978
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESSThe nonacosapeptide corresponding to the entire amino acid sequence of mammalian glucagon was synthesized via the corresponding sulfoxide, [Met (O)27]-glucagon. For synthesis of the protected nonacosapeptide six subunits were prepared to serve for building blocks. The condensations of subunits were achieved by the HONB-DCC method. Finally, all the protecting groups of the protected peptide were removed by the treatment with methanesulfonic acid-anisole to give [Met (O)27]-glucagon. The sulfoxide was then treated with 3% aqueous thioglycolic acid to give mammalian glucagon. The product was successfully crystallized from dilute aqueous sodium chloride solution. The N to O acyl migration of serine and threonine residues with methanesulfonic acid treatment was studied in detail.View full abstractDownload PDF (1383K) -
HITOSHI UNO, MIKIO KUROKAWA1978 Volume 26 Issue 2 Pages 549-555
Published: February 25, 1978
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESSThe base catalyzed ring expansion of 2-substituted 2H-1, 2-benzisoxazolin-3-one (3) to 2-substituted 2H-1, 3-benzoxazin-4-one (4) was observed during the alkylation of 3-hydroxy-1, 2-benzisoxazole (1).View full abstractDownload PDF (601K) -
TETSUJI KAMETANI, MITSUHIRO TAKESHITA, HIDEO NEMOTO, KEIICHIRO FUKUMOT ...1978 Volume 26 Issue 2 Pages 556-562
Published: February 25, 1978
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESSTetrahydronaphthoquinone (8) and naphthoquinone reacted with the o-quinodimethanes, generated in situ from the benzocyclobutenes (7) and (14), to give the naphthacene-5, 12-quinone derivatives (9, 15 and 25).View full abstractDownload PDF (741K) -
MOTOHARU JU-ICHI, YOSHIKO ANDO, AKIKO SATOH, JUNICHI KUNITOMO, TETSURO ...1978 Volume 26 Issue 2 Pages 563-570
Published: February 25, 1978
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESSThe utility of the INDOR and NOE techniques for the determination of the substitution pattern on the aromatic ring of erythrinan alkaloids is demonstrated. Synthesis of 3α, 16-dimethoxyerythrinan-1 (6)-ene (III) was accomplished by a route similar to that developed by Mondon, et al.View full abstractDownload PDF (965K) -
HARUAKI YAJIMA, JUN IWAI, KANAME KOYAMA, MASUHISA NAKAMURA, KENJI MIYA ...1978 Volume 26 Issue 2 Pages 571-578
Published: February 25, 1978
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESSIn a conventional manner, the hexadecapeptide corresponding to the entire amino acid sequence of dogfish β-MSH (Squalus acanthias) was synthesized using protecting groups removable by hydrogen fluoride. The synthetic peptide exhibited the in vitro MSH activity of 1.88×109 MSH U/g.View full abstractDownload PDF (1014K) -
NAKAO KOJIMA, YUKIO SUGIURA, HISASHI TANAKA1978 Volume 26 Issue 2 Pages 579-584
Published: February 25, 1978
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESSThe various physico-chemical studies were made on the complex-formation equilibria between In (III) and sulfhydryl-containing bidentate ligands, such as 2-aminoethanethiol (2-mercaptoethylamine, MEA), 3-mercaptopropionic acid (MPA), and mercaptoacetic acid (thioglycolic acid, TGA). The insoluble and stable complex, InL3, was formed during the titration of the MEA-In (III) solution. The complex formation of In (III) with MPA and TGA was investigated by potentiometric titration over a wide range of the metal concentration. Calculation of the titration data of the MPA-In (III) system indicated that MPA formed the In2L3, In3L4, and In3 (OH) L4 species together with the mononuclear species. In the higher concentration, non-charged species, In3 (OH) L4, was precipitated. In the alkaline solution, the carboxyl group was eliminated from the coordination sphere and the InL4 species was formed. These observations in the MPA-In (III) system were similar to those of the cysteine case. Since TGA forms the stable complex with fivemembered chelate ring, the InL4 or hydrolyzed species were not formed even in the alkaline solution. Calculation indicated the formation of the InL3, In2L3, and In3L5 species in the TGA system.View full abstractDownload PDF (702K) -
CHIEKO KITADA, MASAHIKO FUJINO1978 Volume 26 Issue 2 Pages 585-590
Published: February 25, 1978
