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. 16, No. 7, 1981
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■ Synthesis of Heterocycles: Synthesis of Naphtho[4,5-b]thiazolo[2,3-a][1,2,4]triazepines
Moti Lal Jain and Rajendra Prasad Soni*
*Depatment of Chemistry, University of Jadhpur, Jadhpur, India
Abstract
Some new fluorinated naphtho[4,5-b]thiazolo[2,3-c][1,2,4]triazepines have been synthesized by condensation of 2-hydrazinonaphtho[2,1-d]thiazoles with 1,3-diketones.
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■ Some Reactions of Pyrido[4,3-b]indole (γ-Carboline)
Ching-Shing Lee, Toshiharu Ohta, Koichi Shudo,* and Toshihiko Okamoto
*Faculty of Pharmaceutical Sciences, University of Tokyo, Hongo, Bunkyo-ku, Tokyo 113, Japan
Abstract
Nitration, N-oxidation and N-amination of pyrido[4,3-b]indole (γ-carboline) and reactions of the 2-oxide with phosphorus oxychloride, acetic anhydride, phenyl isocyanate and cyanogen bromide were described.
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■ Alnusiin, a Novel Ellagitannin from Alnus sieboldiana Fruits
Takashi Yoshida, M. Usman Memon, and Takuo Okuda*
*Faculty of Pharmaceutical Sciences, Okayama University, 1-1-1 Tsushima-naka, Okayama 700-8530, Japan
Abstract
A new ellagitannin, named alnusiin has been isolated from the fruits of Alnus sieboldiana, and the structure (I) was elucidated.
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■ The Reactions of Lithium Ester Enolates with N-(ω-Bromoalkyl)phthalimides
Shunsuke Naruto,* Keiko Shimakawa, Hiroyuki Mizuta, Hitoshi Uno, and Haruki Nishimura
*Technical Research Laboratory, Dainippon Pharmaceutical Co., LTD., Ebie 1-5-51, Fukushima-ku, Osaka 553, Japan
Abstract
In the titled reactions, N-(ω-bromoalkyl)phthalimides were ambident electrophiles. The carbanion of straight chain ester enolates(I, R1=H) attacked the carbonyl carbon atom of phthalimide moiety to give several types of compounds.
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■ Reactions of α-Acylimmonium Ions
Jacek W. Morzycki* and Wladyslaw J. Rodewald
*Department of Chemistry, University of Warsaw, Pasteura St.1, 02-093 Warsaw, Poland
Abstract
The reactions of various hydroxylactams proceeding via α-acylimmonium ions are described.
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■ Synthesis of Indolizidine Azasteroids
Jacek W. Morzycki* and Wladyslaw J. Rodewald
*Department of Chemistry, University of Warsaw, Pasteura St.1, 02-093 Warsaw, Poland
Abstract
A synthesis of some indolizidine azasteroids (hydroxylactam 4, unsaturated lactam 5, aldehyde 6, diol 8 and imide 9) by contraction of ring B in unsaturated lactam 1 is described.
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■ Studies in the Sandwicine Series
Abdul Malik, Nighat Afza, Naheed Sultana, and Salimuzzaman Siddiqui*
*H. E. J. Postgraduate Institute of Chemistry, University of Karachi, Karachi-75270, Pakistan
Abstract
As a result of studies in the correlation of structure and activity in the sandwicine series of alkaloids, a number of new derivatives have been obtained through Von Braun BrCN reaction and electrophilic substitutions in the benzene ring. The exact position of the radicals has been located through spectral studies.
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■ Biosynthesis of Citirinin in Aspergillus terreus. Incorporation Studies with [2-13C,2-2H3],[1-13C,18O2] and [1-13C,17O]Acetate
Ushio Sankawa,* Yutaka Ebizuka, Hiroshi Noguchi, Yoshiaki Ishikawa, Shoken Kitagawa, Tsutomu Kobayashi, and Haruo Seto
*Graduate School of Pharmaceutical Sciences, University of Tokyo, 7-3-1 Hongo, Bunkyo-ku, Tokyo 113-0033, Japan
Abstract
Incorporation of 2H and 18O of [2-13C,2-2H3] and [1-13C,18O2]acetate into citrinin(1) was confirmed by using 13C-NMR, and incorporation of 17O from [1-13C,17O]acetate was also detected by 17O-NMR.
