Chemical and Pharmaceutical Bulletin

Studies on Pillaromycin A. I. The Properties of Pillaromycin A and Pillaromycinone

MITSUKO ASAI

1970 Volume 18 Issue 9 Pages 1699-1705
Published: September 25, 1970
Released on J-STAGE: March 31, 2008

DOIhttps://doi.org/10.1248/cpb.18.1699

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A molecular formula, C₃₈H₃₈O₁₁, has been given for pillaromycin A. Acid hydrolysis of pillaromycin A afforded an aglycone, pillaromycinone, C₂₀H₁₈O₇ and a new sugar, pillarose, C₈H₁₂O₅. From the results of spectrometrical and chemical studies on pillaromycinone and its derivatives the presence of the following functional groups was elucidated in pillaromycinone ; two sec-hydroxyls, a tert-hydroxyl, two phenolic hydroxyls, a chelated carbonyl and an acetyl conjugated with α, β-unsaturated double bond.

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Studies on Pillaromycin A. II. The Structure of Pillaromycinone

MITSUKO ASAI

1970 Volume 18 Issue 9 Pages 1706-1712
Published: September 25, 1970
Released on J-STAGE: March 31, 2008

DOIhttps://doi.org/10.1248/cpb.18.1706

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The structure of pillaromycinone (II) was elucidated. The ultraviolet (UV) spectrum of PMN tetraacetate (VI) was similar to that of 1, 2, 3, 4-tetrahydro-1-oxophenanthrene. On oxidative degradation pillaromycinone dimethyl ether (IX) gave 3-methoxy-1, 2, 4, 5-benzenetetracarboxylic acid (X) and 3-methoxyphthalic acid (XI). Zinc dust distillation of II gave anthracene and naphthacene. The UV spectrum of II resembles to that of anhydrodemethyltetracycline. From the chemical and spectrometric data the structure of β-substance (IV) was suggested to be 1, 2, 3, 4, 4a, 5, 12, 12a-octahydro-12-oxo-4, 10, 11, 12a-tetrahydroxynaphthacene. The nuclear magnetic resonance (NMR) and the spin decouplings of isopropylidene PMN (XVI) and PMN (II) gave the structure (3(S), 4(R), 4a(R), 12a(R)) 2-acetyl-3, 4, 4a, 5, 12, 12a-hexahydro-12-oxo-3, 4, 10, 11, 12a-pentahydroxynaphthacene to PMN (II).

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Studies on Pillaromycin A. III. The Structure of Pillarose

MITSUKO ASAI

1970 Volume 18 Issue 9 Pages 1713-1719
Published: September 25, 1970
Released on J-STAGE: March 31, 2008

DOIhttps://doi.org/10.1248/cpb.18.1713

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Pillarose (I), C₈H₁₂O₅, gives positive Fehling's and iodoform reactions. Absorption of an isolated carbonyl is observed in the infrared and ultraviolet region. I formed methyl pillarosides (VIIa, b) and mono-, diacetylpillaroses, and reacted with sodium borohydride to yield methyl dihydropillarosides (Xa, b). I consumed 2 moles of periodate. Periodate oxidation of I in acidic solution gave acetaldehyde, formic acid (and formaldehyde), succinaldehydic acid and carbon dioxide. From these degradation schemes and physico chemical properties of the above derivatives the structure, 2, 3, 6-trideoxy-2-glycoloylhexopyranos-4-ulose, was given to pillarose (I).

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Studies on Pillaromycin A. IV. The Structure of Pillaromycin A

MITSUKO ASAI, EIJI MIZUTA, KOMEI MIZUNO, AKIRA MIYAKE, SUEO TATSUOKA

1970 Volume 18 Issue 9 Pages 1720-1723
Published: September 25, 1970
Released on J-STAGE: March 31, 2008

DOIhttps://doi.org/10.1248/cpb.18.1720

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The structure of pillaromycin A (I, PMA), C₂₈H₂₈O₁₁, is elucidated as I. In PMA (I) 12a hydroxyl of pillaromycinone (II, PMN), C₂₀H₁₈O₇, is linked glycosidicaly to the 1'-anomeric hydroxyl of pillarose (III), C₈H₁₂O₅.

