HETEROCYCLES

■ Preface

Tetsuji Kametani

*Pharmaceutical Institute, Tohoku University, Aobayama, Sendai 980-8578, Japan

■ Preface

Ronald Breslow

*Department of Chemistry, Columbia University, 3000 Broadway, Mail Code 3114, New York, New York 10027, U.S.A.

■ Preface

Vladimir Prelog

*,

■ Profile and Scientific Contributions of Professor Tetsuo Nozoe

Toshio Mukai*

*Department of Chemistry, Faculty of Science, Tohoku University, Aoba-ku, Ssendai 980-8578, Japan

■ Bibliography

Tetsuo Nozoe*

*Tokyo Research Laboratories, Kao Corporation, 2-1-3 Bunka, Sumida-ku, Tokyo 131-0044, Japan

■ An Organometallic Route to 2,7-Dihydrothiepin-1,1-dioxides

Ihsan U. Khand and Peter L. Pauson*

*Department of Pure and Applied Chemistry, University of Strathclyde, 295 Cathedral Street, Glasgow G1 1XL, U.K.

Abstract

Reaction of divinylsulphone with alkyne-cobalt complexes (RC≡CR’)CO₂(CO)₆ is shown to yield 2,7-dihydrothiepin-1,1-dioxides with the alkyne substituents (R=Ph; R’=H or Ph) in the 4 and 5 positions.

■ Studies on the Synthesis of Bisindole Alkaloids. XV. A Synthesis of Vinamidine (Catharinine)

James P. Kutney,* John Balsevich, and Brian R. Worth

*Department of Chemistry, University of British Colombia, 2063 Main Mall, Vancouver, B.C., Canada

Abstract

Oxidation of 4’-deoxyleurosidine with potassium permanganate provided the first synthesis of the alkaloid vinamidine (catharinine). Similar oxidation of leurosine or 3’,4’-dehydrovinblastine gave 3’-hydroxyvinamidine.

■ Transformations of Isoquinolone-Dichlorocarbene Adduct. Synthesis of 2-Benzazepinones

Hans-Paul Soetens and Upendra K. Pandit*

*Organic Chemistry Laboratory, University of Amsterdam, Nieuwe Achtergracht 129, Amsterdam, The Netherlands

Abstract

N-methylisoquinolone reacts with dichlorocarbene to give an 1:1 adduct which upon treatment with alcohols yields 2-benzazepinone derivatives.

■ Photoinduced Oxirane-clevage of a Conjugated ε,ζ -Epoxydienone

Veronica Scherrer, Hans Richard Wolf, und Oskar Jeger*

*Laboratorium für Organische Chemi der Eidg, Technischen Hochschule, 8092 Zürich, Switzerland

Abstract

On UV. — irradiation the conjugated epoxydienone 2 undergoes oxirane-cleavage by scission of the C,O or C,C-bond and forms the isomeric products 9 - 12. Thus evidence is given that dienones can react via photoinduced β-cleavages. In competition to these processes E/Z-isomerization and dimerization of the dienone moiety of 2 is observed (2 → 14,15 and 2 → 16).

■ The Radical Ions of Tetraphenylthieno[3,4-c]thiophene

Peter Fürderer, Fabian Gerson,* Michael P. Cava, and M. V. Lakshmikantham

*Physikalisch-Chemisches Institut der Universität Basel, Kingelbergstrasse 80,4056 Basel, Switzerland

Abstract

The radical anion and the radical cation of 1,3,4,6-tetraphenylthieno[3,4-c]thiophene have been studied by ESR and ENDO spectroscopy. The coupling constants, ^aH_p ^aH_o»^aH_m, of the phenyl protons in the para-, ortho- and meta-positions, respectively, suggest an angle θ<40° of twist about the bonds linking the phenyl substituents with the thieno[3,4-c]thiophene moiety.

■ A New Synthesis of 1,2,4-Oxadiazoles

Joel Polo* and Yuan L. Chow

*Department of Chemistry, Simon Fraser University, 8888 University Drive, Burnaby B. C. V5A 1S6, Canada

Abstract

Irradiation of N-nitroso-N-acyl-α-amino acids under weakly basic condition led to the formation of substituted 1,2,4-oxadiazoles in competition with slow basic decompositions of nitrosamides. The cyclization was shown to occur from the C-nitroso compound 5 but not from its tautomeric oxime 8.

