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. 26, No. 7, 1987
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■ Cycloaddition of 1-Methyl-1-azaazulen-2(1H)-one with Reactive Acetylenes
Noritaka Abe and Toshiyuki Takehiro
*Department of Chemistry, Faculty of Science, Yamaguchi University, 1677-1 Yoshida, Yamaguchi 753-8512, Japan
Abstract
Reactions of 1-methyl-1-azaazulen-2(1H)-one with reactive acetylenes in refluxing acetonitrile gave 1,2-disubstituted azulene (2) , 2-methylcyclopent [de] isoguinolin-3 (2H) -one (3), 1-methylcyclopent [cd] azulen-2 (1H) -ones (4 and 5), and ,3-substituted 1-methyl-1-azaazulen-2 (1H) -ones (6 and 7) . When the reaction was carried out in refluxing t-butylbenzene, the compound 2 and 6,8a-etheno-1 -methyl-1 -azaazulen-2 (1H) -one (8) were obtained as major products.
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■ Three New Coumarins from Murraya exotica
Chihiro Ito and Hiroshi Furukawa
*Faculty of Pharmacy, Meijo University, 150 Yagotoyama, Tenpaku, Nagoya 468-8503, Japan
Abstract
Three new coumarins named peroxyauraptenol (1) having hydroperoxy group, cis-dehydroosthol (3). and murraol (5) were isolated from leaves of Murraya exotica (Rutaceae), and the structures were assigned by chemical and/or spectrometric studies.
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■ Convenient Ruthrenium-complex Catalysed Synthesis of Enterolactone from the Corresponding Dibenzylidene Succinic Acid Moiety
Massimo Bambagiotti-Alberti, Silvia A. Coran, Franco F. Vincieri, and Pierandrea Lo Nostro
*Chemistry Department, Shahid Beheshty University, Evin, P.O. Box 1983963113, Tehran, Iran
Abstract
A convenient synthesis of enterolactone is outlined consisting mainly of a ruthenium carbonyl-hydride complex catalysed hydrogenation of bis(3-methoxybenzylidene)succinic acid.
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■ First Total Synthesis of (±)-Hirsuteine
Takeaki Naito, Okiko Miyata, and Ichiya Ninomiya
*Kobe Women’s College of Pharmacy, Motoyamakita, Higashinad, Kobe, Hyogo 658, Japan
Abstract
First total synthesis of (±)-hirsuteine, 3β-epimer of corynantheine, was achieved via the route involving retro Michael and the subsequent Michael reaction of the furo[3,2-c]pyridone (2b).
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■ Synthesis of Chuangxinmycin Analogues
Masakatsu Matsumoto and Nobuko Watanabe
*Sagami Central Research Center, 4-4-1 Nishi-Ohnuma, Sagamihara, Kanagawa 229-0012, Japan
Abstract
Chuangxinmycin analogues with 3-cyanomethyl, 3-ethoxycarbonylmethyl, and 3-nitromethyl groups were synthesized. They revealed antitumor activity against P388 leukemia cells in vitro.
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■ A New Entry to the Synthetic Route for 6,7-Secoergolene Alkaloids Using Fragmentation Reaction of γ-Aminoalcohols
Toshiko Kiguchi, Takeski Naito, and Ichiya Ninomiya
*Kobe Women’s College of Pharmacy, Motoyamakita, Higashinad, Kobe, Hyogo 658, Japan
Abstract
A new synthetic route involving fragmentation reaction of γ-aminoalcohols for total synthesis of 6,7-secoergolene alkaloids was developed using the model.compounds (1-5).
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■ 1,2,4-Trisubstituted 1,2,3-Triazolium Salts from Nitrilimines and Isocyanides
Dietrich Moderhack and Michael Lorke
*Institut für Phaemazeutische Chemie, Technische Universität , D-38106 Brauschweig, Germany
Abstract
Diarylnitrilimines (from 1 and triethylamine) react with alkyl isocyanides 2 to form, through proton transfer, the quaternary salts 3A. This constitutes a novel synthetic approach to the 1,2,3-triazolium ring having groups on adjacent nitrogens.
