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. 22, No. 3, 1984
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■ Phase-transfercatalysed Reactions of Dihalocarbenes with 3,4-Dihydropyridin-2-ones
Bir Sain, Jogendra Nath Baruah, and Jagir Singh Sandhu*
*Division of Drug and Pharmaceutical Chemistry, Regional Research Laboratory, Jorhat 785 006, Assam, India
Abstract
Dihalocarbenes produced by two phase system (TPS) technique readily reacted with double bond of 3,4-dihydropyridin-2-ones 1 to give 2-azabicyclo[4.1.0]heptanes 2 in good yields.
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■ Synthesis of the C-11 Oxygenated Erythrina Alkaloids
Maria Helena Sarragiotto, Paulo A. da Costa, and Anita J. Marsaioli*
*Instituto de Química, Universidade Estadual de Campinas (UNICAMP), Caixa Postal 6154, CEP 13083-970, Campinas, Sao Paulo, Brazil
Abstract
Introduction of an oxygenated function at C-11 of the Erythrina alkaloid skeleton was obtained by treating erysovine with lead tetraacetate. Unfortunately simultaneous substitution of the C-3 OMe by -OAc has occurred and modifications as changing the reaction conditions and/or the phenolic compound to erysodine did not lead to successful results.
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■ Re-exploratiom of the Thermolysis of Arylazides as a Route to 3H-Azepines: Chemistry of Azidoacetophenones
Yoshihiro Ohba,* Shinji Kubo, Tarozaemon Nishiwaki, and Noritoshi Aratani
*Department of Chemistry, Faculty of Science, Yamaguchi University, 1677-1 Yoshida, Yamaguchi 753-8512, Japan
Abstract
Thermolysis of 3-azidoacetophenone in methanol in a sealed glass ampoule gave 6-acetyl- and 4-acetyl-3H-azepines in moderate yields, whose kinetic data [Ea=132.6 ± 1.7 kJmol-1, ΔS443= -12.1 ± 4.2 JK-1 mol-1] were obtained by means of HPLC. Photolysis of this azide in methanol gave the same pair of the 3H-azepines in poor yields. Thermolysis of 4-azidoacetophenone under the similar conditions afforded a moderate yield of 5-acetyl-3H-azepine. For comparison, photolyses of 4- and 2-azidoacetophenones were also studied.
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■ The Formation of [3+2] Cycloadducts and Their Conversions: Reactions of N-Cycloheptatrienylideneamine Oxide with Isocyanates and Isothiocyanates
Shoji Kajigaeshi, Shingo Matsuoka, Shuji Kanemasa,* and Michihiko Noguchi
*Faculty of Engineering, Yamaguchi University, 2-16-1 Tokiwadai, Ube, Yamaguchi 755-8611, Japan
Abstract
The spiro [3+2] cycloadducts from N-cycloheptatrienylidenemethylamine oxide with alkyl isocyanates were isolated and characterized. The reaction of N-oxide with isothiocyanates afforded cyclohepta[d]imidazole, cyclohepta[d]thiazole, and/or 2-methylaminotropothione, which were brought through the similar [3+2] cycloadducts.
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■ An Extremely Mild Thermolysis of Several 2-(2-Halogeno-2-propenylsulfinyl)tropones
Hitoshi Takeshita,* Hideshi Motomura, Kingo Uchida, and Hiroaki Mametsuka
*Instituete of Advanced Material Study, Kyushu University, 6-1, Kasuga-koen, Kasuga 816-8580, Japan
Abstract
By heating 2-(2-chloro-2-propenylsulfinyl)tropanes at above 110 °C afforded 3-chloro-4H,9H-cyclohepta[b]thiopyran-9-ones and their S-oxides. Accompanied formation of di(2-troponyl)disulfides indicated the thermolysis to be a radical, non-concerted intermolecular reaction.
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■ Synthesis of 4H-1,2,4,6-Thiatriazine 1,1-Dioxide: A Precursor of 4-Cyano-1,2,6-thiadiazine 1,1-Dioxides
Pilar Goya,* Carmen Ochoa, Juan Antonio Páez, Isabel Rozas, and Manfred Stud
*Instituto de Química Médica, C. S. I. C., Calle Juan de Cierva, 3, 28006 Madrid, Spain
Abstract
4H-1,2,4,6-thiatriazine 1,1-dioxide, obtained from sulfamide and ethyl orthoformate, reacted with ethyl cyanoacetate and malononitrile to give the corresponding 4-cyano-1,2,6-thiadiazine 1,1-dioxide derivatives.
