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. 10, 1981
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■ Reduction of Spirohydantoins with Lithium Aluminium Hydride: Synthesis of Spiroimidazolidin-2’-ones and Spiroimidazolidines
Elena de la Cuesta, Palomo Ballesteros, and Gregorio G. Trigo*
*Departamento de Química Orgánica y Farmacéutica, Facultad de Farmacia, Universidad Complutense de Madrid, Ciudad Universitaria, 28040 Madrid, Spain
Abstract
The behaviour of some spirohydantoins against reduction with lithium aluminium hydride as well as the influence of the N3’-substituent on this reaction are analized. N3’-Unsubstituted spirohydantoins yielded the corresponding spiroimidazolidin-2’-ones, while N3’-substituted spirohydantoins originated the spiroimidazolidines. Isomeric (α and β) spiroimidazolidin-2’-ones can be prepared by reduction of the suitable epimeric (α and β) spirohydantoins.
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■ Substitutent Effects on the Course of the Reductive Acylation of Penicillin Sulfoxide Derived Sulfenates
Leilani V. Kapili, Michael S. Kellogg,* and Robert J. Martingano
*Central Research Division, Pfizer Inc., Eastern Point Road, Groton, Connecticut 06340, U.S.A.
Abstract
Reductive acylation of penicillanate sulfoxide derived sulfenates with trivalent phosphorous compounds and acetic anhydride has been shown to give β-lactam products resulting from either oxygen or sulfur transfer to phosphorous dependent on the substituent at the C-6 position of the penicillanate.
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■ Synthesis of Pentacyclic Structure of Griseusin A
Kazuhisa Masamoto, Yoshio Takeuchi, Kei Takeda, and Eiichi Yoshii*
*Faculty of Pharmaceutical Sciences, Toyama Medical and Pharmaceutical University, 2630 Sugitani, Toyama, Toyama 930-0194, Japan
Abstract
A synthetic method of the framework of griseusin A was presented. The key step involved an intramolecular ketalization of the δ,δ’-dihydroxyketone derivative which was prepared from 2-allyl-3-bromo-1,4-dimethoxynaphthalene.
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■ Base-Promoted Isomerization of 4-(Pyrrolylmethyl)-1,2,3,6-tetrahydropyridines
Joan Bosch,* David Mauleón, and Ricardo Granados
*Laboratory of Organic Chemistry, Faculty of Pharmacy, University of Barcelona, Av. de Joan XXIII, s/n, 08028 Barcelona, Spain
Abstract
The base-promoted isomerization followed by acetic acid treatment of two 4-(pyrrolylmethyl)-1,2,3,6-tetrahydropyridines is studied. 1-Methyl-4-(1-pyrrolylmethyl)-1,2,3,6-tetrahydropyridine (3) gave a mixture of the methanopyrrolodiazocine 1 and pyrrole, the latter arising from a fragmentation reaction. 1-Methyl-4-(1-methyl-2-pyrrolylmethyl)-1,2,3,6-tetrahydropyridine (4) afforded a mixture of recovered tetrahydropyridine and a 4-methylenepiperidine 5 instead of the cyclization product 2.
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■ A Simultaneous Detemination of Enantiomeric Purity and Chirality of a Certain Cyclic Enone Relating to the Gibbane Framework
Seiichi Takano,* Chiyoshi Kasahara, and Kunio Ogasawara
*Pharmaceutical Institute, Tohoku University, Aobayama, Sendai 980-8578, Japan
Abstract
A simultaneous determination of enantiomeric purity and chirality of a certain cyclic enone relating to the gibbane framework has been achieved using 1H-nmr spectroscopy.
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■ Synthetic Approach to Diterpene Alkaloids — A Simple and Novel Synthesis of the A, B, C and D Ring Part from 1-Benzyl-1,2,3,4-tetrahydroisoquinoline
Tetsuji Kametani,* Toshio Honda, Keiichiro Fukumoto, Masahiro Toyota, and Masataka Ihara
*Hoshi University, 2-4-41 Ebara, Shinagawa-ku, Tokyo 142-8501, Japan
Abstract
The synthesis of the A,B,C and D ring part (13) of diterpene alkaloid atisine (5) from 1-benzyl-1,2,3,4-tetrahydroisoquinoline (6) by use of an intramolecular Diels-Alder reaction is described.
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■ The Synthesis of 9H-Imidazo[1,2-a][1,3]diazepines
Takushi Kurihara,* Tsutomu Tani, and Keiko Nasu
*Faculty of Pharmaceutical Science, Osaka University of Pharmaceutical Sciences, 4-20-1 Nasahara, Takatsuki, Osaka 569-1094, Japan
Abstract
Ethyl 7-acetyl-2,3-diphenyl-9H-imidazo[1,2-a][1,3]diazepine-5-carboxylate (8) and its acetate (7) were synthesized via the ring-expansion reaction of ethyl 5a-acetyl-4a,5a-dihydro-2,3-diphenyl-5H-cyclopropa[4a,5a]imidazo[1,2-a]pyrimidine-4a-carboxylate (2).