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Studies on Pillaromycin A. V. The X-Ray Analysis of Pillaronone Monobromoacetate

KAZUHIDE KAMIYA, MITSUKO ASAI, MASAO NISHIKAWA, KOMEI MIZUNO, YUJIRO T ...

1970 Volume 18 Issue 9 Pages 1724-1730
Published: September 25, 1970
Released on J-STAGE: March 31, 2008

DOIhttps://doi.org/10.1248/cpb.18.1724

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In order to confirm the chemical and stereochemical structure of pillaronone, a derivative of the aglycone obtained from pillaromycin A, an X-ray analysis of its monobromoacetate has been carried out. Pillaronone monobromoacetate crystallizes in the orthorhombic system, space group P2₁2₁2₁-D⁴₂, with four molecules of C₂₂H₁₉O₆Br in a unit cell. Application of a three-dimensional Patterson superposition method facilitated the elucidation of the structure which is given in formula (I). The final R-value was 0.133. The absolute configuration was determined using the anomalous dispersion of the bromine atom. The molecular structure in the crystal was also discussed.

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Chemistry of Diborane and Sodium Borohydride. VII. Reduction of α-Amino Acid Amides with Sodium Borohydride

ISAO SAITO, YASUO KIKUGAWA, SHUNICHI YAMADA

1970 Volume 18 Issue 9 Pages 1731-1736
Published: September 25, 1970
Released on J-STAGE: March 31, 2008

DOIhttps://doi.org/10.1248/cpb.18.1731

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Tertiary amides of five amino acids and their derivatives were reduced with sodium borohydride in refluxing pyridine to the corresponding diamines in moderate yields. Effects of substituents at the α-position on α-substituted N, N-dimethylhydrocinnamamide were examined.

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Studies on Metabolism of 3-Deoxysteroids. IV. Synthesis of 2, 17-Oxygenated 5-Dehydro- and 5β-Androstanes

TOSHIO NAMBARA, HIROI TAKAHASHI, YAYOI KAMIKAWA

1970 Volume 18 Issue 9 Pages 1737-1741
Published: September 25, 1970
Released on J-STAGE: March 31, 2008

DOIhttps://doi.org/10.1248/cpb.18.1737

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For the studies on metabolic fate of 3-deoxydehydroepiandrosterone in man, 5-dehydro- and 5β-androstanes having oxygen functions at both C-2 and C-17, the possible metabolites, have been synthesized as shown in Chart 1.

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Studies on Tertiary Amine Oxides. XXXIX. Reactions of Aromatic N-Oxides with Indoles in the Presence of Acylating Agents

MASATOMO HAMANA, ITSUMARO KUMADAKI

1970 Volume 18 Issue 9 Pages 1742-1750
Published: September 25, 1970
Released on J-STAGE: March 31, 2008

DOIhttps://doi.org/10.1248/cpb.18.1742

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Indole (II) was found to react as an aromatic analog of enamine with acyl-adducts of quinoline 1-oxide (I) and ethyl nicotinate 1-oxide (VI) under refluxing condition in chloroform, and 3-(2-quinolyl) indole (III) and ethyl 6-(3-indolyl) nicotinate (VII) were obtained, respectively, but no reaction occured with pyridine 1-oxide. Benzoyl chloride was most effective as an acylating agent. 1-Methylindole (VIII) underwent similar reactions. The reaction with I gave 1-methyl derivative of III (IX) as well as 4-quinolyl compound (X). From the reaction with 2-chloroquinoline 1-oxide (XI), 1-methyl-3-(2-chloro-4-quinolyl) indole (XIII) and 1-benzoyloxy-2-hydroxy-4-(1-methyl-3-indolyl)-1, 4-dihydroquinoline (XIV) were produced, the isolation of XIV being significant from the mechanistic view point. 4-Chloroquinoline 1-oxide and VIII afforded 2-quinolyl compound (XVI). Further 2-phenylindole was shown to react with I under similar conditions, but skatole resisted the reaction.

