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. 22, No. 12, 1984
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■ A New Route towards the Synthesis of Dihydropyranoxanthones
Vinod Kumar Ahluwalia* and Ashok Kumar Tehim
*Department of Chemistry, University of Delhi, Delhi-110 007, India
Abstract
A new route towards the synthesis of dihydropyranoxanthones using carboxy-2,2-dimethylchromans as starting material is described.
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■ High Pressure Approach to the Synthesis of 7-Phosphanorbornadienes Form λ5-Phosphole Oxides and Dialkyl Acetylenedicarboxylates
Kiyoshi Matsumoto,* Shiro Hashimoto, Shinichi Otani, and Takane Uchida
*Graduate School of Human and Environmental Studies, Kyoto University, Yoshida-Nihonmatsu-cho, Sakyo-ku, Kyoto 606-8501, Japan
Abstract
Reactions of 1,2,3,4,5-pentaphenylphosphole oxide (4a) with dimethyl and di-t-butyl acetylenedicarboxylates (5a, b) under high pressure afford the tetraphenylphthalates (7a, b) along with the 7-phosphanorbornadiene derivatives (6a, b). The latter adducts have proven too unstable to be submitted to deoxygenation under conventional conditions.
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■ Total Synthesis of (±)-19,20-Dehydroyohimbines
Okiko Miyata, Yumiko Hirata, Takeaki Naito, and Ichiya Ninomiya*
*Kobe Women’s College of Pharmacy, Motoyamakita, Higashinad, Kobe, Hyogo 658, Japan
Abstract
The first total synthesis of three (±)-19,20-dehydroyohimbines (4), (5), and (6) was achieved according to the route involving regioselective acylation of 18,19-dehydroalloyohimbone (1) followed by selective migration of a double bond from the conjugated position to the unconjugated 19-20 position.
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■ Synthesis of Decarine
Satinder Vir Kessar,* Yash Pal Gupta, Taj Mohammad, Achla Khurana, and Kewal Krishan Sawal
*Department of Chemistry, Panjab University, Chandogarh 160014, India
Abstract
The amine (IX), obtained by sodium borohydride reduction of the Schiff base derived from 1-amino-6,7-methylenedioxynaphthalene (VIII) and 3-benzyloxy-6-bromo-2-methoxybenzaldehyde (VII), on treatment with potassium amide in liquid ammonia gave decarine (la).
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■ Synthesis and Characterization of 1H-2,4-Benzodiazepines
Hiroyuki Sawanishi and Takashi Tsuchiya*
*School of Pharmacy, Hokuriku University, 3-Ho, Kanagawa machi, Kanazawa 920-1181, Japan
Abstract
Photolysis of the 4-azidoisoquinolines (1) in the presence of sodium methoxide afforded the 1H-2,4-benzodiazepines (3); this new ring system was characterized by some photochemical and thermal reactions.
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■ Structure of Mulberrofuran K, an Optically Active Natiral Diels-Alder Type Adduct from Chinese Crude Drug "Sang-Bai-Pi" (Morus Root Bark)
Yoshio Hano, Toshio Fukai, Hideaki Kohno, Kazuhiro Hirakura, Taro Nomura,* and Jun Uzawa
*Faculty of Pharmaceutical Sciences, Toho University, 2-2-1, Miyama, Funabashi, Chiba 274-8510, Japan
Abstract
From the methanol extract of the Chinese crude drug “Sang-Bai-Pi” (Japanese name “Sohakuhi”), the root bark of Morus sp. (Moraceae), a 2-arylbenzofuran derivative was isolated and named mulberrofuran K. Its structure was shown to be 1 on the basis of the spectral and chemical evidence. Mulberrofuran K is optically active and regarded biogenetically as a variation of a Dlels-Alder type adduct of a chalcone derivative and a dehydroprenyl-2-arylbenzofuran derivative.
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■ An Enantioselective Synthesis of (+)-Crotanecine
Veejendra Kumar Yadav, Heinrich Rüeger, and Michael Benn*
*Department of Chemistry, University of Calgary, Calgary, Alberta, T2N 1N4, Canada
Abstract
(2S,4R)-4-Hydroxyproline was elaborated into (+)-crotanecine via (1S,5R,8R)-8-hydroxy-2-oxa-6-azabicyclo[3.3.0]octan-3-one.
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■ Synthesis and Spectral Properties of Some Dinucleotide Analogues Containing Bromine in 5-position of Pyrimidine Moieties
Maria Dezor-Mazur, Franciszek Kazmierczak, and Krzysztof Golankiewicz
*Department of Chemistry, Adam Mickiewicz University, ul. Grunwaldzka 6, 60-780 Poznán, Poland
Abstract
The bromination of pyrimidine bases in dinucleotide analogues has been studied. The structures of the brominated products have been established on the basis of analytical and spectral data.
