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. 6, 1981
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■ The Preparation of 3,4-Dihydro-2H-1,5,6-benzodioxazonine Derivatives
Elaine J. Browne*
*Department of Chemistry, University of Tasmania, GPO Box 252C Hobart, Tasmania, 7001, Australia
Abstract
Derivatives (6a-c) of the new 2H-1,5,6-benzodioxazonine ring system have been prepared in low to moderate yields by hydrazinolysis of {2-[3-(1,3-dihydro-1,3-dioxo-2H-isoindol-2-yl)oxypropyloxy]aryl}phenylmethanones (4a-c), and cyclisation of the assumed intermediate O-substituted hydroxylamines (5a-c) under mildly acidic conditions.
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■ Reaction of Cyanogen Bromide with 1-(ω-Hydroxyalkyl)-1,3,4,6,7,11b-hexahydro-2H-benzo[a]quinolizines as a Route to Annelated Benzazecine Derivatives
John B. Bremner* and Narumol Thirasasana
*Department of Chemistry, University of Tasmania, GPO Box 252C Hobart, Tasmania, 7001, Australia
Abstract
Treatment of 1-(2-hydroxyethyl)-9,10-dimethoxy-1,3,4,6,7,11b-hexahydro-2H-benzo[a]quinolizine (4a) with cyanogen bromide in chloroform/potassium carbonate gave the new heterocyclic product, 11,12-dimethoxy-2,3,3a,5,6,8,9,13b-octahydro-furo[3,2-g][3]benzazecine-7(4H)-carbonitrile (5a) in moderate yield. The corresponding octahydro-2H-pyrano[3,2-g]- and decahydrooxepino[3,2-g]-benzazecine-carbonitrile derivatives (5a and 5c) were prepared similarly from the appropriate reduced 1-(ω-hydroxyalkyl)-2H-benzo[a]quinolizines. Elimination products were also isolated in some cases.
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■ 2-Azabicyclo[3.2.0]heptane-3,4-diones (4). Thermal Rearrangement of 3-Ethoxy-2-azabicyclo[3.2.0]hept-2-en-4-ones Leadng to 2-Ethoxy-3,4-dihydropyridines
Takehiro Sano,* Yoshie Horiguchi, and Yoshisuke Tsuda
*Showa Pharmaceutical University, 3-3165, Higashi-tamagawagakuen, Machida, Tokyo 194-8543, Japan
Abstract
Thermolysis of 3-ethoxy-2-azabicyclo[3.2.0]hept-2-en-4-ones yielded 2-ethoxy-3,4-dihydropyridines, which is explained by [1,3] sigmatropic rearrangement followed by cheletropic elimination of CO.
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■ 2-Azabicyclo[3.2.0]heptane-3,4-diones (5). Stereodependecy in Thermal Rearrangement of 7-Vinyl-2-azabicyclo[3.2.0]heptane-3,4-diones and Their Imidates
Takehiro Sano,* Yoshie Horiguchi, Suetaka Kambe, Jun Toda, Jun-ichi Taga, and Yoshisuke Tsuda
*Showa Pharmaceutical University, 3-3165, Higashi-tamagawagakuen, Machida, Tokyo 194-8543, Japan
Abstract
The thermal reaction of the 7-vinyl-2-azabicyclo[3.2.0]heptane-3,4-dione yielded different products depending on the stereochemistry of 7-vinyl group. The endo isomer, either the lactam (3) or the imidates (8) afforded a Cope product (5 or 9) (3,3-sigmatropic shift) exclusively. On the other hand, the exo isomer gave rather complex results. The lactam (2) afforded a hydroindole (4) (1,3-shift) and the Cope product (5) suggesting the formation of a biradical species as an intermediate. The imidate (10) yielded a dihydropyridine (11) (1,3-sigmatropic shift followed by cheletropic loss of CO) as a major product.
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■ Amyris of Jamaica. Coumarins of Amyris elemifera D. C., (Rutaceae)
Basil A. Burke* and Saleela Philip
*Department of Chemistry, University of the West Indies, Mona, Kingston 7, Jamaica
Abstract
Two new coumarins, marmesin acetate and 3-(3’,3’-dimethylallyl)-marmesin, are reported from A.elemifera.
