Chemical and Pharmaceutical Bulletin

Studies on Streptomyces Antibiotic, Cycloheximide. IV. Some Observations on Stereochemical Configurations of Naramycin-A (Cycloheximide) and Naramycin-B.

Tomoharu Okuda

1959 Volume 7 Issue 6 Pages 659-665
Published: September 20, 1959
Released on J-STAGE: March 31, 2008

DOIhttps://doi.org/10.1248/cpb.7.659

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The configuration of two isomeric antibiotics, Naramycin-A (cycloheximide) and Naramycin-B was elucidated as follows, the plane structure being depicted as (I) : 1) Asymmetric carbon at α-position in both antibiotics has the same configuration. 2) Absolute configuration of asymmetric carbons at 4-position is the same in both antibiotics and belongs to (S)-series. 3) Both antibiotics have an equatorially oriented 6-[α-hydroxy-β-(2, 6-dioxo-4-piperidinyl) ethyl] group, but the configuration of asymmetric carbon at 6-position is different in the two antibiotics. 4) Assuming that the partial rotation due to α-carbon in both antibiotics is the same, because their absolute configuration is the same, Naramycin-A has (4S : 6S)-structure and Naramycin-B has (4S : 6R)-structure.

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Studies on Streptomyces Antibiotic, Cycloheximide. V. Synthesis and Stereochemistry of Deoxycycloheximide.

Tomoharu Okuda

1959 Volume 7 Issue 6 Pages 666-670
Published: September 20, 1959
Released on J-STAGE: March 31, 2008

DOIhttps://doi.org/10.1248/cpb.7.666

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Deoxycycloheximide (VII), obtained as the main product of catalytic reduction of anhydrocycloheximide, was thought to have 2e, 4e, 6e-conformation and exhibited a single positive Cotton-effect curve. This fact verifies the correctness of the author's consideration for elucidation of the R.D. curves of Naramycins.

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Studies on Streptomyces Antibiotic, Cycloheximide. VI. The Absolute Configuration of Naramycin-A (Cycloheximide) and its Isomeric Naramycin-B.

Tomoharu Okuda

1959 Volume 7 Issue 6 Pages 671-679
Published: September 20, 1959
Released on J-STAGE: March 31, 2008

DOIhttps://doi.org/10.1248/cpb.7.671

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The stereochemical considerations of dihydrogenated cycloheximide and its acylates were made and it was found that α-hydroxyl group in cycloheximide is situated quite closely to equatorial 1-hydroxyl group which is obtainable by reducing the carbonyl group in the molecule. This finding, together with previously reported information, leads to the conclusion that Naramycin-A should have (4S : 6S : αS)-configuration, and its isomeric Naramycin-B should have (4S : 6R : αS)-configuration.

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Studies on Analgesics. IV. A Recording Apparatus for Pain Reaction on the Hot Plate.

Keijiro Takagi, Tsutomu Kameyama

1959 Volume 7 Issue 6 Pages 680-684
Published: September 20, 1959
Released on J-STAGE: March 31, 2008

DOIhttps://doi.org/10.1248/cpb.7.680

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Separatory Determination of Glucuronic Acid and Glucuronides in Biological Fluid by Ion-Exchange Resin.

Morizo Ishidate, Mitsuo Watanabe

1959 Volume 7 Issue 6 Pages 685-689
Published: September 20, 1959
Released on J-STAGE: March 31, 2008

DOIhttps://doi.org/10.1248/cpb.7.685

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For the separatory determination of free glucuronic acid and conjugated glucuronic acids of various types, such as N-glucuronides and ester-type or ether-type O-glucuronides in urine, a revised method using a column of anion-exchange resin was investigated. A column of Amberlite IRA-411, after passing a mixed solution of sodium glucuronate, sodium aniline or 2-naphthylamine glucosiduronate, and phenyl glucosiduronic acid or potassium menthyl O-glucosiduronate, was first eluted with ammonium chloride solution at pH 8 to separate the free glucuronic acid, and then eluted with hydrochloric acid to hydrolyse and remove the N-glucuronide. The column was further eluted with methanolic hydrochloric acid to remove the stable O-glucuronide. For the colorimetric measurement of glucuronic acid in each of eluted fractions, a modified procedure of Dische's method using carbazole was employed, in which carbazole was added with sulfuric acid to the sample in order to save the time required for the whole procedure. By this improved method, so far as the present samples were concerned, the separatory and recovery determination of glucuronic acid, N-glucuronide, and O-glucuronide, excluding ester-type O-glucuronide, in urine, was quite satisfactory.

