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. 2, No. 5, 1974
Published online:
■ Chemistry of Nitrosoimines. VII. Reactions of 3-Substituted 2-Nitrosoimino-2,3-dihydrobenzothiazoles with Grignard and Lithium Reagents of the Corresponding 2-Imino Compounds
Kin-ya Akiba, Kiyofumi Ishikawa, and Naoki Inamoto*
*Department of Chemistry, Scool of Science, University of Tokyo, 7-3-1 Hongo, Bunkyo-ku, Tokyo 113-0033
Abstract
Reactions of 3-substituted 2-nitrosoimino-2,3-dihydrobenzothiazoles with Grignard and lithium reagents of the corresponding 2-imino compounds gave azamethinecyanine hydroxides and their hydrolysis products, respectively, in high yields.
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■ A Novel Formation of 1-Hydroxymethyl-4,5-dimethoxy-7H-azirino[1,2-a]indole-7a-carboxylic Acid γ-Lactone
Tetsuji Kametani,* Frank F. Ebetino, Keiichiro Fukumoto, and Albert I. Meyers
*Pharmaceutical Institute, Tohoku University, Aobayama, Sendai 980-8578, Japan
Abstract
α-(6-Nitroveratrylidene)-γ-butyrolactone (1) rearranges to 3-(6-nitroveratryl)-2(5H)-furanone (5), and is deoxygenated to 1-hydroxymethyl-4,5-dimethoxy-7H-azirino[1,2-a]indole-7a-carboxylic acid γ-lactone (6) in triethyl phosphite at 140 - 150 °. Although frequently postulated in triethyl phosphite reductions of nitro compounds, aziridines have not, heretofore, been isolated.
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■ Bromination of 2-Ethylthio- and 2-Ethanesulfonyl-3-substituted Indoles with N-Bromosuccinimide. Isolation and Reactiviries of 1-Bromoindoles and 3-Bromoindolenines
Tohru Hino,* Mamoru Endo, Masakatsu Tonozuka, and Masako Nakagawa
*Faculty of Pharmaceutical Sciences, Chiba University, 1-33 Yayoi-cho, Inage-ku, Chiba 263-8522, Japan
Abstract
1-Bromoindole (4) ond 3-bromoindolenines (5) were obtained by the reaction of 3 with NBS. Both compounds could brominate a 3-substituted indole to give the 2-bromo derivative. The bromine at the 3-position of 5 migrated to the 5- or 6-position on heating in an aprotic solvent.
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■ Asymmetric Synthesis of Salsolidine
Tadashi Okawara and Tetsuji Kametani*
*Pharmaceutical Institute, Tohoku University, Aobayama, Sendai 980-8578, Japan
Abstract
Optically active salsolidine (8) was isolated by reduction of 2-alkyl-3,4-dihydro-6,7-dimethoxy-l-methylisoquinolinium iodides (6) with sodium borohydride followed by hydrogenolysis of N-alkylsalsolidines (7) with 10 % palladium hydroxide on charcoal. The optical purities ranged from 15 to 44 %.
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■ The Rection of 1-(1-Pyrrolidinyl)cyclohexene with Pyrrole and Pyrazole
Masashi Tashiro, Yoko Kiryu, and Otohiko Tsuge*
*Research Institute of Industrial Science, Faculty of Engineering, Kyushu University, 6-1, Kasuga-koen, Kasuga 816-8580, Japan
Abstract
Michael type adducts of pyrrole (2) and pyrazole (2) to enamine (1), 4 and 5, decompose at elevated temperature to regenerate 1 and 2 or 3. On prolonged heating of 4, the novel hexahydro-4H-pyrrolo[1,2-a]indole-4-spiro-1’-cyclohexane derivative (8) was obtained along with four cyclohexenyl-substituted pyrroles, 6a, 6b, 7a, and 7b. The reaction of 1 with 2 under forcing conditions directly afforded 6, 7, and 8, whose relative amounts depended on the reaction conditions. On the other hand, both the thermal decomposition of 5 and the reaction of 1 with 3 under forcing conditions gave 4-(1-cyclohexenyl)pyrazole (13) as a sole isolated product.
