HETEROCYCLES

■ Spiropenicillins. Synthesis of a New Spiro(1,2,4-triazino)-3,6’-penicillin

Piero Bellani, Paolo Ventura, and Giorgio Pifferi*

*Laboratories for Biomedical Research, ISF, Trezzano s/N, Milan, Italy

Abstract

Acylalion of 6β-amino-6α-methoxypenicillanate (3) with the α-hydrazinoacid chloride (2), afforded the new spirotriazinopenicillin (1a). This unusual ring formation might proceed via an acylimino intermediate.

■ Acid Catalysed Cyclodehydration versus Sulphur Extrusion of 2-(4-Quinazolinylthio)ketones

Harjit Singh,* Chander S. Gandhi, and Mohinder S. Bal

*Department of Chemistry, Guru Nanak Dev University, Amritsar -143 005, Punjab, India

Abstract

2-(4-Quinazolinylthio)ketones on keeping in minimum amount of sulphuric acid provide only 2-(4(3H)quinazolinylidene)ketones but in an excess of the acid, thiazolo[3,2-c]quinazolin-4-ium cations are also formed.

■ Synthesis of 1,5-Benzodiazepines

Atsuyuki Ushirogochi, Yoshinori Tominaga, Yoshiro Matsuda, and Goro Kobayashi*

*Faculty of Pharmaceutical Sciences, Nagasaki University, 1-14, Bunkyo-machi, Nagasaki 852-8521, Japan

Abstract

Reaction of α-oxoketene S,S-acetals (1a, b, c, d) with o-phenylenediamines gave the corresponding 1,5-benzodiazepines, 8-substituted 4-aryl-2-methylthio-3H-1,5-benzodiazepines (3a, b, c, d, e) in good yields. 2-Amino-4-aryl-8-nitro-3H-1,5-benzodiazepines (5a, b, c) were prepared by the displacement of methylthio group on compound 3b with amines (benzylamine, morpholine, 1-methylpiperazine).

■ Total Synthesis of Pseudo Type Protopine Alkaloids

Kazuhiko Orito,* Shigekazu Kudoh, Kinji Yamada, and Mitsuomi Itoh

*Division of Molecular Chemistry, Graduate School of Engineering, Hokkaido University, Kita 13 Nishi 8, Kita-ku, Sapporo, Hokkaido 060-0828, Japan

Abstract

Photolysis of the chloroacetamides (1) gave the benzazepinones (2), whose benzyl derivatives (3) were cyclized to the benz[d]indeno[1,2-b]azepines (4) by treatment with phosphoryl chloride. Dye-sensitized photo-oxygenation of 4, followed by lithium aluminum hydride reduction and manganese dioxide oxidation of the products 5, led to a total synthesis of pseudoprotopine (7a) and fagarine II (7b) as well as their analogs 7c and 7d.

■ Some Novel Reactions of Benzoxazole Derivatives with Dimethyl Acetylenedicarboxylate

Norio Kawahara,* Michiko Katsuyama, Tsuneo Itoh, and Haruo Ogura

*Hokkaido College of Pharmacy, 7-1 Katsuraoka-cho, Otaru 047-02, Japan

Abstract

Benzoxazole derivatives (1) and dimethyl acetylenedicarboxylate (DMAD) gave novel tricyclic compound (6) through the [2+4] cycloaddition of 3 and DMAD together with a solvent addition product (4) and a ring-opened compound (5) in alcoholic solvent at room temperature.

■ Reexamination of the Reaction of Pyridine 1-Oxide with Phenyl Isocyanate. The Isolation of 2,3-Dihydropyridine Intermediate and the Study on the Reaction Course

Takuzo Hisano,* Toshikazu Matsuoka, Masataka Ichikawa, and Masatomo Hamana*

*Faculty of Pharmaceutical Sciences, Kumamoto University, 5-1 Oe-hon-machi, Kumamoto 862-0973, Japan

Abstract

A 2,3-dihydropyridine (4a) was isolated from the reaction of pyridine 1-oxide (1a) with phenyl isocyanate (2) at 90° in DMF. Heating 4a at 110° in DMF gave 2-anilinopyridine (5a). The time course studies on the reactions of 1a and 2 demonstrated that the initially formed 1,2-dihydropyridine (3a) immediately rearranged to 4a, and 5a was formed not from 3a but from 4a.

■ The Total Synthesis of Diacetyloxodenudatine

Sat Paul Sethi, Roman Sterzycki, Wing Wah Sy, Rinaldo Marini-Bettolo, Thomas Y. R. Tsai, and Karel Wiesner*

*Natural Products Research Center, Department of Chemistry, University of New Brunswick, Bag Service #45222, Fredericton, New Brunswick, E3b 5A3, Canada

Abstract

The total synthesis of racemic diacetyloxodenudatine (2) is described. Treatment of this material with LiAlH₄ in dioxane at reflux caused the reduction of not only the lactam but also the exocyclic double bond and yielded racemic dihydrodenudatine (23).