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■ Casuarictin and Casuarinin, Two New Ellagitannins from Casurina stricta
Takuo Okuda,* Takashi Yoshida, and Mariko Ashida
*Faculty of Pharmaceutical Sciences, Okayama University, 1-1-1 Tsushima-naka, Okayama 700-8530, Japan
Abstract
Two new ellagitannins, casuarictin (1) and casuarinin (2) were isolated from the leaves of Casuarina stricta, and their structures were elucidated. Pedunculagin (3) and tellimagrandin-I were also isolated, and the structure 3 including S-configurations of hexahydroxydiphenoyl groups was established.
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■ Novel NADH Models. Steroids Bearing Pendent 1,4-Dihydronicotinamides
Piet C. Keijzer, Adriaan Oudeman, Alida M. v. d. Burg, and Upendra K. Pandit*
*Organic Chemistry Laboratory, University of Amsterdam, Nieuwe Achtergracht 129, 1018 WS Amsterdam, The Netherlands
Abstract
Steroids bearing 1,4-dihydronicotinamides at the 3-position have been synthesized and studied as potential chiral reducing agents.
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■ Synthesis of 3,4-Dihydroquinazolines via Cyclic N-Diazonium Ions
Richard Kreher* and Udo Bergmann
*Institut für Chemie, Medizinische Hochschule Lübeck, Ratzeburger Allee 160, D-2400, Germany
Abstract
The condensation of 2-azidomethylanilines with aromatic aldehydes leads to tne formation of the corresponding azomethines. Treatment with tetrafluoroboric acid results in the generation of phenylogous azidomethyl-iminium salts giving rise to the formation of 2-aryl-3,4-dihydroquinazolines. Cyclic N-diazonium ions are involved as reactive intermediates and synthetic precursors for the annelation of the 6-membered nitrogen heterocycle.
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■ Reactions of Indolizines with Tropone
Yoshiro Yamashita, Daisuke Suzuki, and Mitsuo Masumura*
*Department of Applied Chemistry, Faculty of Engineering, University of Tokushima, Minamijosanjima-cho, Tokushima 770-8506, Japan
Abstract
Reactions of indolizine derivatives with tropone gave the Michael type adducts 2 and 2-indolizin-3-yltropone derivatives 3. The tropones 3 were formed by dehydrogenation of the adducts.
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■ Synthesis of New Macrocyclic Polythiaether
Hisashi Fujihara, Koji Imaoka, Naomichi Furukawa, and Shigeru Oae*
*Department of Chemistry, University of Tsukuba, 1-1-1 Ten-nodai, Tsukuba-shi, Ibaraki, 305-8571, Japan
Abstract
Synthesis of a new macrocyclic polythiaether (12) which is easily obtained in a good yield via 2,6-dithia-4-spiroheptane (6) is described. Several reactions of pentaerythrityl bromide (1) with nucleophiles and a few ring opening reactions of 6 with methyl iodide are also described.
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■ 2-Methylene-3-phenacylbenzothiazoline: Dimerization and Reactions with Electron-deficient Acetylenes and Olefins
Otohiko Tsuge,* Minoru Tanaka, Hiroshi Simoharada, and Michihiko Noguchi
*Research Institute of Industrial Science, Faculty of Engineering, Kyushu University, 6-1, Kasuga-koen, Kasuga 816-8580, Japan
Abstract
On treatment with triethylamine in acetonitrile at 0°C, 2-methy-3-phenacylbenzothiazolium bromide gave a dimer of 2-methylene-3-phenacylbenzothiazoline in a quantitative yield. The methylene base, generated in situ, reacted with electron-deficient acetylenes and olefins to give 3-substituted 2-phenylpyrrolo[2,1-b]benzothiazole via a Michael type adduct; in some cases Michael type adducts were isolated. On the other hand, the methylene base reacted with tetracyanoethylene to give 2-butadienylidenebenzothiazoline derivative, which on heating in acetic anhydride afforded 1-benzoyl-2-cyanopyrrolo[2,1-b]benzothiazole with the elimination of malononitrile.
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■ A Selective One-step Introduction of Hydroxylic Functions at the C-5 and C-7 Positions of 20(S)-Camptothecin, an Alkaloid Having Antitumor Activity
Tadashi Miyasaka,* Seigo Sawada, and Ken’ichiro Nokata
*School of Pharmaceutical Sciences, Showa University, 1-5-8 Hatanodai, Shinagawa-ku, Tokyo 142-8555, Japan
Abstract
20(S)-Camptothecin was selectively hydroxymethylated at the C-7 position by a simple process using hydrogen peroxide-methanol in the presence of ferrous ion as the radical source. Formation of diastereomers of 5-hydroxycamptothecin was observed by using ammonium persulfate-bromoacetic acid in the presence of ferrous or silver ion. The hydroxylic compounds prepared by the processes were converted further into acyloxyl, alkoxyl, and carboxylic acid derivatives.