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■ Indolizine Derivatives. II. Indolizines from the Perkin Reaction of 2-Pyridinecarbaldehyde
Esko Pohjala*
*Department of Chemistry, Technical University of Helsinki, P.O. Box 6100, FIN-02150 HUT Espoo, Finland
Abstract
The Perkin reaction of 2-pyridinecarbaldehyde (I) gives the indolizines IIIa-f and the pyrrolo [2,1,5-cd]indolizine IVa. In the presence of active methylene compounds the indolizines IIIg-n are formed.
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■ A Novel Reaction of 6-Nitroquinoline with Active Methylene Compounds in the Presence of Potassium Cyanide
Yukihiko Tomioka, Akihumi Mochiike, Junko Himeno, and Motoyoshi Yamazaki*
*Faculty of Pharmaceutical Sciences, Fukuoka University, 8-19-1 Nanakuma, Jonan-ku, Fukuoka 814-0180, Japan
Abstract
6-Nitroquinoline (I) reacts with ethyl cyanoacetate in the presence of potassium cyanide or sodium hydride to produce 6-ethoxalylaminoquinoline-5-carbonitrile (IIa) and diethyl 2-cyano-3-(5-cyano-6-quinolylamino)fumalate (III). Reactions with some other active methylene compounds in the presence of potassium cyanide also afforded respective products corresponding to IIs (IIb, IIc and IId).
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■ Ratio of Seven- to Six-membered Ring Sulfones in the Cyclization of a Sulfonyl Carbene
Rudolph A. Abramovitch* and Vazken Alexanian
*Department of Chemistry, University of Alabama, Box 870336, University
Tuscaloosa, Alabama 35478-0336, U. S. A.
Abstract
The ratio of 7- to 6-membered ring intramolecular cyclization product increases with decreasing solvent polarity in the (C6F5Cu)4 catalyzed decomposition of 1 and with increasing temperature in the uncatalyzed decompositions. Possible explanations are discussed.
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■ A General Method for Alkylating Butenolides; Reduction of Products to 3-, 2,3-, and 3,4-Substituted Furans
S. William Pelletier,* Zoltan Djarmati, Ivan V. Micovic, and Stevan D. Lajsic
*Institute for Natural Products Research and Department of Chemistry, Chemistry Building, The University of Georgia, Chemistry Building, Athens Georgia 30602-2556, U.S.A.
Abstract
A simple method for the alkylation of butenolides is investigated. The method involves addition of appropriate diazo compounds to butenolides, followed by thermal decomposition and affords 4-, 3,4-, and 4,5-substituted γ-crotonolactones in high yields. Reduction of those products with DIBALH, provides the substituted furans in good to excellent yields.
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■ Total Synthesis of (±)-Angustoline
Ichiya Ninomiya* and Takeaki Naito
*Kobe Women’s College of Pharmacy, Motoyamakita, Higashinad, Kobe, Hyogo 658, Japan
Abstract
(±)-Angustoline, an alkaloid of Strychnos angustiflora, was synthesized via the route including enamide photocyclization.
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■ 1,4-Dipolar Reaction of 2,3-Dimethylisoquinolinium-4-dithiocarboxylate with Dimethyl Acetylenedicarboxylate
Kazumichi Mizuyama, Yoshinori Tominaga, Yoshiro Matsuda, and Goro Kobayashi*
*Faculty of Pharmaceutical Sciences, Nagasaki University, 1-14, Bunkyo-machi, Nagasaki 852-8521, Japan
Abstract
Reaction of 2,3-dimethylisoquinolinium-4-dithiocarboxylate with dimethyl acetylene-dicarboxylate in dimethylformamide gave 1,4a,6,10b-tetrahydro-3,4,11,12-tetramethoxycarbonyl- 4a,5-dimethyl-l-thioxo-6,10b-ethenothiapyrano[4,3-c]isoquinoline which might be resulted in both cycloaddition reactions, simultanious 1,4-dipolar cycloaddition and Diels-Alder reaction.