■ Syntheses and Reactions of Cyclopentadienones Possessing Five-membered Heterocycles as Substituents

Yoshiro Yamashita and Mituo Masumura*

*Department of Applied Chemistry, Faculty of Engineering, University of Tokushima, Minamijosanjima-cho, Tokushima 770-8506, Japan

Abstract

The syntheses and reactions of 3,4-di(2-furyl)-2,5-dimethylcyclopentadienone (1a) and 2,5-dimethyl-3,4-di(2-thienyl)-cyclopentadienone (1b) are described. They exist as dimers 3a,b at room temperature, while upon heating in solvents, the dimers become monomeric and undergo the Diels-Alder reaction with olefins.

■ Rapid Rearrangement of Quaternized Oxazoles and Thiazoles through Base Treatment

Hans-Jürgen Federsel* and Jan Bergman

*Department of Organic Chemistry, Royal Institute of Technology, SE-100 44 Stockholm, Sweden

Abstract

Isolation and structure elucidation of some new compounds obtained through the base-induced rearrangement of oxazolium and thiazolium compounds.

■ The Reaction of Heteroaromatic Amine Oxides with TiCl₄/NaBH₄

Shinzo Kano,* Yasuyuki Tanaka, and Satoshi Hibino

*School of Pharmacy, Tokyo University of Pharmacy and Life Science, 1432-1 Horinouchi, Hachioji, Tokyo 192-0392, Japan

Abstract

Treatment of 2-, 3-, 4-picoline N-oxides and 2,6-dimethylpyridine N-oxide with TiCl₄ /NaBH₄ in dimethoxyethane afforded the corresponding picolines and 2,6-dimethylpyridine in acceptable yields. The same reaction of quinaldine N-oxide and benzo[h]quinoline N-oxide successfully gave quinaldine and benzo[h]quinoline, respectively. In the case of quinoline N-oxide, 1,2,3,4-tetrahydroquinoline and quinoline were obtained. On the other hand, lepidine N-oxide and isoquinoline N-oxide afforded the corresponding 1,2-dihydro derivatives. Similarly, papaverine N-oxide gave 1,2-dihydropapaverine as a major product accompanying with papaverine.

■ A Synthesis of (±)-Laevigatin

Shinzo Kano,* Tsutomu Ebata, and Shiroshi Shibuya

*School of Pharmacy, Tokyo University of Pharmacy and Life Science, 1432-1 Horinouchi, Hachioji, Tokyo 192-0392, Japan

Abstract

Reduction of α-anilinomethyl-1,2-butenolides with diisobutylaluminium hydride yielded the corresponding 3-anilinomethylfurans. Hydrogenolysis of 3-anilinomethyl-5,6,7,8-tetrahydro-7-methylbenzo[b]furan over 10 % Pd-C afforded (±)-menthofuran. This synthetic way leading to 3-methylfuran derivatives was applied to a synthesis of (±)-laevigatin starting from 4,7-dimethyl-1-tetralone.

■ Syntheses of Methyl 3-Alkyl-2-(2-benzamidophenyl)acrylates and Their Ring Closure to Indoline or Oxindole Derivatives

Shinji Kawai and Chikara Kaneko*

*Faculty of Pharmaceutical Scicences, Kanazawa University, 13-1 Takara-machi, Kanazawa 920-0934, Japan

Abstract

Syntheses of methyl 3-dialkoxycarbonylmethyl- and -(α,α-dialkoxycarbonylethyl)-2-(2-benzamidophenyl)acrylates from methyl 2-phenyl-3,1-benzoxazepine-5-carboxylate were reported. Treatment of these two kinds of acrylates with base afforded entirely different products. Thus, while the former afforded 2,3-disubstituted indoline, the latter gave the oxindole, exclusively. The stereochemistries of the products as well as the mechanisms for these ring closure reactions are discussed.

■ Benzodioxole Chemistry. 4. Concerning the Aromatization of Carbonyl-bridged Cyclic Carbonates Effected by Potassium Carbonate in Aqueous Dimethylformamide

Ernest A. Harrison, Jr.*

*Department of Chemistry, The Pennsylvania State University, York Campus, P1031 Edgecomb Avenue, York, Pennsylvania 17403, U.S.A.

Abstract

Three 4,5,6,7-tetrasubstituted 3a,4,7,7a-Tetrahydro-4,7-methano-1,3,-benzodioxole-2,8-diones (1a-c) containing electron-withdrawing groups in the 4- and 7-positions undergo clean, high-yield conversion to aromatic products 6a-c in 4% aqueous dimethylformamide containing no added potassium carbonate. By comparison, one benzodioxoledione (1d) containing electron-donating groups in the same positions yields no aromatic product under these conditions. By allowing the reaction of 1b with DMF/H₂O to proceed for only 24 h good yields of hydroxyacid 4b (36%) and hydrocarbon 6b (40%) are obtained. Taken in conjunction with the substituent-dependent reactivity, isolation of 4b lends strong support to a previous mechanistic proposal; while discovery of the fact that the aromatization reaction can proceed without added base broadens the scope of its synthetic potential.

■ Use of N,N-Dimethyl(methylene)ammonium Chloride in the Functionalization of Indoles

Alan P. Kozikowski* and Hitoshi Ishida

*Department of Chemistry, University of Pittsburgh, Parkman Avenue & University Drive, Pittsburgh, PA 15260 , U.S.A.

