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. 53, No. 3, 2000
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■ Electrochemistry of 1,3-Diazadihydroazulanone: Electrochemical Reduction and Oxidation of 1-Tosyl-3-aryl-1,3-diazadihydroazulanone Leading to Migration and Elimination of the Tosyl Group
Katsuhiro Saito,* Takayasu Ido, Yasutaka Awadu, Takashi Kanie, and Satoru Kondo
*Department of Applied Chemistry, Nagoya Institute of Technology, Gokiso-cho, Showa-ku, Nagoya 466-8555, Japan
Abstract
Electrochemical oxidations of 1-tosyl-3-aryl-1,3-diazadihydroazulanones gave 6-tosyl-3-aryl-1,3-diazadihydroazulanones via migrations of the tosyl group. On the other hand, electrochemical reductions of the 1-tosylazulanones afforded 3-aryl-1,3-diazadihydroazulanones through eliminations of the tosyl group.
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■ Synthesis and Structure of Novel Dibenzo[b,i]-1-oxa-6-heteroecines Containing Group 15 Heavier Elements
Shuji Yasuike, Satoshi Tsukada, Jyoji Kurita,* Takashi Tsuchiya, Yoshisuke Tsuda, Humiyuki Kiuchi, and Shinzo Hosoi
*Faculty of Pharmaceutical Sciences, Hokuriku University, Kanagawa-machi, Kanazawa 920-1181, Japan
Abstract
A series of novel dibenzo[b, i]-1-oxa-6-heteroecines (4a-d) containing Group 15 heavier elements (P, As, Sb, and Bi) have been prepared via common 1,9-dilithium intermediate (3). Single crystal X-Ray analysis of oxastibecine (4c) reveals that the two olefinic bonds in the ring system are both cis configuration and the distance between the antimony and oxygen atoms is shorter than the sum of the van der Waals radiis of each element, indicating the presence of a transannular interaction between the oxygen and hetero atoms.
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■ 1,3-Dihydro-1,3-diacetyl-2H -benzimidazol-2-one: A New Versatile and Selective Acetylating Agent
In Hwa Chung, Ki Suk Cha, Jae Hong Seo, Joong Hyup Kim, Bong Young Chung, and Choong Sup Kim*
*Biochemicals Research Center, Korea Institute of Science and Technology, P.O. Box 131, Seoul 130-650, Korea
Abstract
1,3-Dihydro-1,3-diacetyl-2H-benzimidazol-2-one (4, DABI) was proven to be a versatile and selective acetylating agent for amines. Selectivity and reactivity are not only superior than those of other known acetylating agents, but also products could be easily separated with excellent yield.
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■ Crystal Structures of Mercury(II) Dichloride Complexes of 5,8-Dioxa-2,11-dithiabicyclo[10.4.1]heptadeca-1(16),12,14-trien-17-one and 5,8,11-Trioxa-2,14-dithiabicyclo[13.4.1]icosa-1(19),15,17-trien-20-one
Kanji Kubo,* Nobuo Kato, Akira Mori,* and Hitoshi Takeshita
*Institute of Advanced Material Study, 86, Kyushu University, Kasuga-koen, Kasuga, Fukuoka 816-8580, Japan
Abstract
5,8-Dioxa-2,11-dithiabicyclo[10.4.1]heptadeca-1(16),12,14-trien-17-one (1b) and 5,8,11-trioxa-2,14-dithiabicyclo[13.4.1]icosa-1(19),15,17-trien-20-one (1c) formed 1b-2HgCl2 and 1c-2.5HgCl2-H2O complex with HgCl2 and H2O, respectively. The Hg(II) ions were coordinated to both the tropone carbonyl group and the thioether sulfur atom to form a side-on complex.