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■ Compounds Related to Acridine. XI. Reaction of 1,3-Di(9-acridinyl)propane with p-Nitroso-N,N-dimethylaniline
Akiyoshi Torii, Hideki Higashiuchi, and Otohiko Tsuge*
*Research Institute of Industrial Science, Faculty of Engineering, Kyushu University, 6-1, Kasuga-koen, Kasuga 816-8580, Japan
Abstract
Although 9-propylacridine (II) did not react with p-nitroso-N,N-dimethylaniline (I) under various conditions, 1,3-di(9-acridinyl)propane (III) reacted with I under the influence of HCl to give the mono-nitrone compound (IV) and cleaved products V- VII, whose relative yields were greatly affected by the reaction conditions.
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■ Photochemical Synthesis of an Oxazolo[4,3-a]isoindole-1-spiro Ring System
Hideo Nakai, Yasuhiko Sato, Hiroshi Ogiwara, Tomishige Mizoguchi, and Yuichi Kanaoka*
*Faculty of Pharmaceutical Sciences, Hokkaido University, Sapporo 060-0812, Japan
Abstract
On irradiation certain N-β-sec-alkoxyalkyl-substituted phthalimides 6 afforded an oxazolo[4,3-a]isoindole-1-spiro ring system 7 in moderate yields demonstrating a photochemical synthesis of spiro heterocycles by utilizing the excited imide carbonyl.
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■ Tetrahydroprotoberberines Derived from R- ans S-1-(3,4-Dihydroxybenzyl)-1,2,3,4-tetrahydroisoquinoline
Sindey Teitel* and Jay P. O’Brien
*The Department of Chemistry Research, Hoffman-La Roghe Inc., Nutley, New Jersey 07110, U.S.A.
Abstract
The syntheses of the optically-active diphenolic-substituted tetrahydroisoquinolines (5a,b), tetrahydropseudoberberines (7a,b), and tetrahydroprotoberberines (8a,b), all related to the anti-Parkinson agent apomorphine (1), are described. None exhibited dopamimetic activity.
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■ Derivatives of 1,2-Dithiole-3-thiones. VIII. Reduction of N-Benzenesulfonyl Thione S-Imides with Trivalent Phosphines
Seizo Tamagaki, Keishi Sakaki, and Shigeru Oae*
*Department of Chemistry, University of Tsukuba, 1-1-1 Ten-nodai, Tsukuba-shi, Ibaraki, 305-8571, Japan
Abstract
The reduction of N-benzenesulfonyl thione S-imide (I) with trivalent phosphines was kinetically studied. The reaction is considered to proceed via the formation of a metastable 1,3-dipolar adduct of (I) and the phosphine. Meanwhile, the addition of protic acid to the reaction mixture was found to change the pattern of the reaction.
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■ A New Synthetic Method for the Key Intermediate of the Eudesmane Class of Sesquiterpenes through Furan Derivatives
Tetsuji Kametani,* Hideo Nemoto, and Keiichiro Fukumoto
*Pharmaceutical Institute, Tohoku University, Aobayama, Sendai 980-8578, Japan
Abstract
A versatile synthetic method for the key intermediate (VIII), which has properly protected carbonyl functions at both the C-1 and C-5 positions, for the synthesis of the eudesmane sesquiterpenes, is described.
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■ Reaction of 3-Amino-2-cyclohexen-1-ones with Dibenzoylethylene: Regioselective Synthesis of 4-Oxotetrahydroindoles and 5-Oxotetrahydroquinolines
Yasumitsu Tamura,* Toshiko Sakaguchi, Tomomi Kawasaki, and Yasuyuki Kita
*Faculty of Pharmaceutical Sciences, Osaka University, 1-6 Yamadaoka, Toyonaka, Osaka 560-0043, Japan
Abstract
Reaction of 3-amino-2-cyclohexen-1-ones (Ia-c) with dibenzoylethylene gave either 4-oxotetrahydroindoles (IIa-c) or 5-oxotetrahydroquinolines (IVa-c) by the selection of reaction conditions.