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Oxidative Addition of Alkyl Mercaptans to Steroidal Δ^{4, 6}-3-Ketones

HIDEHIKO KANEKO, YUZURU YAMATO, MIKIO KUROKAWA

1970 Volume 18 Issue 9 Pages 1751-1758
Published: September 25, 1970
Released on J-STAGE: March 31, 2008

DOIhttps://doi.org/10.1248/cpb.18.1751

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Addition of ethyl mercaptan to 6-dehydro-17α-methyltestosterone (I) in the presence of the organic bases afforded two oxidative addition products together with the corresponding 7α-ethylthio derivative (II) in minor yields. Both of them were formulated as 6α-hydroxy-7β-ethylthio- and 6β-hydroxy-7α-ethylthio-17α-methyltestosterone (III and IV) by chemical evidences and the spectral data. Under similar condition, androsta-4, 6-diene-3, 17-dione (XII) gave an unexpected compound, 4-ethylthio-7β-hydroxyandrost-4-en-3-one (XXIII) accompanied with 7α-ethylthio (XIII), 6α-hydroxy-7β-ethylthio (XIV) and 6β-hydroxy-7α-ethylthio derivative (XV).

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Studies on the Proton Magnetic Resonance Spectra in Aromatic Systems. XVI. On the Electronic Indices of Substituted Benzene and Naphthalene Derivatives

YOSHIO SASAKI, MIYOKO SUZUKI

1970 Volume 18 Issue 9 Pages 1759-1773
Published: September 25, 1970
Released on J-STAGE: March 31, 2008

DOIhttps://doi.org/10.1248/cpb.18.1759

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The Electronic Indices : π-Electron charge density ρ, F_r, S_r^(E), S_r^(R) and S_r^(N) : were obtained for monosubstituted-benzene, 1-substituted-3, 4-dimethoxybenzene, 2-substitutednaphthalene and 2-substituted-6-methoxy-naphthalene derivatives, and the following results were obtained. 1. The ρ values are linearly related with the substituent constant σ_π. 2. F_r, S_r^(E), S_r^(R) and S_r^(N) are linearly related with the substituent constant σ_π when the substituent groups are electron releasing, but not when they are electron attracting. 3. The electronic indices of polysubstituted benzene derivatives expressed by the simple sum of the excess value Δ with reference to benzene are comparable with calculated values.

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Studies on the Proton Magnetic Resonance Spectra in Aromatic Systems. XVII. On the Electronic Indices of 3-and 4-Substituted Pyridine, 6-Substituted Quinoline and 6-Substituted Quinoxaline Derivatives

YOSHIO SASAKI, MIYOKO SUZUKI

1970 Volume 18 Issue 9 Pages 1774-1787
Published: September 25, 1970
Released on J-STAGE: March 31, 2008

DOIhttps://doi.org/10.1248/cpb.18.1774

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The electronic indices : π-electron charge density ρ, F_r, S_r^(E), S_r^(R) and S_r^(N) : were obtained for 3-and 4-substituted pyridine, 6-substituted quinoline and 6-substituted quinoxaline derivatives, and the following results were obtained. 1. The ρ values are linearly related to the substituent constant σ_π. 2. F_r, S_r^(E), S_r^(R) and S_r^(N) are linearly related with σ_π for electron releasing substituent group sites, but this linear relation does not hold for electron attracting substituent group sites. 3. The reliability of the simple sum rule of molecular electronic indices was confirmed.

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Studies on the Racemization of Amino Acids and Their Derivatives. II. On the Deuterium-Hydrogen Exchange Reaction of Amino Acid Derivatives in a Medium of Deuterated Acetic Acid

HISAYUKI MATSUO, YUTAKA KAWAZOE, MOTOMU SATO, MASAKO OHNISHI, TAKASHI ...

