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. 9, No. 11, 1978
Published online:
■ New Syntheses of Flavopereirine and Yohimbanes by Enamide Photocyclization
Ichiya Ninomiya,* Yukiko Tada, Toshiko Kiguchi, Okiko Yamamoto, and Takeaki Naito
*Kobe Women‘s College of Pharmacy, Motoyamakita, Higashinad, kobe, Hyogo 658, Japan
Abstract
As an extension of the application of enamide photocyclization to the synthesis of protoberberine alkaloids1 , new total syntheses of flavopereirine (6), one of the simplest alkaloids of Strychnos plants, and yohimbanes (11a, b, and c), the basic structures of the alkaloid yohimbine, are described.
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■ Antimicrobial Agents from Higher Plants, Glycyrrhiza glabra L. (var. Spanish). I. Some Antimicrobial Isoflavans, Isoflavenes, Flavanones and Isoflavones
Lester A. Mitscher,* Young Han Park, Shiji Omoto, George W. Clark, III, and Donna Clark
*Department of Medicinal Chemistry, University of Kansas, 4070 Malott Hall, Lawrence, Kansas 66045-2506, U.S.A.
Abstract
The isolation, structure determination and bioactivity of antimicrobial isoflavans hispaglabridin A (1), hispaglabridin B (2) and 4’-O-methylglabridin (3) from Glycyrrhiza glabra L. (Spanish variety) are reported. Isolation of previously known substances glabridin (5), glabrene, glabrol, formononetin and phaseollinisoflavan are also described.
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■ Effective Catalytic Asymmetric Synthesis of R-(—)-Pantolactone with Polymer Supported Chiral Pyrrolidinephosphine-Rhodium Complexes
Kazuo Achiwa*
*Faculty of Pharmaceutical Sciences, University of Tokyo, Hongo, Bunkyo-ku, Tokyo 113, Japan
Abstract
The syntheses of new polymer supported chiral pyrrolidine-phosphine ligands; 4VB-PPM-MMA (1) and 4VB-PPM-tBuMA (2) and their application to the asymmetric hydrogenation of keto-pantolactone were described. Thus, 4VB-PPM-MMA-Rh and 4VB- PPM-tBuMA-Rh gave R-(-)-pantolactone in 73.4 and 75.7% optical yield respectively.
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■ Base-Induced Reactions of N-Methyl Quaternary Salts of 1-Azadibenzo[c,f]bicyclo[3.3.1]nona-3,6-diene and Related Compounds
Hiroaki Takayama,* Takashi Nomoto, Takayoshi Suzuki, Masayuki Takamoto, and Toshihiko Okamoto
*Faculty of Pharmaceutical Sciences, Teikyo University, 1091-1 Suarashi, Sagamiko-machi, Tsukui-gun, Kanagawa 199-0195, Japan
Abstract
Reactions of N-mthyl quaternary salt (2) of 1-azadibenzo[c,f]bicyclo[3.3.1]nona-3,6-diene (1) with various bases were examined, and consequently, 6-aza-6-methyldibenzo[b,i]bicyclo[3.2.2]nona-2,8-dime (4) was selectively obtained by the reaction of 2 with potassium t-butoxide in dioxane, in contrast 1-aza-1-methyl-5-methylenedibenzo[c,f]octa-3,6-diene (3) was provided as a sole product by the reaction with potassium hydroxide in water, respectively. Isopavine alkaloids, (±)-amurensinine and (±)-reframine were also derived.
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■ Photo-sensitized Oxygenation of 1H-1,2-Benzodiazepines
Takashi Tsuchiya,* Jyoji Kurita, and Kazuko Takayama
*School of Pharmacy, Hokuriku University, 3-Ho, Kanagawa machi, Kanazawa 920-1181, Japan
Abstract
The dye-sensitized photooxygenation of 1H-1,2-benzodiazepines (6) and 1-methyl-1H-1,2-benzodiazepines (18) affords fragment products (7) to (11) and (20), respectively, which may be formed via 3- and 5-hydroperoxides. The other possible dioxides and their decomposition products are not obtained.
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■ Synthesis of a Novel Macrocyclic System: 1,3,5-Tri[2.6]pyridacyclohexaphane-2,4,6-trione
George R. Newkome,* Joe D. Sauer, Peter K. Mattschei, and Ashutosh Nayak
*Department of Chemistry, Louisiana State University, Baton Rouge, Louisiana 70803-1804, U.S.A.
