HETEROCYCLES

■ Pyrolysis and Photolysis of 6-(Benzoyldene-1’-methylhydrazino)-1,3-Dimethyluracils. A Method to Convert Aldehydes to Nitriles. A New Synthesis of Pyrazolo[3,4-d]pyrimidines

Fumio Yoneda* and Tomohisa Nagamatsu

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

Abstract

Azomethines (I) resulting from the condensation of aliphatic, aromatic or heterocyclic aldehyde with 1,3-dimethyl-6-(1’-methylhydrazino)uracil underwent decomposition by pyrolysis to yield the respective nitriles and 1,3-dimethyl-6-methylaminouracil, while the photolysis of I led to the exclusive formation of the respective pyrazolo[3,4-g]pyrimidines.

■ Synthetic Approach to Pakistanamine by Phenolic Oxidative Coupling

Tetsuji Kametani,* Hirofumi Terasawa, and Fumio Satoh

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

Abstract

The synthesis of a racemic mixture of pakistanamine (I) by oxidation of a racemic mixture of berbamunine (magnoline) (III) with potassium ferricyanide is described.

■ The Reaction of 3,5-Dibromopyridine N-Oxide with Phenyl Isocyanate

Takuzo Hisano,* Toshikazu Matsuoka, and Masataka Ichikawa

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

Abstract

3,5-Dibromopyridine N-oxide (IV) reacted with phenyl isocyanate (I) at 110 ° in DMF to give 2,3-dihydro-2-oxo-3-phenyl-6-bromooxazolo[4,5-b]pyridine (V) in 70% yield, although it was noticed that the reaction of pyridine N-oxide with I directly affords α-anilinopyridine and that 3-picoline N-oxide under the similar reaction two isomeric 1,3-cycloadducts (II and III).

■ Reaction of 3-Substituted Quinoline N-Oxides with Phenyl Isocyanate

Masatomo Hamana,* Hiroshi Noda, and Michiyo Aoyama

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

Abstract

3-Nitro- and 3-bromoquinoline N-oxides react with phenyl isocyanate at 80 ° in DMF to afford 3H-2-oxo-3-phenyloxazolo[ 4,5-b]quinoline through the primary adduct of the 1,3-dipolar cycloaddition reaction. 3,6-Dibromoquinoline N-oxide similarly gives the corresponding 7-bromo derivative.

■ One-Step Synthesis of Dihydropyridocarbazole Derivatives

Tetsuji Kametani,* Yoshifumi Ichikawa, Toshio Suzuki, and Keiichiro Fukumoto

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

Abstract

Heating indole and 4,5-dibromomethy1-3-hydroxy-2-methylpyridine hydrobromide (7) in the presence of sodium iodide, followed by acetylation, gave the dihydropyrido[3,4-b]carbazole derivative (9) along with four other coupling but not cyclized products (14), (15), (16), and a dimer. On the other hand, the same reaction without sodium iodide afforded the desired dihydropyrido[4,3-b]carbasole (8) and its structural isomer (9). The structures of 8 and 9 were determined by ultraviolet spectral investigations of the corresponding dehydrogenated products, 4-acetoxy-3-methyl-6H-pyrido[4,3-b]carbazole (12) and 4-acetoxy-3-methyl-10H-pyrido [3,4-b]carbazole (13).

■ Transannular Cyclizations of Tetracyclo[6.3.0.0^2,60^5,9]undecan-3,11-dione to 4-Hetero-9,10-secobird-cage System

Tadashi Sasaki,* Shoji Eguchi, and Osamu Hiroaki

*Institute of Applied Organic Chemistry, Faculty of Engineering, Nagoya University, Chikusa, Nagoya, Aichi 464-8601, Japan

Abstract

Transannular cyclizations of dione (2) in the title were observed on NaBH₄ reduction, and on additions of morpholine, piperazine, and p-toluenesulfonylhydrazine, affording the corresponding 4-oxa- and -aza-9,10-secobirdcage compounds.

■ The Reaction of Heterocyclic Lithio Salts with Styrene Oxide

Albert I. Meyers* and Edward D. Mihelich

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

Abstract

A study of temperature and reaction duration for several heterocyclic lithio salts on styrene oxide has led to reaction conditions which allow high yields of SN₂ ring opening.

■ A New Synthetic Method using Thiazoline Derivatives

Koichi Hirai* and Yukichi Kishida

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

Abstract

Reaotions involving carbon-oarbon bond formation are oonsidered to be one of the main objectives in the field of synthetic organic chemistry. This article desoribes approaohes of a new methodology based on thiaeoline derivatives to iodo- methylation (-CH21) and tm-iodopropenylation (-CH-CH-CH I) of alkyl halides, synthesis of heterooyolio oompounds, and syntheses of natural products squalene and piperovatine.

■ Synthesis of Heterocycles through Nitrenes

Tetsuji Kametani, Frank F. Ebetino, Tohru Yamanaka, and Kiyosato Nyu

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

Abstract

The reaction of triethyl phosphite with aromatic nitro compounds in which a nitrene intermediate was expected to intervene was investigated. Syntheses of certain indole derivatives, such as harman, pseudorutaecarpine , benz[a]- carbaaole and p-carboline; and quinoline derivatives that are related to natural products are described in this review.