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■ Structures of Mulberrofurans F and G, Two Natural Hypotensive Diels-Alder Type Adducts from the Cultivated Mulberry Tree (Morus lhou (ser.) Koidz.)
Toshio Fukai, Yoshio Hano, Kazuhiro Hirakura, Taro Nomura,* Jun Uzawa, and Kazutaka Fukushima
*Faculty of Pharmaceutical Sciences, Toho University, 2-2-1, Miyama, Funabashi, Chiba 274-8510, Japan
Abstract
From ethyl acetate extract of the root bark of cultivated mulberry tree (Morus Lhou(ser.) Koidz.), two 2-arylbenzofuran derivatives were isolated and named mulberrofurans F and G, whose structures were shown to be 1 and 2, respectively, on the basis of spectral and chemical evidences. Mulberrofurans F (1) and G (2) were derived from chalcomoracin (3) and mulberrofuran C (4), respectively, by the photocyclization in the acidic solution. Intravenous injection of mulberrofurans F (1), as well as G (2), caused a marked depressor effect in rabbit.
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■ Synthesis of Pyrazolo[3,4-d]pyridazine Derivatives — Two Comparable Approaches, Ring Contraction through Extrusion of Sulphur and Photochemical Cyclisation
Kenji Kaji, Hiromu Nagashima, Yusho Ohta, Shigeto Nagao, Yoshihiko Hirose, and Hirohisa Oda*
*Gifu Pharmaceutical University, 6-1 Mitahora-higashi 5-chome, Gifu 502-8585, Japan
Abstract
Ring contraction of 7-substituted 2-phenyl-4H-pyridazino[4,5-e][1,3,4]thiadiazin-8(7H)-ones (5a-d) to 5-substituted 3-phenyl-1H-pyrazolo[3,4-d]pyridazin-4(5H)-ones (7a-d), through base-induced extrusion of sulphur, is described. Similar reactions proceed, not only on the 4-acetyl derivatives (4a-d) in basic media, but on 5a and the 4-methyl derivative (6a) thermally. Probable mechanisms of these reactions are discussed. A comparable approach to the ring contraction, photochemical cyclisation of 2-substituted 5-(1-alkyl-2-benzylidenehydrazino)-4-chloro-3(2H)-pyridazinones (9a-e) to the corresponding 1-alkylpyrazolo[3,4-d]-pyridazinone derivatives (8a-e) is also performed.
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■ New Synthetic Route to Perhydrohistorionicotoxin Using (3Z)-4-Butyl-3-trichloroacetamido-1,3-butadiene
Toshiro Ibuka,* Hiroyuki Minakata, Masaya Hashimoto, Larry E. Overman, and Robert L. Freeks
*Department of Chemistry, University of California, Irvine, Irvine, California 92697, U.S.A.
Abstract
A formal synthesis of perhydrohistrionicotoxin via the Diels-Alder cycloadduct obtained by reaction of (3Z)-4-butyl-3-trichloroacetamido-1,3-butadiene with methyl acrylate is presented.
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■ Organic Synthesis Using 1-Methoxy-1,2,3-butatrienylborates. II. A Facile Synthesis of 2,5-Dialkyl-3-methylfurans from 1,4-Dimethoxy-2-butyne, B-Alkylcatecholboranes and Aldehydes
Junji Koshino, Takahiro Sugawara, and Akira Suzuki*
*Faculty of Engineering, Hokkaido University, Kita 13 Nishi 8, Kita-ku, Sapporo, Hokkaido 060-0828, Japan
Abstract
2,5-Dialkyl-3-methylfurans are obtained in excellent yields by the reaction of acetic acid with 1-methoxy-1,2,3-butatrienylborates prepared from 1-methoxy-1,2,3-butatrienyllithium and B-alkylcatecholboranes, followed by treatment with aldehydes.
