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. 32, No. 2, 1991
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■ Bicyclic Ketals. A Tandem Oxymercuration-Solvomercuration Protocol
Richard R. Copp, Dan R. Bruss, Timothy R. Schwartz, and Bradford P. Mundy
*Department of Chemistry, Montana State University, Bozeman, Montana 59717, U.S.A.
Abstract
Oxymercuration of an enol ether takes palce faster than oxymercuration of an isolated alkene. When both functional groups are present in the same molecule, one can use a properly oriented hydroxyl group fixed from the oxymercuration process to participate in a solvomercuration of the second site. This tandem oxymercuration-solvomercuration protocol was applied to the synthesis of two natural products in the 6,8-dioxabicyclo[3.2.1]octane series.
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■ Thallium Selective 6-Methylpyrimidine-2,4(1H,3H)-dione Based Podands
Subodh Kumar,* Rummi Saini, and Harjit Singh*
*Department of Chemistry, Guru Nanak Dev University, Amritsar -143 005, Punjab, India
Abstract
Sequential reactions of dihalides and amino alcohols with 6-methyl-1,3-oxazine-2,4(3H)-diones provide title podands. 8a Selectively extracts and transports Tl+ picrate over Li+, Na+, K+ and NH4+ picrates. Compounds (4), (6), and (8) are effective ionophores.
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■ A Convenient, One-Pot Azulene Synthesis from 2H-Cyclohepta[b]furan-2-ones with Vinyl Ether and Its Analogues III. Orthoesters as a reagent
Tetsuo Nozoe,* Hidetsugu Wakabayashi,* Kimio Shindo, Sumio Ishikawa, Chi-Phi Wu, and Paw-Wang Yang*
*Department of Chemistry, Faculty of Science, Josai University, 1-1 Keyakidai, Sakado, Saitama 350-0295, Japan
Abstract
2-Alkoxy and 2,4-dialkoxyazulene derivatives were synthesized in one-pot and in good yields by the reaction of 2H-cyclohepta[b]furan-2-ones with orthoesters on heating either neat or in an aprotic solvent at 160 - 190 °C
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■ Preparation of 1-Hydroxyindole Derivatives and a New Route to 2-Substituted Indoles
Toshiya Kawasaki, Atsushi Kodama, Tokiko Nishida, Kazuhisa Shimizu, and Masanori Somei*
*Faculty of Pharmaceutical Sciences, Kanazawa University, 13-1 Takara-machi, Kanazawa 920-0934, Japan
Abstract
An easy handling method of 1-hydroxyindole is developed. Based on the metod, preparation and reaction of 1-hydroxyindole derivatives are investigated. A new regioselective lithiation of 1-methoxyindole and its application for the synthesis of 2-substituted indoles are also reported.
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■ Acid-catalyzed Photoreaction of 6-Chloro-1,3-dimethyluracil in Benzene; Synthesis of Cyclooctapyrimidine-2,4-dione
Koh-ichi Seki,* Nobuhiko Kanazashi, and Kazue Ohkura
*Faculty of Pharmaceutical Sciences, Higashi-Nippon-Gakuen University, Ishikari-Tobetsu, Hokkaido 061-0293, Japan
Abstract
The photolysis of 6-chloro-1,3-dimethyluracil in benzene afforded 1,3-dimethyl-6-phenyluracil, while the photoreaction in the presence of trifluoroacetic acid afforded 1,3-dimethylcyclooctapyrimidine-2,4-dione as a major product.
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■ Bridgehead Nitrogen Heterocycles. Part III. Synthesis of Fused Heterocycles from 3-(2,4-Dichlorophenyl)-5-mercapto-1,2,4-s-triazoles
Probin C. Gogoi and Jibon C. S. Kataky*
*Regional Research Laboratory, Jorhat 785 006, Assam, India
Abstract
The condensation reaction of 3-(2,4-dichlorophenyl)-5-mercapto-1,2,4-s-triazole with chloroacetic acid, aromatic aldehydes, oxalyl chloride, dimethyl acetylenedicarboxylate, 1,2-diaminocompounds and 1,2-diketones leading to the formation of fused heterocycles was carried out.
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■ Bridgehead Nitrogen Heterocycles. Part IV. Reactions of 3-Acyl/Aroyl-5-(2,4-dichlorophenyl)-1,3,4-oxadiazol-2(3H)-ones with Diamines
Probin C. Gogoi and Jibon C. S. Kataky*
*Regional Research Laboratory, Jorhat 785 006, Assam, India
Abstract
The condensation reaction of 3-acyl/aroyl-5-(2,4-dichlorophenyl)-1,3,4-oxadiazol-2(3H)-ones (4a-f) with diamino compounds leading to the formation of fused heterocycles (7, 8 and 9) was carried out.
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■ The Synthesis of β-Lactones and β-Lactams from Malonates and Malonamides
Vernon G. S. Box,* Nash Marinovic, and George P. Yiannikouros
*Department of Chemistry, City College of The City University of New York, New York, NY 10031, USA
Abstract
The rhodium diacetate induced insertion reactions of some simple esters and amides of diazomalonic acid result in the formation of β-lactones and β-lactams.
