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. 14, No. 2, 1980
Published online:
■ Heterocyclic Systems Containing Bridgehead Nitrogen Atom. Part XXXVII. Reaction of Marcapto-as-benzotriazines with Halogenoacetic Acid, α-Halogenoketones and Alkyl Halides
Saroj Bala, Madan Lal Sachdeva, Ram Nath Handa, and Hrushi Kesh Pujari*
*Department of Chemistry, Kurukshetra University, Kurukshetra-136119, India
Abstract
Mercapto-as-benzotriazines (IIa,b) obtained by the reaction of corresponding o-phenylenediamines (Ia,b) with thiosemicarbazide, on condensation with halogenoacetic acid, yields benzotriazine-3-thiolacetic acids (IIIa,b) which on treatment with acetic anhydride underwent cyclodehydration to furnish 9H-thiazolo[2,3-c]-as-benzotriazin-3(2H)-ones (IVa,b) and not 5H-thiazolo[3,2-b]-as-benzotriazin-3(2H)-ones (VIIIa,b) as revealed by NMR spectral data. Similar condensation of IIa,b with α-halogenoketones followed by the PPA cyclization of the intermediate ketones (Va,b) yields 9H-thiazolo[2,3-c]-as-benzotriazines (VIa,b). The reaction of IIa with 1,2-dibromoethane yields 9H-2,3-dihydro-6,7-dimethylthiazolo[2,3-c]-as-benzotriazine (VII). Thiazolo-benzotriazine (IV, VI and VII) is a novel and hitherto unknown heterocyclic system and is reported here for the first time.
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■ Some Novel Reactions of 1,3-Dimethyluracils
Tsuneo Itoh,* Haruo Ogura, Norio Kawahara, and Kyoichi A. Watanabe
*School of Pharmaceutical Sciences, Kitasato University, 5-9-1, Shirokane, Minato-ku, Tokyo 108-8641, Japan
Abstract
Treatment of 6-chloro-1,3-dimethyluracil (1) with diazomethane and tertiary amines gave the dimeric compound (2) as the sole product and 1 with secondary amines deduced to the 6-amino dimeric compounds (6). The structural assignment of the dimers is based on physical and chemical evidences.
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■ A New 2-Pyrone Synthesis and Its Application to Bufadienolide Synthesis
Yoshio Takeuchi, Yutaka Makino, Koichi Maruyama, and Eiichi Yoshii*
*Faculty of Pharmaceutical Sciences, Toyama Medical and Pharmaceutical University, 2630 Sugitani, Toyama, Toyama 930-0194, Japan
Abstract
A synthetic method of 4-, 5-, and 6-alkyl-2-pyrones from an appropriately substituted α,β-unsaturated ketone or aldehyde was presented. The reaction sequence consisted of 1) conjugate addition of a methylthio- or phenylthioacetate to the enone by use of the corresponding thiomalonate, 2) acid-catalyzed enol lactonization of the adduct, and 3) oxidative elimination of the thio group. Application of this method to a 21-oxo-20-methylenepregnane leading to a new method for the synthesis of bufadienolides was also described.
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■ Stereoselective Synthesis of dl-Carpamic Acid and dl-Azimic Acid
Mitsutaka Natsume* and Masashi Ogawa
*Research Foundation Itsuu Laboratory, 2-28-10 Tamagawa, Setagaya-ku, Tokyo 158, Japan
Abstract
Carpamic acid and azimic acid, which are constructing units of dimeric lactone alkaloids, carpaine and azimine, were synthesized stereoselectively from endoperoxide of 2-methyl-1,2-dihydropyridine derivative.
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■ Bisaknadinine, a New Dimeric Hasubanan Alkaloid from Stephania sasakii Hayata
Jun-ichi Kunitomo,* Megumi Oshikata, Yoshiko Murakami, and Tetsuro Shingu
*Faculty of Pharmaceutical Science, Mukogawa-Women’s University, 11-68 Koushien Kyuban-Cho, Nishinomiya, Hyogo 663-8179, Japan
Abstract
A new type base, bisaknadinine, was isolated from Stephania Sasakii Hayata, and its structure was decided as (I) from spectral data, especially by the application of nuclear Overhauser effect and internuclear double resonance. The chemical oxidation of aknadinine (II) afforded bisaknadinine (I), thus the absolute configuration of (I), except the steric configuration concerning the mode of biphenyl linkage, was proved.