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■ Synthesis of (±)-(3R*, 4S*, 4aR*)- 4,8-Dihydoxy-3-methyl-3,4,4a,5-tetrahydro-1H-2-benzopyran-1-one
Kanako Uchida, Hidenori Watanabe, and Takeshi Kitahara*
*Department of Applied Biological Chemistry, Graduate School of Agricultural and Life Sciences, The University of Tokyo, 1-1-1 Yayoi, Bunkyo-ku, Tokyo 113-8657, Japan
Abstract
The insecticidal tetrahydroisocoumarin, (3R, 4S, 4aR)-4,8-dihydroxy-3-methyl-3,4,4a,5-tetrahydro-1H-2-benzopyran-1-one, was synthesized as a racemate using one-pot esterification—Michael addition—aldol reaction of δ-hydroxy-α,β-unsaturated aldehyde and diketene as a key step.
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■ Dimerization and Denitration of 1-Methyl-3,6,8-trinitro-2-quinolone
Nagatoshi Nishiwaki, Mayumi Azuma, Chitose Tanaka, Noriko Asaka, Makoto Shoda, Yasuo Tohda, and Masahiro Ariga*
*Department of Chemistry, Osaka Kyoiku University, Asahigaoka 4-698-1, Kashiwara, Osaka 582-8582, Japan
Abstract
The reaction of 1-methyl-3,6,8-trinitro-2-quinolone (1) with tertiary amine caused dimerization and denitration. Dimerization predominantly proceeded at room temperature, and denitration mainly occurred under heated conditions.
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■ Synthesis of (+)-Hupeol from (-)-Cytisine: Transformation of a Cyclic Imine into a Cyclic Hemiacetal
Yong-Hong Wang, Kimio Higashiyama, Hajime Kubo, Jia-Shi Li, and Shigeru Ohmiya*
*Institute of Medicinal Chemistry, Hoshi University, Ebara 2-4-41, Shinagawa-ku, Tokyo 142-8501, Japan
Abstract
A possible intermediate in the metabolism of lupin alkaloids, (+)-hupeol, was synthesized from (—)-cytisine by transformation of a cyclic imine into a cyclic hemiacetal by treatment with HNO2. The absolute stereochemistry of (+)-hupeol was confirmed to be 7S, 9R, which is the same as that of (—)-cytisine.
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■ Synthesis of Methylenebis(4-hydroxy-2-pyrone) or Methylenebis(4-hydroxycoumarin) Derivatives by Organic Solid State Reaction
Hisahiro Hagiwara,* Norikazu Fujimoto, Toshio Suzuki, and Masayoshi Ando
*Graduate School of Science and Technology, Niigata University, 8050, 2 no-cho, Ikarashi, Niigata 950-2181, Japan
Abstract
Methylenebis(4-hydroxy-2-pyrone) or methylenebis(4-hydroxycoumarin) derivatives (5) have been synthesized from 4-hydroxy-2-pyrones or 4-hydroxycoumarin (3) with aldehydes (4) by organic solid state reaction.
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■ Total Synthesis of Yuehchukene
Minoru Ishikura,* Katsuaki Imaizumi, and Nobuya Katagiri
*Faculty of Pharmaceutical Sciences, Health Sciences University of Hokkaido, Ishikari-Tobetsu, Hokkaido 061-0293, Japan
Abstract
Total synthesis of yuehchukene could be realized through the palladium catalyzed carbonylative cross-coupling reaction of indolylborate (2b) with cyclohexadienyl triflate (9) as a key reaction.
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■ Synthesis of the New Triheterocyclic System C3N-C4N-C6N. 3-Aryl-2,5,5-trimethyl-9a-methylsulfanyl-9-phenoxy-4,5,6,8,9,9a-hexahydro-3H-azeto[1,2-a]pyrrolo[3,2-c]azepin-8-ones
Roberto Martínez,* José Gustavo Avila-Zárraga, Gema López-López, and Víctor Oswaldo Nava-Salgado
*Instituto de Química, Universidad Nacional Autónoma de México, Circuito Exterior, Ciudad Universitaria, 04510 Mexico D.F., México
Abstract
The regio- and stereoselective synthesis of the cis-3-aryl-2,5,5-trimethyl-9a-methylsulfanyl-9-phenoxy-4,5,6,8,9,9a-hexahydro-3H-azeto[1,2-a]-pyrrolo[3,2-c]azepin-8-ones (1) was performed. A four-step sequence, which yields are good, constitutes the first synthetic way for the preparation of the first member of this new C3N-C4N-C6N series.