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■ Synthesis of 4-Substituted Indoles from o-Nitrotoluenes
Lawrence I. Kruse*
*Chemical Reserch and Development, Smith Kline and French Laboratories, Philadelphia, PA 19101, U.S.A.
Abstract
A facile two- or three-step transformation of o-nitrotoluenes into 4-substituted indoles is described. Treatment of o-nitrotoluenes 1 with DMF acetal, or sometimes more advantageously with tris(N,N-dimethylamino)methane, affords β-(N,N-dimethylamino)styrenes 2 which are readily converted to o-nitrophenylacetaldehyde semicarbazones 3 without isolation. Reduction of either 2 or 3 affords 4-substituted indoles 4. Use of the very insoluble semicarbazones results in vastly superior yields of 4 by minimizing competing bimolecular condensation reactions during reduction. This new procedure has been applied to efficiently and conveniently prepare a series of 4-substituted indoles 4.
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■ A New Synthetic Route to the Corynanthe Type Indole Alkaloids Using (±)-Norcamphor
Seiichi Takano,* Kimiyuki, Shibuya, Mikoto Takahashi, Susumi Hatakeyama, and Kunio Ogasawara
*Pharmaceutical Institute, Tohoku University, Aobayama, Sendai 980-8578, Japan
Abstract
Conversion of (±)-norcamphor (5) into a number of the corynanthe alkaloids in racemic forms has been achieved. The conversion allows a formation of the 18,19-saturated alkaloids with all four possible configurations and the Δ18,19-unsaturated alkaloids with three of four possible configurations.
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■ Photosensitized Chemiluminescent Desulfurization of Arenethiones
Nobutaka Suzuki,* Kaniti Sano, Noriyuki Tani, and Yasuji Izawa
*Faculty of Engineering, Mie University, 1515 Uehama-cho, Tsu, Mie 514-5807, Japan
Abstract
Photosensitized oxygenation of N-methylacridanethione (1a), xanthione (1b), and thioxanthione (1c) gave the corresponding ketones (3) quantitatively and weak chemiluminescence.
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■ Reductive Photocyclization of Enamides
Takeaki Naito, Yukiko Tada, Yoshino Nishiguchi, and Ichiya Ninomiya*
*Kobe Women’s College of Pharmacy, Motoyamakita, Higashinad, kobe, Hyogo658, Japan
Abstract
Irradiation of the enamides (1a and b) and (7a and b), prepared from N-cyclohexylidenebenzylamine and 3,4-dihydro-1-methylisoquinoline, in the presence of a hydride agent led to the reductive photocyclization to afford the hydrogenated lactams (3a and b), (4a and b), and (9a and b), respectively.
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■ Reductive Photocyclization of Enamide in the Presence of a Chiral Metal Hydride Complex — Asymmetric Synthesis of Xylopinine
Takeaki Naito, Yukiko Tada, and Ichiya Ninomiya*
*Kobe Women’s College of Pharmacy, Motoyamakita, Higashinad, kobe, Hyogo658, Japan
Abstract
Total synthesis of optically active xylopinine (3b) was achieved by reductive photocyclization of enamide (1) in the presence of a chiral hydride complex.
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■ The Reagent Design and Study of Thiophene Derivatives on the Basis of the Concept of the Cyclic Conjugation
Ken Kanematsu,* Kazunobu Harano, and Hirokazu Dantsuji
*Research Institute of Industrial Science, Faculty of Engineering, Kyushu University, 6-1, Kasuga-koen, Kasuga 816-8580, Japan
Abstract
The concept of continuity and discontinuity of the cyclic conjugation provides us a reliable way of predicting the cycloadditivity of five-membered heterocyclic compounds as 4π-source in the cycloaddition.
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■ Regio- and Stereo-controlled Diels-Alder Reaction of Dioxopyrrolines with Activated Butadienes: Facile Syntheses of Ring D Finctionalized Erythrinans
Takehiro Sano,* Jun Toda, Noriaki Kashiwaba, Yoshisuke Tsuda, and Yoichi Iitaka
*Showa Pharmaceutical University, 3-3165, Higashi-tamagawagakuen, Machida, Tokyo 194-8543, Japan
Abstract
Diels-Alder reaction of Δ2-pyrroline-4,5-diones with activated butadienes proceeds in regio- and stereo-selective manner. Thus, isoquinolinopyrrolinediones (prepared in 3 steps from β-arylethylamines) gave single erythrinan derivatives which are functionalized at ring D in acceptable yields. The structure and stereochemistry of the adducts were established by chemical and spectroscopic means and finally by X-ray analysis of the derived diacetate (19).
