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. 23, No. 3, 1985
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■ High-pressure Synthesis of Cryptands with Aliphatic Bridging Units
Marek Pietraszkiewicz, Piotr Salanski, and Janusz Jurczak*
*Institute of Organic Chemistry, Polish Academy of Sciences, ul. Kasprzaka 44/52, P.O.Box 58, PL-01-224 Warszawa 42, Poland
Abstract
N,N’-Dimethyl diazacoronands react with α,ω-diiodoalkanes under high pressure (10 kbar) to give the bis-quaternary salts which are transformed into cryptands via demethylation with triphenylphosphine.
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■ An Aromatic Version of Claisen Rearrangements of Ester Silyl Enolates — A Facile Synthesis of 2,3-Disubstituted Furans
Hideo Nomoto, Eiki Shitara, Keiichiro Fukumoto,* and Tetsuji Kametani
*Pharmaceutical Institute, Tohoku University, Aobayama, Sendai 980-8578, Japan
Abstract
The [3,3]sigmatropic rearrangement of furfuryl ester silyl enolates (4)~(6) was studied and found to proceed under very mild conditions to give the carboxylic acids (13)~(15) after acid treatment.
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■ Synthesis of Substituted Tetrahydrofurans and Tetrahydropyrans 1. Oxidative Cyclization of p-Methoxystyrene Derivatives with DDQ
Yuji Oikawa, Kiyoshi Horita, and Osamu Yonemitsu*
*Faculty of Pharmaceutical Sciences, Hokkaido University, Kita 12 Nishi 6, Kita-ku, Sapporo, Hokkaido 060-0812, Japan
Abstract
In the course of synthetic studies of polyether antibiotics, we tried to develop a new synthetic method of substituted tetrahydrofuran and tetrahydropyran rings. When p-methoxystyrene derivatives having a hydroxy group at a suitable position was treated with DDQ, an oxidative cyclization of E-olefins, not Z-olefins, occurred yielding substituted tetrahydrofurans and tetrahydropyrans, though in low yields.
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■ Studies on Indenopyridine Derivatives and Related Compounds. IV. Synthesis and Stereochemistry of Ethyl 9,9-Dimethyl-1,2,3,9a-tetrahydro-9H-indezo[2,1-b]pyridine-3-carboxylate and Its Derivatives
Ryuji Yoneda, Tatsuya Terada, Shinya Harusawa, and Takushi Kurihara*
*Faculty of Pharmaceutical Science, Osaka University of Pharmaceutical Sciences, 4-20-1 Nasahara, Takatsuki, Osaka 569-1094, Japan
Abstract
The simplified analogs of lysergic acid, namely ; 4-diethylphosphoryl or 3-methyl derivatives (15a, 15b, and 22) of ethyl 1,9,9-trimethyl-1,2,3,9a-tetrahydro-9H-indeno[2,1-b]pyridine-3-carboxylate are synthesized. The structure and stereochemistry of these products as well as some intermediates are also discussed.
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■ A Novel Stereoselective Synthesis of Morphinan Skeleton
Tetsuji Kametani,* Yukio Suzuki, and Toshio Honda
*Hoshi University, 2-4-41 Ebara, Shinagawa-ku, Tokyo 142-8501, Japan
Abstract
A basic skeleton of morphinan alkaloids was stereoselectively synthesized by employing a thermolysis of a benzocyclobutene derivative.
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■ A Modified Synthesis of the (+)-8α-phenylsulfonyl-des-AB-cholestane via an Intramolecular Nucleophilic Attack to Epoxide — A Total Synthesis of Vitamine D3
Hideo Nomoto, Hiroshi Kurobe, Keiichiro Fukumoto,* and Tetsuji Kametani
*Pharmaceutical Institute, Tohoku University, Aobayama, Sendai 980-8578, Japan
Abstract
An intramolecular alkylation of the phenylsulfonyl epoxide (6), which was readily obtained from the aldehyde (5), gave a separable mixture of the alcohols (7a) and (8a). The alcohol (8a) was then dehydrated via the corresponding mesylate (8b) to afford the olefin (9) which on hydrogenation furnished (+)-8α-phenylsulfonyl-des-AB-cholestane (1). Further this product was converted into vitamin D3 (4).