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESSA new test for racemization was developed and used to assess known coupling reagents and procedures. The procedure consists of coupling between BOC-Ala-Met-Leu-OH and tert-butyl ester of amino acid [Leu, Ile or Asp (OBut)], cleaving of the resulting peptide by cyanogen bromide to form dipeptide diastereomers, and analyzing both isomers with an amino acid analyzer. The following results were obtained : 1) The DCC-additive (Eintopf) method, especially the HONB-DCC procedure, was somewhat superior to the standard azide method. 2) Even in the azide method, epimerization during peptide bond formation considerably increased in the presence of excess base. 3) Significant racemization was observed in some of the known coupling methods which have been shown, by the Young or Anderson test, to be free from racemization.View full abstractDownload PDF (703K) -
TOSHIO NAMBARA, JUNICHI GOTO, HIROKO FURUYAMA, HIROAKI KATO1978 Volume 26 Issue 2 Pages 591-595
Published: February 25, 1978
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESSFor the purpose of obtaining antisera used for direct radioimmunoassay of estriol glucuronides, two new haptens, estriol 3- and 16-glucoside derivatives possessing a carboxyl group, have been synthesized. Condensation of estriol 3-carboxymethyl ether with 1-bromo-1-deoxy-α-D-glucopyranose tetraacetate in the presence of cadmium carbonate provided the 16-glucoside together with a small amount of the 17-isomer. The Koenigs-Knorr reaction with 6-oxoestriol 16, 17-diacetate under similar conditions afforded the 3-glucoside which in turn was led to the 6-(O-carboxymethyl) oxime. Removal of the protecting groups in estriol 3- and 16-glucoside derivatives was effected by treatment with methanolic alkali to yield the desired compounds.View full abstractDownload PDF (652K) -
MINORU MACHIDA, TETSUO TAKAHASHI, KAZUHIKO ITOH, TAKAMITSU SEKINE, YUI ...1978 Volume 26 Issue 2 Pages 596-604
Published: February 25, 1978
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESSN-(3-Acridinyl) maleimide (3-AM) and N-(9-acridinyl) maleimide (9-AM) were prepared and their reactions with thiol compounds including egg albumin were examined. Both 3-AM (7) and 9-AM (9) react readily with thiol compounds to form strongly fluorescent addition products. Their absorption and fluorescence spectra were measured, and it was found that they are useful fluorescence thiol reagents. Comparative use of the both reagents will afford information on the states of thiols and they serve as a special kind of hydrophobic probe for microenvironment of thiols in macromolecules.View full abstractDownload PDF (966K) -
MATAO KANAOKA, TOSHIHARU ISHIDA, TOHRU KIKUCHI1978 Volume 26 Issue 2 Pages 605-610
Published: February 25, 1978
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESSCholine esters of peptides related to tetragastrin, Z-Asp (OBut)-Phe-OCh+ Br-(XII), Z-Met-Asp (OBut)-Phe-OCh+ Br-(XIII), Z-Trp-Met-Asp(OBut)-Phe-OCh+ Br-(XIV), and BOC-Trp-Met-Asp (OBut)-Phe-OCh+ Br- (XV) were synthesized by the condensation of N-protected peptides, (VI), (VII), (VIII), and (IX), with β-dimethylaminoethyl bromide followed by methylation with methyl bromide. Selective removal of the protective groups from the above peptide choline esters was achieved by conventional acid treatment under mild conditions.View full abstractDownload PDF (706K) -
TAKUO KOSUGE, KUNIRO TSUJI, KEIJI WAKABAYASHI, TOSHIHIKO OKAMOTO, KOIC ...1978 Volume 26 Issue 2 Pages 611-619
Published: February 25, 1978
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESSThe present paper describes the detail of the serach of mutagenic principles in tars from amino acids, especially from tryptophan. A series of amino acids was pyrolyzed and was tested their mutagenicity to find that basic fractions from pyrolysates of tryptophan, ornitine, glutamic acid, serine, lysine and creatine showed potent mutagenicities to TA98 than the fractions from pyrolysates of other amino acids. Among them the active principles in the pyrolysate of tryptophan were identified as 3-amino-1, 4-dimethyl-5H-pyrido-[4, 3-b] indole (designated as Trp-P-1) and 3-amino-1-methyl-5H-pyrido [4, 3-b] indole (designated as Trp-P-2). Among several antimicrobial tar constituents, it was found that 2-amino-5-phenylpyridine, benzo [f] quinoline and phenanthridine also were mutagenic.View full abstractDownload PDF (846K) -