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■ Synthesis of Furo[3,4-d]pyrimidine Derivatives Using Ethyl 4-Bromoacetoacetate
Takuo Chiba,* Hirotoshi Sato, and Tetsuzo Kato
*Pharmaceutical Institute, Tohoku University, Aramaki, Aoba-ku, Sendai 980-8578, Japan
Abstract
Reaction of ethyl 4-bromoacetoacetate (1) with benzaldehyde (2a) and urea in the presence of hydrochloric acid gave 6-bromomethyl-5-ethoxycarbonyl-4-phenyl-3,4-dihydro-2(1H)-pyrimidinone (3a). Similarly, reaction of 1 and urea with p-anisaldehyde (2b), p-hydroxybenzaldehyde (2c), and furfural (2d) afforded the corresponding 6-bromomethyl-3,4-dihydro-2(1H)-pyrimidinones 3b-3d. Thermolysis of compounds 3a-3d gave rise to the corresponding 4,7-dihydrofuro[3,4-d]pyrimidine-2,5(1H,3H)-diones 4a-4d.
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■ Syntheis of Pyrimido[4,5-b][1,4,6]benzoxadiazocines, a New Class of Heterocycles
Keitaro Senga,* Junko Ohwaki, Hashime Kanazawa, Misuzu Ichiba, and Sadao Nishigaki
*Pharmaceutical Institute, School of Medicine, Keio University, Shinanomachi 35, Shinjuku, Tokyo 160-0016, Japan
Abstract
The dehydrogenative cyclization of 5-(N-arylarylamidino)-1,3-dimethylbarbituric acids with diethyl azodicarboxylate afforded pyrimido[4,5-b][1,4,6]benzoxadiazocines, a new class of heterocycles.
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■ Reactions of 4-Pyrimidinone Derivatives with Methyl Isocyanate: Formation of Pyrimido[1,2-a][1,3,5]triazine-2,4-dione RIng System
Masami Sawada, Yoshiro Furukawa, Yoshio Takai, and Terukiyo Hanafusa*
*The Institute of Scientific and Industrial Research, Osaka University ,8-1, Mihogaoka, Ibaraki, Osaka 567-0047, Japan
Abstract
Base-catalysed reactions of 4-pyrimidinone and 4-quinazolinone with methyl isocyanate gave the compounds with a pyrimido[1,2-a][1,3,5]triazine-2,4-dione ring system (3 and 5, respectively; 1:2-cyclic adducts). In contrast, some uracil derivatives afforded the 1-methylcarbamoyl compounds (7, 1:1-adducts) .
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■ The Preparation of Some 1-Vinylpyridinium Salts
Alan R. Katritzky* and Maria J. Mokrosz
*Center for Heterocyclic Compounds, Department of Chemistry, University of Florida, P. O. Box 117200, Gainesville, FL 32611-7200, U.S.A.
Abstract
A variety of substituted pyridines are converted into the corresponding 1-vinylpyridinium bromides or perchlorates. The conjugation in these salts is discussed with reference to the ir spectral characteristics.
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■ Reactions of Uracils; 3. Pyrazolo[3,4-d]- and Pyrido[2,3-d]pyrimidines from 5-Formyl-1,3-dimethyluracils
Péter Mátyus, Pál Sohár, and Heinrich Wamhoff*
*Institut für Organische Chemie und Biochemie, Universität Bonn, Gerhard-Domagk-Str. 1, D-5300 Bonn 1, Germany
Abstract
Starting from the known 5-fomyl-1,3-dimethyluracils (1a-b) some novel derivatives having a great biological interest have been synthesized. The constitutions of the products obtained were established based on spectral data.
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■ Studies on the Condensation Products of Some α,β-Unsaturated Carbonyl Compounds with 4-Hydroxycoumarin
Sunil K. Talapatra,* Ramaprasad Chakrabarti, Pradyot K. Mukhopadhyay, Prabir K. Das, and Bani Talapatra
*Chemistry Department, University College of Science, 92 Acharya Prafulla Chandra Road, Calcutta-700009, India
Abstract
The base catalysed condensation products of mesityl oxide and benzalacetone with 4-hydroxycoumarin have been studied. The reported structures (III) and (IX) of two condensation products are revised as (V) and (X) respectively. Chemical transformations of (V) to (VI), (VII) and (VIII) are enumerated. 13C NMR spectra studies to distinguish between (IV) and (VI) and to establish structure (V) are also recorded. The plausible mechanisms for the formation of two novel compounds having the coumarin lactone ring ruptured, viz. (VIII) from (V) and the condensation product (XI) from 4-hydroxycoumarin and cinnamaldehyde have also been delineated.