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■ The Absolute Configuration of (+)-Thalictricavine
Kinuko Iwasa and Mark Cushman*
*Department of Medicinal Chemistry and Molecular Pharmacognosy, School of Pharmacy and Pharmacal Sciences, Purdue University, 1333 Robert E. Heine Pharmacy Building, West Lafayette IN 47907, Indiana 47907, U.S.A.
Abstract
(+)-Thalictricavine (7) and (+)-canadine (1) have been synthesized from an optically resolved (+)-13-carboxy-7,8,13,14-tetrahydro-8-oxoprotoberberine 15. This establishes the absolute configuration of (+)-thalictricavine (7) as 13S, 14R.
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■ Synthesis of Thromboxane A2 Analogue. (±)-(9,11),(11,12)-Dideoxa-(9,11a)-oxathromboxane A2
Tetsuji Kametani,* Toshio Suzuki, Akiko Tomino, Shinko Kamada, and Katsuo Unno
*Pharmaceutical Institute, Tohoku University, Aobayama, Sendai 980-8578, Japan
Abstract
A synthesis of the thromboxane A2 analogue, (±)-(9, 11) ,(11, 12)-dideoxa-(9, 11a)-oxathromboxane A2 (TXA2) starting from the exo-adduct 3 of meleic anhydride and furan is described.
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■ 7,9-Dialkyladeninium Salts. An Alternative Synthesis, Ring Opening, and Rearrangement to N6,7-Dialkyladenines
Tozo Fujii,* Tohru Saito, and Isao Inoue
*Faculty of Pharmaceutical Scicences, Kanazawa University, 13-1 Takara-machi, Kanazawa 920-0934, Japan
Abstract
Alkylation of N’-alkoxy-1-alkyl-5-formamidoimidazole-4-carboxamidine (type I or II) (in the absence of any base) followed by hydrogenolysis of the N’-alkoxy group and cyclization (or vice versa) yielded the corresponding 7,9-dialkyladeninium salts (type VII), which readily rearranged to N6,7-dialkyladenines (type X) in boiling 1 N NaOH. Under milder basic conditions, VII underwent hydrolysis to produce 4-alkylamino-6-amino-5-formamidopyrimidines (VIII). The NaBH4 reduction of 7,9-dimethyladeninium iodide (VIIa, X = I) gave the 7,8-dihydro derivative (XI).
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■ A Simple Route to (±)- and (+)-Trachelanthamidine
Seiichi Takano,* Naoyoshi Ogawa, and Kunio Ogasawara
*Pharmaceutical Institute, Tohoku University, Aobayama, Sendai 980-8578, Japan
Abstract
Starting from a single substrate (1a) (±)- and (+)-trachelanthamidine (6) has been synthesized in three steps.
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■ An Alternate Synthesis of a 2,8-Dioxo-1,7-cycloerythrinan, a Key Intermediate to Erythrinan Alkaloids of Dienoid-type
Yoshisuke Tsuda,* Yuki Sakai, Mari Kaneko, Kazuko Akiyama, and Kimiaki Isobe
*School of Pharmacy, Hokuriku University, 3-Ho, Kanagawa machi, Kanazawa 920-1181, Japan
Abstract
Starting from homoveratrylamine, 15,16-dimethoxy-2,8-dioxo-1,7-cycloerythrinan 1a, a key intermediate to erythrinan alkaloids of dienoid-type, was synthesized in 35% overall yield by 10 steps reactions including deethoxycarbonylation of a 6-ethoxycarbonylerythrinan derivative.
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■ A Stereoselective Synthesis of (±)-Corynantheal
Tetsuji Kametani,* Naoaki Kanaya, and Masataka Ihara
*Pharmaceutical Institute, Tohoku University, Aobayama, Sendai 980-8578, Japan
Abstract
A stereoselective synthesis of (±)-corynantheal (10) was achieved via novel epimerization at C3 position of an indolo[2,3-a]quinolizine and the corresponding lactam by Adams catalyst. This synthesis constitutes a formal total synthesis of (±)-corynantheine (11) and (±)-ajmalicine (12).
