HETEROCYCLES

■ Propellanes. LIX. Propellane Carbinol-lactams

Iman Landheer and David Ginsburg*

*Department of Chemistry, Israel Institute of Technology, Haifa 32000, Israel

Abstract

Lithium Borohydride reduced propellane imides to the respective epimeric carbinol-lactams.

■ Studies on Lactams IX. A Convenient Synthesis of Lactam Rings

Haruo Ogura* and Kazuyoshi Takeda

*School of Pharmaceutical Sciences, Kitasato University, 5-9-1, Shirokane, Minato-ku, Tokyo 108-8641, Japan

Abstract

The auto-cyclization reaction has been employed for the synthesis of lactam rings by means of reduction from ω-carbobenzoxyamino acid active esters in high dilution method.

■ Synthesis of Heterocycles through Ring Closure of 2-(substituted)amino-1-phenylpropanols

Thomas J. Schwan*

*Chemical Research Division, Norwich-Eaton Pharmaceuticals, Division of Morton-Norwich Products, Inc., Norwich, New York 13815, U.S.A.

Abstract

The cyclization of 2-(substituted)amino-1-phenylpropanols in 48% hydrobromic acid or polyphosphoric acid to a variety of nitrogen-containing heterocycles is described.

■ Photochemistry of the Semicyclic Imide System. I. Evidence for Competitive Type I and Type II Processes

Minoru Machida, Haruko Takechi, Akiyo Sakushima, and Yuichi Kanaoka*

*Faculty of Pharmaceutical Sciences, Hokkaido University, Kita 12 Nishi 6, Kita-ku, Sapporo, Hokkaido 060-0812, Japan

Abstract

Photolyses of a series of N-acylpyrrolidones (4) show that semicyclic imides are capable of undergoing competitive type I and type II processes.

■ Reissert Compound Studies. XXXVIII. Preliminary Observations on 3,4-Dihydro-β-carboline

Frank D. Popp* and Seshadri Veeraraghavan

*Department of Chemistry, University of Missouri-Kansas City, Kansas City, Missouri 64110, U.S.A.

Abstract

3,4-Dihydro-β-carboline and its 9-benzyl derivative have been converted to Reissert compounds. The anion of these Reissert compounds has been alkylated with methyl iodide. A compound with great potential as an intermediate in the synthesis of indole alkaloid systems has been prepared by treatment of the Reissert compound formed from 9-benzyl-3,4-dihydro-β-carboline and 2-chloromethylbenzoyl chloride with sodium hydride.

■ Triazolo[4,5-d ]pyrimidines. VII. The Photochemical Transformation of 3-phenyl-3H -1,2,3-triazolo[4,5-d ]pyrimidines into 9H -Pyrimido[4,5-b ]indoles

Takeo Higashino,* Eisaku Hayashi, Hideaki Matsuda and Tatsuhiko Katori

*Shizuoka College of Pharmacy, 2-2-1, Oshika, Shizuoka-shi, 442 Shizuoka, Japan

Abstract

The photolysis of 3-phenyl-3H-1,2,3-triazolo[4,5-d]pyrimidines in dioxane, benzene and methanol gave 9H-pyrimido[4,5-b]indoles in moderate yields. Similarly, 3-phenyl-3H-1,2,3-triazolo[4,5-b]pyridines were easily transformed by the photolysis into 9H-pyrido[2,3-b]indoles.

■ Syntheses of Some 2,3-Benzo-1-thiaoctems

Masayuki Shibuya* and Seiju Kubota

*Faculty of Pharmaceutical Sciences, University of Tokushima, Sho-machi 1, Tokushima 770-8505, Japan

Abstract

2,3-Benzo-1-thiaoctems 2, 9, and 6 were synthesized from 4-acetoxyazetidin-2-one (3). Oxidation of 2 and 9 afforded the corresponding sulfoxides and sulfones. The relative stereochemistries of the products were determined from nmr aromatic solvent induced shifts (ASIS).