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■ Synthesis of New Heterocyclic Systems: Spirothiadiazolepyrazolo[1,5,4-ef ][1,5]benzodiazepines
El Mostapha Rakib, Mohammed Benchidmi, El Mokhtar Essassi, Abdelaziz El Bouadili, Mostafa Khouili, Jean M. Barbe, and M. Dolors Pujol*
*Laboratori de Química Farmacèutica, Departament de Farmacologia i Química Terapèutica, Facultat de Farmàcia, Universitat de Barcelona, Av. Diagonal 643, 08028-Barcelona, Spain
Abstract
New derivatives spiro type of pyrazolo-1,5-benzodiazepines have been synthesized by 1,3-dipolar cycloaddition of nitrile imines with pyrazolo[1,5,4-ef][1,5]benzodiazepin-6-thione. When the nitrile oxide was used the corresponding pyrazolobenzodiazepin-6-one was obtained from the intermediate spirooxathiazole by elimination of isothiocyanate group. These cycloadditions are peri- and regioselectives.
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■ Synthesis of Spiroisoxazoline[5,31]chroman-41-one
Santhanaraman Manikandan, Muthian Shanmugasundaram, Raghavachary Raghunathan,* and Ezekiel J. Padma Malar
*Department of Organic Chemistry, University of Madras, Guindy campus, Chennai 600 025, India
Abstract
Synthesis of a series of spiro[3,4-diaryl-4,5-dihydroisoxazole-5,31-chroman-41-one] has been accomplished in good yields by regioselective 1,3-dipolar cycloaddition of nitrile oxide to 3-arylidene-4-chromanone. X-Ray crystal structure analysis of one of the products confirms the structure and the regiochemistry of cycloaddition.
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■ Synthesis of 2H -Naphtho[2,3-b ]thiopyranoquinones and Density Functional Study for the Diels-Alder Reaction of a Benzothiopyranoquinone
Ricardo A. Tapia,* Miriam C. Garate, Jaime A. Valderrama, Fernando Zuloaga, Paul R. Jenkins, John Fawcett, and David R. Russell
*Facultad de Quimica, Pontificia Universidad Catolica de Chile. Casilla 306, Santiago 22, Chile
Abstract
The synthesis of benzothiopyranoquinone (6) in three step from benzothiopyran (3) is described. Diels-Alder reaction of quinone (6) with 1,3-pentadiene (7), cyclopentadiene, 1-methoxy-1,3-cyclohexadiene (11) and 1-dimethylamino-1-aza-1,3-pentadiene (14) was studied. The Density Functional Theory was applied to explain the orientation of the cycloaddition reaction of quinone (6) with dienes (7), (11) and (14).
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■ Hydrogenation Derivatives of Neo-clerodanes and Their Antifeedant Activity
Maurizio Bruno, Sergio Rosselli, Ivana Pibiri, Franco Piozzi,* and Monique S. J. Simmonds
*Department of Organic Chemistry, Palermo University, Viale delle Scienze-Parco d’Orleans II, 90128 Palermo, Italy
Abstract
Hydrogenation of some natural neo-clerodanes on 10% Pd/C resulted in the saturation of the furan ring and in some cases hydrogenolysis of the epoxide system and or γ-lactone ring. Overall, reduction of the furan ring found in the natural compounds resulted in a decrease in the antifeedant activity of the compounds against the lepidopteran pests, Heliocoverpa armigera and Spodoptera frugiperda. However, two of the most active derivatives had both the furan ring and the lactone ring hydrogenated but the epoxide intact.
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■ Synthesis and Structural Features of New Cyclofunctionalized Benzimidazoles
Alba Chimirri,* Anna Maria Monforte, Pietro Monforte, Francesco Nicolò, Angela Rao, and Maria Zappalà
*Dipartimento Farmaco-Chimico, Università di Messina, Viale Annunziata, 98168 Messina, Italy
Abstract
The synthesis of new tricyclic derivatives having sulfur-containing six or seven-membered rings fused to the «a» edge of benzimidazole system, is reported. The stereochemical characteristics of thiazino- and thiazepinobenzimidazoles (4-7) are described and comparative NMR data are discussed. The synthetic approach to new benzo- or pyridothiazinobenzimidazole tetracyclic systems (8) is also reported.