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■ 2’-Deoxy-3,7-dideazanebularine and 2’-Deoxy-3,7-dideazainosine: Synthesis of Pyrrolo[3,2-c]pyridine β-D-2’-Deoxyribofuranosides by Solid-liquid Phase-transfer Glycosylation
Frank Seela and Werner Bourgeois
*Laboratorium für Organische und Bioorganische, Institut für Chemie, Universität Osnabrück, Barbarastr. 7, D-4500 Osnabrück, Germany
Abstract
1-(2-Deoxy-β-D-erythro-pentofuranosyl)-1H-pyrrolo-[3,2-c]pyridine (2’-deoxy-3,7-dideazanebularine,1) and 1- (2-deoxy-β-Derythro- pentofuranosy1)-1H-pyrrolo[3,2-c]pyridin-4(5H)-one (2’-deoxy-3,7-dideazainosine, 2a) have been synthesized by regio- and diastereospecific solid-liquid phase-transfer glycosylation. Employing the cryptand TDA-1, solid KOH, and an aprotic solvent the nucleoside 6 was formed in almost quantitative yield. It was converted into compounds 2b or 3b by selective displacement of the 4-chloro group. Compounds 1, 2a, or 3c were obtained after catalytic hydrogenation. The nucleoside 2a is extremely stable under acidic as well as under alkaline conditions. Compound 1 is strongly fluorescent.
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■ Dialkyl Anhydro Sugars in Organic Synthesis. Synthesis of (-)-Invictolide
Takeshi Wakamatsu, Yuji Nishikimi, Hiromi Kikuiri, Hideo Nakamura, and Yoshio Ban
*Faculty of Pharmaceutical Sciences, Hokkaido University, Kita 12 Nishi 6, Kita-ku, Sapporo, Hokkaido 060-0812, Japan
Abstract
The levorotatory invictolide 1a has been synthesized via the stereocontrolled oxirane ring opening of dianhydro sugars, which are conveniently prepared from levoglucosan(1,6-anhydro-β-D-glucopyranose).
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■ A Promising Cyclization of the 3-Arylidene-6-arylmethyl-2,5-piperazinedione to Construct Tricyclic Lactam as an Intermediate to Saframycin Synthesis
Akinori Kubo, Naoki Saito, Madoka Nakamura, Koreharu Ogata, and Shin-ichiro Sakai
*Meiji Pharmaceutical University, 2-522-1 Noshio, Kiyose, Tokyo 204-8588, Japan
Abstract
Regioselective reduction of the 3-arylidene-6-arylmethyl-2,5-piperazinedione (7b) at the C-2 position, followed by effective intramolecular cyclization to afford the tricyclic lactam (10b)is described. The structure of 16 as an intermediate to saframycin synthesis is confirmed by an X-ray crystallographic analysis.
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■ Mild Reduction of Indoles with Zinc Borohydride
Hiyoshizo Kotsuki, Yasuyuki Ushio, and Masamitsu Ochi
*Department of Material Science, Faculty of Science, Kochi University, 2-5-1, Akebono-cho, Kochi 780-8520, Japan
Abstract
Mild reduction of indoles to indolines was achieved by using zinc borohydride as a neutral reducing agent.
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■ A Facile Synthesis of Chuangxinmycin
Masakatsu Matsumoto and Nobuko Watanabe
*Sagami Central Research Center, 4-4-1 Nishi-Ohnuma, Sagamihara, Kanagawa 229-0012, Japan
Abstract
Chuangxinmycin was synthesized by means of intramolecular C-H bond insertion of carbene (carbenoid) generated by Bamford-Stevens type reaction.
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■ Synthesis of Depyrrolo Analogue of Reserpine
Okiko Miyata, Etsuko Doi, Takeaki Naito, and Ichiya Ninomiya
*Kobe Women’s College of Pharmacy, Motoyamakita, Higashinad, Kobe, Hyogo 658, Japan
Abstract
Depyrrolo analogue (19) of reserpine was synthesized via the route involving hydrocyanation reaction of the β-methoxyenone (7) followed by the Michael reaction of the α,β-unsaturated nitrile (11) with sodium methoxide.