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■ Chemical Modification of Antitumor Alkaloid Camptothecin. Acid-Catalyzed Conversion of 7-Hydroxymethylcamptothecin into the Aldehyde and Its Acetals
Tadashi Miyasaka,* Seigo Sawada, and Ken-ichiro Nokata
*School of Pharmaceutical Sciences, Showa University, 1-5-8 Hatanodai, Shinagawa-ku, Tokyo 142-8555, Japan
Abstract
Camptothecin-7-carbaldehyde (3) was prepared from 7-hydroxymethylcamptothecin (2) by treatment with such cationoid agent as sulfuric acid, acetic acid, p-toluenesulfonyl chloride, phosphoryl chloride, thionyl chloride, or triphenylphosphine-carbon tetrachloride. On heating with sulfuric acid in an alcoholic solution, 2 afforded 7-alkoxymethylcamptothecin (4) and 7-dialkoxymethylcamptothecin (5), the product-ratio depending upon the acid-concentration.
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■ Structure of Deoxyjesaconitine. A New Diterpene Alkaloid from Aconitum subcuneatum Nakai
Hideo Bando, Yoshio Kanaiwa, Koji Wada, Takao Mori, and Takashi Amiya*
*Hokkaido College of Pharmacy, 7-1 Katsuraoka-cho, Otaru 047-02, Japan
Abstract
A new diterpene alkaloid, deoxyjesaconitine, was isolated from Aconitum subcuneatum and its structure was determined on the basis of spectral data. This compound along with deoxyaconitine and hypaconitine was purified with high performance liquid chromatography, and 13C-NMR spectra of those compounds were measured to afford the relationship with each compound.
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■ Structure and Absolute Configuration of Serpenticine, a New Anhydronium Base from Rauwolfia vomitoria Afzuelia
Abdul Malik, Nighat Afza, and Salimuzzaman Siddiqui*
*H. E. J. Postgraduate Institute of Chemistry, University of Karachi, Karachi-75270, Pakistan
Abstract
The structure and absolute configuration 9 of serpenticine, a new anhydronium base isolated from Rauwolfia vomitoria Afz., has been determined with the aid of UV, IR and 13C-nmr spectral data of the base along with ORD, proton nmr and high resolution mass spectra of its tetrahydro product 8.
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■ A New Product in the Photooxidation of Berberine: A Lactamic Aldehyde
M. Leonor Contreras* and Roberto Rozas
*Department of Chemistry, Facluty of Science, University of Santiago of Chile, Casilla 56559, Santiago-2, Chile
Abstract
Berberinium chloride (1) unsensitized photooxidation in the presence of sodium methoxide affords the lactamic aldehyde (2) in contrast to the already informed sensitized reaction that furnishes the betaine (3).
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■ The Conformational Behavior in Thia- and Dithiametacyclophanes
Yee-Hing Lai*
*Department of Chemistry, University of Victoria, Victoria, BC V8W 3V6, Canada
Abstract
Thia- and dithiametacyclophanes have been shown to undergo several types of interesting conformational behavior. The coalescence temperature method has been widely used to estimate the various conformational energy barriers. Dithia[n]metacyclophanes exhibit a unique flipping process, the barrier of which largely depends on the substituent at the [n+6]-position. An inversion process is common among thia- and dithia[m.n]metacyclophanes (m = n or m ≠ n). However, substituent(s) at the 9- and/or 18-position(s) of dithia[3.3]metacyclophanes results in variability of the conformer preferred. Most medium-sized dithiametacyclophanes seem to be conformationally very mobile but three dithia[3.1.3.1]metacyclophanes are known to demonstrate a novel “twist-inversion” fluxional behavior.
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■ Ring Transformations of Heterocycles over Synthetic Zeolites
Yoshio Ono*
*Department of Chemical Technology, Faculty of Engineering, Tokyo Institute of Technology, 2-12-1,Oh-Okayama, Meguro-ku, Tokyo 152-8552, Japan
Abstract
Synthetic zeolites are found to be very effective and selective catalysts for the vapor phase ring transformations of oxygen-containing heterocycles into nitrogen or sulfur-containing heterocycles. For example, tetrahydrofuran is converted into pyrrolidines and tetrahydrothiophene, while γ-butyrolactone is converted into pyrrolidinones and γ-thiobutyrolactone by the reactions with primary amines and hydrogen sulfide, respectively. The most effective catalysts differ with reactions. For the reaction of tetrahydrofuran with ammonia, acidic zeolites such as HL(proton form of L-type zeolite) are most effective, while for the reaction of γ-butyrolactone with hydrogen sulfide, basic zeolites like CsY(CS+ exchanged Y-type zeolite) are highly active. The kinetics of the ring transformations are studied and the reaction mechanisms are discussed.