■ Molecular Design by Cycloaddition Reactions of Heterocycles with Some Dienophiles

Tadashi Sasaki,* Ken Kanematsu, Yusuke Yukimoto, Toshiyuki Hiramatsu, and Eiji Kato

*Institute of Applied Organic Chemistry, Faculty of Engineering, Nagoya University, Chikusa, Nagoya, Aichi 464-8601, Japan

■ Oxygenation of Tryptamine and Tryptophan Derivatives

Masako Nakagawa,* Takao Kaneko, Kensei Yoshikawa, Haruo Okajima, and Tohru Hino

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

■ Mechanism of C-C Bond Formation during Fischer Indolization and Pseudocontact Shift of Ethyl Indole-2-Carboxylate Derivatives

Hisashi Ishii,* Yasuoki Murakami, Haruki Takeda, and Nisaburo Ikeda

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

■ A New Synthetic Route of Pyrrolo[2,3-b]indole Derivatives

Noboru Shoji, Yoshikazu Kondo, and Tsunematsu Takemoto

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

■ The Reaction of Enamines with Pyrrole

Otohiko Tsuge,* Masashi Tashiro, and Yoko Kiryu

*Research Institute of Industrial Science, Faculty of Engineering, Kyushu University, 6-10-1 Hakozaki, Higashi-ku, Fukuoka 812-8581, Japan

■ Formation of 6a-Thiothiophthen Analogues Based on [1,2,4]Thiadiazolo[5,1-e][1,2,4]thiadiazole System. Novel Cycloaddition of “Hetero’s Base” with Nitriles

Kin-ya Akiba,* Tohru Tsuchiya, and Naoki Inamoto

*Department of Chemistry, Scool of Science, University of Tokyo, 7-3-1 Hongo, Bunkyo-ku, Tokyo 113-0033

■ Synthesis of Derivatives of 4-Substituted Isoxazole-3,5-dicarboxylic Acids

Shonosuke Zen and Eisuke Kaji*

*School of Pharmaceutical Sciences, Kitasato University, Shirokane, Minato-ku, Tokyo 108-8641, Japan

■ Tautomerism of 3,5-Disubstituted 1,2,4-Triazoles

Masayuki Uda and Seiju Kubota*

*Faculty of Pharmaceutical Sciences, University of Tokushima, Sho-machi, Tokushima 770-8505, Japan

■ Reactivities of Dewar Thiophene Containing Trifluoromethyl Groups

Yoshiro Kobayashi,* Itsumaro Kumadaki, Akio Ohsawa, Yasuo Sekine, and Hiroyuki Mochizuki

*Tokyo University of Pharmacy, Kitashinjuku, Shinjyuku-ku, Tokyo 160, Japan

■ Synthesis of 5,6-Dihydrothiazolo[2,3-b]thiazolium Salts and their Reaction with Nucleophilic Reagents

Kiichi Arakawa, Tadashi Miyasaka, Hiroko Ohtsuka, and Hatsunori Toyofuku

*School of Pharmaceutical Sciences, Showa University, 1-5-8 Hatanodai, Shinagawa-ku, Tokyo 142-8555, Japan

■ Synthesis and Reactions of N-Aminoimidazolium and N-Aminothiazolium Salts

Yasumitsu Tamura, Hironori Hayashi, Joong-Heup Kim, Jun-ichi Minamikawa, Eiko Saeki, and Masazumi Ikeda

*Faculty of Pharmaceutical Sciences, Osaka University, 1-6 Yamadaoka, Toyonaka, Osaka 560-0043, Japan

■ A New Approach to the Mechanism on Photorearrangements of Thiazoles

Minoru Maeda* and Masaharu Kojima

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

■ The Photochemistry of Five-Membered Dihydroheteroaromatics

Teruo Matsuura and Yoshikatsu Ito*

*Department of Synthetic Chemistry, Faculty of Engineering, Kyoto University, Yoshida, Sakyou-ku, Kyoto 606-8501, Japan

■ Sensitized Photooxidation of N-Methylpyridinium-3-oxide and Its Related Compounds

Akira Mori,* Shumei ohta, and Hitoshi Takeshita

*Instituete of Advanced Material Study, Kyushu University, 6-1, Kasuga-koen, Kasuga 816-8580, Japan

■ Cyclization and Cycloaddition Reactions of 1,3-Oxazepine and 1,2-Diazepine Derivatives

Toshio Mukai,* Hiroshi Sukawa, Yoshiro Yamashita, and Takahiro Tezuka

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

■ Effects of the ortho-Substituents in the Enamide Photocyclization

Ichiya Ninomiya,* Toshiko Kiguchi, andTakeaki Naito

*Kobe Women’s College of Pharmacy, Motoyamakita, Higashinad, Kobe, Hyogo 658, Japan

■ Reactions of Cyclic Sulfoxides and Sulfonium Salts with Organometallic Reagents

Mikio Hori,* Tadashi Kataoka, Hiroshi Shimizu, and Ken’ichi Narita

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

■ Synthesis of Condensed Thiophenes by Thermal Reactions of Aryl Propargyl Sulfoxides

Yasuo Makisumi* and Susumu Takada

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

■ The Roles of Heteroatoms in Epoxide Opening

Shiro Ikegami,* Jun-ichi Ohishi, Takeshi Asai, and Sanya Akaboshi

*Faculty of Pharmaceutical Sciences, Teikyo University, 1091-1, Sagamiko, Kanagawa 199-0195, Japan

■ The Alkaline Decomposition of Quaternary Fused Hydrazinium Iodides

Akitada Nakamura* and Shozo Kamiya

*National Institute of Hygienic Sciences

■ Reaction of 2,4,6-Triphenyl-1,3-oxazinium Salt and -1,3,5-oxadiazinium Salt with Various Amino Compounds

Isao Shibuya and Masahiro Kurabayashi

*National Chemical Laboratory for Industry, Yatabe, tsukuba, Ibaraki 305, Japan