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Studies on Carcinostatic Substances. XX. Studies on the Culture of Yoshida Sarcoma Cells in vitro.

Morizo Ishidate, Yoshio Sakurai, Hiroshi Imamura, Ayako Moriwaki

1959 Volume 7 Issue 6 Pages 690-694
Published: September 20, 1959
Released on J-STAGE: March 31, 2008

DOIhttps://doi.org/10.1248/cpb.7.690

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A method of culturing the Yoshida sarcoma in vitro was established. The tumor cells maintained constant vitality and growth for at least 72 hours in a simple and convenient medium. The method is believed to be applicable in the wide field of research on cancer chemotherapy.

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Microdetermination of Reducing Sugars in Blood.

Michio Ui

1959 Volume 7 Issue 6 Pages 695-698
Published: September 20, 1959
Released on J-STAGE: March 31, 2008

DOIhttps://doi.org/10.1248/cpb.7.695

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An assay method suitable for reducing sugars present in 0.02cc. of normal blood was described.

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Studies on the Structure of Sciadopitysin, a Flavonoid from the Leaves of Sciadopitys verticillata SIEB. ET ZUCC. VII.

Nobusuke Kawano

1959 Volume 7 Issue 6 Pages 698-701
Published: September 20, 1959
Released on J-STAGE: March 31, 2008

DOIhttps://doi.org/10.1248/cpb.7.698

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1) 2, 2', 4, 6-Tetramethoxybiphenyl was obtained from substance B monomethyl ether, C₁9H₂0O₇, by oxidation followed by decarboxylation, (II)→(III)→(IV)→(V), and it was also newly synthesized by the Ullmann reaction. 2) 4-Methoxyisophthalic acid was obtained from substance A (VIII) and B (VI) by oxidation. 3) The structure of sciadopitysin trimethyl ether was established as a new-type bisflavonoid of formula (VII) or (VII'), the former being preferable. 4) Formula (IX) or (X) was deduced as the structure of sciadopitysin.

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Studies on Acylase Activity and Microorganisms. XI. A New Method for resolving DL-Amino Acids by Metabolism of Soil Bacteria.

Yukio Kameda, Etsuko Toyoura, Katsuhiko Matsui

1959 Volume 7 Issue 6 Pages 702-707
Published: September 20, 1959
Released on J-STAGE: March 31, 2008

DOIhttps://doi.org/10.1248/cpb.7.702

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Four strains (KT-230, KT-231, KT-232, and KT-233) of soil bacteria were isolated and their metabolic activities were tested on ε-N-benzoyl-lysine, methionine, phenylalanine, leucine, threonine, and their benzoyl derivatives (Tables I and II). KT-230, KT-231, KT-232, and KT-233 metabolized dibenzoyl-DL-lysine to produce ε-N-benzoyl-L-lysine and dibenzoyl-D-lysine respectively in good yield. KT-230 and KT-231 metabolized benzoyl-DL-methionine to produce L-methionine and benzoyl-D-methionine, but KT-232 and KT-233 produced DL-methionine instead of L-methionine. It was demonstrated that cell-free extract of KT-232 or bacterial mass of KT-233 could racemize L-methionine to yield-DL-methionine. KT-230 and KT-231 metabolized benzoyl-DL-phenylalanine and benzoyl-DL-leucine to yield L-phenylalanine, benzoyl-D-phenylalanine, L-leucine, and benzoyl-D-leucine. By the metabolism of KT-233 L-threonine and N-benzoyl-D-threonine were obtained from N-benzoyl-DL-threonine in a good yield. α-N-Butyroyl-ε-N-benzoyl-DL-lysine was metabolized by KT-232 to yield ε-N-benzoyl-L-lysine and α-N-butyroyl-ε-N-benzoyl-D-lysine.

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Synthesis of Quinolizine Derivatives. V. Studies on Diastereoisomer of Ethyl 3-Quinolizidinecarboxylate.