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■ Synthesis of Some New Spiropyrazolo[4’,5’:5,6]pyrano[2,3-d]pyrimidines
Marzoog S. Al-Thebeiti*
*Department of Chemistry, Faculty of Applied Sciences, Umm Al-Qura University, Makkah Almukkarramah, P. O. Box 6876, Saudi Arabia
Abstract
3-Methylpyrazolin-5-ones (1a,b) were reacted with cycloalkanones (2a-d) in the presence of fused sodium acetate to give the corresponding cycloalkylidene derivatives (3a-h). Reaction of compounds (3a-h) with malononitrile gave the pyrano derivatives (4a-h), which were cyclized to pyranopyrimidines with acetic anhydride/pyridine, formamide and formamide/formic acid.
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■ A Novel Synthesis of 2,3-Dialkylpyridine Derivatives from Dialkyl-N-silylimines and 1,3-Diaryl-2-propen-1-one or (E)-1,1,1-Trifluoro-4-phenyl-3-buten-2-one
Marhaba Hojahmat, Takeo Konakahara,* and Sanae Tamura
*Department of Industrial Chemistry, Faculty of Science and Technology, Science University of Tokyo, Noda, Chiba 278-8510, Japan
Abstract
A series of 2,3-dialkylpyridine derivatives (4a-h) have been prepared by the reaction of dialky-N-silylimines (1a-c) with 1,3-diaryl-2-propen-1-one (3a-c) or (E)-1,1,1-trifluoro-4-phenyl-3-buten-2-one (3d). Dialkyl-N-trimethylsilylimines (1a-c), generated from alkyl cyanides and MeLi or n-BuLi and trimethylchloro- silane, reacted with a slight excess amount of 1,3-diaryl-2-propen-1-one (3a-c) or (E)-1,1,1-trifluoro-4-phenyl-3-buten-2-one (3d) in the presence of LDA in dry tetrahydrofuran to afford the corresponding 2,3-dialkylpyridine derivatives (4a-h) in 62-86 % yields, respectively.
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■ Studies on the Rh(II)-catalyzed C-H Insertion Reaction of Some Derivatives of N-[4-{(S)-1,2-Dihydroxy- butyl}]-α-diazoanilides: Site-Selectivity
Andrew G. H. Wee* and Douglas D. McLeod
*Department of Chemistry, University of Regina, Regina, Saskatchewan, S4S 0A2, Canada
Abstract
The Rh(II)-catalyzed reactions of diazoamides (la, c-e) were investigated. The results show that both steric and electronic effects work in concert to govern the regio- and chemo-selectivity of the reaction. The diastereoselectivity of the reaction in the formation of 5a was determined to be 74% de and the sense of 1,2-induction was found to be S at the newly formed C-4 stereogenic centre.
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■ Synthesis of Tetrahydrofuro[2,3-b][1]benzopyranones by the Ring-Expansion Reaction of Methanochromanone with Symmetric Ketones
Yoshiaki Sugita,* Kazuyoshi Kawai, and Ichiro Yokoe
*Faculty of Pharmaceutical Sciences, Josai University, Sakado, Saitama 350-0295, Japan
Abstract
In the presence of SnCl4, 2,3-dimethoxycarbonylmethanochromanone (8) was transformed into a zwitterion which easily reacted with symmetric ketones to give the tetrahydrofuro[2,3-b][1]benzopyranone derivatives in good yields with high diastereoselectivity.