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■ 5-Fluorouracil Derivatives. VI. Alkylation of 5-Fluorouracil Using the (Octylthio)carbonyl Group as a Protectiong Function
Shoichiro Ozaki,* Yutaka Watanabe, Hiroshi Fujisawa, and Tomonori Hoshiko
*Faculty of Engineering, Ehime University, 3 Bunkyo-cho, Matsuyama, 790-8577 Ehime, Japan
Abstract
N1- and N3-alkyl-5-fluorouracils are prepared in good yields by the alkylation of 5-fluorouracil protected by the (octylthio)carbonyl group.
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■ Oxidation Studies on Beta-Lactam Antibiotics Synthesis of Penam and Cephem Sulfoxides and Sulfones
Ronald G. Micetich,* Rajeshwar Singh, and Samarendra N. Maiti
*Faculty of Pharmacy , University of Alberta, Edmonton, Alberta T6G, 2N8, , Canada
Abstract
Penicillin and cephalosporin sulfoxides are conveniently prepared by oxidation of the respective penicillin or cephalosporin in methylene chloride using hydrogen peroxide and acetic acid. Replacement of the acetic acid by formic acid produces the respective penicillin and cephalosporin sulfones in high yields.
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■ Cycloaddition Reactions of 1,3-Benzothiazines IV. Intermolecular 1,3-Dipolar Cycloaddition of 2H-1,3-Benzothiazines with Nitrilimines
Lajos Fodor, Mohamed-Sami El-Gharib, János Szabó,* Gábor Bernáth, and Pál Sohár
*Institute of Pharmaceutical Chemistry, University of Szeged, H-6720 Szeged, Eötvös u. 6, Hungary
Abstract
Thermal [3+2] intermoleculer cycloaddition of nitrilimines to 2H-1,3-benzothiazines (1,2) gives new fused tricyclic ring systems (5,6).
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■ Mitomycin Antibiotics: Synthesis of 9a-Functionalized Mitosanes
Wilhelm Flitsch* and Petra Rußkamp
*Organisch-Chemisches Institut, Universität Münster, Orleansring 23, D-4400 Münster, Germany
Abstract
Two closely related rapid entries into the mitosane ring system are described which allow for structural modifications. First examples of a hydroxylation and a methoxylation at the 9a-position of mitosanes are reported.
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■ A New Synthesis of Nornicotyrine
Seitaro Saeki,* Takaaki Hayashi, and Masatomo Hamana
*Faculty of Pharmaceutical Sciences, Kyushu University, 3-1-1 Maidashi, Higashi-ku, Fukuoka 812-8582, Japan
Abstract
The reaction of 3-aminopyridine 1-oxide (1) and 1-methanesulfonylpyrrole (2) with amyl nitrite in acetic acid gave 1-methanesulfonyl-2-(1-oxido-3-pyridyl)pyrrole (3), which was converted into nornicotyrine (4) by successive treatment with phosphorous tribromide and sodium hydroxide solution.
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■ 1-Azadienes as a Synthon for Heterocyclic Synthesis
Yoshiki Ohshiro,* Mitsuo Komatsu, Masatoshi Uesaka, and Toshio Agawa
*Department of Applied Chemistry, Faculty of Engineering, Osaka University, 2-1 Yamadaoka, Toyonaka, Osaka 560-0043, Japan
Abstract
1-Azabutadienes 1 were found to be a good building block for three- to five-membered heterocycles having a functional group. Oxidation of 1 with mCPBA afforded 3-alkenyloxaziridines 2. Cycloaddition of 1 with ketenes gave the 4-alkenylazetidinones 6. Addition of a nitrile imine occurred across the C=N bond to give the 3-alkenyltriazoline 8, while that of a nitrile ylide occurred on the C=C bond to give the 3-formylpyrrole 14 formed by hydrolysis of the C=N bond.
