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. 4, No. 5, 1976
Published online:
■ A New Alkylating Method at the 4-Position of Isoquinoline Deivatives
Tetsuji Kametani,* Hideo Nemoto, Mie Takeuchi, Mitsuhiro Takeshita, and Keiichiro Fukumoto
*Pharmaceutical Institute, Tohoku University, Aobayama, Sendai 980-8578, Japan
Abstract
Alkylation of 3,4-dihydro-6,7-dimethoxy-1-methylisoquinoline (I) with 2-methylcyclohex-2-en-1-one and phenethyl bromide in the presence of sodium hydride and dimethyl sulphoxide gave 6,7-dimethoxy-1-methyl-4-(2-methyl-3-oxocyclohexyl)isoquinoline (V) and 6,7-dimethoxy-1-methyl-4-phenethylisoquinoline (VII), respectively. On the other hand, reaction of 3,4-dihydro- 6,7-dimethoxyisoquinoline (VIII) with 3,4-methylenedioxyphenethyl bromide under the same conditions gave 6,7-dimethoxy-1-methylisoquinoline (XI) and methyl 3-(3,4-methylenedioxyphenyl)propyl sulphoxide (XII).
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■ Alternative Synthesis of Protoberberine Alkaloid (±)-Xylopinine
Tetsuji Kametani,* Toshio Honda, Toshiji Sugai, and Keiichiro Fukumoto
*Pharmaceutical Institute, Tohoku University, Aobayama, Sendai 980-8578, Japan
Abstract
Treatment of 2-(2-bromo-4,5-dimethoxybenzoyl)-1,2,3,4-tetrahydro-6,7-dimethoxy-1-methyleneisoquinoline (3) with sodium amide in liquid ammonia afforded the oxoberbine (4) together with the styrene derivative (5) and the hydrolysed product (6). Chlorination of the lactam (4) with phosphoryl chloride gave the chloride, which was then reduced with sodium borohydride to afford (±)-xylopinine (8).
Furthermore, a photolysis of the bromo-enamide (3) also gave the oxoberbine (4) in good yield.
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■ A Study of the Reaction between 1-Halogenobenzyl-2-benzazepines and Dimsylsodium
Shinzo Kano,* Tsutomu Yokomatsu, and Shiroshi Shibuya
*School of Pharmacy, Tokyo University of Pharmacy and Life Science, 1432-1 Horinouchi, Hachioji, Tokyo 192-0392, Japan
Abstract
The reaction between a series of 1-(2-bromobenzyl)-1,2,3,4-tetrahydro-5H-2-benzazepines (1), (2), (3) and dimsylsodium was examined to give 5,6,7,8-tetrahydrodibenz[b,f]azecines possessing a cis and trans double bond at the 13,14-position together with formation of 14-(methylsulfinyl)methyldibenz[b,f]azecine derivatives.
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■ Reaction of Isoquinolinium Ylide with Ketenethioacetals
Hiroshi Fujito, Yoshinori Tominaga, Yoshiro Matsuda, and Goro Kobayashi*
*Faculty of Pharmaceutical Sciences, Nagasaki University, 1-14, Bunkyo-machi, Nagasaki 852-8521, Japan
Abstract
Reaction of isoquinolinium ylides with ketenethioacetals gave isoquinolinium allylides, pyrrolo[2,1-a]isoquinolines, and imidazo[2,1-a]isoquinolines, in fairly good yield.
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■ Hydrazinolysis of Some Azolopyrazines
Bojan Vercek, Branko Stanovnik, and Miha Tisler*
*Department of Chemistry, University of Ljubljana, 61000 Ljubljana, Yugoslavia
Abstract
The reaction of hydrazine hydrate with some azolopyrazines (2, 6 and 8) was investigated. From the reaction mixture derivatives of 1,2,4-thiazole a imidazole were isolated and identified. The mechanism of these transformations is outlined and discussed.
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■ A Novel Synthesis of the Phenanthroindolizidine Alkaloid Ring System from Phenanthrene
Seiichi Takano,* Kohtaro Yuta, and Kunio Ogasawara
*Pharmaceutical Institute, Tohoku University, Aobayama, Sendai 980-8578, Japan
Abstract
A novel synthesis of the phenanthroindolizidine alkaloid ring system (16) from phenanthrene (2) is described.