1970 Volume 18 Issue 9 Pages 1788-1793
Published: September 25, 1970
Released on J-STAGE: March 31, 2008

DOIhttps://doi.org/10.1248/cpb.18.1788

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Studies on the Racemization of Amino Acids and Their Derivatives. III. The Effect of Alkyl-, Aralkyl- and Aryl-Side Chain at α-Position of Amino Acids on Their Base-Catalyzed Racemization

MOTOMU SATO, TAKASHI TATSUNO, HISAYUKI MATSUO

1970 Volume 18 Issue 9 Pages 1794-1798
Published: September 25, 1970
Released on J-STAGE: March 31, 2008

DOIhttps://doi.org/10.1248/cpb.18.1794

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Kinetical study was carried out in the base-catalyzed racemization reaction of N-benzoyl anilide derivatives of six neutral amino acids, such as alanine, α-aminobutyric acid, valine, leucine, phenylalanine and phenylglycine. From the comparison of rate-constants thus obtained, it was concluded that the susceptibility of amino acids tested to the racemization may be expressed in thrm of acidity of α-proton related to the electronnegativity of alkyl-, aralkyl- and aryl-side chains at α-carbon.

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Grignard Reaction and Products. I. 1, 4-Addition of Arylmagnesium Bromide to 2-Alkylidenecyclohexanone and the Oxidative Cleavage therein

KAZUKO MIYANO, TANEZO TAGUCHI

1970 Volume 18 Issue 9 Pages 1799-1805
Published: September 25, 1970
Released on J-STAGE: March 31, 2008

DOIhttps://doi.org/10.1248/cpb.18.1799

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Phenylmagnesium bromide reacted with 2-cyclohexylidenecyclohexanone (I) affording 2-(1-phenylcyclohexyl) cyclohexanone (II) in main, via 1, 4-addition. Besides, it accompanied 6-(1-phenylcyclohexyl)-6-oxo-hexanoic acid (III) as by-product, even though the reaction was carried out in a stream of nitrogen, using purified ether as a solvent. It was found that (a) III itself did not exist just after the Grignard reaction and appeared after heating of the reaction mixture at 70-80° ; (b) the ketone II, even in the enol form, did not produce a substance which convert into III by the absorption of oxygen. This suggested that the III-precursor, presumably a peroxide, was produced in the course of the Grignard reaction, thereafter transformed to III. Reactions for the identification of III and the Grignard reaction of other α, β-unsaturated ketones were persued.

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Grignard Reaction and Products. II. A Novel Intramolecular Cyclization in the Grignard Reaction of Alicyclic Ketoxime containing an Aromatic Nucleus

KAZUKO MIYANO, TANEZO TAGUCHI

1970 Volume 18 Issue 9 Pages 1806-1814
Published: September 25, 1970
Released on J-STAGE: March 31, 2008

DOIhttps://doi.org/10.1248/cpb.18.1806

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A novel intramolecular cyclization reaction was found in the reaction of 2 (1'-phenyl)-cyclohexylcyclohexanone oxime (I-oxime) with aromatic Grignard reagent, either phenyl- or p-tolylmagnesium bromide, which worked as a catalyst. The reaction required at least 3 equivalent moles of Grignard reagent. The structure of the cyclization product (II) was established as spiro [bicyclo [3.3.1]-3, 4-benzononan-9-one-2, 1'-cyclohexane]. The structural feature of oximes which suffer the cyclization reaction was preliminary discussed.

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Quantitative Estimation of Auxins and Antiauxin in Etiolated Seedlings of Phaseolus Bean by Gas Chromatography and Colorimetry. I

TOSHIHIKO OKAMOTO, YO ISOGAI, TORU KOIZUMI

1970 Volume 18 Issue 9 Pages 1815-1821
Published: September 25, 1970
Released on J-STAGE: March 31, 2008

DOIhttps://doi.org/10.1248/cpb.18.1815

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The quantitative estimation methods were established for Me-IAA, IAN, PAM, IAM, IAA, and PHCA by gas chromatography and colorimetry.