Sadao Ohki, Yoshiya Noike

1959 Volume 7 Issue 6 Pages 708-712
Published: September 20, 1959
Released on J-STAGE: March 31, 2008

DOIhttps://doi.org/10.1248/cpb.7.708

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Steric configuration of the two diastereoisomers of ethyl 3-quinolizidinecarboxylate (I) was examined and it was proved from following facts that (Ia) (picrate, m.p. 160∼161°) has the A-type and (Ib) (picrate, m.p. 144∼146°) has the B-type orientation. It was shown that (i) quinolizidine ring is in trans type ; (ii) basic isomerization of (I) and (Ia) afforded a fair amount of (Ib) ; and that (iii) reduction of (Ia) and (Ib) with lithium aluminum hydride resulted in their derivation to 3-lupinine (IIa) and 3-epi-lupinine (IIb), respctively. The steric configuration of (IIa) and (IIb) had previously been approximately determined from measurement of their infrared spectra and dipole moment. It was confirmed through preparation of the tosylates of (IIa) and (IIb), and comparison of their chemical properties that (IIa) had an axial -CH₂OH group and (IIb), the equatorial-CH₂OH.

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The Isolation of Alkaloids from Vinca (Lochnera) rosea (L.) REICHB.

Masao Shimizu, Fumihiko Uchimaru

1959 Volume 7 Issue 6 Pages 713-715
Published: September 20, 1959
Released on J-STAGE: March 31, 2008

DOIhttps://doi.org/10.1248/cpb.7.713

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From the root of Vinca rosea (L.) REICHB. (Apocynaceae), three alkaloids, tetrahydroalstonine, δ-yohimbine, and serpentine were isolated, and the presence of alstonine was also presumed.

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Synthetic Studies on Antituberculous Agent. VIII. Reaction between 4-Picoline and Aromatic Primary Amines in the Presence of Sulfur.

Haruo Saikachi, Takuzo Hisano

1959 Volume 7 Issue 6 Pages 716-720
Published: September 20, 1959
Released on J-STAGE: March 31, 2008

DOIhttps://doi.org/10.1248/cpb.7.716

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Condensation of 4-picoline with various aromatic primary amines was carried out in the presence of sulfur at elevated temparature. This reaction proceeded favorably under the condition of duration of 40 hours, the temperature of 160∼165°, and the molar ratio of 1 : 1.5 : 2.5 of 4-picoline, aniline, and sulfur.

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Syntheses of Heterocyclic Compounds of Nitrogen. CXIX. Syntheses of Oxazolopyridines and Related Compounds. (5).

Torizo Takahashi, Akira Koshiro

1959 Volume 7 Issue 6 Pages 720-725
Published: September 20, 1959
Released on J-STAGE: March 31, 2008

DOIhttps://doi.org/10.1248/cpb.7.720

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3-Amino-5-bromo-2-hydroxypyridine (II) was successfully converted to 2-substituted 6-bromoxazolo [5, 4-b] pyridines by treatment with acetic anhydride, benzoic anhydride, or potassium methylxanthate and some of their properties were examined. An attempt to obtain 2-amino-6-bromoxazolo [5, 4-b] pyridine by the application of cyanogen bromide to (II) ended fruitless and only (5-bromo-2-hydroxy-3-pyridyl) urea was obtained.

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Syntheses of Heterocyclic Compounds of Nitrogen. CXX. Syntheses of Oxazolopyridines and Related Compounds. (6).

Akira Koshiro

1959 Volume 7 Issue 6 Pages 725-730
Published: September 20, 1959
Released on J-STAGE: March 31, 2008

DOIhttps://doi.org/10.1248/cpb.7.725

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1) 2-Alkyl (or aryl) oxazolo [5, 4-b] pyridines were prepared by distillation of 3-acylamino-2-hydroxypyridine which was obtained by acylation of 3-amino-2-hydroxypyridine (I). 2) 2-Aminoxazolo [5, 4-b] pyridine, which could not be obtained by the reaction of (I) with cyanogen bromide, was successfully prepared by heating (2-hydroxy-3-pyridyl) thiourea with mercuric oxide in water. 3) Oxazolo [5, 4-b] pyridin-2 (1H)-one was prepared by distillation of (2-hydroxy-3-pyridyl) urethan and also the synthesis of 1-substituted oxazolo [5, 4-b] pyridin-2 (1H)-ones was established by treatment of 2-hydroxy-3-(substituted) aminopyridines with carbonyl chloride.

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Metabolism of Drugs. XXI. Isolation and Detection of Hydroxyl Derivatives from the Urine of Rabbits receiving Ethylhexabital (EHB, 5-Cyclohexenyl-5-ethylbarbituric Acid) and Normethylhexabital (Nor-MHB, 5-Cyclohexenyl-5-methylbarbituric Acid).

