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. 2, No. 6, 1974
Published online:
■ Diazapolycyclic Compounds. IX. Substituted Diazaquinone Adducts with Dimethylenecyclohexane, Dimethylenecyclohexene and nSubstituted Butadienes
Berta López, Manuel Lora-Tamayo,* Pilar Navarro, and José Luis Soto
*Biochemistry Department, Kuwait University, Safat 13060, P.O. Box 5969, Kuwait
Abstract
Substituted tetracyclic diaza compounds with varying positions of the nitrogen bridge have been synthesized by Diels-Alder reaction of substituted phthalazindiones with 1,2-dimethylenecyclohexane or 1,2- dimethylene-Δ4-cyclohexene and of naphthalazindiones with substituted butadienes in order to obtain compounds referable to tetracyclines of known activity.
Published online:
■ The Novel Formation of a Dibenzocyclohepta[b]pyridine by an Abnormal Hofmann Degradation of a Diphenolic Tetrahydroprotoberberinium Salt
Tetsuji Kametani,* Makoto Takemura, Keiichi Takahashi, Mitsuhiro Takeshita, Masataka Ihara, and Keiichiro Fukumoto
*Pharmaceutical Institute, Tohoku University, Aobayama, Sendai 980-8578, Japan
Abstract
Heating coreximine methiodide (5) with methanolic potassium hydroxide gave the secoprotoberberine (14) and 5,5a,6,7,8-pentahydro-3,11-dihydroxy-2,10-dimethoxybenz[b,e]-4H-azuleno[3,2,1-ij]isoquinoline (15), but not the methine base (10) usually formed by Hofmann degradation. The possible biogenesis of these two abnormal Hofmann degradation products from protoberberine alkaloids is discussed.
Published online:
■ Phenyllithium-Induced Rearrangement of N-Methyltetrahydroberberinium Salts
Yoshikazu Kondo,* Tsunematsu Takemoto, and Kazue Kondo
*Pharmaceutical Institute, Tohoku University, Aobayama, Sendai 980-8578, Japan
Abstract
In the presence of phenyllithium or lithium alanate, dl-N-methyltetrahydroberberinium salts underwent rearrangement to N-methyl-7,8-dimethoxy-1,2,3,4-tetrahydroisoquinoline-3-spiro-1’-5’,6’-methylenedioxyindane (V). The structure of V has been proven by chemical and spectral means.
Published online:
■ Photochemistry of Heterocyclic Compounds. III. Photochemical Reaction of O-Acetylindoxyl
Koji Oe, Masashi Tashiro, and Otohiko Tsuge*
*Research Institute of Industrial Science, Faculty of Engineering, Kyushu University, 6-1, Kasuga-koen, Kasuga 816-8580, Japan
Abstract
Irradiation of O-acetyl indoxyl (I) in benzene solution by a high-pressure mercury lamp afforded indigo (II) and diacetyl (III), and no photo-Fries rearranged products were formed. Upon irradiation of I in the presence of excess benzophenone (IV), however, 2-diphenylmethyleneindolin-3-one (Va) was obtained as a predominant product. The pathways for the formation of II, III, and Va are discussed.
Published online:
■ Cyclic Hydroxylamines; A Review of Preparative Methods and Properties
Ronald T. Coutts* and Abdel-monaem M. K. El-hawari
*Faculty of Pharmacy and Pharmaceutical Sciences, University of Alberta, Edmonton, Alberta, T6G 2G2, Canada
Abstract
The preparation of cyclic hydroxylamines by various methods is discussed. These methods include (a) direct N-oxidation of amines, (b) reduction of cyclic nitrones, (c) addition to cyclic nitrones, (d) reductive and non-reductive cyclization reactions, as well as other miscellaneous methods.
The physical and chemical properties of cyclic hydroxylamines which are also discussed are (a) solubility and salt formation, (b) qualitative and quantitative analysis, (c) molecular spectroscopy and mass spectrometry, (d) stability, (e) tautomerism, (f) oxidation, (g) reduction, (h) alkylation reactions, (i) acylation and sulfonation reactions, (j) reactions with nucleophilic reagents, and (k) reactions with electrophilic reagents. Some comments on the biological importance of cyclic hydroxylamines and related compounds are included in an introductory section.