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■ The 5-Alkoxymethyl-, 5-Alkylthiomethyl-, and 5-Dialkylaminomethylisoxazoles
Ronald G. Micetich,* Chia C. Shaw, Tse W. Hall, Paul Spevak, Robert A. Fortier, Peter Wolfert, Brian C. Foster, and Buljit K. Bains
*Faculty of Pharmacy , University of Alberta, Edmonton, Alberta T6G, 2N8, Canada
Abstract
A variety of methods were used for the preparation of the 5-alkoxymethyl-, 5-alkylthiomethyl-, and 5-dialkylaminomethylisoxazoles. A novel method for the separation of the isomeric mixture of 3-(5-)methoxymethyl-5-(3-)methylisoxazoles (obtained by reaction of 1-methoxypentane-1,3-dione with hydroxylamine), based on the difference in reactivity with n-butyllithium, is described. Methods for the preparation of 5-alkylthimethylisoxazoles from the 5-methylisoxazoles; and 5-alkoxymethylisoxazoles from the 5-hydroxymethylisoxazoles are also reported.
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■ Lithiation Reactions of 5-Alkoxymethyl-, 5-Alkylthiomethyl-, and 5-Dialkylaminomethylisoxazoles
Ronald G. Micetich,* Chia C. Shaw. Tse W. Hall, Paul Spevak, and Buljit K. Bains
*Faculty of Pharmacy , University of Alberta, Edmonton, Alberta T6G, 2N8, Canada
Abstract
The 5-alkoxymethyl- and 5-alkylthiomethylisoxazoles undergo exclusive lateral lithiation at the C-5 methylene, the products reacting separately with methyl iodide, dimethyl disulfide, and carbon dioxide to give after work up the respective 5α-alkoxyethyl, 5α-alkylthioethyl , the mixed acetal, the thioacetal, the α-alkoxy acid and the α-thioalkoxy acid of the isoxazoles. This reaction can be repeated to give the mixed ortho ester, the thio ortho ester, the mixed α-ketal acid, and the mixed-thioketal acid. This method provides a very convenient route to these classes of compounds. The 5-dialkylaminomethylisoxazole is lithiated at the C-4 position.
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■ On the Synthesis of (±)-Mesembranone by the Dissolving Metal Reduction of 4-Aryl-4-aminoethylcyclohexenones. Isolation of N-Methyl-5-(3’,4’-dimethoxyphenyl)-2-azabiocyclo[3.3.1]nonan-8-one
Ignacio H. Sánchez,* María Larraza, Humbert J. Flores, Eduardo Díaz, and Krzysztof Jankowski
*Facultad de Química, Universidad Nacional Autónama de México, Circuito Exterior, Ciudad Universitaria, Coyoacán 04510, Mexico
Abstract
The novel 2-azabicyclo[3.3.1]nonan-8-one derivative 4 has been isolated as byproduct in the synthesis of (±)-mesembranone (2) by the dissolving metal reduction of the 4-aryl-4-aminoethylcyclohexenone 1.
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■ Reaction of 4-Bromoalkyl-4-methoxy-2,5-oxazolidione with Alcohol or α-Amino Acid Ester and Transformation of the Products
Chung-gi Shin,* Naoyuki Takamatsu, Yoshiaki Sato, and Yasuchika Yonezawa
*Departmnet of Applied Chemistry, Faculty of Engineering, Kanagawa University, 3-27-1 Rokkakubashi, Kanagawa-ku, Yokohama 221-8686, Japan
Abstract
Reaction of N-carboxy α-dehydroamino acid anhydride with methanol in the presence of NBS gave 4-bromoalkyl-4-methoxy-2,5-oxazolidione, which was further treated with alcohol or α-amino acid ester to give extremely different two types of products, 2-oxazolinone and α-(oximino)acyl-α-amino acid derivatives respectively.
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■ The Synthesis and Aminolysis of Some 4-Chloro-2-(substituted) Thiopyrimidines
Derek T. Hurst* and Matthew Johnson
*School of Analytical and Biological Chemistry, Kingston Polytechnic, Kingston-on-Thames, KT1 2EE, U.K.
Abstract
Some 2-methylthio,2-methylsulphinyl and 2-methylsulphonyl-4-chloropyrimidines have been prepared. In each case which was studied except one the chloride ion was that which was preferentially displaced by diethylamine. The pseudo first order rate constant for each reaction was determined the results showing that oxidation of the 2-methylthio group greatly enhances the rate of displacement of the 4-chloro group.
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■ Isolation and Structure of a New Alkaloid from the Roots of Rauwolfia Serpentina Benth
Salimuzzaman Siddiqui,* S. Salman Ahmad, S. Imtiaz Haider, and Bina Shaheen Siddiqui
*H. E. J. Postgraduate Institute of Chemistry, University of Karachi, Karachi-75270, Pakistan
Abstract
A new dihydroindole alkaloid sandwicoline has been isolated from undried winter roots of Rauwolfia serpentina of Nepalies origin and its structure detemined as 21-monohydro-N-methylsandwicine through chemical and spectral studies.