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■ Rearrangement under Alkaline Conditions of Compounds Related to Tetracyclic Strychnos Indole Alkaloids
Joan Bosch,* Mercedes Amat, and Antonio Domingo
*Laboratory of Organic Chemistry, Faculty of Pharmacy, University of Barcelona, Av. de Joan XXIII, s/n, 08028 Barcelona, Spain
Abstract
Treatment of 6-oxo-1,2,3,4,5,6-hexahydro-1,5-methanoazocino[4,3-b]indoles under Wolff-Kishner conditions gave 2,3-dihydro-1H-pyrrolo[2,3-a]carbazoles.
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■ Synthesis of Some 2-Deoxy-2-fluoro[18F]hexopyranoses, Potential Diagnostic Imaging Agents
Masao Tada,* Taiju Matsuzawa, Hiroshi Ohrui, Hiroshi Fukada, Tatsuo Ido, Toshihiro Takahashi, Makoto Shinohara, and Kumiko Komatsu
*Research Institute for Tuberculosis and Cancer, Tohoku University, Seiryo-machi, 4-1, Aobaku, Sendai, 980-, Miyagi, Japan
Abstract
2-Deoxy-2-fluoro[18F]-D-galacto-, -D-altro-, and -L-gluco-pyranose have been prepared by the reactions of corresponding glycals with fluorine[18F] gas followed by acidic hydrolysis, respectively. The gas was produced by the 20Ne(d, α) 18F nuclear reaction using the cyclotron. D-Galactopyranose derivative showed markedly diagnostic liver-imaging activity.
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■ Aziridine in Alkaloid Synthesis. VI. Alternative Synthetic Approach to the Basic Skeleton of Erythrina Alkaloids
Tetsuji Kametani,* Kimio Higashiyama, Yoshio Honda, and Hirotaka Otomatsu
*Hoshi University, 2-4-41 Ebara, Shinagawa-ku, Tokyo 142-8501, Japan
Abstract
Treatment of the aziridine (2) with 3-bromocyclohex-2-en-1-one afforded the bromo derivative (4), which was then thermally cyclized to give the enaminone (8) siteselectively. Reaction of 10 with mercuric acetate furnished 12 instead of the desired erythrinan-type compound, whereas the acid-catalyzed cyclizetion of 8 yielded the desired cyclized product (14).
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■ Synthesis of 3-Substituted 5,6-Diphenylpyrimidin-4-ones from Diphenylcyclopropenone and N-Substituted Amide Oximes
Masahiko Takahashi,* Takayuki Nogami, and Ken-ichi Nidaira
*Department of Materials Sciences, Faculty of Engineering, Ibaraki University, 4-12-1 Nakanarusawamachi, Hitachi, Ibaraki 316-8511, Japan
Abstract
3-Substituted 5,6-diphenylpyrimidin-4-ones were prepared regioselectively from diphenylcyclopropenone and N-substituted amide oximes.
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■ Some Recent Work on Schiff Bases, Imines and Iminium Salts in Synthetic Heterocyclic Chemistry — a Review
Tuticorin R. Govindachari, Pennamuthiriar Chinnasamy, Sundaramoorthy Rajeswari, Sundaram Chandrasekaran, Manakkal S. Premila, Sankaran Natarajan, Kuppuswamy Nagarajan, and Bantwal R. Pai*
*Research and Development Laboratory, Amrutanjan Limited, Mylapore, Madras-600 004, India
Abstract
This review summarizes the versatile use of Schiff bases, imines and iminium salts for synthesizing a great variety of heterocyclic compounds. Addition reactions of Schiff bases with acid anhydrides, acid chlorides and esters have led to the synthesis of penicillins, β-lactams, pyrrolidinones and piperidinones. Condensations of homophthalic anhydrides with Schiff bases have been the key steps for synthesizing isoquinolinones, protoberberines, 8-oxoberbines, benzophenanthridines and indole alkaloids. Reactions of phthalide anions with iminium salts have been utilized for synthesizing protoberberines, phthalide isoquinolines and related alkaloids. Addition of lithium methyl methylthiomethylsulfoxide to Schiff bases and electroreductive addition of alkyl halides to iminium salts are also discussed.