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■ Addition of Chlorosulphonyl Isocyanate to Tetrasubstituted Cyclopentadienes: A Facile Route for the Synthesis of Azepines
Krishna Narasimhan,* Perumal Raja Kumar, and Thamari Selvi
*Department of Organic Chemistry, Guindy Campus, University of Madras, Chennai-600 025, India
Abstract
The β-lactams 2, 2a obtained by the cycloaddition of chlorosulphonyl isocyanate to the dienes 1, 1a give the azepinones 5, 5a through the sulphonate estere 4, 4a. The sulphonate ester 6 obtained from 4, when treated with sodium hydride gives the dihydroazepine 8.
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■ The Chlorinolysis of Azetidinone Disulfides
Ronald G. Micetich,* Rajeshwar Singh, Werner O. Merlo, Daniel M. Tetteh, Chia-Cheng Shaw, and Robert B. Morin
*Faculty of Pharmacy and Pharmaceutical Sciences, University of Alberta, Edmonton, Alberta, T6G 2G2, Canada
Abstract
The chlorinolysis of dithiazeneazetidinones, unsym-azetidinone disulfides, and 2-chloromethylpenams, with sulfuryl chloride produce the 2-[2’(R and S)-chloro-4’-oxoazetidin-1’-yl]-3-chloromethyl-3-chlorosulfenylbutyric acid ester isomers in which the S-isomer predominates. Treatment of this compound (R and S isomers) with pyridine results in elimination of HSCl and formation of the Z and E isomers in which the Z isomer predominates.
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■ Stereospecific Synthesis of (E)- or (Z)-α-Stylbazole from 2-(Trimethylsilylmethyl)pyridine and Benzaldehyde Phenylhydrazones
Takeo Konakahara,* Hiromi Nishigaki, Atsuo Watanabe, and Kenji Sato
*Department of Industrial Chemistry, Faculty of Science and Technology, Science University of Tokyo, 2641 Yamazaki, Noda, Chiba 278-8510, Japan
Abstract
In the presence of crown ethers, [2.1.1]-cryptand, di-, tri-, or tetraglyme, lithiated 2-(trimethylsilylmethyl)pyridine reacts with benzaldehyde methylphenylhydrazone to give stereospecifically (E)- or (Z)-α-stylbazole in good yield.
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■ Synthesis of N-Substituted 1,6-Dihydro-3(2H)-pyridinones and 1-Acyl-3-piperidines
Ling-Ching Chen,* Eng-Chi Wang, Jen-Hom Lin, and Shihn-Sheng Wu
*Graduate Institute of Natural Products, Kaohsiung Medical College, 100 Shih Chuen 1st Rd., Kaohsiung 80708, Taiwan, R.O.C.
Abstract
Synthesis of the N-substituted 1,6-dihydro-3(2H)-pyridinones (3, 6, and 9) and 1-acyl-3-piperidones (7 and 10) is described. 1-Benzylpiperidine-3,5-dione (1) was converted into N-substituted 1,6-dihydro-3(2H)-pyridinones (3, 6, and 9) via the methyl enol ethers (2, 5, and 8). Selective reduction of 6 and 9 with Et3SiH in the presence of TiCl4 produced the 1-acyl-3-piperidones (7 and 10).
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■ On the Synthesis of Unsaturated 4(5H)-Imidazolones
Carlos Cativiela, Javier Chueca, José I. García, and Enrique Meléndez*
*Department of Chemistry, University of Zaragoza, 50009-Zaragoza, Spain
Abstract
(Z)-2,3-Diphenyl-5-benzylidene-4(5H)-imidazolone and (Z)-2,3-diphenyl-5-(α-phenylethylidene)-4(5H)-imidazolone were obtained from the corresponding (Z)-2-phenyl-4-benzylidene-5(4H)-oxazolone and (Z)-2-phenyl-4-(α-phenylethylidene)-5(4H)-oxazolone and aniline. (2)-2,3-Diphenyl-5-benzylidene-4(5H)-imidazolone reacted with diazomethane to afford a mixture of stereoisomeric spirocyclopropanes and (Z)-2,3-diphenyl-5-(α-phenylethylidene)-4(5H)-imidazolone, the product ratios being modified with the appropriate solvent. Anilide of 1-phenyl-4-methyl-3-isoquinolincarboxylic acid or (Z)-2,3-diphenyl-5-(α-phenylethylidene)-4(5H)-imidazolone were obtained from anilide of (Z)-2-benzamidocinnamic acid depending upon the reaction conditions.
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■ A Convenient Synthesis of Propyl Substituted Benzofurocoumarins
Vinod Kumar Ahluwalia,* Rishi Pal Singh, and Rama Pati Tripathi
*Department of Chemistry, University of Delhi, Delhi-110 007, India
Abstract
A convenient synthesis of propyl substituted benzofurocoumarins has been achieved by condensation of 2-bromocyclohexan-1-one with hydroxy-4-propyl-2H-1-benzopyran-2-ones followed by ring closure with PPA and subsequent dehydrogenation using DDQ.