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Studies on Tertiary Amine Oxides. XL. Reactions of Aromatic N-Oxides with Oxindoles in the Presence of Acylating Agents

MASATOMO HAMANA, ITSUMARO KUMADAKI

1970 Volume 18 Issue 9 Pages 1822-1830
Published: September 25, 1970
Released on J-STAGE: March 31, 2008

DOIhttps://doi.org/10.1248/cpb.18.1822

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1-Methyloxindole (II) reacted as an active methylene compound with acyl-adducts of quinoline 1-oxides (I, IX and VIII), forming 1-methyl-3-(2- or 4-quinolyl)oxindoles (III, XV or XI). The reaction with I in the presence of acetic anhydride or benzoyl chloride further proceeded and gave bis-quinolyl compound (IV) besides mono-quinolyl one (III). The order of effectiveness of acylating agents was acetic anhydride>benzoyl chloride>tosyl chloride. Pyridine 1-oxide (XVII) itself was also able to react with II in hot acetic anhydride to give four kinds of products, 2-pyridyl- (XX), bis-2-pyridyl- (XIX), 4-pyridyl-product (XXI) and acetate of XXI (XVIII). The reaction of oxindole (XXVI) with I progressed similarly and 3-(2-quinolyl)-oxindole (XXVII) was obtained.

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Usnic Acid. VII. The Pyrolysis of Methyldihydrousnic Acid

KOTARO TAKAHASHI, MASAKO TAKANI

1970 Volume 18 Issue 9 Pages 1831-1840
Published: September 25, 1970
Released on J-STAGE: March 31, 2008

DOIhttps://doi.org/10.1248/cpb.18.1831

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1) The structures of two pyrolysis products of methyldihydrousnic acid (I) were established to be II and III, respectively. 2) The mechanism of the formation of II and III from I were discussed. 3) The mass spectra of V and isoanhydromethyldihydrousnic acid monoacetate, and X and anhydromethyldihydrousnic acid monoacetate were studied.

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Syntheses of Aminoisoquinolines and Related Compounds. VIII. Total Synthesis of dl-Homolinearisine

SABURO ISHIWATA, KEIICHI ITAKURA

1970 Volume 18 Issue 9 Pages 1841-1845
Published: September 25, 1970
Released on J-STAGE: March 31, 2008

DOIhttps://doi.org/10.1248/cpb.18.1841

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8-Amino-1, 2, 3, 4-tetrahydro-7-methoxy-1-(4-methoxybenzyl)-2-methyl-6-isoquinolinol (IIa) was synthesized and the Pschorr reaction of this compound under alkaline conditions gave dl-homolinearisine, which could not be synthesized by the phenolic oxidative coupling method. Infrared and nuclear magnetic resonance spectra of the synthesized sample were superimposable with those of the natural product.

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Synthesis of Aminoisoquinolines and Related Compounds. IX. Synthesis of dl-O-Methylcaseadine

SABURO ISHIWATA, KEIICHI ITAKURA

1970 Volume 18 Issue 9 Pages 1846-1849
Published: September 25, 1970
Released on J-STAGE: March 31, 2008

DOIhttps://doi.org/10.1248/cpb.18.1846

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The Mannich reaction of tetrahydroisoquinolines (IVa, b) with 36% formalin in acetic acid gave respectively protoberberines (Va, b) and each compounds were converted to tetramethoxyprotoberberines (Ic, d). Ic was identified by the infrared and nuclear magnetic resonance spectral comparisons with caseadine methyl ether derived from natural caseamine or caseadine. Hydrochloric acid catalyzed condensation of 7, 8-disubstituted tetrahydroisoquinoline (VIII) with 36% formalin gave the same compound (Ic).

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Synthesis of Aminoisoquinolines and Related Compounds. X. A Modified Synthesis of dl-Cularine

SABURO ISHIWATA, TATSUJI FUJII, NOBUYUKI MIYAJI, YOSHIYUKI SATOH, KEII ...