■ Effect of Crown Ether on the Formation of Flavanones

Toyoshi Katagi,* Taeko Shirota, Masako Kashiwagi, and Kayo Hayashi

*School of Pharmaceutical Science, Mukogawa University, Edogwa-cho, Nishinomiya, Hyogo 663, Japan

Abstract

The condensation of 2-hydroxyacetophenone with benzaldehydes was catalysed with crown ether and directly gave flavanones in fair yield.

■ The Electrooxidation of Pyrrole, Indole, Carbazole, and Their Derivatives

James M. Bobbitt,* C. L. Kulkarni, and Jhon P. Willis

*Department of Chemistry, University of Connecticut, Storrs, CT 06269-3060, U.S.A.

Abstract

The electrooxidations of pyrrole, indole, carbazole and a number of their substituted and partially reduced derivatives are described. The overall mechanistic aspects are summarized and discussed. Certain aspects of indole alkaloid biosynthesis involving oxidation are considered. The experimental conditions used in a number of reactions are summarized.

■ Progress in the Development of New Epoxidation Reagents

Julius Rebek, Jr.*

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

■ Recent Progress in the Chemistry of Azaazulenes : Synthetic Methodology and Chemical Reactions

Tarozaemon Nishiwaki and Noritaka Abe

*Department of Chemistry, Faculty of Science, Yamaguchi University, 1677-1 Yoshida, Yamaguchi 753-8512, Japan

Abstract

Synthetic methods of azaazulenes including some of their hydro and oxo derivatives and the cyclazines incorporating an azaazulene ring are surveyed. Nucleophilic and electrophilic substitutions and pericyclic reactions of azaazulenes and their derivatives are reviewed.

■ Conversion of Simple Pyrimidines into Derivatives with a Carbon Functional Group

Takao Sakamoto and Hiroshi Yamanaka*

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

Abstract

The synthesis of pyrimidine derivatives bearing carbon functional groups, such as CH₂OH, CHO, COR (or COAr), CN, CONR₂, and COOR, at the 2- or 4-position is described. The most practical and experimentally simplistic methods for the preparation of these pyrimidines are concluded to be as follows.
Hydroxymethylpyrimidines are best prepared by direct hydroxymethylation of pyrimidines with a free 2- or 4-position using hydroxymethyl radical. Pyrimidinealdehydes are readily obtained by oxidation of methylpyrimidines with a limited amount of selenium dioxide. It is recommended that acylpyrimidines are prepared from the corresponding nitriles by Grignard reaction. In some cases homolytic acylation, rather than the above method, can be used for their preparation.
The synthesis of pyrimidinecarboxylic acids and related compounds is described together with the interconversion of nitriles, amides, and esters. In addition, selectivity of reactions on the pyrimidine ring occasionally observed during our investigations is discussed briefly in the last chapter of this paper.

■ Total Synthesis of Lycopodium Alkaloids

Yasuo Inubushi* and Takashi Harayama

*Faculty of Pharmaceutical Sciences, Kyoto University, 46-29 Yoshida-shimoadachi-machi, Sakyo-ku, Kyoto 606-8501, Japan

Abstract

This review described developments of total syntheses of seven Lycopodium alkaloids.

■ Synthetic Applications of Dimethyl Acetylenedicarboxylate in Phosphorus Heterocyclic Chemistry

Alan N. Hughes

*Department of Chemistry, Lakehead University, Thunder Bay, Ontario, P7B 5E1, Canada

Abstract

The reactions of tertiary phosphorus compounds with dimethyl acetylenedicarboxylate and, on occasion, other acetylenic systems are discussed with emphasis upon the synthesis of phosphorus heterocycles. The discussion is divided into two sections. The first section surveys the reactions of open-chain tertiary phosphines, bis-phosphines and vinylphosphines with acetylenic systems while the second section is concerned with similar reactions of cyclic phosphines with these alkyne derivatives. Both sections record syntheses of novel heterocyclic systems which, for the most part, are inaccessible by more conventional routes.