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■ Total Syntheses of Indoe Alkaloids, Annonidine A and 7-(3-Methyl-2-buten-1-yl)indole
Masanori Somei, Tetsuo Funamoto, and Toshiharu Ohta
*Faculty of Pharmaceutical Sciences, Kanazawa University, 13-1 Takara-machi, Kanazawa 920-0934, Japan
Abstract
Practical total syntheses of annonidine A and 7-(3-methyl-2-buten-1-yl)indole are reported.
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■ Preparation of Dihydrothiopyran-3-ones by Aldol Condensation of Diketo Sulfides and Acid-catalyzed Rearrangement of Ketol Intermediates Leading to Thiolan-3-one Derivatives
Juzo Nakayama, Keiko Hidaka, and Masamatsu Hoshino
*Department of Chemistry, Faculty of Science, Saitama University, Saitama, Saitama 338-8570, Japan
Abstract
Acid-catalyzed intramolecular aldol condensation of diketo sulfides generally affords 2,6-dihydrothiopyran-3-ones and/or their 2,4-dihydro isomers in good yields. The ketol intermediates, in a few cases, undergo sulfur-participated rearrangement to give thiolan-3-one derivatives in addition to dihydrothiapyranones.
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■ A Formal Synthesis of N-Acetyl-L-acosamine
Tetsuji Kametani, Yukio Suzuki, Chieko Ban, Kiyoshi Kanada, and Toshio Honda
*Hoshi University, 2-4-41 Ebara, Shinagawa-ku, Tokyo 142-8501, Japan
Abstract
N-Acetyl-L-acosamine (1a) was formally synthesized from optically active cyclopentane derivative (2) which was easily derived from (S)-(+)-carvone.
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■ Preparation of α-Quater-, α-Sexi-, and α-Octithiophenes
Juzo Nakayama, Toru Konishi, Shigeru Murabayashi, and Masamatsu Hoshino
*Department of Chemistry, Faculty of Science, Saitama University, Saitama, Saitama 338-8570, Japan
Abstract
α-Quaterthiophene (1), α-sexithiophene (2), and α-octithiophene (3) (the highest member of α-oligothiophenes ever synthesized) were prepared from α-bithiophene, α-terthiophene, and α-quaterthiophene, respectively, via monobromination with N-bromosuccinimide followed by reductive coupling reaction with an activated nickel (0) reagent.
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■ The Comparative Reactions of Forphin, 5-Bromoporphin, 2-Bromoporphin, and 5-Nitroporphin
Louis R. Nudy, Cherylann Schieber, Frederick R. Longo, and Vinod S. Agarwala
*Department of Chemistry, Drexel University, Philadelphia, Pennsylvania 19104, U.S.A.
Abstract
In a continuing study of the aromaticity of the parent parphyrin, porphin, we have conducted the nitration of 5-bromoporphin and the bromination of 5-nitroporphin to determine the presence of substituent directing effects. In addition we have compared the rates of Cu(II) incorporation by these structures with the rate for porphin. Our results substantiate the Fleischer-Webb model for the II-electron pathway in porphin.
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■ Transformation of Heterocyclic N-Oxides into Derivatives of α-Heteroaryl Substituted α-Amino Acids and Dipeptides
Branko Stanovnik, Irena Drofenik, and Miha Tisler
*Department of Chemistry, E. Kardelj University, Murnikova 6, 61000 Ljubljana, Slovenia
Abstract
Heterocyclic N-oxides 1 were converted with oxazolidinone 2 into oxazolinylidene derivatives 3. The opening of the oxazolinone ring produced various derivatives of α heteroaryl substituted α-amino acids, such as sodium salt 4 and hydrazides 5. Acyl azides 6, obtained by treatment of hydrazides 5 with nitrous acid, were transformed into dipeptides 7. All these compounds exist in tautomeric forms 10 and 14 shown i n Schemes.