Abstract
Trione (I), which possesses an unusual 6N-electron-rich cavity, has been synthesized and is the first reported member of this heterocyclic class.
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■ Simple Entry into the 1,6-Diazaphenalene Ring System
Mustafa I. El-Sheikh, Jen-C. Chang, and James M. Cook*
*Department of Chemistry, University of Wisconsin-Milwaukee, Milwaukee, Wisconsin 53201, U.S.A.
Abstract
A facile synthesis of the dihydro-1,6-diazaphenalene ring system has been developed by heating one equivalent of methyl-1,2,3,4-tetrahydro-5-oxocoumarin-4-y1 acetate (5) with three equivalents of hydroxylamine hydrochloride in aqueous ethanol; 7,8-dihydro-2,5- dihydroxy-1,6-diazaphenalene-1,6-dioxide (2) was produced in this manner in 88% yield.
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■ Synthesis of 1,6-Dimethylpyrimido[4,5-c]pyridazine-5,7-(1H,6H)-dione (4-Deazatoxoflavin) Derivatives and Their Use in the Oxidation of Alcohols
Fumio Yoneda,* Masatsugu Higuchi, Mitsuko Kawamura, and Yoshihiro Nitta
*Faculty of Pharmaceutical Sciences, Kumamoto University, 5-1 Oe-hon-machi, Kumamoto 862-0973, Japan
Abstract
Treatment of 3-methyl-6-(1-methylhydrazino)uracil (I) with phenacyl bromides afforded the corresponding 3-aryl-1,6-dimethylpyrimido[4,5-c]pyridazine-5,7 (1H,6H)-diones (3-aryl-4-deazatoxoflavins) (IIa-c) and 3-aryl-1,7-dimethyl-6,8-dioxo-1,4,6,7,8-pentahydropyrimido[4,3-c]-as-triazines (IIIa-c). The reaction of arylaldehyde N-methyl-N-(3-methyluracil-6-yl)hydrazones (IVa-e) with triethyl ortho-formate in DMF also gave the respective 4-deazatoxoflavins (IIa-e) .
3-Phenyl-4-deazatoxoflavin (IIa) thus obtained oxidized alcohols under alkaline conditions in the dark to yield the corresponding carbonyl compounds, while it is itself hydrogenated to 4,8-dihydro-3-phenyl-4-deazatoxoflavin (V).
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■ Addition Products of Indazole and Nitrilimides. Synthesis of 1-Phenyl-5-(o-aminophenyl)-1,2,4-triazoles and Their Annelation to 1,2,4-Triazolo[1,5-f]phenanthridines
Michele Ruccia,* Nicolò Vivona, Giuseppe Cusmano, and Anna Maria Almerico
*Instituto de Chimica Organica , Facolta de Scienze, Università digli Studi di Palermo, 20 via Archirafi, 90123 Palermo, Italy
Abstract
Treatment of indazole with nitrilimines (IIIa-c) afforded the corresponding phenylhydrazone adducts (Va-c), which undergo an acid-catalysed transformation to give the hitherto unknown 1-phenyl-5-(o-aminophenyl)-1,2,4-triazole derivatives (XIa-c). Diazotization of (XIa-c) followed by treatment with hypophosphorous acid gave 1,2,4-triazolo[1,5-f]phenanthridines (XIIa-c).
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■ Modified Total Synthesis of Arborine, Glycosminine, and Glomerine by Condensation of Sulfinamide Anhydride with Thioamides
Tetsuji Kametani,* Chu Van Lao, Masataka Ihara, and Keiichiro Fukumoto
*Pharmaceutical Institute, Tohoku University, Aobayama, Sendai 980-8578, Japan
Abstract
Treatment of the sulfinamide anhydrides (3 and 4), prepared from anthranilic acids (1 and 2), with thioamides gave the corresponding 4-quinazolone derivatives. This reaction was applied to the synthesis of arborine (5), glycosminine (6), glomerine (7), 2-methyl-4-quinazolone (8), and 4-quinazolone (9).
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■ Mulberrofuran A, a New Isoprenoid 2-Arylbenzofuran from the Root Bark of the Cultivated Mulberry Tree (Morus alba L.)