■ Kinetics of 1,3-Dipolar Cycloaddition Reactions of Aryl - and Diaryldiazomethanes

Rolf Huisgen* and Jochen Geittner

*Institut für Organische Chemie, Universität München, Karlstrasse 23, D-80333 München, Germany

Abstract

The cycloadditions of diazomethane and its aryl derivatives to olefins ore HO(1,3-dipole) — LU(dipolarophile) controlled. Accordingly, electron-attracting substituents in the dipolarophile or electron-releasing substituents in diazomethane accelerate the addition. The log K₂ for the reactions of substituted phenyldiazomethanes with ethyl acrylate and norbornene obey Hammett relations with ρ = -1.5 and -0.8. Substituents influence the rate constants of diphenyldiazomethane less.

■ Solvent Dependence of Cycloaddition Rates of Phenyldiazomethane and Activation Parameters

Jochen Geittner, Rolf Huisgen,* and Hans-Ulrich Reissig

*Institut für Organische Chemie, Universität München, Karlstrasse 23, D-80333 München, Germany

Abstract

The small influence of solvent polarity on the rate constants of phenyldiazomethane additions to ethyl acrylate and norbornene as well as the Eyring activation parameters of diazoalkane cycloadditions are interpreted as evidence for early transition states of these concerted reactions.

■ 7-Azanorbornadiene — 3-Azaquadricyclane

Horst Prinzbach* and Horst Babsch

*Chemusches Laboratorium, Universität Freiburg, Albertstr. 21, D-7800 Freiburg, Germany

Abstract

A synthesis for the C-unsubstituted 7-azanorbornadiene skeleton (9) has been devised. Its transformation to the 3-azaquadricyclane (10) by sensitised photoexcitation is uniform and quantitative. The latter can, without any competition, be thermally isomerised into the N-tosylazepine (11). The clear preference for this [4+2]-cycloreversion reaction via the ylid (17) can be understood on the basis of the kinetic data.

■ ¹⁵N Nuclear Magnetic Resonance Spectroscopy of Some Nitrogen Heterocycles

Kenneth L. Williamson* and John D. Roberts

*Institute Professor of Chemistry, Emeritus and Lecturer, Gates and Grellisn Laboratories of, Chemistry, 164-30, California Institute of Technology , Pasadena, CA 91125, U.S.A.

Abstract

The potential power and utility of ¹⁵N NMR spectroscopy in heterocyclic chemistry is illustrated by the natural-abundance high-resolution ¹⁵N NMR spectra of representative thiadiazoles and related compounds. The ¹⁵N chemical shifts in these compounds were found to range over 250 ppm. The advantages and limitations of the method are discussed.

■ Oxazolines as Activating Groups in Aromatic Substitution. Selective Metalation or Addition to the 4-Position of Pyridine. A New Synthesis of 1,4-Dihydropyridines

A. I. Meyers* and Richard A. Gabel

*Department of Chemistry, Colorado State University, Fort Collins, CO 80523-1872, U.S.A.

Abstract

The use of the oxazoline moiety as an activating group on the 3-position of a pyridine ring has allowed formal electrophilic substitution via metalation-addition and nucleophilic substitution via oxidation of the intermediate 1,4-dihydropyridine.

■ The Reaction of Amides with Diethylthiocarbamoyl Chloride: A New Procedure for the Preparation of Nitriles and Thioamides

Masaru Ogata* and Hiroshi Matsumoto

*Shionogi Research Laboratories, Shionogi & Co. Ltd., Fukushima-ku, Osaka 553-0002, Japan

Abstract

Primary amides reacted with diethylthiocarbamoyl chloride to give their nitriles, and also tertiary amides gave their thioamides smoothly. In the presence of amines, the above reactions yielded the amidines, quinazolines or ureas, according to a variety of amides and amines used.