TAKEFUMI MOMOSE, SHUJI UCHIDA, ETSUKO HOSOYA, MASAHIKO KINOSHITA, TAKE ...1978 Volume 26 Issue 2 Pages 620-626
Published: February 25, 1978
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESSThe isomerization reaction of N-nonsubstituted (1 and 3), N-benzylated (4 and 5), and N-benzoylated octahydro-7 (1H)-quinolones (6 and 7) and decahydroquinoline-2, 7-dione derivatives (8-15) was investigated under various acidic and basic conditions. Except for the N-benzoyl-7-ones (6 and 7), isomerization features were interpreted as the phenomenon associated both with the facility of the cis-isomers and the difficulty of the trans-ones in the retro-Michael ring opening to form amino enone intermediates and with predominance of the cis-ring junction over the trans-one in the subsequent recyclization of the intermediates. Isomerization of N-benzoyloctahydro-7 (1H)-quinolone resulted in the exclusive formation of the cis-ketone (6) and in the successful isolation of the intermediate (18). The contrasting feature was interpreted by assuming both the facile ring opening of the trans-ketone (7) possibly via a cyclic process (7') and the retarded recyclization of 18, due to a reduced nucleophilicity of the amido nitrogen, resulting in a failure in the formation of 7.View full abstractDownload PDF (826K) -
KAZUKO OHGI, HIDEAKI WATANABE, MASACHIKA IRIE1978 Volume 26 Issue 2 Pages 627-630
Published: February 25, 1978
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESSIn order to investigate whether carboxyl-terminal amino acid is involved in the active site of a base non-specific ribonuclease from Asp. saitoi (RNase Ms), removal of carboxyl-terminal amino acid residues by digestion with carboxypeptidase A was investigated. By 24 hours digestion, about 3 serine residues and 1.0 alanine residue were removed from RNase Ms and its activity decreased to about 70% of the native enzyme so far as measured with ribonucleic acid (RNA) as a substrate. The pH optimum and Km of carboxypeptidase treated RNase Ms (CP-RNase Ms) were very similar to those of native RNase Ms so far as measured with RNA as a substrate. However, Km of CP-RNase Ms using ApC as a substrate seemed to be larger than that of native RNase Ms. The large increase in Km value was not observed in the early stage of digestion where about 3 serine residues were removed. The gross structure of CP-RNase Ms was quite similar to that of the native RNase Ms by judging from circular dichroism spectrum at wavelength between 230-205 nm. From the results described above, it was concluded that carboxyl-terminal amino acid was not involved directly in the active site of RNase Ms.View full abstractDownload PDF (534K) -
MASANAO TERASHIMA, KOICHI KOYAMA, YUICHI KANAOKA1978 Volume 26 Issue 2 Pages 630-632
Published: February 25, 1978
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESSPhotocyclization of N-(5, 6, 7, 8-tetrahydro-1-naphthyl) phthalimide (3) afforded 5, 10, 11, 12, 12a, 12b-hexahydro-12b-hydroxyisoindolo [2, 1-α] benz [cd] indol-5-one (4) in good yield. On acid treatment, 4 was readily dehydrated to give 5, 10, 11, 12-tetrahydroisoindolo [2, 1-α] benz [cd] indol-5-one (5).View full abstractDownload PDF (463K) -
TETSUZO KATO, MASAYUKI SATO, YOSHINORI KITAGAWA1978 Volume 26 Issue 2 Pages 632-635
Published: February 25, 1978
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESSPhotoreaction of diketene with 3-acetoxy-5, 5-dimethyl-2-cyclohexenone (1) gives 6-acetoxy-7-hydroxy-4, 4-dimethyl-cis-bicyclo [4.2.0] octan-2-one-7-acetic acid β-lactone (2 and 3). Treatment of 2 with dimethylamine affords 3-acetoxy-7-hydroxy-N, N, 4, 4-tetramethyl-cis-bicyclo [4.2.0] octan-2-one-7-acetamide (4), while similar treatment of 3 affords 1-acetoxy-N, N, 4, 4-tetramethylcyclooctane-2, 6-dione-1-acetamide (5). This result suggests the spiro-configuration of 2 is the trans (acetoxy and oxetane O), while that of 3 being the cis.View full abstractDownload PDF (527K) -
SHIGERU KOBAYASHI, MASARU KIHARA, SATOSHI MINEO1978 Volume 26 Issue 2 Pages 635-639
Published: February 25, 1978