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■ Synthesis of 5-Substituted Indole Derivatives, Part II. Synthesis of Sumatriptan through the Japp-Klingemann Reaction
Béla Pete,* István Bitter, Kálmán Harsányi, and László Tõke
*Organic Chemical Technology Research Group of the Hungarian Academy of Sciences at the Technical University of Budapest, H-1521 Budapest, Hungary
Abstract
Synthesis of selective 5-HT1B/1D receptor agonist, sumatriptan (1) was accomplished through decarboxylation of 2-carboxy-3-[2-(dimethylamino)ethyl]-N-methyl-1H-indole-5-methanesulfonamide (2) in quinoline with copper powder. The preparation of the acid (2) was effected through the Japp-Klingemann method thus avoiding the need for the formation of hydrazine from diazonium salt. Attempted decarboxylation in N,N-dimethylacetamide resulted in the formation of the β-carboline (16).
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■ Gaulthrins C and D, Two New Lignans from the Roots of Gaultheria yunnanensis
Zhizhen Zhang, Dean Guo,* Junhua Zheng, Kazuo Koike, Zhonghua Jia, and Tamotsu Nikaido
*School of Pharamceutical Sciences, Beijing Medical University, Beijing, 100083, China
Abstract
Two new lignans, designated as gaultherins C (1) and D (2), were isolated from roots of Gaultheria yunnanensis. Their stuctures were determined as 1,3,3aα,4α,9,9aβ-hexahydro-4-(4-hydroxy-3,5-dimethoxyphyenyl )-5,7-dimethoxynaphtho[2,3-c]furan-6-ol (1) and 1,3,3aα,4α,9,9aβ-hexahydro-4-(4- hydroxy-3,5-dimethoxyphenyl)-7-methoxynaphtho[2,3-c]furan-6-ol(2) based on the physico-chemical properties and the extensive NMR (DEPT, DQF-COSY, HETCOR, phase-sensitive NOESY, and HMBC experiinents) studies.
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■ Two New Pentacyclic Triterpenoids from the Aerial Parts of Lantana camara Linn.
Bina S. Siddiqui, Aneela Wahab, and Sabira Begum*
*H. E. J. Research Institute of Chemistry, University of Karachi, Karachi-75270, Pakistan
Abstract
Two new constituents camarolide (1) and lancamaric acid (4) along with two known compounds oleanonic acid (2) and ursonic acid (3) have been isolated from the aerial parts of Lantana camara Linn. Structures of the new compounds have been established as 3-keto-urs-11-en-13β(28)-olide (1) and 3,25-epoxy-3α-ethoxy-olean-12-en-28-oic acid (4) through spectral studies including 1D (1H-, 13C-NMR) and 2D (COSY-45, NOESY, J-resolved, HMQC and HMBC) NMR.
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■ Nimbolinins, C-Seco Limonoids from the Fruits of Melia toosendan
Munehiro Nakatani,* Yukari Fukuman, Takashi Sakumoto, Nobuyuki Yamashita, Hiroaki Okamura, and Tetsuo Iwagawa
*Department of Chemistry and Bioscience, Faculty of Science, Kagoshima University, 1-21-35 Korimoto, Kagoshima 890-0065, Japan
Abstract
Three new nimbolinin-type limonoids, named nimbolinins A, C and D, were isolated together with five known limonoids, trichilinin D and E, nimbolinin B, 1-O-cinnamoyltrichilinin and toosendanin, from the unripe fruits of a Chinese Meliaceae plant Melia toosendan. The structures of these new compounds were elucidated by spectrospcopic means and their antifeedant property is also described.
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■ Chemistry of Heterocyclic Pseudobasic Amino-Carbinols. Part 37. Correction of a Structure - A New Heterocyclic Ring System
Csaba Szántay,* Lajos Szabó, Csaba Szántay Jr., Gábor Tárkányi, and Mátyás Czugler
*Department of Organic Chemistry, Technical University, Gellért tér 4, H-1521 Budapset, Hungary
Abstract
A previously published structure (1) and the rationalization of its formation must be corrected. The modified structure of the new heterocyclic ring system can be depicted as 2.