1970 Volume 18 Issue 9 Pages 1850-1855
Published: September 25, 1970
Released on J-STAGE: March 31, 2008

DOIhttps://doi.org/10.1248/cpb.18.1850

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The Bischler-Napieralski reaction of the phenethylamides (VIIa and VIIb) gave respectively the 6-ethoxycarbamido-3, 4-dihydroisoquinolines, formed by the cyclization at the position para to the ethoxycarbamido group, and both 3, 4-dihydroisoquinolines were converted to the 6-aminoisoquinolines (Xa and Xb). Each 7, 8-disubstituted isoquinolines (XIIa and XIIb), prepared by deamination reaction of Xa and Xb, were submitted to the Ullmann reaction to give respectively 6-methoxy-1-methyl-1, 2, 3, 12, 12a-pentahydrobenzoxepino [2, 3, 4-i, j] isoquinoline (XIII) and dl-cularine (Ia).

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Uber die Monoterpenglucoside. X. Secoiridoid-Glucoside aus Swertia japonica. Isolierung von funf Secoiridoid-Glucosiden sowie die Strukturaufklarung des Swerosids, des Swertiamarins und des Gentiopicrosids

HIROYUKI INOUYE, SHINICHI UEDA, YUSHIN NAKAMURA

1970 Volume 18 Issue 9 Pages 1856-1865
Published: September 25, 1970
Released on J-STAGE: March 31, 2008

DOIhttps://doi.org/10.1248/cpb.18.1856

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Aus Swertia japonica MAKINO wurden neben Swertiamarin (I) folgende vier Glucoside isoliert, die auch bitter schmecken und zu den Secoiridoid-Glucosiden zu zahlen sind : Amarogentin, Amaroswerin, Gentiopicrosid (II) und Sweroid (III). Weiter wurden die Absolutstrukturen des Swertiamarins (I), des Gentiopicrosids (II) und des Sweroids (III) klargestellt.

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Colorimetric Determination of Ammonia. IV. A New Method with o-Chlorophenol and 2, 6-Dichloroisocyanurate

RYOJI YAMAGUCHI, HANA SUZUKI, HIROKO HIRASHIMA

1970 Volume 18 Issue 9 Pages 1866-1871
Published: September 25, 1970
Released on J-STAGE: March 31, 2008

DOIhttps://doi.org/10.1248/cpb.18.1866

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Use of o-chlorophenol instead of salicylate improved the sensitivity of salicylate-2, 6-dichloroisocyanurate method for the determination of ammonia. By the use of 2, 6-dichloroisocyanurate, the stored oxidant solution became more stable than sodium hypochlorite, which had been commonly used up to now. The presence of a micro-amount of sodium nitroprusside was necessary. Apparent molar extinction coefficient on the basis of nitrogen atom and coefficient of variation at 15.15μg/ml ammonium sulfate were 3.14×10⁴ and 1.83%, respectively. Absorbance of the reagent blank at 665 mμ was as low as 0.058±0.005.

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Plant Growth Regulators in the Pea Plant (Pisum sativum L.)

YO ISOGAI, YASUO KOMODA, TOSHIHIKO OKAMOTO

1970 Volume 18 Issue 9 Pages 1872-1879
Published: September 25, 1970
Released on J-STAGE: March 31, 2008

DOIhttps://doi.org/10.1248/cpb.18.1872

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A pea inhibitor was isolated as natural free acid and as its methyl ester from the garden peas (Pisum sativum L.) and they were identified with (+)-abscisic acid (Ia) and its methyl ester (Ib), respectively. On the other hand, sayanedine, mp 165-166°, C₁₇H₁₄O₅, which is a new isoflavone and which had kinetin-like activity in the tabacco pith callus bioassay, was also isolated from the same plant, and its chemical structure was confirmed to be 4'-hydroxy-7, 3'-dimethoxyisoflavone (VI) on the basis of spectral and synthetic evidences.

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Structure of Serratinidine and Fawcettidine. A New Type of Lycopodium Alkaloid

HISASHI ISHII, BOMPEI YASUI, RYUICHI NISHINO, TAKASHI HARAYAMA, YASUO ...