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESSThe apogalanthamine analogs, 5, 6, 7, 8-tetrahydrodibenz [c, e] azocine (10) and its Nsubstituted derivatives (11-15) were synthesized. Boron tribromide was found to be effective for cleavage and bromination of the lactone ring in diphenide (25). This is the first time it has been employed as a cleaving and brominating agent for a lactone.View full abstractDownload PDF (648K) -
ATSUSHI SUGII, KUMIKO HARADA1978 Volume 26 Issue 2 Pages 640-642
Published: February 25, 1978
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESSA subtractor column for aldehydes and ketones in gas chromatography was proposed. Crude acrylhydrazide, without troublesome purification, was used for the coating material. The column showed a stronger affinity for carbonyl compounds than the porous polymer containing hydrazide groups reported previously. Alcohols, hydrocarbons, ethers, and esters were not subtracted by this column. Concentration of the liquid phase and column temperature affected the subtraction of carbonyl compounds and the column life.View full abstractDownload PDF (423K) -
TAKAO MURAKAMI, MINORU KUDO, SATOSHI TAGUCHI, NOBUTOSHI TANAKA, YASUHI ...1978 Volume 26 Issue 2 Pages 643-645
Published: February 25, 1978
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESSDie erneute Untersuchung von Pteris inaequalis BAKER var. aequata (MIQ.) TAGAWA ergab zwei neue Verbindungen, Hydroxymaltol-3-O-β-D-glukosid (I) und 2-Deoxy-D-glukonsauremethylester (II). I wurde ebenfalls aus Pteris formosana BAKER isoliert.View full abstractDownload PDF (502K) -
TOZO FUJII, SHIGEYUKI YOSHIFUJI, MASASHI OHBA1978 Volume 26 Issue 2 Pages 645-649
Published: February 25, 1978
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESSA highly stereoselective, efficient synthetic route to ethyl trans-5-ethyl-2-oxo-4-piperidineacetate (11a) from 1-benzyl-2, 4-dioxo-5-ethylpiperidine (2) is described. The steps involved are conversion of 2 into 1-benzyl-5-ethyl-2-oxo-1, 2, 5, 6-tetrahydropyridine (6) through the lactam alcohol (5), the Michael condensation of 6 with diethyl malonate followed by alkaline hydrolysis, decarboxylation of the resulting trans-lactam dicarboxylic acid (8a) to the trans-lactam acid (9a), and debenzylation of 9a followed by esterification.View full abstractDownload PDF (714K) -
NOBUTAKA FUJII, TAKASHI SASAKI, SUSUMU FUNAKOSHI, HIROSHI IRIE, HARUAK ...1978 Volume 26 Issue 2 Pages 650-653
Published: February 25, 1978
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESSSodium perborate can be used for oxidation of Nα-protected Met derivatives to the corresponding (R, S)-sulphoxide. Thus a new derivative, Z(OMe)-Met-(R, S)-sulphoxide was easily prepared in good yield. Sodium metaperiodate was also employed for this purpose.View full abstractDownload PDF (558K) -
YOJI OHASHI, YOSHIYASU TERAO, MINORU SEKIYA1978 Volume 26 Issue 2 Pages 653-655
Published: February 25, 1978
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESSA new application of N-[(N-nitrosobenzylamino) methyl] benzamide as a direct benzylating agent has been realized by benzylation of several protic materials. Ferric chloride functions as a catalyst in the benzylation of ethanol, acetic acid, phenol, and thiols.View full abstractDownload PDF (446K) -
MINEO SHIMIZU, MUNEHISA ARISAWA, NAOKATA MORITA, KARUHISA KIZU, TSUYOS ...1978 Volume 26 Issue 2 Pages 655-659
Published: February 25, 1978
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESSFour triterpenoid saponins, tentatively named saponins K3, K6, K10 and K12, were isolated from the stems of Hedera rhombea BEAN (Araliaceae). They were identified with hederagenin glycosides represented as formulae I, III, V and IX, respectively.View full abstractDownload PDF (634K) -
MATAO KANAOKA, YUJI KURATA1978 Volume 26 Issue 2 Pages 660-664
Published: February 25, 1978
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESS4, 5-Diaryl-4-oxazolin-2-one [V : R=CH3O (AOX) and R=Cl (COX)] derivatives of amino acids were prepared by condensation of 4, 5-diaryl-1, 3-dioxol-2-one (III : R=CH3O and R=Cl) with amino acids. These oxazolinone derivatives were stable to NaOH-aq. EtOH and liquid hydrogen fluoride at room temperature, but were cleaved by hydrogenolysis over pd-carbon. Pentagastrin protected with AOX group, AOX-Gly-Trp-Met-Asp-Phe-NH2, was prepared and its biological effect was examined on gastric secretion in young chicken.View full abstractDownload PDF (608K)