■ Isomerization of 2,7-Diphenyltropone-2,3-oxide to 1,3-Diphenyl-8-oxabicyclo[3.3.0]octa-3,6-diene-2-one

Takahiro Tezuka,* Miyoshi Shinba, Takaharu Abe, Ryoichi Miyamoto, and Toshio Mukai

*Department of Chemistry, University of Tsukuba, 1-1-1 Ten-nodai, Tsukuba-shi, Ibaraki, 305-8571, Japan

Abstract

2,7-Diphenyltropone-2,3-oxide (1b) isomerizes thermally to its bicyclic isomer (2) probably via ionic intermediate species such as 3, while benzo- and dibenzotropone oxides (8 and 9) are converted to aromatic compounds by thermal reaction. Photochemical reaction of 1b is also reported.

■ Relative Reactivities of 2H-Cyclopenta[d]pyridazine and the 2-Methyl and 2-Phenyl Derivatives to Monochlorination

Arthur G. Anderson, Jr.* and Taran Tober

*Department of Chemistry, University of Washington, Seattle, WA 98195-1700, U.S.A.

Abstract

For electrophilic monochlorination with NCS, competitive reactions of pairs of the title compounds has shown the relative reactivities to be 7.1 : 1.7 : 1 for the 2-methyl, 2-phenyl, and 2-hydrogen compounds, respectively.

■ The Early Stages of Papaver Alkaloid Biosynthesis. Cell-Free Synthesis of Benzykisoquinolines

A. Ian Scott,* Siu-Leung Lee, and Toshifumi Hirata

*Department of Chemistry, Texas A & M University, College Station, Texas 77843-3255, U.S.A.

Abstract

A cell-free system of Papaver somniferum has been isolated, capable of synthesizing norlaudanosoline-1-carboxylic acid, dehydronorlaudanosoline, and norlaudanosoline from 3,4-dihydroxyphenethylamine (dopamine) and 3,4-dihydroxyphenylpyruvic acid. The enzyme activity lies in a Triton X-100 solubilized protein fraction.

■ Semidione Derivatives of Silacycloalkenes

Glen A. Russell,* C. E. Osuch, and W. Chau

*Department of Chemistry, Iowa State University, Ames, Iowa 50011, U.S.A.

Abstract

The structures of 1 (X=CH₂) and 2 (X= Si(CH₃)₂) have been studied by esr spectroscopy from -30 to +100 °C. Ring inversion can be observed for the cis semidiones 2 (n=2,3) and 1 (n=3), but not for 1 with n=2. Trans semidiones are observed for 2 (n=3-5) and 1 (n=4-6), but not for 1 with n=3.

■ A Mechanistic Suggestion for Pummerer Rearrangement of Cyclic β-Keto Sulfoxides. Synthesis of 3-Methoxy-16-thia-D-homoestra-1,3,5(10),8,14-pentaene-17,17a-diols

Tadao Terasawa* and Toshihiko Okada

*Shionogi Research Laboratories, Shionogi & Co. Ltd., Fukushima-ku, Osaka 553-0002, Japan

Abstract

Synthesis of the title compound via Pummerer rearrangement of corresponding β-keto sulfoxides is reported. The mechanism and stereochemistry of the rearrangement are also discussed.

■ Unusual Pummerer Rearrangement of 3-Methoxy-16-thia-D-homoestra-1,3,5(10),8,14-pentaen-17a-ol Sulfoxides

Tadao Terasawa* and Toshihiko Okada

*Shionogi Research Laboratories, Shionogi & Co. Ltd., Fukushima-ku, Osaka 553-0002, Japan

Abstract

The reaction of acetic anhydride with the title steroidal sulfoxides leading to an unusual rearrangement is described.

■ The Oxidative Cyclization of α,β-Unsaturated Ketoximes

Katsuo Kikuchi,* Yuji Maki, Megumi Hayashi, and Noriyuki Murakoshi

*Faculty of Science, Department of Chemistry, Yamagata University

Abstract

The autoxidation of dibenzalacetone oxime in the presence of several kinds of transition metal salts gave 4-hydroxy-5-phenyl-3-styryl-4,5-dihydroisoxazole, accompanied with cinnamonitrile and benzaldehyde. Similar treatment of benzalacetophenone oxime, benzalacetone oxime and their p-substituted derivatives also afforded 4-hydroxy-4,5-dihydroisoxazole derivatives.