Abstract

The use of a preformed iminium salt has been found to provide superior yields in the generation of Mannich products from indoles.

■ Recent Advances in the Chemistry of Berbine Alkaloids

Ganesh D. Pandey* and Kamla P. Tiwari

*Department of Chemistry, University of Allahabad, Allahabad, 211002, India

Abstract

Some aspects of the recent chemical progress in the field of berbine alkaloids have been reviewed.

■ Synthesis of Thienamycin and Related Compounds

Tetsuji Kametani,* Shyh-Pyng Huang, Shuichi Yokohama, Yukio Suzuki, Masataka Ihara, and Keiichiro Fukumoto

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

■ A [15]Annulenone-[15]annulenyl Ion Cycle Driven by Proton Gradient

Haru Ogawa,* Taiji Imoto, Hidefumi Kato, and Yoichi Taniguchi

*Faculty of Pharmaceutical Sciences, Kyushu University, 3-1-1 Maidashi, Higashi-ku, Fukuoka 812-8582, Japan

■ The Chemical Transformation of Gardnerine to 2-Acylindole Alkaloid Ochropine

Shin-ichiro Sakai,* Yoshikuni Yamamoto, and Sugio Hasegawa

*Faculty of Pharmaceutical Sciences, Chiba University, 1-33 Yayoi-cho, Inage-ku, Chiba 263-8522, Japan

■ New Method for the Introduction of Oxygen Function to the Aromatic Ring of Indoline Alkaloid

Mineo Fuki, Yumiko Endo, Yoichi Yamada, Ayako Asakura, and Takeshi Oishi*

*The Institute of Physical and Chemical Research, Wako-shi, Saitama 351-0198, Japan

■ Synthetic Studies on Some Indole Alkaloids via Fischer Base Type Intermediates

Seiichi Takano,* Kohtaro Yuta, Susumi Hatakeyama, Masaaki Sato, Kozo Shishido, and Kunio Ogasawara

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

■ Synthesis of Isoquinoline or Indole Alkaloids and Their Related Compounds by Using Electororeduction of Immonium Cations as a Key Step

Tatsuya Shono,* Yoshihiro Usui, Tetsuya Miyamoto, and Hiroshi Hamaguchi

*Kinki University, 3-4-1, Kowakae, Higashi-Osaka 577-8502, Japan

■ Structures of Desmethylpsychotrine: A Stereoselective Syntehsis of (+)-9-Demethylpsychotrine

Tozo Fujii* and Masashi Ohba

*Faculty of Pharmaceutical Scicences, Kanazawa University, 13-1 Takara-machi, Kanazawa 920-0934, Japan

■ Reaction of Diketene with Carbenes and Nitrenes

Tetsuzo Kato,* Takuo Chiba, Masayuki Sato, Nobuya Katagiri, Yuji Suzuki, Renzo Sato, and Toshimitsu Yashima

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

■ Ring Expansion Reactions of Thiirene 1,1-Dioxides

Yasuo Yoshida,* Masatoshi Uesaka, Mituso Komatsu, Yoshiki Ohshiro, and Toshio Agawa

*Department of Petroleum Chemistry, Faculty of Engineering Science, Osaka University, 2-1 Yamadaoka, Toyonaka, Osaka 560-0043, Japan

■ Azetidine-2,4-diones via Photoinduced Ring Contraction of Succinimides

Kazuhiro Maruyama,* Takeshi Ishitoku, Yasuo Kubo, and Takuji Ogawa

*Department of Chemistry, Faculty of Science, Kyoto University, Sakyo, Kyoto 606-8502, Japan

■ Total Syntheses of 1-Carbacephem Derivatives

Shoichiro Uyeo and Hisao Ona*

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

■ Diels-Alder Reaction of Dewar Thiophene and Pyrrole

Yoshiro Kobayashi,* Akira Ando, Kosuke Kawada, and Itsumaro Kumadaki

*Tokyo University of Pharmacy and Life Science, 1432-1 Horinouchi, Hachioji, Tokyo 192-0392, Japan

■ Novel Reactions of Benzothiazoline Derivatives

Mikio Hori,* Tadashi Kataoka, Hiroshi Shimizu, Yutaka Imai, and Norihiro Ueda

*Department of Pharmacognosy, Gifu College of Pharmacy, 6-1 Mitahora-higashi 5-chome, Gifu 502-8585, Japan

■ Cycloaddition Reactions of 1,3-Diphenylthieno[3,4-c]-1,2,5-oxadiazole and Thermal Behaviour of Cycloadducts

Otohiko Tsuge* and Toshiaki Takata

*Research Institute of Industrial Science, Faculty of Engineering, Kyushu University, 6-1, Kasuga-koen, Kasuga 816-8580, Japan

■ Reaction of N,N’-Carbonyldiimidazole and N,N’-Thionyldiimidazole with Carbonyl Compounds: A New Imidazole Transfer Reaction

Masaru Ogata,* Hiroshi Matsumoto, Shiro Kida, and Sumio Shimizu

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