Taro Nomura,* Toshio Fukai, Jun Uno, and Tadashi Arai
*School of Pharmaceutical Sciences, Toho University, 2-2-1, Miyama, Funabashi, Chiba 274-8510, Japan
Abstract
From the benzene extract of the root bark of the cultivated mulberry tree (a variety of Morus alba L.), a novel isoprene-substituted 2-arylbenzofuran derivative, mulberrofuran A, was isolated whose structure was shown to be I on the basis of spectral data. The antimicrobial activities of I are reported.
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■ A Mild Autoxidation of 3,4-Diohenyl-2-furyl Carbamates to 3,4-Diohenyl-5-hydroxy-3-pyrrolin-2-ones
Kazuo Ito* and Kenichi Yakushijin
*Faculty of Pharmacy, Meijo University, 150 Yagotoyama, Tenpaku, Nagoya 468-8503, Japan
Abstract
3,4-Diphenyl-2-furyl carbamates (1a-c) react with oxygen in benzene at room temperature to give 3,4-diphenyl-5-hydroxy-3-pyrrolin-2-ones (2a-c) as the sole product.
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■ A Synthetic Approach to the Mitomycins
Mitsuo Akiba, Yoshiyuki Kosugi, and Toyozo Takada*
*Tokyo University of Pharmacy and Life Science, 1432-1 Horinouchi, Hachioji, Tokyo 192-0392, Japan
Abstract
The photo-induced reaction of 2-acetyl-3-[2-(4-bromopheny1)-2,3,4,7-tetraazabicyclo[3.3.0]oct-3-en-7-yl]-5-methyl-1,4-benzoquinone tosyl-hydrazone (1b) or 2-acetyl-3-[6-(4-bromophenyl)-3,6-diazabicyclo[3.1.0]hex-3-yl]-5-methyl-1,4-benzoquinone tosylhydrazone (1c) gave the hydroxyquinols (2a and b), which were converted to 1-(4-bromophenylimino)-6,9-dimethyl-5,8-dioxo-1H-pyrrolo[1,2-a]indole (5). 1-(4-bromophenylimino)-2,3-dihydro-6,9-dimethyl-5,8-dioxo-1H-pyrrolo[1,2-a]indole (6), 2-(4-bromophenylamino)-2,3-dihydro-6,9-dimethyl-5,8-dioxo-1H-pyrrolo[1,2-a]indole (7), and 1,2-disubstituted pyrrolo[l,2-a]indoloquinone (8) via the oxazolines (4a and b). These compounds, 6, 7, and 8, were also prepared in a one step synthesis by the thermal decomposition reaction of 1b.
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■ Electric Dipole Moment of 5H-1,2,3-Dithiazole Derivative Equilibrated with 2,4,6-Tri-t-butyl-N-thiosulfinylaniline
Yoshio Inagaki, Renji Okazaki, and Naoki Inamoto*
*Department of Chemistry, Scool of Science, University of Tokyo, 7-3-1 Hongo, Bunkyo-ku, Tokyo 113-0033
Abstract
Electric dipole moment of 2,4,6-tri-t-butyl-7,8,9-dithiazabicyclo[4.3.0]nona-2,4,9-triene (1α) was estimated to be about 3.0 D by measuring the dielectric constants of dilute benzene solutions of the equilibrium mixture of 1α and 2,4,6-tri-t-butyl-N-thiosuifinylaniline (1β) with a known molar ratio. This value is much larger than the estimated value of (1.5 D).
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■ Pyrroloquinolines IV. 3H-Pyrrolo[2,3-c]quinolines
Misbahul Ain Khan* and João Ferreira da Rocha
*Seção de Quimica, Instituto Militar de Engenharia, Urca, 20.000 Rio de Janeiro, RJ, Brazil
Abstract
A review of the chemistry of 3H-pyrrolo[2,3-c]quinoline ring system is presented. It includes the synthesis and reactions together with the recorded spectral data of some of the derivatives.
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■ 1,2,4-Triazinoindoles
William A. Romanchick and Madeleine M. Joullié*
*Department of Chemistry, University of Pennsylvania, 231 South 34th Street Philadelphia, PA 19104-6323, U.S.A.
Abstract
This article surveys the synthesis and chemistry of 1,2,4-triazinoindoles. Spectral data for several substituted 1,2,4-triazinoindoles are reported.1