■ An Antibiotic SEN-34

Masakuni Ozaki, Yoji Ezure, Takashi Okubo, Kimio Yamane, and Shingo Matsumura*

*Research Laboratories, Nippon Shinyaku Co., Ltd., 14, Nishinosho-Monguchi-cho, kisshoin, Minami-ku, kyoto, 601-8550, Japan

Abstract

Production, isolation and characterization of antibiotic SEN-34 are described.

■ Chemical Transformation of 3’-Chloro-3’-deoxyaminoglycosides into New Cyclic Pseudo-trisaccharides

Tsunehiko Asako,* Kouichi Yoshioka, Hiroshi Mabuchi, and Kentaro Hiraga

*Central Research Division, Takeda Chemical Industries, Ltd., 17-85 Jusohonmachi 2-chome, Yodogawa-ku, Osaka 532-8686, Japan

Abstract

Cyclic pseudo-trisaccharides (2a,b) and 3’-epi-aminoglycosides (4a,b) were obtained from 3’-chloro-3’-deoxyaminoglycosides (1a,b) by treatment with a base.

■ Synthesis of 5-Hydroxy-4,5-dihydro-6H-1,3-thizaine-4,4-dicarboxylate Derivatives

Toshihiko Hashimoto and Tetsuo Miyadera*

*Chemical Research Laboratories and Analytical & Metabolic Research Laboratories, Sankyo Co., Ltd., 1-2-58 Hiromachi, Shinagawa-ku, Tokyo 140-8710, Japan

Abstract

Dihydro-1,3-thiazines, the title compounds (IV-VI), were prepared as possible intermediates for cephalosporin synthesis. The process involves a few steps starting from diethyl aminomalonate (I).

■ Total Synthesis of dl-7-Amino-3-deacetoxycephalosporanic Acid (7-ADCA) Involving a Short Step Synthesis of a 4,5-Dihydro-6H-1,3-thizaine

Toshihiko Hashimoto, Taiichiro Watanabe, Yoichi Kawano, Teruo Tanaka, and Tetsuo Miyadera*

*Chemical Research Laboratories and Analytical & Metabolic Research Laboratories, Sankyo Co., Ltd., 1-2-58 Hiromachi, Shinagawa-ku, Tokyo 140-8710, Japan

Abstract

A 1,3-thiazine, tert-butyl 5-hydroxy-5-methyl-4,5-dihydro-6H-1,3-thiazine-4-carboxylate (VIII) was prepared by a two step process starting from glycine tert-butyl ester (V). Interestingly the thiazine formation proceeded stereoselectively to afford almost exclusively the cis isomer (VIIIa). Utilizing the 1,3-thiazine the title compound (XV) was synthesized by the established synthetic method.

■ Synthetic Purine-Pyrimidine Base Paris. N-(5-Pyrimidinyl)purine-6-carboxamides

Isarael Agranat* and Ayala Barak

*Department of Organic Chemistry, The Hebrew University of Jerusalem, Jerusalem 91904, Israel

Abstract

N-(4-Amino-5-pyrimidinyl)purine-6-carboxamide (I) synthesized by condensation of 4,5-diaminopyrimidine with 6-purinoyl chloride in pyridine or with 6-trichloromethylpurine in buffer citrate. Related purine-pyrimidine pairs of the form Pu-CONH-Py were prepared similarly. The spectral properties of the base pairs suggest a preferred conformation involving hydrogen bonding between the amide hydrogen and the purine N(7).

■ Thiabenzenes X. Possible Roles for Sulfurane Intermediates in “Oligomer” Formation

Charles C. Price* and Joanne Follweiler

*Department of Chemistry, University of Pennsylvania, 231 South 34th Street Philadelphia, PA 19104-6323, U.S.A.

Abstract

We fully confirm the already convincing evidence presented by Mislow et al. that materials we once identified as “stable thiabenzenes” are oligomers (of unknown structure). We present some experimental observations related to the hypothesis that these oligomers may have formed from reaction of a thiabenzene with phenyllithium through sulfurane-type intermediates.