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■ Carbenoid Rearrangements of a Cycloadduct from Phenyl Azide
Kari Skinnemoen and Kjell Undheim*
*Department of Chemistry, University of Oslo, P.O.Box 1033, Blindern, N-0315 Oslo, Norway
Abstract
Cycloaddition between phenyl azide and 2H-thiopyran-3(6H)-one is followed by isomerisation of the adduct to 5-anilino-4-diazo-4,5-dihydro-2H-thiopyran-3(6H)-one 4. On heating, 4-(anilinomethylene)-4,5-dihydrothiophen-3(2H)-one 5 and N-phenyl-2,5-dihydrothiophene-3-carboxamide 7 are formed by carbenoid rearrangements.
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■ Reactions of 3- and 7-Acetyl-2-chlorotropones with Hydrazines. Formation of 1(2H)-Phthalazinones
Zhong-Tian Jin, Kimiaki Imafuku,* and Hisashi Matsumura
*Department of Chemistry, Faculty of Science, Kumamoto University, Kurokami 2-39-1, Kumamoto 860-8555, Japan
Abstract
3-Acetyl- and 7-acetyl-2-chlorotropones (2a and 2b) reacted with hydrazine to afford a rearrangement product, 4-methyl-1(2H)-phthalazinone (3). In the reactions with methylhydrazine, 2a and 2b gave 1,3-dimethyl-7-methylamino-1,8-dihydrocycloheptapyrazol-8-one (4) and 2,4-dimethyl-1(2H)-phthalazinone (5), respectively.
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■ Selective Monoalkylation of Carbon Nucleophiles with Gramine
Masanori Somei,* Yoshio Karasawa, and Chikara Kaneko
*Faculty of Pharmaceutical Sciences, Kanazawa University, 13-1 Takara-machi, Kanazawa 920-0934, Japan
Abstract
Mono-alkylation method of carbon nucleophiles, especially for nitroalkanes, with gramine derivatives is reported.
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■ An Alternative Synthesis of (S)-(+)-γ-Hydroxymethyl-γ-butyrolactone from (D)-(+)-Mannitol
Seiichi Takano,* Emiko Goto, Michiyasu Hirama, and Kunio Ogasawara
*Pharmaceutical Institute, Tohoku University, Aobayama, Sendai 980-8578, Japan
Abstract
(S)-(+)-γ-Hydroxymethyl-γ-butyrolactone (6), which has been obtained from (S)-glutamic acid, is synthesized alternatively starting from (D)-(+)-mannitol (1).
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■ A Convenient Synthesis of 2,2-Dimethylchromenes from 2,2-Dimethylchromanones
Masao Tsukayama,* Tsukasa Sakamoto, Tokunaru Horie, Mitsuo Masumura, and Mitsuru Nakayama
*Department of Chemical Science and Technology, Faculty of Engineering, University of Tokushima, Minamijosanjima-cho, Tokushima 770-8506, Japan
Abstract
2,2-Dimethylchromanones were very easily reduced to the corresponding alcohols by sodiun borohydride-palladium chloride, and the alcohols were converted into the corresponding 2,2-dimethylchromenes by dehydration with potassium hydrogen-sulfate in high yields based on 2,2-dimethylchromanones.
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■ Synthesis of an Intermediate to the Tetracyclic Ergot Alkaloids
Mitsutaka Natsume,* Hideaki Muratake, and Yoshihiro Kanda
*Research Foundation Itsuu Laboratorym 2-28-10 Tamagawa, Setagaya-ku, Tokyo 158, Japan
Abstract
4-Nitro-5-[3-hydroxy-2-(1,3-dioxolan-2-ylidene)propyl]-5H-benz[c,d]indole (1b) was synthesized from 4-(1-methoxycarbonyl-2-pyrrolyl)crotonaldehyde (7) as a useful intermediate to the tetracyclic ergot alkaloids.