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■ 3-Phenylhexahydro-1(3H)-isobenzofuranones
Seiji Miyano, Nobuhiro Abe, Fumiko Fujisaki, and Kunihiro Sumoto
*Faculty of Pharmaceutical Sciences, Fukuoka University, 8-19-1 Nanakuma, Jonan-ku, Fukuoka 814-0180, Japan
Abstract
Highly stereoselective syntheses of four stereoisomers of 3-phenylhexahydro-1(3H)-isobenzofuranone (1) and the reevaluation of stereochemical assignments of these lactones are described.
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■ Isonimolide and Isolimbolide, Two New Tetranortriterpenoids from the Twigs of Azadirachta indica A.Juss (Meliaceae)
Salimuzzaman Siddiqui, Tariq Mahmood, Bina Shaheen Siddiqui, and Shaheen Faizi
*H. E. J. Postgraduate Institute of Chemistry, University of Karachi, Karachi-75270, Pakistan
Abstract
Two new tetranortriterpenoid γ-hydroxybutenolides named as isonimolide and isolimbolide along with isonimocinolide, have been isolated from the acidic fraction of the fresh, undried, spring twigs of Azadirachta indica (neem). The structures of these limonoids have been established through chemical and spectral studies.
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■ Studies in Spiroheterocycles: Part X: Reactions of Diazomethane with 3-Aroylmethylene-indole-2-ones and Synthesis of Some Novel Fluorine Containing Spiro[cyclopropane-1,3’(3H)indol]2’(1’H)-ones
Krishna C. Joshi, Renuka Jain, and Seema Arora
*Department of Chemistry, University of Rajasthan, Jaipur 302 004, India
Abstract
Reaction of ethereal diazomethane with fluorinated 3-aroylmethylene-indol-2-ones has been investigated for the first time yielding spiro [cyclopropane-1,3’(3H)indol]-2’ (1’H)-ones. The structures of a l l compounds have been confirmed on the basis of elemental analysis, ir, 1H-nmr and mass fragmentation pattern.
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■ A Novel Rearragement of a Papaverine Derivative into Isoquino[1,2-b]quinozoline Derivative
Yusuf Ahmad, Tahira Begum, Izhar Hussain Qureshi, Atta-ur-Rahman, Khurshid Zaman, Xu Changfu, and Jon Clardy
*Pharmaceutical and Fine Chemicals Division, P.C.S.I.R. Laboratories, karachi-39, Pakistan
Abstract
Anthranilopapaverine (2) was rearranged by pyrolysis or photolysis into a new heterocycle (3). The structure of (3) has been elucidated by X-ray crystallography and by Spectroscopic methods. Pyrolysis of (2) also gives an isomeric mesoionic szaberbinone (5).
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■ Factors Influencing the Pathway of Reactions of 1-Hydrazinophthalazine with Di- and Tricarbonyl Compounds
Adel Amer, Klaus Weisz, and Hans Zimmer
*Frank J. Seiler Research Laboratory, U.S.A.F. Academy, CO 80840, U.S.A.
Abstract
The reaction of 1-hydrazinophthalazine (hydralazine) (1) with substituted ethyl benzoylpyruvates (3) leads under neutral reaction conditions to 3-[2-oxo-2-(substituted phenyl)ethyl]-4H-as-triazino[3,4-a]phthalazin-5-ones (4).Under acidic but otherwise identical conditions depending on the substituent of 3, 4 and/or 3-carbethoxya-triamlo[3,4-a]phthalazine (5) with simultaneous elimination of the appropriate acetophenone were obtained. 1-HCI and substituted ethyl cinnamoylpyruvates (6a-e) give rise to formation of 1-(1-phthalazinyl)-3-carbethoxy-5-(3-or 4-substituted styry1)pyrazoles (7). Under neutral conditions the reaction of 1 with 6 gives as-triazino[3,4-a]phthalazine (8). The structures of 4, 5, 7, and 8 are based on elemental analysis and extensive ms- and 1H-nmr investigations.