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■ A New Synthesis of (-)-(5R,6S)-6-Acetoxy-5-hexadecanolide, the Mosquito Culex pipiens fatigans Oviposition Attractant Pheromone
John K. Gallos,* Demetrios S. Mihelakis, Constantinos C. Dellios, and Minodora E. Pozarentzi
*Department of Chemistry, Aristotle University of Thessaloniki, Thessaloniki 540 06, Greece
Abstract
A new synthesis of (-)-(5R,6S)-6-acetoxy-5-hexadecanolide, the main component of the mosquito Culex pipiens fatigans oviposition attractant pheromone, from D-ribose is reported.
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■ A Simple and Efficient Synthetic Method for Fluorine-containing 7H -[1]Benzothiopyrano[3,2-h ]quinolines
Etsuji Okada* and Norikado Tsukushi
*Department of Chemical Science and Engineering, Faculty of Engineering, Kobe University, Rokkodai-cho, Nada-ku, Kobe 657-8501, Japan
Abstract
Acid-catalyzed cyclization of 8-quinolyl aryl sulfides (2), prepared by aromatic nucleophilic nitrogen-sulfur exchange reaction of N,N-dimethyl-5,7-bis(trifluoroacetyl)-8-quinolylamine (1) with p-substituted benzenethiols, afforded the corresponding fluorine-containing 7H-[1]benzothiopyrano[3,2-h]quinolines (3-5) in excellent yields.
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■ 12-Acetoxypseudopterolide: A New Diterpene from Pseudopterogorgia elisabethae
Athar Ata and Russell G. Kerr*
*Department of Chemistry and Biochemistry, Center for Molecular Biology and Biotechnology, Florida Atlantic University, 777 Glades Road, Boca Raton, Florida 33431, U.S.A.
Abstract
Chemical studies on the non polar fraction of the methanolic extract of Pseudopterogorgia elisabethae Bayer collected from the Florida Keys has yielded 12-acetoxypseudopterolide (1), a new diterpene of the pseudopterane series. The structure was established through spectroscopic analysis. Compound (1) was shown to exhibit modest anti-cancer activity against a human prostate cancer cell line (LnCap).
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■ Two Isocoumarins from the Cultured Lichen Mycobiont of Graphis Sp.
Takao Tanahashi,* Yukiko Takenaka, Naotaka Nagakura, Nobuo Hamada, and Hiromi Miyawaki
*Kobe Pharmaceutical University, 4-19-1 Motoyamakita-machi, Higashinada-ku, Kobe 658-8558, Japan
Abstract
From the cultures of spore-derived mycobionts of lichen Graphis sp., two isocoumarins, 8-methyldichlorodiaportin (1) and 6,8-dimethylcitreoisocoumarin (2), were isolated. Their structures were determined by spectroscopic and chemical methods. This is the first instance of isolation of isocoumarin metabolites from lichen mycobiont.
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■ Efficient Route to 1-Dimethylsulfamoyl-4-iodoimidazole, Isomerisation of 1-Dimethylsulfamoyl-5-iodoimidazole to 1-Dimethylsulfamoyl-4-iodoimidazole
Lakshmi Bhagavatula, Ramiya H. Premchandran,* Daniel J. Plata, Steven A. King, and Howard E. Morton
*PPD Process Research, D45N. Bldg. R8, Abbott Laboratories, N. Chicago, IL60064, U.S.A.
Abstract
An efficient method has been developed for regioselective protection of 4-iodoimidazole using N,N-dimethylsulfamoyl chloride and 50% aqueous NaOH in THF leading to N,N-dimethylsulfamoyl-4-iodoimidazole(1) in 97% yield and >98% purity. The rearrangement of by-product 5-iodosulfonamide (2) to the desired product (1) is a key feature of this procedure.
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■ Short Step Synthesis of (4R)-4-Hydroxymethyl-4-methyl-2-hexene-1,5-diol: A Useful Chiral Synthon for Natural Product Synthesis with Quaternary Carbon Center
Kunisuke Okada,* Daisuke Nakamura, and Yuhji Hattori
*Faculty of Pharmacy, Meijo University, Tenpaku, Nagoya 468-8503, Japan
Abstract
A chiral synthon (2), prepared previously via 1,2-acyl migration of the optically active α,β-epoxy ketone (1), was synthesized from Koga’s chiral keto ester (6) in 4 steps.