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■ Studies on Furan Derivatives. XIII. Thermolysis of Methyl 5-(2-Azidophenoxy)-2-furoate
Akira Tanaka* and Toshinao Usui
*Faculty of Pharmaceutical Sciences, Josai University, 1-1 Keyakidai, Sakado, Saitama 350-0295, Japan
Abstract
In thermolysis of methyl 5-(2-azidophenoxy)-2-furoate, the first conversion of this into 2-(2-methoxalylvinyl)benzoxazole has been found.
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■ Synthesis of Pyrimidine Derivatives Having Olefinic Substituents by Palladium-catalyzed Cross-coupling Reaction of Iodopyrimidines
Takao Sakamoto,* Hiroko Arakida, Kiyoto Edo, and Hiroshi Yamanaka
*Graduate School of Pharmaceutical Sciences, Tohoku University, Aramaki, Aoba-ku, sendai 980-8578, Japan
Abstract
The palladium-catalyzed cross-coupling reactions of 2- and 4-iodopyrimidines with olefins were investigated on the stand-point of synthetic chemistry. The reaction was well catalyzed by use of palladium(II) acetate alone, palladium black, or palladium charcoal, and various olefinic pyrimidines were obtained in satisfactory yields.
The homo-coupling reaction of 4-iodopyrimidines caused by palladium(II) acetate with triphenylphosphine was resisted by removing triphenylphosphine from the catalyst-system.
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■ Synthesis of Alkaloids, Tortuosamine, N-Formyltortuosamine, and Related Compound
Junko Koyama, Teruyo Sugita, Yukio Suzuta, and Hiroshi Irie*
*Faculty of Pharmaceutical Sciences, Nagasaki University, 1-14, Bunkyo-machi, Nagasaki 852-8521, Japan
Abstract
Synthesis of alkaloids, tortuosamine, N-formyltortuosamine, and related compound , was accomplished by application of a new method constructing cycloalkenopyridines by thermal rearrangement of oxime O-allyl ethers as a key step.
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■ Total Synthesis of Prosophylline
Mitsutaka Natsume* and Masashi Ogawa
*Research Foundation Itsuu Laboratory, 2-28-10 Tamagawa, Setagaya-ku, Tokyo 158, Japan
Abstract
The SnCl2-effected reaction of 4 with ethyl vinyl ether and 1-trimethylsilyloxybutadiene afforded 5a, 17, and 18. Prosophylline (1), a racemic alkaloid of Prosopis africana, was first synthesized by differentiating the double bonds of 17.
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■ Structure of Moracenin D, a Hypotensive Principle of Morus Root Barks
Yoshiteru Oshima, Chohachi Konno, and Hiroshi Hikino*
*Pharmaceutical Institute, Tohoku University, Aobayama, Sendai 980-8578, Japan
Abstract
A new isoprenoid flavone derivative, moracenin D, showing hypotensive activity has been isolated from the crude drug “sohakuhi”, the root barks of Morus sp. Chemical and physico-chemical studies have established the structure of moracenin D as shown in formula I.
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■ The Formation of Moracenin D from Kuwanon G
Taro Nomura,* Toshio Fukai, Eriko Sato, and Kazutaka Fukushima
*School of Pharmaceutical Sciences, Toho University, 2-2-1, Miyama, Funabashi, Chiba 274-8510, Japan
Abstract
From the ethyl acetate extract of the root bark of the cultivated mulberry tree (a variety of Morus alba L.), a novel flavone derivative, moracenin D, containing condensed dihydrochalcone partial structure was isolated. The structure was shown to be I on the basis of the formation of moracenin D (I) from kuwanon G (II).
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■ Absorption Spectra of Benzologs of Quinolizinium Ions
Sayeed-Ud-Din Saraf*
*Department of Chemistry, Faculty of Science, University of Kuwait, Safat 13060, P.O. Box 5969, Kuwait
Abstract
The ultraviolet absorption spectra of quinolizinium ions are reviewed.
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■ Recent Developments in the Chemistry of o-Benzoquinone-diimines
Willy Friedrichsen* and Andreas Böttcher
*Institut für Organische Chemie, Universität Kiel, Olshausenstrasse. 40, D-24098 Kiel, Germany
Abstract
This article presents a survey of recent developments in the chemistry of o-benzoquinone-diimines, especially the achievements thus far realized in the reactions of these compounds.