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■ Synthesis of 4-Hydroxy-3-mercaptobenzoic Acid and 2,3-Dihydro-5,6-tetramethylene-1,4-dithiine from Dithiolane Derivatives
Seiichi Takano,* Shinichi Yamada, Keizo Tanigawa, Susumi Hatakeyama, and Kunio Ogasawara
*Pharmaceutical Institute, Tohoku University, Aobayama, Sendai 980-8578, Japan
Abstract
Efficient synthesis of 4-hydroxy-3-mercaptobenzoic acid (9) and 2,3-dihydro-5,6-tetramethylene-1,4-dithiine (16) from dithiolane derivatives was reported.
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■ Azafulvenes 3. Cycloaddition Reaction of 6-Amino-1-azafulvene to Electron-deficient Olefin and Acetylene
Sigeo Mori, Masanori Watanabe, Shoji Kajigaeshi, and Shuji Kanemasa*
*Research Institute of Industrial Science, Faculty of Engineering, Kyushu University, 6-1, Kasuga-koen, Kasuga 816-8580, Japan
Abstract
6-Amino-1-azafulvene (1) reacted with the electron-deficient olefins such as acrylate, vinyl ketone, acrylonitrile and N-arylmaleimide affording the regio- and stereospecific [6+2] cycloadducts (4a-4g), some of which were readily deaminated to give the corresponding 3H-pyrrolizines (5a-5c). On the other hand, 1 gave the 1:2 cycloadduct with acetylenedicarboxylate.
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■ Derivatives of 1,2-Dithiole-3-thiones. XII. The Reactions of 1,2-Dithiole-3-thione with Bis-arylsulfonyldiazomethane
Seizo Tamagaki* and Ryoichi Ichihara
*Department of Applied Chemistry, Faculty of Engineering, Osaka City University, Sugimoto, Sumiyoshi-ku, Osaka 558-8585, Japan
Abstract
4,5-Benzo-l,2-dithiole-3-thione reacted with bis-sulfonyldiazomethane to give the rearranged products of a new type. The same was found to take place for 1,3-dithiole-2-thione.
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■ Synthesis and Reduction of 2H-Cyclohepta[c]pyrrol-6-ones
R. Alan Jones* and Santokh Singh
*School of Chemical Sciences, University of East Anglia, Norwich, Northfolk NR4 7TJ, U.K.
Abstract
The base catalysed condensation of 3,4-diformyl-2,5-dimethylpyrrole with propanone derivatives to give 2H-cyclohepta[c]pyrrol-6-ones is described. The reaction of the intermediate 1-(2,5-dimethyl-3-pyrrolyl)prop-1-en-3-ones with hydrazine yields 5,7-dimethyl-6H-pyrrolo[3,4-d]pyridazine. Catalytic hydrogenation of the 2H-cyclohept[c]pyrrol-6-ones produces the 4,5,7,8-tetrahydro ketones and the corresponding alcohols.
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■ Synthesis of the Clavine Skeletons by Photocyclisation of N-Methacrylnaphthalides
Ichiya Ninomiya,* Toshiko Kiguchi, and Takeaki Naito
*Kobe Women’s College of Pharmacy, Motoyamakita, Higashinad, Kobe, Hyogo 658, Japan
Abstract
Photocyclisation of N-methacrylnaphthalides (Ia-d, and VIII), prepared from various 2-naphthylamines and 4-aminonaphthostyril, afforded the benzo[f]quinolones (IIa-d) and indolo[4,3-f,g]quinoline-5,8-dione (IX), providing a route for the preparation of the clavine alkaloids.
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■ A Disproportionation of 6-Amino-5-benzylindeneamino-1,3-dimethyluracils in Formamide. Formation of 6,7-Diaryl-1,3-Dimethyllumazines and Theophylline
Masatsugu Higuchi, Tetsuya Nagamura, and Fumio Yoneda*
*Faculty of Pharmaceutical Sciences, Kumamoto University, 5-1 Oe-hon-machi, Kumamoto 862-0973, Japan
Abstract
Heating of 6-amino-5-benzylideneamino-l,3-dimethyluracils in formamide led to the formation of the corresponding 6,7-diaryl-1,3-dimethyllumazines and theophylline.
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■ The Partial Synthesis of Burnamicine
Shin-Ichiro Sakai,* Estuji Yamanaka, and Lloyd J. Dolby
*Faculty of Pharmaceutical Sciences, Chiba University, 1-33 Yayoi-cho, Inage-ku, Chiba 263-8522, Japan
Abstract
The indole alkaloid burnamicine and its 19,20-dihydro derivative were partially synthesized from geissoschizine methyl ether and hirsutine respectively, using a C/D ring opening reaction with ethyl chlorocarbonate.