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■ Reaction Mechanism and Structure of New Heterocycles via 1,4-Dipolar Cycloaddition of Imidazo[2,1-b]thiazolium-betaine
Kyung Ho Yoo, Dong Jin Kim, Dong Chan Kim, and Sang Woo Park*
*Division of Chemistry, Korea Institute of Science and Technology, P.O.Box 131, Cheongryang, Seoul 130-650, Korea
Abstract
New heterocycles, (12RS,13SR)- and (12SR,13SR)-12-benzoyl-2,4-dioxo-1,3,9-triphenyl-6,7-dihydro-12H-thiazino[3’,4’; 2,3]imidazo[1,2-a][1,3,5]triazines (4a and 4b), were synthesized via 1,4-dipolar cycloaddition from 5,6-dihydro-3-phenyl-7-[N-phenyl(carbamoyl)]imidazo[2,1-b]thiazolium-betaine (2) by the treatment of phenacyl bomide.
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■ Reaction of N-Benzoyl-4,7-phenanthrolinium Salt with Trimethyl Phosphite and Crystal Structure of Dimethyl N,N’-Dibenzoyl-3,4,7,8-tetrahydro-4,7-phenanthroline-3,8-diphosphonate
Isao Takeuchi, Yoshiki Hamada,* and Zenei Taira
*Faculty of Pharmacy, Meijo University, 150 Yagotoyama, Tenpaku, Nagoya 468-8503, Japan
Abstract
The reaction of 4,7-phenanthroline (1) with some substituted benzoyl chlorides and trimethyl phosphite in the presence of sodium iodide gave the corresponding α,α’-diphosphonates, α,γ’-diphosphonates, α-phosphonates, and γ-phosphonates respectively. 3,8-Diphosphonates (2a1, 2a2) were separated by thin layer chromatography and the crystal structure of 2a2 was determined by X-ray analysis.
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■ Phosphorus Heterocycles. Part I. Synthesis of Thiadiazaphosphol-2-ones and Thiadiazaphophol-2-thiones
Probin C. Gogoi and Jibon C. S. Kataky*
*Regional Research Laboratory, Jorhat 785 006, Assam, India
Abstract
The condensation reaction of 3-(2,4-dichlorophenyl)-4-amino-5-mercapto-1,2,4-triazole with various alkyl dichlorophosphate and alkyl dichlorothiophosphate leading to the formation of fused phosphorus heterocycles was carried out.
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■ Cycloaddition of 1-Methoxy-3-trimethylsilyloxybutadiene with Halogenated Carbonyl Compounds
Akira Sera,* Yasuji Iwasaki, Michio Umeda, and Kuniaki Itoh
*Department of Chemistry, Faculty of Science, Kobe University, Nada-Ku, Kobe 6557-8501, Japan
Abstract
Cycloadditions of 1-methoxy-3-trimethylsilyloxy-1,3-butadiene (1) with halogenated carbonyl compounds (2) yielded corresponding substituted tetrahydro- and/or dihydropyran-4-ones (3 and/or 4). Lewis acids were found to be effective as catalysts. Reactions with less reactive carbonyl compounds (2c,d) afforded p-hydroxyacetophenone (5) produced by cyclodimerization of 1. Stereochemistry of the adducts was deduced by 1H nmr spectroscopy.
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■ Synthesis and E/Z Stereoisomerism of 6-Carbaldoxime Derivatives of Pyrazino[2,3-c]-1,2,6-thiadiazine 2,2-Dioxide
Ibon Alkorta, Pilar Goya,* and Juan Antonio Páez
*Instituto de Química Médica, C. S. I. C., Calle Juan de Cierva, 3, 28006 Madrid, Spain
Abstract
The synthesis of 6-carbaldoxime derivatives of pyrazino[2,3-c]-1,2,6-thiadiazine 2,2-dioxide is reported. Tautomerism and E/Z stereoisomerism are discussed on the basis of uv and nmr spectral data.
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■ Studies on hindered Phenols and Analogues. 4. Formation of 3,9-Dioxabicyclo[4.3.1]decanes and Its Application for Antidiabetic Agents
Yuichi Aizawa, Tsutomu Kanai, Takashi Fujita, Hiroyoshi Horikoshi, and Takao Yoshioka*
*Medicinal Chemistry Research Laboratories, Sankyo Co., Ltd., 1-2-58 Hiromachi, Shinagawa-ku, Tokyo 140-8710, Japan
Abstract
6-Acetoxy-2,5,7,8-tetramethyl-2-phenoxymethylchroman-4-ol (2) gave a couple of dehydration products, the corresponding chromene (3), and a bicyclo compound (4). The product ratios 3/4 changed with the reaction conditions and the substituent of the phenoxymethyl group. The bicyclo compound (4) was confirmed to be given via the chromene (3). Using the bicyclo ring system, a new thiazolidine-2,4-dione (16) was prepared. This compound (16) showed hypoglycemic activity.