Hisao Tsukamoto, Yukio Kuroiwa

1959 Volume 7 Issue 6 Pages 731-734
Published: September 20, 1959
Released on J-STAGE: March 31, 2008

DOIhttps://doi.org/10.1248/cpb.7.731

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3-OH-EHB was isolated from the urine of rabbits receiving EHB besides 3-keto-EHB and identified with the reduction product of 3-keto-EHB. After the administration of nor-MHB to rabbits, 3-OH-nor-MHB was also detected from the urine, using buffered paper chromatography. Both 3-OH-EHB and 3-OH-nor-MHB have no hypnotic action.

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Organic Analysis. XIV. Infrared Spectra of Phenylsulfonyl Derivatives. (3). The C-H Deformation Vibrations of Benzene Ring, the CH₃ Rocking Frequencies of SO₂CH₃ Group, and the Characteristic Absorption Bands of SO₂NH₂ Group.

Tsutomu Momose, Yo Ueda, Tatsuo Shoji

1959 Volume 7 Issue 6 Pages 734-739
Published: September 20, 1959
Released on J-STAGE: March 31, 2008

DOIhttps://doi.org/10.1248/cpb.7.734

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The C-H in-plane deformation vibrations of benzene ring may be intensified by the polar and heavy SO₂ group in phenylsulfonyl compounds. The CH₃-rocking vibrations in SO₂CH₃ group have smaller wave numbers than that of dimethyl sulfide, and are in the region of 980∼950 cm^-1 and 790∼760 cm^-1. RSO₂NH₂ compounds have characteristic frequencies in the region of 919∼896 cm^-1, which may be assigned to S-N stretching vibration.

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Synthesis of Guanosine 5'-Diphosphate.

Tohru Ueda, Eiko Ohtsuka

1959 Volume 7 Issue 6 Pages 740-743
Published: September 20, 1959
Released on J-STAGE: March 31, 2008

DOIhttps://doi.org/10.1248/cpb.7.740

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Guanosine 5'-diphosphate was synthesized from guanosine 5'-monophosphate by the reaction of benzyl hydrogen phosphoramidate, followed by the catalytic hydrogenolysis, in a yield of 38%. The effect of water in the reaction media and correlation of the yield with the amount of reagents are discussed.

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Ableitung von Dihydrocinchonamin aus Cinchonidin

Eiji Ochiai, Masayuki Ishikawa, Yoshikazu Oka

1959 Volume 7 Issue 6 Pages 744-745
Published: September 20, 1959
Released on J-STAGE: March 31, 2008

DOIhttps://doi.org/10.1248/cpb.7.744

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A New α-Acylaminoalkylation of Aromatic Compounds

Minoru Sekiya, Noboru Yanaihara

1959 Volume 7 Issue 6 Pages 746
Published: September 20, 1959
Released on J-STAGE: March 31, 2008

DOIhttps://doi.org/10.1248/cpb.7.746

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Isolation of 22-Dehydrocholesterol from Hypnea japonica

Kyosuke Tsuda, Kiyoshi Sakai, Katsumi Tanabe, Yukichi Kishida

1959 Volume 7 Issue 6 Pages 747
Published: September 20, 1959
Released on J-STAGE: March 31, 2008

DOIhttps://doi.org/10.1248/cpb.7.747

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Synthesis of Ginkgetin Tetramethyl Ether

Koichi Nakazawa

1959 Volume 7 Issue 6 Pages 748-749
Published: September 20, 1959
Released on J-STAGE: March 31, 2008

DOIhttps://doi.org/10.1248/cpb.7.748

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On the Selenium-dehydrogenation of Cynanchogenin

Hiroshi Mitsuhashi, Yuzuru Shimizu

1959 Volume 7 Issue 6 Pages 749-750
Published: September 20, 1959
Released on J-STAGE: March 31, 2008

DOIhttps://doi.org/10.1248/cpb.7.749

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α-Lipoic Acid-Thiourea Adduct

Hiroyuki Mima, Yutaka Asahi, Hiroshi Okuto, Tokunosuke Kanzawa

1959 Volume 7 Issue 6 Pages 750
Published: September 20, 1959
Released on J-STAGE: March 31, 2008

DOIhttps://doi.org/10.1248/cpb.7.750

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