HETEROCYCLES
An International Journal for Reviews and Communications in Heterocyclic ChemistryWeb Edition ISSN: 1881-0942
Published online by The Japan Institute of Heterocyclic Chemistry
Regular Issue
Vol. 2, No. 1, 1974
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■ Molecular Design by Cycloaddition Rections. XIII. Cycloaddition of 1,3-Diphenylisobenzofuran with cis-Bicyclo[6.1.0]nona-2,4,6-triene
Tadashi Sasaki,* Ken Kanematsu, and Yusaku Yukimoto
*Institute of Applied Organic Chemistry, Faculty of Engineering, Nagoya University, Chikusa, Nagoya, Aichi 464-8601, Japan
Abstract
Cycloaddition reaction of 1,3-diphenylisobenzofuran with cis-bicyclo[6.1.0]nona-2,4,6-triene gave four 1 : l adducts. The structural elucidation of major products was accomplished by spectral evidences and chemical properties. Possible mechanism for the reaction is also discussed.
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■ Reissert Compound Studies. Part XXV. A Novel Reaction with 2-Nitrobenzaldehyde and the Anion of 2-Acetyl-1,2-dihydroisoquinaldonitrile
Harry W. Gibson and Frank D. Popp*
*Department of Chemistry, Clarkson College of Technology, Potsdam, New York 13676, U.S.A.
Abstract
In contrast to the reaction of the anion of 2-benzoyl-1,2-dihydroisoquinaldonitrile with aldehydes, the reaction of the anion of 2-acetyl-1,2-dihydroisoquinaldonitrile with 2-nitrobenzaldehyde involves the formation of a novel type of product (VII).
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■ A Synthesis of Benzocarbazole Derivatives by Thermolysis
Tetsuji Kametani,* Toshio Suzuki, Kimio Takahashi, and Keiichiro Fukumoto
*Pharmaceutical Institute, Tohoku University, Aobayama, Sendai 980-8578, Japan
Abstract
A thermal reaction of indolylmagnesium bromide (1) with 1- cyano-4,5-dimethoxybenzocyclobutene (2) gave a mixture of 6-cyano-5a,6,11,11a-tetrahydro-8,9-dimethoxy-5H-benzo[b]carbasole (3a) and 6-cyano-5a,6,11,11a-tetrahydro-9-hydroxy-8-methaxy-5H-benzo[b]carbazole (4). Compound (3a) was easily converted to 6-cyano-8,9-dimethoxy-5H-benzo[b]carbazole (6) by dehydrogenation on 30 % Pd-C.
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■ Synthesis of a Non-Saccharical Analog of Puromycin
Frans M. Kaspersen, Hans Bieräugel, and Upendra K. Pandit*
*Organic Chemistry Laboratory, University of Amsterdam, Nieuwe Achtergracht 129, 1018 WS Amsterdam, The Netherlands
Abstract
The synthesis of (2S,4S)-N-(p-methoxyphenyl-L-alanyl)-2-hydroxymethyl-4-[N9-6- (dimethylamino)purinyl]pyrrolidine (1), a non-saccharidal analog of puromycin, is described.
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■ Cyclization of β-Ketosulfoxide. IV. Synthesis of Indole, Benzothiophene and Carbazole Derivatives
Yuji Oikawa, Osamu Setoyama, and Osamu Yonemitsu*
*Faculty of Pharmaceutical Sciences, Hokkaido University, Sapporo 060-0812, Japan
Abstract
On acid-treatment, β-ketosulfoxides having pyrrole, thiophene and indole nuclei were converted to indoles, benzothiophenes and carbazoles, respectively, through intramolecular nucleophilic substitution.
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■ Studies of Polyazapentalenes. V. The Cycloaddition Reaction of 8-Methyldibenzo[b,e]-1,3a,6a-triazapentalene with Asymmetrical Acetilenes
Otohiko Tsuge* and Hideo Samura
*Research Institute of Industrial Science, Faculty of Engineering, Kyushu University, 6-1, Kasuga-koen, Kasuga 816-8580, Japan
Abstract
Triazapentalene (I) reacted with asymmetrical acetylenes (II) to give the corresponding [3+2] cycloadducts as major products. It has been found that phenyl- and p-chlorophenylacetylene added to I in different directions, and that methyl phenylpropiolate gave two [3+2] cycloadducts.