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■ A Study of the Preparation and Reactions of the Unusually Labile 5-Methyl[1,2,4]oxadiazolo[2,3-c]quinazolin-2-one
Darshan Ranganathan,* Shakti Bamezai, and P. Veeraraghavan Ramachandran
*Department of Chemistry, Indian Institute of Technology, Kanpur 208016, India
Abstract
A Π2s + Π2s + ω2s cycloaddition of 4-isocyanato-2-methyl quinazoline 3-oxide leads to the title compound, 5-methyl[1,2,4]oxadiazolo[2,3-c]quinazolin-2-one (1) . Surprisingly, the weakest bond in 1 is 4-5. Rupture of this bond takes place thermally as well as with P(OR)3 leading to the isomeric, 5-methyl[1,2,4]oxadiazolo[3,4-c]quinazolin-3-one (11). A detailed thermolytic study of 1 has given products arising from scission of the bonds 2-3, 3-4 and 4-5. The 3-4 bond is preferentially broken on photolysis of 1 in MeOH.
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■ Synthesis of α-Hydroxydimethylacetals from Nitrogen Heterocyclic Ketones Using Hypervalent Iodine Oxidation
Robert M. Moriarty,* Om Prakash, Cyriac T. Thachet, and Hikmat A. Musallam
*Department of Chemistry, University of Illinois at Chicago, 845 West Taylor St., Chicago, IL 60607-7061, U.S.A.
Abstract
The synthesis of various α-hydroxydimethylacetals (2a-2j) has been achieved by the oxidation of nitrogen containing heterocyclic ketones (1a-1j) using C6H5I(OAc)2-KOH-MeOH . The nmr and mass spectra of the acetals are discussed.
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■ Pyrazolo[5,1-c]-1,2,4-tiazoles from 1,2,4-Triazolium Salts and Substituted Acetonitriles
Pedro Molina,* Mateo Alajarín, and María-Jesús Vilaplana
*Departmento de Química Orgánica, Facultad de Ciencias, Universidad de Murcia, 30071 Murcia, Spain
Abstract
3-Substituted 4-amino-1-methyl-5-methylthio-1,2,4-triazolium salts react with acetonitriles activated by another electron-delocalizing group to give enamines which undergo cyclization by action of hydrogen chloride to give pyrazolo[5,1-c]-1,2,4-triazole derivatives.
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■ Reactivity of Cyanodithioformate towards Primary Amiens
Carmen de Diego, Encarnación Gómez, and Carmen Avendaño*
*Departamento de Química Orgánica y Farmacéutica, Facultad de Farmacia, Universidad Complutense de Madrid, Ciudad Universitaria, 28040 Madrid, Spain
Abstract
The two electrophilic carbon atoms of methyl cyanodithioformate 1 are able to react with primary amines giving a variety of different products depending upon the nature of amines. The one step reaction with o-dinucleophiles giving condensed heterocompounds in moderate to good yields is of interest.
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■ A New Route to Hexahydropyrrolizines Derivatives via Nonstabilized Ylide Generated from N-Methylpyrrolidine N-Oxide
Jacqueline Chastanet and Georges Roussi*
*Institut des Chimie des Substances Naturelles, C.N.R.S., 1 avenue de la Terrasse, Bat. 27, 91198 Gif-sur-Yvette Cedex, France
Abstract
N-Methylpyrrolidine N-oxide treated with lithium diisopropylamide in the presence of various olefins, leads to the corresponding hexahydropyrrolizines(6) via the ylide intermediate (5).
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■ Synthesis of (±)-Gaddain, a New Lignan from Jatropha gossypifolia Linn (Euphorbiaceae)
Julie Banerji* and Biswanath Das
*Chemistry Department, University College of Science, 92 Acharya Prafulla Chandra Road, Calcutta-700009, India
Abstract
(±)-Gadain, a new lignan isolated from Jatropha gossypifolia, has been synthesised by the condensation of 3-(3,4-methylenedioxybenzyl)-butyrolactone with piperonal in the presence of sodium methoxide in methanol. The key intermediate lactone was prepared by the Stobbe condensation of piperonal with dimethyl succinate followed by hydrogenation to the butanoic acid derivative and the reduction of the potassium salt of butanoic acid with calcium borohydride.
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■ Cyclopentenone from Furan: An Unususal Marckwald Reaction
Giovanni Piancatelli* and Enzo Castagnino
*del C. N. R., c/o Istituto do Chimica Organica, Università degli Studi di Roma "La Sapienza", Piazzale Aldo Moro 2 - 00185 Roma, Italy
Abstract
A “one pot” conversion of methyl furfurylidenepyruvate 5 directly to the cyclopentenone 8, by means of the Marckwald reaction, is described.