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■ Synthesis of (±)-Jatropham, an Antitumor Alkaloid from Jatropha macrorhiza
Kenichi Yakushijin, Rika Suzuki, Ren Hattori, and Hiroshi Furukawa*
*Faculty of Pharmacy, Meijo University, 150 Yagotoyama, Tenpaku, Nagoya 468-8503, Japan
Abstract
The synthesis of jatropham, assigned as 5-hydroxy-3-methyl-3-pyrrolin-2-one 4, and of its 4-methyl isomer 14 is achieved utilizing an autoxidation of 2-furylcarbamates 2 and 11 as the key step.
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■ Stannylation-Iodination Reaction on Pyridine Nuclei. A Facile Method for Synthesis of Iodopyridines and Iodoquinolines
Yutaka Yamamoto* and Akihiko Yanagi
*Faculty of Pharmaceutical Sciences, Tohoku Pharmaceutical University, 4-4-1 Komatsushima, Aoba-ku, Sendai 981-8558, Japan
Abstract
Pyridines and quinolines bearing trimethylstannyl substituent at 2-, 3-, or 4-position were synthesized by the reaction of the respective chloro or bromo derivatives with trimethylstannyl sodium, generated in situ from chlorotrimethylstannane and sodium, in the range of 61-88% yields. Upon treatment with iodine, these trimethylstannyl derivatives smoothly underwent iododemetallation to give the corresponding iodo derivatives of pyridine and quinoline in satisfactory yields.
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■ Studies on 1,3-Benzoxazines V. Reaction of Imidoyl Chlorides of 1,3-Benzoxazines with 2-Aminophenol, o-Phenylenediamines and 2-Aminothiophenols
Ryuji Tachikawa, Kazuyuki Wachi, and Atsusuke Terada*
*Central Research Laboratories, Sankyo Co.,Ltd., 1-2-58 Hiromachi, Shinagawa-ku, Tokyo 140 Japan
Abstract
A general synthetic method for benzoxazoles, benzimidazoles and benzthiazole is described. Treatment of the imidoyl chloride of 1,3-benzoxazine with 2-aminophenols gave the corresponding 2-hydroxyphenylbenzoxazoles in good yields. Similarly, 2-hydroxyphenylbenzimidazoles and 2-hydroxyphenyl-benzthiazole were obtained using o-phenylenediamines and 2- aminothiophenol, respectively.
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■ Alkaloid Production in Catharanthus roseus Cell Cultures. IX. Biotransformation Studies with 3’,4’-Dehydrovinblastine
James P. Kutney,* Barbara Aweryn, Lewis S. L. Choi, Pawel Kolodziejczyk, W. G. W. Kurz, K. B. Chatson, and F. Constabel
*Department of Chemistry, The University of British Columbia, 2036 Main Mall, Vancouver, B.C., V6T 1Z1, Canada
Abstract
The biotransformation of 3’,4’-dehydrovinblastine by suspension cultures of the “916” cell line from Catharanthus roseus is reported. It is shown that leurosine, catharine and several other bisindole alkaloids are the products formed.
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■ The Total Synthesis of a Mitosene
J. Rebek, Jr.* and S. H. Shaber
*Department of Chemistry, University of Pittsburgh, Parkman Avenue & University Drive, Pittsburgh, PA 15260 , U.S.A.
Abstract
The conversion of L-hydroxyproline to a mitosene (degradation product of a mitomycin) is described. The synthesis involves 19 steps and the key stereochemical feature arises from an unusual cis opening of an epoxide. The synthetic product, 1-methoxy-2,7-diamino-mitosene is shown to be identical with the trans isomer obtained from acid-catalyzed methanolysis of mitomycin C.
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■ Syntheses and Reactions of Silylated Diaminosulfanes
Richard Neidlein* and Werner Lehr
*Pharmazeutisch-Chemishces Institut, Universität Heidelberg, Im Neuenheimer Feld 364, 69120 Heidelberg, Germany
Abstract
The synthesis of unsymmetrically substituted silylated diaminosulfanes 3a - 3e with different alkylgroups at both nitrogen atoms are described; the reactions of 3a, 3b with oxalyl chloride yields the unsymmetrically substituted 2,5-dialkyl-1,2,5-thiadiazolidine-3,4-diones 5a, 5b in moderate yields; 5a, 5b were oxidized to the S-oxides 6a, 6b by H2O2. The reactions of 3c, 3d with oxalyl chloride lead to a mixture of reaction - products - S8, oxalic acid-amides 7, 8 and a corresponding ester 9b.