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■ The Stereochemistry of (±)-6a-β-Ethyl-1,2,5,6,6a,7,8,9,9a-α,9b-α-decahydro-4H-pyrrolo[3,2,1-i,j]quinolin-9β-ol
Kyoyu Sasaki, Yuji Sendo, Masao Akagi, and Yoshio Ban*
*Faculty of Pharmaceutical Sciences, Hokkaido University, Sapporo 060-0812, Japan
Abstract
The methiodide(V) of the entitled compound was submitted to X-ray analysis, and the structure was established to be the one shown in Fig. 1, which is represented by the formula (V).
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■ Derivatives of 1,2-Dithiole-3-thiones. III. A Novel Desulfurization of 4,5-Benzo-1,2-dithiole-3-thione Imide or Its Selemium Analogue
Seizo Tamagaki, Keishi Sakaki, and Shigeru Oae*
*Department of Chemistry, University of Tsukuba, 1-1-1 Ten-nodai, Tsukuba-shi, Ibaraki, 305-8571, Japan
Abstract
N-Benzenesulfonylimide of 4,5-benzo-1,2-dithiole-3-thione(C=35S) was thermally desulfurized to afford a corresponding 3-(N-benzenesulfonyl)imine with predominant extrusion of the exocyclic thiono sulfur atom, while with its selenium analogues, the exclusive loss of thiolo sulfur instead of exocyclic selenium atom was observed, resulting in the formation of the selenium-migrating product, i.e., 4,5-benzo-1,2-thiaselenole-3-(N-benzenesulfonyl)imine.
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■ Derivatives of 1,2-Dithiole-3-thiones. IV. Oxidation of 4,5-Benzo-3-selenoxo-1,2-dithiole
Seizo Tamagaki, Keishi Sakaki, and Shigeru Oae*
*Department of Chemistry, University of Tsukuba, 1-1-1 Ten-nodai, Tsukuba-shi, Ibaraki, 305-8571, Japan
Abstract
The desulfurizative oxidation of 1,2-dithiole-3-thiones with various oxidizing reagents was reexamined using 4,5-benzo-3-selenoxo-1,2-dithiole as a typical substrate. The product thus obtained was 4,5-benzo-1,2-thiaselenole-3-one, but not an expected 4,5-benzo-1,2-dithiole-3-one. The reaction pathway via a selenine1 is postulated.
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■ Photodehydroxylation of Some 3-Hydroxyoxindoles
Noboru Shoji, Yoshikazu Kondo,* and Tsunematsu Takemoto
*Pharmaceutical Institute, Tohoku University, Aobayama, Sendai 980-8578, Japan
Abstract
Photoreduction of 3-substituted 3-hydroxyoxindoles I-IV in the presence of sodium hydrosulfite led to loss of the 3-hydroxyl group. Irradiation at longer wavelengths (λ> 3000 Å) did not cause this photodehydroxylation.
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■ Total Synthesis of (±)-Mecambridine
Tetsuji Kametani,* Akira Ujiie, and Keiichiro Fukumoto
*Pharmaceutical Institute, Tohoku University, Aobayama, Sendai 980-8578, Japan
Abstract
Hydroxymethylation of the phenolic tetrahydroprotoberberine (VII) yielded O-demethylmecambridine (VIII), which on methylation with diazomethane afforded (±)-mecambridine (XII). This work proved the structure of this base to be 7,8 ,13,14-tetrahydro-12-hydroxymethyl-1 ,10,11-trimethoxy-2,3-methylenedioxyprotoberberine.
