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. 12, No. 9, 1979
Published online:
■ β-Carboline Derivatives from an Aminoacetaldehyde Dimethylacetal
Kenneth Curness and Stanley Dyke*
*School of Chemistry, University of Bath, Bath, Avon. BA2 7AY, U.K.
Abstract
Cyclisation of the acetal (3) with dilute HCl gave the hydroxy-β-carboline (8), and not the hydroxy-γ-carboline (4), as previously reported.
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■ Chemical Precedence for Reduction of the “Exocyclic Methylene” Intermediate in a Tetrahydroquinoxalyl Model of Thymidylate (TMP) Synthetase
Ronald Plemp and Upendra K. Pandit*
*Laboratory of Organic Chemistry, University of Amsterdam, Nieuwe Achtergracht 129,1018 WS Amsterdam, The Netherlands
Abstract
1,2,3,4-Tetrahydro-1-(thyminyl)quinoxaline undergoes thermal conversion to thymine and tetrahydroquinoxaline. The formation of thymine has been shown to involve an intermolecular hydrogen transfer to an exocyclic methylene intermediate analogous the one proposed in the TMP synthetase reaction.
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■ The Bromination of 2,3-Dimethylindole
Gary I. Dmitrienko*
*Guelph-Waterloo Centre for Graduate Work in Chemistry, University of Waterloo, Waterloo, Ontario, N2L 3G1, Canada
Abstract
The product of bromination-hydrolysis of 2,3-dimethylindole, previously reported to be 3-hydroxymethyl-2-methylindole, has now been shown to be the known dimer of 2,3-dimethyl-3-hydroxyindolenine. A mechanistic interpretation of this result is presented and a simple preparation of 3-methoxyindolenines is described.
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■ Stereoselective Olefin Cyclisations of tert-α-Acyliminium Ions
J. Dijkink and W. N. Speckamp*
*Organic Chemistry Laboratory, University of Amsterdam, Nieuwe Achtergracht 129, 1018 WS Amsterdam, The Netherlands
Abstract
Tert α-acyliminium ions are shown to exhibit excellent properties for inducing stereoselective olefin cyclisations. Starting from the appropriate alkene precursor bicyclic and tetracyclic ring systems are formed in good to excellent yields.
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■ Strained Cyclic Acetylenes, VII. Addition of Sulfur and Pyridine-N-oxide to Seven Membered Cycloalkynes
Adolf Krebs,* Horst Colberg, Ulrich Höpfner, Horst Kimling, and Johannes Odenthal
*Institute of Organic Chemistry and Biochemistry, University of Hamburg, Martin-Luther-King-Platz 6, D-2000 Hamburg 13, Germany
Abstract
The first isolable dialkyl dithietes, 3 and 4, which are not stabilized by strongly electron withdrawing substituents, have been prepared from sulfur and the seven membered cycloalkynes, 1 and 2, respectively. The first 2H-azepine, 9, has been synthesized by reaction of 1 with pyridine-N-oxide, and its structure has been determined by an X-ray analysis. It rearranges on heating to the pyridine derivative 11.
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■ Synthesis of s-Triazolo[1,5-a]pyridine 1-Oxides
Alenka Tomazic, Miha Tisler, and Branko Stanovnik*
*Department of Chemistry, University of Ljubljana, 61000 Ljubljana, Slovakia
Abstract
The preparation of several hydroxylaminopyridines is described. From 1-amino-2-hydroxyimino-1,2-dihydropyridine (8) s-triazolo[1,5-a]pyridine 1-oxides (9) were synthesized and from 3-hydroxylamino-6-chloropyridazine (11) an imidazo[1,2-b]pyridazine 1-oxide derivative (12) was prepared.
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■ Regioselective Synthesis of Naphthacenequinones Using Sulfolene
Seiichi Takano,* Susumi Hatakeyama, Kunio Ogasawara, and Tetsuji Kametani
*Pharmaceutical Institute, Tohoku University, Aobayama, Sendai 980-8578, Japan
Abstract
Starting with naphthazarin diacetate (2) and sulfolene (3), naphthacenequinones, (14) and (15), have been synthesized regioselectively.
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■ A Novel One-step Synthesis of 3-Substituted 5,6-Dihydrothiazolo[2,3-c]-1,2,4-triazoles and -6,7-Dihydro-5H-1,2,4-triazolo[3,4-b][1,3]thiazines
L. G. Payne, M. T. Wu,* and A. A. Patchett
*Department of Process Reseach, Merck Research Laboratories, Division of Merck & Co., Inc., P. O. Box 200,0, Rahway, New Jersey 07065, U.S.A.
Abstract
3-Substituted-5,6-dihydrothiazolo[2,3-c]-1,2,4-triazoles and -6,7-dihydro-5H-1,2,4-triazolo[3,4-b][1,3]-thiazines have been synthesized in one step by reaction of the acid hydrazides with haloalkyl isothiocyanates.