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■ The Partial Synthesis of 16-epi-Pleiocarpamine
Shin-ichiro Sakai* and Nobuo Shinma
*Faculty of Pharmaceutical Sciences, Chiba University, 1-33 Yayoi-cho, Inage-ku, Chiba 263-8522, Japan
Abstract
An indole alkaloid, 16-epi-pleiocarpamine was partially synthesized from geissoschizine methylether, using C/D ring opening and reclosing reactions with cyanogen bromide and HOAc-NH4OAc respectively; determination of the absolute configuration of pleiocarpamine was accomplished by this chemical correlation.
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■ Reactions of Dihydroindeno-1,3,4-oxaziazepine Derivative with Aryl Isocyanates and Dimethyl Acetylenedicarboxylate
Koji Oe and Otohiko Tsuge*
*Research Institute of Industrial Science, Faculty of Engineering, Kyushu University, 6-1, Kasuga-koen, Kasuga 816-8580, Japan
Abstract
The reaction of dihydroindeno[3,2-f]-1,3,4-oxadiazepine derivative 1 with excess of phenyl (2a) and p-tolyl isocyanate (2b) afforded novel 1:1 adducts, tetrahydroindeno[2,3-e]-3H-1,3,4-triazepin-2-ones 3a and 3b, in good yields respectively. Similarly, 1 reacted with dimethyl acetylenedicarboxylate to yield dihydroindeno[3,2-d]-2,3-diazepine compound 6. The reaction pathways for the formation of 3 and 6 are also proposed.
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■ Studies on the Sythesis of Bisindole Alkaloids. III. The Synthesis of Leurosine and 3’-Hydroxyvinblastine
James P. Kutney,* John Balsevich, Gordon H. Bokelman, Toshihiko Hibino, Isamu Itoh, and Arnold H. Ratcliffe
*Department of Chemisry, University of British Columbia, Vancouver 8, V5T 1W5, Canada
Abstract
An interesting reaction which allows direct functionalization of the 3,4-double bond in the cleavamine series has been developed. Application of this reaction to the previously synthesized 3’,4’-dehydrovinblastine (VIII, R = CO2CH3) allows a direct synthesis of the dimeric Vinca alkaloid leurosine (IX, R = CO2CH3).
In another series of investigations directed at functionalizing the 3’,4’-double band of VIII (R = CO2CH3) osmylation of the N-oxide intermediate of the latter has allowed the synthesis of 3’-hydroxyvinblastine (XI, R = CO2CH3), a close relative of the alkaloid vincadioline.
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■ Benzo- and Indoloquinoline Derivatives. Part IX. A Novel Route to the Tribenzo[a,c,h]quinolizine System by Electrophilic and Photolytic Cyclisation of Immonium Salts
Robert Salsmans and Georges Van Binst*
*Laboratoium voor organische Chemie, Vrije Universiteit Brussel, Pleinlaan 2, B-1050 Brussel, Belgium
Abstract
Photocyclisation of immonium salts, followed by reduction, has been used successfully in the synthesis of tribenzo[a,c,h]quinolizine systems, in cases where the electrophilic cyclization failed.
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■ A Synthesis of Aporphine Derivatives
Shinzo Kano,* Youko Takahagi, Eiji Komiyama, Tsutomu Yokomatsu, and Shiroshi Shibuya
*School of Pharmacy, Tokyo University of Pharmacy and Life Science, 1432-1 Horinouchi, Hachioji, Tokyo 192-0392, Japan
Abstract
A variety of 1-hydroxyaporphines have been synthesized via 6a,7-dehydroaporphines, obtained by the reaction between a series of 1-halogenobenzyl-3,4-dihydro-2- methylisoquinolinium iodides and dimsylsodium.
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■ Studies on the Furan Series. Part VI. A Facile Method of Acylating Furans and Thiophenes
Seppo I. Pennanen*
*Laboratory of Organic Chemistry, Helsinki University of Technology, P.O. Box 6100,FIN-02015 HUT, Espoo, Finland
Abstract
A convenient acylation of some furans and thiophenes in 75-96% yield is described. The results of the acetylation with acetyl p-toluenesulfonate are tabulated.