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■ Semisynthetic β-Lactam Antibiotics. V. Synthesis of α-Sulfobenzylpenicillin by Using Mixed Anhydride and Active Ester of α-Sulfophenylacetic Acid
Shiro Morimoto,* Hiroaki Nomura, Toshihiro Ishiguro, Takeshi Fugono, and Kihachiro Maeda
*Central Research Division, Takeda Chemical Industries, Ltd., 17-85 Jusohonmachi 2-chome, Yodogawa-ku, Osaka 532-8686, Japan
Abstract
The synthesis of α-sulfobenzylpenicillin (V) was first accomplished in our Research Laboratory. The compound exhibits the peculiar activity against G(+) and G(-) bacteria. For the preparation of this penicillin several activated derivatives of α-sulfophenylacetic acid (I) have been obtained in the purified form.
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■ Semisynthetic β-Lactam Antibiotics. VII. New Semisynthetic Cephalosporins Derived from α-Sulfhenylacetic Acid
Hiroaki Nomura,* Takeshi Fugono, Takenori Hitaka, Isao Minami, Toshiyuki Azuma, Shiro Morimoto, and Toru Masuda
*Central Research Division, Takeda Chemical Industries, Ltd., 17-85 Jusohonmachi 2-chome, Yodogawa-ku, Osaka 532-8686, Japan
Abstract
The preparation of derivatives of α-sulfophenylacetic acid has been made from 7-aminocephalosporanic acid. New semisynthetic cephalosporins exhibit a peculiar inhibitory effect against Pseudomonas aeruginosa.
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■ Studies on Vinca Alkaloids. The Structure of Vincarodine
James P. Kutney,* Gloria Cook, James Cook, Isamu Itoh, Jon Clardy, Jose Fayos, Peter Brown, and Gordon H. Svoboda
*Department of Chemisry, University of British Columbia, Vancouver 8, V5T 1W5, Canada
Abstract
The structure and stereochemistry of vincarodine (1) have been determined by an investigation of its spectroscopic properties, particularly NMR, electron impact and field ionization mass spectrometry and finally by X-ray analysis of the hydrobromide derivative.
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■ Synthesis of Pentazocine
Tetsuji Kametani,* Kazuo Kigasawa, Mineharu Hiiragi, and Nagatoshi Wagatsuma
*Pharmaceutical Institute, Tohoku University, Aobayama, Sendai 980-8578, Japan
Abstract
Synthetic studies of pentazocine and its intermediates are described and classified.
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■ Application of Enamide Photocyclization to the Synthesis of Natural Products
Ichiya Ninomiya*
*Kobe Women’s College of Pharmacy, Motoyamakita, Higashinad, Kobe, Hyogo 658, Japan
Abstract
Enamide photocyclization has been shown to be a new and useful tool for the synthesis of various nitrogen-containing heterocyclic systems, particularly alkaloids. By this means, the synthesis of crinan, benzo(c)phenanthridine, aporphine, protoberberine and yohimbine alkaloids has been achieved.
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■ Concerting the Biosynthesis of Vitamin B12
A. Ian Scott*
*Sterling Chemistry Laboratory, Yale University, 225 Prospect St., New Haven, CT 06511, U.S.A.
Abstract
The use of 13C FT-NMR has led to the observation that while 8 molecules of [2-13C] -ALA are incorporated into vitamin B12 in P. shermanii, [5-13C]-ALA labels only seven of the carbon atoms of cyanocobalamin i.e. one of the amino methyl groups of ALA is “lost” in the process. It has also been confirmed that seven of the methyl groups of B12 are derived from 13CH3 enriched methionine and further that the chirality of the gem-dimethyl grouping at C12 labeled with [13CH3]-methionine is R. A soluble enzyme mixture from the 37,000 g supernatant of disrupted cells of P. shermanii converts both 14C-labeled ALA and 14C-uro’gen III to cobyrinic acid, the simplest corrinoid material on the pathway to vitamin B12 and the coenzyme in presence of NADPH, Co++ , Mg++, S-adenosylmethionine and glutathione. A detailed hypothesis of the mechanism of corrin synthesis from uro’gen III has been developed.