1970 Volume 18 Issue 9 Pages 1880-1888
Published: September 25, 1970
Released on J-STAGE: March 31, 2008

DOIhttps://doi.org/10.1248/cpb.18.1880

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Structures of two Lycopodium alkaloids, serratinidine (I) from Lycopodium serratum THUNB. var. serratum f. serratum and fawcettidine (XIX) from Lycopodium fawcettii LYLOYD et UNDERWOOD, were examined. In the previous papers, the authors suggested the biogenesis of serratinine and in connection of this, the skeletal structure ((B) in Chart 1) for serratinidine was selected as a working hypothesis. The validity of this assumption was shown by chemical correlation of serratinine ((C), R=OH, in Chart 1) of established structure with serratinidine through the route shown in Chart 2. On the other hand, fawcettidine was first isolated by Burnell from a Jamaican Lycopodium plant but since then there has been no report on the structure. From physical and spectral properties of this alkaloid appeared in the literature, the authors postulated the same skeletal structure for fawcettidine as that of serratinidine. Then, this assumption was proved by chemical conversion of serratinine into fawcettidine along the schemes shown in Chart 5. The present study reveals a new structural type of Lycopodium alkaloid.

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Uber die Monoterpenglucoside. XI. Chemische Korrelation des Asperulosids mit Swerosid

HIROYUKI INOUYE, TAKASHI YOSHIDA, YUSHIN NAKAMURA, SHUSAKU TOBITA

1970 Volume 18 Issue 9 Pages 1889-1899
Published: September 25, 1970
Released on J-STAGE: March 31, 2008

DOIhttps://doi.org/10.1248/cpb.18.1889

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Durch die Uberfuhrung des in der Absolutstruktur abgeklarten Asperulosids (IV) und des Swerosids (III) zu 9-Epidihydroswerosid-tetraacetat ist die chemische Korrelation der beiden Naturstoffe festgestellt. Dabei wurde weiter die Stereochemie der Aglucone von Dihydroswerosid (XXVIII), α-Tetrahydrogentiopicrosid (XXV) und 9-Epidihydroswerosid sowie die der aus diesen Agluconen abgeleiteten Dilactone diskutiert.

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The Metabolic Fate of 1-(4-Methoxy-6-methyl-2-pyrimidinyl)-3-methyl-5-methoxypyrazole (Mepirizole, DA-398) in Rats and Rabbits

EIGO TAKABATAKE, RYUHEI KODAMA, YOSHIAKI TANAKA, RENZO DOHMORI, HARUO ...

1970 Volume 18 Issue 9 Pages 1900-1907
Published: September 25, 1970
Released on J-STAGE: March 31, 2008

DOIhttps://doi.org/10.1248/cpb.18.1900

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The metabolic fate of 1-(4-methoxy-6-methyl-2-pyrimidinyl)-3-methyl-5-methoxy-pyrazole (mepirizole, DA-398) was investigated in rat and rabbit. Four metabolites were isolated as crystals from the urine of medicated rats and identified as 1-(4-methoxy-5-hydroxy-6-methyl-2-pyrimidinyl)-3-methyl-5-methoxypyrazole (UNM-1), 1-(4-methoxy-6-methyl-2-pyrimidinyl)-3-hydroxymethyl-5-methoxypyrazole (UNM-2), 1-(4-methoxy-6-methyl-2-pyrimidinyl)-5-methoxypyrazole-3-carboxylic acid (UAM-1) and 1-(4-methoxy-6-methyl-2-pyrimidinyl)-3-methyl-4-hydroxy-5-methoxypyrazole sulfate (URM-1). From the rabbit urine, UAM, UNM-2, UNM-4 (1-(4-methoxy-6-hydroxymethyl-2-pyrimidinyl)-3-methyl-5-methoxypyrazole) were isolated and the excretion of UNM-1, UNM-3 (2-hydroxy-4-methoxy-6-methylpyrimidine) and UNM-5 (1-(4-methoxy-6-methyl-2-pyrimidinyl)-3-methyl-4-hydroxy-5-methoxypyrazole) were identified on thin-layer chromatogram. The major metabolite was UAM-1 both in rat and in rabbit.

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Syntheses of the Urinary Metabolites of 1-(4-Methoxy-6-methyl-2-pyrimidinyl)-3-methyl-5-methoxypyrazole (Mepirizole, DA-398)

RENZO DOHMORI, RYUICHI YOSHIMURA, SHINICHI KITAHARA, YOSHIAKI TANAKA, ...