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■ Photocycloaddition of Uracils with Dimethyl Acetylenedicarboxylate
Tsuneo Itoh,* Haruo Ogura, Norio Kawahara, and Kyoichi A. Watanabe
*School of Pharmaceutical Sciences, Kitasato University, 5-9-1, Shirokane, Minato-ku, Tokyo 108-8641, Japan
Abstract
Photocycloaddition of dimethyl acetylenedicarboxylate (DMAD) with 1,3-dimethyl uracils gave new 2 + 2 + 2 cycloaddition products which contain a bicyclo[2.2.0]hexane system in the molecule.
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■ Preparation and Base-catalyzed Rearrangement of Thioxanthenium Biscarbomethoxymethylides
Yasumitsu Tamura,* Chisato Mukai, and Masazumi Ikeda
*Faculty of Pharmaceutical Sciences, Osaka University, 1-6 Yamadaoka, Toyonaka, Osaka 560-0043, Japan
Abstract
Thioxanthenium biscarbomethoxymethylide and its trans-9-methyl derivative were prepared by thermal reaction of the corresponding thioxanthenes with dimethyl diazomalonate in the presence of copper sulfate. These sulfonium ylides underwent base-catalyzed rearrangement to the corresponding 9-(biscarbomethoxymethyl)thioxanthenes.
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■ The Facile Synthsis of an Important Key Intermediate for the Synthesis of (±)-8S*-Thienamycin — A Formal Total Synthesis of (±)-8S*-Thienamycin
Tetsuji Kametani,* Shyh-Pyng Huang, and Masataka Ihara
*Pharmaceutical Institute, Tohoku University, Aobayama, Sendai 980-8578, Japan
Abstract
8S*-Isomer of the potent antibiotic thienamycin (1) was formally synthesized in short steps via trans-4-methoxycarbonyl-3-(2’,2’-dimethoxyethyl)-5-methylisoxazoline (5).
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■ Total Synthesis of (±)-8S*-Descysteaminylthienamycin Protected woth o-Nitrobenzyl Groups
Tetsuji Kametani,* Shyh-Pyng Huang, and Masataka Ihara
*Pharmaceutical Institute, Tohoku University, Aobayama, Sendai 980-8578, Japan
Abstract
(±)-trans-4-(2’,2’-Dimethoxyethyl)-3-(1’S*-hydroxyethyl)-2-azetidinone (4), prepared from an isoxazoline derivative (3), was converted to (±)-8S*-descysteaminylthienamycin protected with o-nitrobenzyl groups (8) using an intramolecular Wittig reaction.
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■ A Novel Synthetic Scheme for 2-Ethylthioisonicotinamide
Cheng-Hsia Wang,* Fang-Yu Hwang, Jhy-Ming Horng, and Chao-Tung Chen
*Department of Chemistry, National Taiwan Normal University, 88, Sec. 4, Tingchow Road, Taipei, 116, Taiwan, R.O.C.
Abstract
4-Picoline was converted to 4-cyanopyridine by ammoxidation in 98% yield. The latter was ethylated by radicals generated from silver nitrate catalyzed oxidative decarboxylation of propionic acid to form 2-ethyl-4-cyanopyridine, which was treated with ammonium sulfide to give 2-ethylthioisonicotinamide. A setup for laboratory ammoxidation was designed. Pyridine was alkylated with decarboxylating acetic, propionic, n-butanoic, isobutyric, and n-pentanoic acids to form the corresponding 2- and 4-alkylpyridines. 4-Cyanopyridine was also alkylated similarly to obtain 2-alkyl- and 2,6-dialkyl-4-cyanopyridines.
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■ Heterocycles from Chlorosulfonyl Isocyanate II. Reaction with Isothioureas
Sandor Karady,* Joseph S. Amato, Daniel Dortmund, Arthur A. Patchett, Robert A. Reamer, Roger J. Tull, and Leonard M. Weinstock
*Department of Process Reseach, Merck Research Laboratories , Division of Merck & Co., Inc., P. O. Box 200,0, Rahway, New Jersey 07065, U.S.A.
Abstract
2-Aminothiazoline and open chain isothioureas react with CSI to afford substituted thiatriazenes. The structure proof of these compounds is the subject of this paper.
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■ The Reaction of 3-Hydroxycoumarins with Chalcone
V. K. Ahluwalia,* K. Bhat, and Chandra Prakash
*Department of Chemistry, University of Delhi, Delhi-110 007, India
Abstract
The reaction of 3-hydroxycoumarins with chalcone in presence of pyridine-piperidine afforded 2-hydroxy-2,4-diphenyl-10-oxo-3,4-dihydropyrano (2,3-c) (1) benzopyrans. The structures have been established spectroscopically.
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■ 1,10-Phenanthroline and Its Complexes
Wanda Sliwa*
*Institute of Organic and Physical Chemistry, Politechnical University, 30-370 Wroclaw, Poland
Abstract
The literature concerning 1,10-phenanthroline and its complexes has been reviewed with respect to their reactivity and properties.