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■ The Reaction of 4-Methoxyquinoline 1-Oxide with Dimethyl Acetylenedicarboxylate
Yasuhisa Ishigura, Kazuhisa Funakoshi, Seitaro Saeki, Masatomo Hamana,* and Ikuhiko Ueda
*Faculty of Pharmaceutical Sciences, Kyushu University, 3-1-1 Maidashi, Higashi-ku, Fukuoka 812-8582, Japan
Abstract
4-Methoxyquinoline 1-oxide reacts with dimethyl acetylenedicarboxylate in boiling dioxane affords N-quinolinium ethylide (1), 2-substituted quinoline (2), furo[3,2-c]quinoline (3) and 9-oxo-tetrahydro-cis-furo[3,2-b]quinoline (4). Similar reactions readily proceed at low temperatures in dichloromethane, acetonitrile and DMF to give 2, 3 and 4.
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■ 1,3-Dipolar Addition Reactions with Vinylpyrroles
R. Alan Jones* and Michael T. P. Marriott
*School of Chemical Sciences, University of East Anglia, Norwich, Northfolk NR4 7TJ, U.K.
Abstract
Diphenylnitrilimine and methyl nitrile oxide add regioselectively to 1-substituted vinylpyrroles to give 5-substituted-4,5-dihydropyrazoles and 4,5-dihydroisoxazoles, respectively. These reactions and the corresponding cycloadditions involving p-chlorophenyl sydnone and C-phenyl-N-phenylnitrone are LUMO(dipole) controlled.
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■ Preparation of Some Spirocyclic Oxetanes
A. M. S. Odeh, J. A. Usta, and C. H. Issidorides*
*Department of Chemistry, American University of Beirut, Beirut, Lebanon
Abstract
Syntheses and spectroscopic properties of some oxetanes derived from pentaerythritol are discussed.
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■ New Clerodane Diterpenoids from Teucrium spinosum L.
Giuseppe Savona, Mariapia Paternostro, Franco Piozzi,* and Benjamin Rodriguez
*Instituto de Chimica Organica, Facolta de Scienze, Università digli Studi di Palermo, 20 via Archirafi, 90123 Palermo, Italy
Abstract
Two new diterpenoids, isolated from Teucrium spinosum (Labiatae) have been shown to possess the clerodane structures [I] and [II] respectively.
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■ Hydrolytic Ring Cleavage of Thiadiazolo[3,2-a]pyrimidinones
Tadakazu Tsuji* and Yoshimi Otsuka
*Department of Chemical and Biological Sciences, Faculty of Science, Japan Women’s University, 2-8-1 Mejirodai, Bunkyoku, Tokyo 112-0015, Japan
Abstract
The alkali and acid hydrolysis of 2-substituted 7-methyl-5H-thiadiazolo[3,2-a]pyrimidin-5-ones gave 3-amino-6-methyluracil, 3-amino-6-methyl-2-thiouracil and 2-amino-1,3,4-thiadiazole derivatives according to the kind of substituents. While, the treatment of 7-methyl-5H-thiadiazolopyrimidin-5-one with methanolic hydrochloric acid gave 6-methyl-2-thiouracil.
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■ 3ζ-Hydroxyvobtusine, a Key-link between Vobtusine and Amataine
Bruno Danieli, Giordano Lesma, Giovanni Palmisano, and Bruno Gabetta*
*Dipartimento di Chimica Organica e Industriale, Università degli Studi di Milano, Via Venzian 21, 20133 Milano, Italy
Abstract
The title compound, a ‘bisindoline’ alkaloid from the root bark of Voacanga chalotiana (Apocynaceae) has structure (4) proved by correlation with vobtusine (1) and amataine (2).
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■ 1,3-Aninoic Cycloadditions of 2-Azaallyllithium Compounds to Ethylene. Synthesis of 2,5-Diarylpyrrolidines
Kazuyuki Kamata and Masanao Terashima*
*Faculty of Pharmaceutical Scicences, Higashinihonngakuen University, 1757 Kanazawa, Toubetu-cho, Ishikari-gun, Hokkaodo 061-0212, Japan
Abstract
Anionic cycloaddition of 1,3-diaryl-2-azaallyllithiums with the ethylene formed in situ by the cleavage of THF by n-butyllithium gave cis-2,5-diarylpyrrolidines in synthetically useful yields. The same cycloadducts were obtained from the reaction of 2a and 2c with ethylene itself.
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■ A Simple Relationship between Stereosturcture and Specific Rotation for the Bisbenzylisoquinolines
Bruce K. Casseles and Maurice Shamma*
*Department of Chemistry, The Pennsylvania State University, York Campus, P1031 Edgecomb Avenue, York, Pennsylvania 17403, U.S.A.
Abstract
Within a stereochemical subgroup of bisbenzylisoquinolines, the sign of the specific rotation is characteristic of that particular subgroup. The absolute configuration of tiliamosine has been assigned for the first time.