1970 Volume 18 Issue 9 Pages 1908-1914
Published: September 25, 1970
Released on J-STAGE: March 31, 2008

DOIhttps://doi.org/10.1248/cpb.18.1908

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All the metabolites (UAM-1, UNM-1, UNM-2, UNM-4, and URM-1), which were isolated from the urine of rats and rabbits administered 1-(4-methoxy-6-methyl-2-pyrimidinyl)-3-methyl-5-methoxypyrazole (mepirizole, DA-398) were synthesized and their structures were established by direct comparison with the synthetic samples.

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Studies on the Active Site of Papain. II. Inhibition by Cyclic Imide Compounds

HARUO KANAZAWA, AKIRA OHARA, MASASHICHI YOSHIOKA

1970 Volume 18 Issue 9 Pages 1915-1917
Published: September 25, 1970
Released on J-STAGE: March 31, 2008

DOIhttps://doi.org/10.1248/cpb.18.1915

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Studies on the Active Site of Papain. III. Inhibition by Dibasic Acids

HARUO KANAZAWA, SUSUMU ISHIMITSU, YASUHIRO SHIMIZU, SHIGERU TANAKA, TO ...

1970 Volume 18 Issue 9 Pages 1918-1920
Published: September 25, 1970
Released on J-STAGE: March 31, 2008

DOIhttps://doi.org/10.1248/cpb.18.1918

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In the previous paper, it was reported that the cyanide-activated papain is apparently inhibited by active methylene group and active imide group in barbituric acid. The active methylene group in barbituric acid is derived from malonic acid. Morgan and Friedmann have been shown that maleic acid and SH-compounds interact with the formation of stable addition compounds. They have applied this reaction to the study of some SH-enzyme reaction. The present research has been planed to clarify relation between activity of papain and influence of the dibasic acids.

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Studies on the Mixed Ligand Complexes. I. Synthesis of Glycine Oxine Cobalt (III) Complex

YOSHINORI KIDANI, YUKIMASA KATO, HISASHI KOIKE

1970 Volume 18 Issue 9 Pages 1921-1924
Published: September 25, 1970
Released on J-STAGE: March 31, 2008

DOIhttps://doi.org/10.1248/cpb.18.1921

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A Convenient Chlorination of Pyrimidines with Thionyl Chloride

SADAO NISHIGAKI, KEITARO SENGA, FUMIO YONEDA

1970 Volume 18 Issue 9 Pages 1925-1926
Published: September 25, 1970
Released on J-STAGE: March 31, 2008

DOIhttps://doi.org/10.1248/cpb.18.1925

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The Inductive Effect of Mepirizole on the Drug Metabolizing Enzymes of Rat Liver

EIGO TAKABATAKE, RYUHEI KODAMA

1970 Volume 18 Issue 9 Pages 1927-1929
Published: September 25, 1970
Released on J-STAGE: March 31, 2008

DOIhttps://doi.org/10.1248/cpb.18.1927

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Synthesis of Methyl O-Acetyl-griseoluteate

KAN UEDA, ITIRO YOSIOKA

1970 Volume 18 Issue 9 Pages 1931-1933
Published: September 25, 1970
Released on J-STAGE: March 31, 2008

DOIhttps://doi.org/10.1248/cpb.18.1931

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Feasibility of Gas Chromatography for Ultra-micro Analysis of Aluminum in Biological Materials

MOTOICHI MIYAZAKI, HARUICHI KANEKO

1970 Volume 18 Issue 9 Pages 1933-1934
Published: September 25, 1970
Released on J-STAGE: March 31, 2008

DOIhttps://doi.org/10.1248/cpb.18.1933

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Ultra-micro Analysis of Serum Protein in a Few Nanoliter of Samples

TERUMI NAKAJIMA, HITOSHI ENDOU, FUMINORI SAKAI, ZENZO TAMURA

1970 Volume 18 Issue 9 Pages 1935
Published: September 25, 1970
Released on J-STAGE: March 31, 2008

DOIhttps://doi.org/10.1248/cpb.18.1935

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