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■ Cycloaddition Reactions of Ketenes to Sulfer Diimides
Richard Neidlein* and Werner Lehr
*Pharmazeutisch-Chemishces Institut, Universität Heidelberg, Im Neuenheimer Feld 364, 69120 Heidelberg, Germany
Abstract
The reactions of sulfur diimides 1 with substituted ketenes 2, 5 were studied and the structures of the reaction products 3, 4, 6, 7 were cleared up; the syntheses of new sulfur diimides 9a, 9b are described.
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■ Revised Structure for “A Novel Peroxide, 4,5-Diphenyl-1,2-dioxa-3,6-diazine”
Nobutaka Suzuki,* Satoshi Wakatsuki, and Yasuji Izawa
*Faculty of Engineering, Mie University, 1515 Uehama-cho, Tsu, Mie 514-5807, Japan
Abstract
Benzaldoxime does not give 4,5-diphenyl-1,2-dioxa-3,6-diazine (Ia) on oxidation with N2O3, but gives a furoxane (Ib) in spite of Beckmann’s report.
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■ Lactams. XXI. Spectroscopic Characterization of 3-, 4-, 5-, and 6-tert-Butyl-1-methyl-2(1H)-pyridones
Tozo Fujii,* Masashi Ohba, and Takashi Hiraga
*Faculty of Pharmaceutical Scicences, Kanazawa University, 13-1 Takara-machi, Kanazawa 920-0934, Japan
Abstract
4-tert-Butyl-1-methyl-2(1H)-pyridone (II), its 6-tert-butyl isomer (IV), and 4-tert-butyl-1-(3,4-dimethoxyphenethyl)-2(1H)-pyridone (V) were prepared by the alkaline ferricyanide oxidation of the corresponding 1-substituted 4- and 6-tert-butylpyridinium ions (X, XI, and XII). Infrared and ultraviolet spectroscopic analysis was found to be a convenient diagnostic method for distinguishing between the four possible positional isomers (I-IV) of tert-butyl-1-methyl-2(1H)-pyridone.
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■ A New and Efficient Approach to a 4H-1,3-Benzothiazine Ring Thet Utilises the Photo-cyclisation of N-o-Iodobenzoylthioamides: the Ring Trasformation of Isothiazoles
Tarozaemon Nishiwaki,* Etsuko Kawamura, Noritaka Abe, Yoshiro Sasaoka, and Hirafumi Kochi
*Department of Chemistry, Faculty of Science, Yamaguchi University, 1677-1 Yoshida, Yamaguchi 753-8512, Japan
Abstract
The photo-cyclisation of N-o-iodobenzoylthioamides has been found to provide a novel and efficient synthesis of 4H-1,3-benzothiazin-4-ones.
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■ Studies on the Synthesis of Chemotherpeutics. Part XI. Synthesis and Antibacterial Activities of Phosphonopeptides
Tetsuji Kametani,* Kazuo Kigasawa, Mineharu Hiiragi, Kikuo Wakisaka, Seiji Haga, Hideo Sugi, Keizo Tanigawa, Yukio Suzuki, Kazunaga Fukawa, Osamu Irino, Osamu Saita, and Shigeru Yamabe
*Hoshi University, 2-4-41 Ebara, Shinagawa-ku, Tokyo 142-8501, Japan
Abstract
A variety of phosphonopeptides, shown in 2 as a general formula, containing natural and/or unnatural amino acids were synthesized, and their in vitro antibacterial activities were examined. N-Protected amino acids were condensed with 1-aminoethylphosphonic acid or its ester followed by deprotection and hydrolysis to give the requisite phosphonopeptides. Several compounds showed higher levels of activity against certain members of Gram-negative bacteria than those of Alafosfalin (1) as the standard phosphonopeptide. A brief discussion on structure-activity relationships is also described.
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■ Proton Magnetic Resonance Spectra of Acridizinium Adducts
Sayeed-Din Saraf*
*Department of Chemistry, Faculty of Science, University of Kuwait, Safat 13060, P.O. Box 5969, Kuwait
Abstract
The structural determination of the acridizinium adducts using the technique of nuclear magnetic resonance has been discussed in detail.