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■ Synthesis of Vinca Alkaloids and Related Compounds. XXIII. Transposition of Functionality on the Indolo-quinolixidine Seleton
Mária Incze, Ferenc Sóti, Zsuzsa Kardos-Bologh, Mária Kajtár-Peredy, and Csaba Szántay*
*Central Research Institute for Chemistry, Hungarian Academy of Sciences, H-1025 Budapest, Pusztaszeri ut 59-67, P.O.Box 17, Hungary
Abstract
Bromination and subsequent reactions with nucleophiles of a substituted indolo[2,3-a]quinolizidine derivative yielded instead of the expected indolenine derivatives 7-substituted indolo[2,3-a]quinolizidines.
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■ New Synthesis of Functionalized β-Lactams from Azabutadiene Analogues and Ester Enolates
Mitsuo Komatsu, Shinji Yamamoto, Yoshiki Ohshiro,* and Toshio Agawa
*Department of Applied Chemistry, Faculty of Engineering, Osaka University, 2-1 Yamadaoka, Toyonaka, Osaka 560-0043, Japan
Abstract
Reaction of the 2-azabutadiene 1 with α-lithioesters 2a,b gave N-styryl-2-azetidinones 3a,b in high yields in contrast to the δ-lactam formation of 1-azadienes with 2. The azines 7a,b also reacted with the enolate 2a to result in β-lactam formation: N-alkylidenamino-2-azetidinones 8a,b and/or 1,1’-bi(2-azetidinone)s 9a,b were obtained in good yields.
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■ 4-Nitro- and 4-Cyanopyridazines
Antonius T. M. Marcelis and Henk C. van der Plas*
*Laboratory of Organic Chemistry, Agricultural University, De Dreijen 5, 6703 BC Wageningen, The Netherlands
Abstract
3-Acyl-1,2,4,5-tetrazines react with 1-nitro-2-dimethylaminoethene and 1-cyano-2-morpholinoethene by an inverse electron demand Diels-Alder reaction to give, after elimination of nitrogen and the secondary amine, the corresponding 3-aryl-5-nitro- and 3-aryl-5-cyanopyridazines. Besides these compounds, 1-benzylidene-2-dialkylaminomethylenehydrazines were isolated. They are also obtained from reaction of the 3-aryl-1,2,4,5-tetrazines with secondary aliphatic amines. Tetrazines with two electron-withdrawing groups like 3,6-bis(2-pyridyl)-1,2,4,5-tetrazine, 3,6-bis(4-pyridyl)-1,2,4,5-tetrazine and 3,6-bis(piperidinocarbonyl)-1,2,4,5-tetrazine also react with the nitro- or cyanoenamine to give the corresponding 3,6-disubstituted 4-nitro- or 4-cyanopyridazines.
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■ D-Ribonolactone in Organic Synthesis — A Review
Krishna L. Bhat, Shin-Yih Chen, and Madeleine M. Joullié*
*Department of Chemistry, University of Pennsylvania, 231 South 34th Street Philadelphia, PA 19104-6323, U.S.A.
Abstract
The use of D-ribonolactone, on inexpensive, commercialiy available sugar, as a chiral template in organic synthesis is described. The versatility of this compound is illustrated with selected examples from the literature. The regio- and stereoselective functionalizaotion of D-ribonolactone and its use in the synthesis of precursors for many natural products demonstrate that D-ribonolactone is a valuable alternative to other sugars.
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■ Ring Annelations via Reissert Compounds
Frank D. Popp* and Barrie C. Uff
*Department of Chemistry, University of Wisconsin-Milwaukee, Milwaukee, Wisconsin 53201, U.S.A.
Abstract
Conversion of isoquinoline and related heterocycles to the corresponding Reissert compound provides a starting point for the annelation of an additional ring. This has proved an attractive route to a wide range of ring systems. The review discusses the versatility of such procedures which include cycloaddition of cyclic Reissert salts with alkynes, addition of Reissert compound conjugate bases to suitable Michael acceptors, intramolecular cyclisations of Reissert compounds derived from chloroalkyl-substituted acid chlorides, the reaction of conjugate bases of chloroformate derived Reissert compound analogs with suitable electrophiles including heterocumulenes, and other methods. Annelations are exemplified with a variety of heterocycles in addition to isoquinoline and quinoline, including phthalazine, phenanthridine and 3,4-dihydro-β-carboline.