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■ A Convenient Access to Furo[3,2-h]quinolines and to Furo[3,2-b]pyridines via SRN1 Reactions
René Beugelmans and Michèle Bois-Choussy
*Institut des Chimie des Substances Naturelles, C.N.R.S., 1 avenue de la Terrasse, Bat. 27, 91198 Gif-sur-Yvette Cedex, France
Abstract
The two steps route to furo[3,2-h]quinolines 4 or to furo[3,2-b]pyridines 17 involves an SRN1 reaction between 5-chloro-7-iodo-8-isopropoxyquinoline 1a or 2-bromo-3-isopropoxypyridin 15 and enolates derived from ketones. The subsritution products 3 or 16, lead to the title compounds under acidic treatment.
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■ Two New Acridone Alkaloids from Genus Citrus Plants
Motoharu Ju-ichi, Mami Inoue, Chihiro Ito, Miyuki Matsuoka, Hiroshi Furukawa, and Ichiro Kajiura
*Faculty of Pharmaceutical Science, Mukogawa-Women‘s University, 11-68 Koushien Kyuban-Cho, Nishinomiya, Hyogo 663-8179, Japan
Abstract
Two new acridone alkaloids named citrusamine (1) and 1,3-dihydroxy-10-methylacridone (2) were obtained from the root of the hybrid seedlings of Okitsu No.17 x Hyuganatsu and also from Kawano-Natsudaidai.
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■ Preparation of Synthetically Useful 2-Acyl-1H-imidazoles by an Autooxidation of 1H-Imidazolyl-2-methanol Derivatives
Satoshi Hayakawa, Yoshimi Tamai, Teruyuki Yuasa, Masao Okamoto, and Shunsaku Ohta
*Kyoto Pharmaceutical University, Misasagi, Yamashina, Kyoto 607-8414, Japan
Abstract
1-Methyl-1H-imidazolyl-2-methanol derivatives (4) were autooxidized in a reaction medium consisting of air, sodium hydride, pyrazole and tetrahydrofuran to give the corresponding 2-acyl-1-methyl-1-H- imidazoles (1) in good yields.
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■ A Facile and Alternative Synthesis of Quinoline Nucleus Using Thermal Cyclization of 2-Azahexatriene System Generated from 2-Alkenyl-Acylaniline with POCl3
Satoshi Hibino and Eiichi Sugino
*Graduate School of Pharmacy and Pharmaceutical Sciences, Faculty of Pharmacy and Pharmaceutical Sciences, Fukuyama University, Fukuyama, Hiroshima 729-0292, Japan
Abstract
The thermal cyclization of 2-alkenyl acylanilines with POCl3 in toluene or xylene gave quinoline derivatives in good yield via 2-azahexatriene system in situ.
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■ Thermolysis of Sodium Salts of Tosylhydrazones of Some Heterocyclic Aldehydes in the Presence of Silver Chromate: 1,3 N→C Migration of Tosyl Group
Katsuhiro Saito and Hiraku Ishihara
*Faculty of Engineering, Nagoya Institute of Technology, Gokiso-cho, Showa-ku, Nagoya 466-8555, Japan
Abstract
The thermal decompositions of sodium salts of tosylhydrazones of furfural. thiophene-2-aldehyde, 1-methylpyrrole-2-aldehyde, and pyridine-2-aldehyde in the presence of silver chromate gave 2-furyl(ptoluenesulfony1) methane. thiophene-2-(p-toluenesulfony1)methane, 1- methylpyrrole-2-(p-toluenesulfonyl)methane, and pyridine-2-(p-toluenesulfonyl) methane, respectively, via 1,3 N→C migration of tosyl group. The same type of reactions with sodium salts of tosylhydrazones of thiophene-3-aldehyde, pyridine-3-aldehyde, and pyridine-4-aldehyde also afforded the corresponding p-toluenesulfonylmethanes but the yields were slightly lower comparing to the above cases.
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■ Benzopyran-4-ones Containing a 2,3-Fused Heterocyclic Ring
Trevor M. Romney-Alexander
*Department of Applied Chemsitry, Institute of Science and Technology, University of Wales, PO Box 13, Cardiff CF1 3XF, U.K.
Abstract
The chemistry and biological properties of 4-oxo-[l]benzopyrano-2,3-fused heterocycles are reviewed.