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■ 2,3-Dibromo-3,4-dihydro-4H-1,4-benzoxazines and Their Nucleophilic Displacement Reactions: The First Synthesis of 4-Acetyl-4H-1,4-benzoxazine-3-carbonitrile
Herbert Bartsch,* Maria Ofner, Otto Schwarz, and Walter Thomann
*Institute of Organic Chemistry, University of Graz, Heinrichstr. 28, A-8010 Graz, Austria
Abstract
The synthesis of 2,3-dibromo-3,4-dihydro-2H-1,4-benzoxazines is described. Their reaction with alcohols afforded the corresponding 2-bramo-3-alkoxy- and 2,3-dialkoxy derivatives, respectively, which were converted into various 1,4-benzoxazine-3-carbonitriles.
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■ Synthesis and Structure of 5-Phenylcyclophosphamides
Yun-Er Shih, Jy-Shih Wang,* and Ling-Kang Liu
*Institutue of Chemistry, Academia Sinica, 128, Yan-Chiu-Yuan Road, Sec II, Nankang, Taipei,11529, Taiwan, R.O.C.
Abstract
5-Phenylcyclophosphamides have been synthesized from benzyl cyanide via carbethoxylation, reduction, and finally condensation with bis(2-chloroethyl)-phosphoramidic dichloride. The two diastereomers have been separated and their structures have been assigned on the basis of ir, P-31 nmr and X-ray crystallography.
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■ Structures of Mulberrofurans B and L, 2-Arylbenzofuran Derivatives from the Root of the Cultivated Mulberry Tree (Morus lhou (SER.) Koidz.)
Toshio Fukai, Tomoko Fujimoto, Yoshio Hano, Taro Nomura,* and Jun Uzawa
*Faculty of Pharmaceutical Sciences, Toho University, 2-2-1, Miyama, Funabashi, Chiba 274-8510, Japan
Abstract
Mulberrofuran L, a new 2-arylbenzofuran derivative, was isolated from benzene extract of the cultivated mulberry tree (Japanese name “Roso”, a cultivated variety of Morus lhou (SER.) KOIDZ ), and the structure was shown to be 3 on the basis of the spectral and chemical data. The structure of mulberrofuran B was reversed from the structure (2) to 2’ on the basis of the formation of 3 from 2’.
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■ Novel Heterocycles. 11. Synthesis of the Spiro[pyrrolidine-3,2’(1’H)-quinazoline]ring System
Gary M. Coppola* and Michael J. Shapiro
*Sandoz Research Institute, Sandoz, Inc., Route 10, East Hanover, New Jersey 07936, U.S.A.
Abstract
The reaction of amines with 1 and 2 was investigated. When 1 or 2 was treated with ammonia only the monoamide 3 was formed. An analogous reaction of 2 with methylamine produced the diamide 4 whereas 1 yielded the spiro imide 6 contaminated with minor amounts of 4. Compound 6 was also obtained from the alkylation of 3 with methyl iodide. The reaction of equimolar amounts of 2 and benzylamine furnished the spiro imide 5. Some spectral data, including carbon-13 assigments, are also discussed.
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■ Furoquinoline Alkaloids from Haplophyllum vulcanicum
Amarendra Patra,* Emir Valencia, Robert D. Minard, Maurice Shamma, Nevin Tanker, Belkis Gözler, Mustafa A. Önÿr, and Tekant Gözler
*Department of Chemistry, The Pennsylvania State University, York Campus, P1031 Edgecomb Avenue, York, Pennsylvania 17403, U.S.A.
Abstract
The new furoquinoline alkaloids (+)-nigdenine (5) and (+)-nkolbisine (7) were obtained from Turkish Haplophyllum vulcanicum Boiss. et Heldr. (Rutaceae).
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■ Synthesis of 1,3-Thiazolidine-2-thione and (4R)-Methoxycarbonyl-1,3-thiazolidine-2-thione Using N,N‘-Thiocarbonyldimidazole
Kenso Soai* and Miyuki Ishizaki
*Department of Applied Chemistry, Faculty of Science, Science University of Tokyo, Kagurazaka 1-3, Shinjuku-ku, Tokyo 162-8601, Japan
Abstract
1,3-Thiazolidine-2-thiones are synthesized from β-aminothiols and N,N’-thiocarbonyldiimidazole in good yields.
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■ Activated Nitriles in Heterocyclic Synthesis: A New Synthesis of 3-Furan-2-ylidene- and 1-Thiophen-2-ylidene-3,6-dihydropyridine Derivatives
Galal Eldin Hamza Elgemeie,* Ebtisam Abdel Aziz Hafez, Galal Abdel Moein Nawar, and Mohamed Hilmy Elnagdi
*Chemistry Department, Faculty of Science, Minia University, Minia, Egypt
Abstract
Synthesis of 3-furan-2-ylidene- and 3-thiophen-2-ylidene-3,6-dihydropyridine derivatives via the reaction of cyanothioacetamide with furan-2-ylidene and thiophen-2-ylidene derivatives of malononitrile, ethyl cyanoacetate and benzoylacetonitrile.