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■ Three New Phenolic Metabolites from Penicillium Species
Sheng Lai, Yoshikazu Shizuri, Shosuke Yamamura,* Kazuaki Kawai, and Hideyuki Furukawa
*Department of Chemistry, Faculty of Science and Technology, Keio University, Hiyoshi, Kohoku-ku Yokohama 223-8522, Japan
Abstract
Citreochlorol (7), citreoisocoumarin (9), and citreoisocoumarinol (12) have been isolated from the mycelia of Penicillium citreo-viride B. (IFO 4692), P. citreo-viride B. (IFO 4692) on addition of sodium bromide, and P. citreovirens (IFO 6030), respectively. Citreoisocoumarin was tentatively assigned as 3-(2S-hydroxy-4-oxopentyl)-6,8-dihydroxyisocoumarin and citreoisocoumarinol was identified as 3-(2S,4S-dihydroxypentyl)-6,8-dihydroxyisocoumarin. Both of them are new members of the small group of naturally occurring isocoumarins. The structure of the new phenolic metabolite citreochlorol has also been established on the basis of spectral data analysis.
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■ Biosynthesis of Some Curvularin-Type Metabolites by a Hybrid Strain ME 0005 Derived from Penicillium citreo-viride B. IFO 6200 and 4629
Sheng Lai, Yoshikazu Shizuri, Shosuke Yamamura,* Kazuaki Kawai, Masatake Niwa, and Hideyuki Furukawa
*Department of Chemistry, Faculty of Science and Technology, Keio University, Hiyoshi, Kohoku-ku Yokohama 223-8522, Japan
Abstract
13C Nmr analyses were carried out to deduce the labeling patterns of the curvularin-type metabolites of the hybrid strain ME 0005 derived from [1,2-13C2] acetate, indicating that eight acetate molecules are incorporated into these metabolites. And citreofuran, 12-oxocurvularin, and 11β-hydroxy-12-oxocurvularin are presumably formed from curvularin by enzymatic oxygenation. In addition, the structure of 11β-hydroxy-12-oxocurvularin was also supported by the present experiments.
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■ Reaction of Chloro Derivatives of 10-Benzyl- and 10-(4’-Fluorobenzyl)phenothiazines with Nitriles and Amines under Aryne-forming Conditions
Jennifer L. Self, Subhash P. Khanapure, and Edward R. Biehl*
*Department of Chemistry, Southern Methodist University, P.O. Box 750314, Dallas, TX 75275-0314, U.S.A.
Abstract
2-Chloro-10-benzylphenothiazine (1) and 2-chloro-10-(4’-fluorobenzyl)phenothiazine (2) react with aliphatic nitriles (3 and 4) and LDA to yield typical 2-substituted aryne products (9a,b and 9g,h, respectively). However, treatment of 1 with aromatic nitriles (5-8) and LDA supplies 2-(arylmethyl)-1-cyano rearranged nitriles (10c-f), whereas 2, when treated similarly, affords both rearranged nitriles (10i-l) and typical 2-arylated nitrile products (9i-j). An explanation in terms of the effect of substituents on the competing aryne and tandem addition-rearrangement pathways is presented. The crystal structure of one of the rearranged 1-cyanophenothiazines (10c) was obtained and reveals that the molecule adopts the "extra" conformation in which the 10-benzyl group is in the psuedo axial position. The reaction of 1 and 2 with various lithium amides in the corresponding free amine solvents gives the corresponding 2-aminated products (11) and (12) in excellent yields. Both 1-chloro-10-benzylphenothiazine (18) and 1 supply the same products, 10-benzyl-2-N,N-diisopropylaminophenothiazine (11a), when made to react with LDA in diisopropylamine solvent, indicating that each of these reactions proceeds via the same aryne intermediated, and not through the SRN1 mechanism.
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■ Quinolizidines. XXIX. Preparation of (-)-Dihydrocorynantheol
Masashi Ohba, Takako Ohashi, and Tozo Fujii*
*Faculty of Pharmaceutical Scicences, Kanazawa University, 13-1 Takara-machi, Kanazawa 920-0934, Japan
Abstract
An alternative, total synthesis of the indoloquinolizidine alkaloid (-)-dihydrocorynantheol [(-)-1], adaptable to that on a gram scale preparation, has been achieved via a "lactim ether route". The route started with an initial condensation between the lactim ether [(+)-4] and 3-(chloroacetyl)indole and proceeded through the lactam ketone [(+)-5], oxazolium salt (6), N-substituted lactam [(+)-8], quaternary iminium salt (9), and tetracyclic ester [(-)-11].
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■ Prototropic Tautomerism of Heteroaromatic Compounds
Alan R. Katritzky,* Mati Karelson, and Philip A. Harris
*Department of Chemistry, University of Florida, P. O. Box 117200, Gainesville, FL 32611-7200, U.S.A.
Abstract
This review deals mainly with the prototropic side chain tautomerism of heteroaromatic compounds. Particular reference is made to molecular orbital calculations of equilibrium constants.