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. 4, No. 10, 1976
Published online:
■ Photooxygenation of 9-Keto-7-methoxy-6-methyl-9H-pyrrolo[1,2-a]indole as a Synthetic Approach to the Mitomycins
Tetsuji Kametani,* Tatsushi Ohsawa, Kimio Takahashi, Masataka Ihara, and Keiichiro Fukumoto
*Pharmaceutical Institute, Tohoku University, Aobayama, Sendai 980-8578, Japan
Abstract
Sensitized photooxidation in methanol of 9-keto-7-methoxy-6-methyl-9H-pyrrolo[1,2-a]indole (9), prepared from 2-bromo-5-methoxy-4-methylbenzaldehyde (5) via 2-(2-bromo-5-methoxy-4-methylbenzoyl)pyrrole (8), afforded 9,9a-dihydro-3-hydroperoxy-9-keto-7,9a-dimethoxy-6-methyl-3H-pyrrolo[1,2-a]indole (11) and the 3-hydroxy compound (12), the latter of which is considered as a potential precursor of the mitomycins.
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■ Decarboxylation of Phenolic Tetrahydroisoquinolione-1-carboxylic Acids in Air
James M. Bobbitt,* Chidambar L. Kulkarni, and Pichaet Wiriyachitra
*Department of Chemistry, The University of Conneticut, Storrs, Conneticut 06268, U.S.A.
Abstract
When stirred in air under basic conditions (NaHCO3, triethylamine, or NaOMe), tetrahydroisoquinoline-1-carboxylic acids containing at least one free phenol group in the aromatic ring decarboxylate oxidatively to yield 3,4-dihydroisoquinolines.
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■ An Intramolecular Rearrangement of 1-Arylazetidin-2-ones in an Acidic Solution
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
Several kinds of 1-arylazetidin-2-ones were treated with trifluoroacetic acid to give 1,2,3,4-tetrahydroquinolin-4-ones. In the case of 1-arylazetidin-2-ones possessing a substituent at the 3-position, the rearrangement occurred at both ortho- and para-positions to the substituent located at the 3-position.
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■ A 1,3-Dipolar Cycloaddition Reaction of 1-Methylindazole
Michele Ruccia,* Nicolò Vivona, and Giuseppe Cusmano
*Dipartimento di Chimica Organica, Università digli Studi di Palermo, Via Archirafi 20 90123 Palermo, Italy
Abstract
A 1,3-dipolar cycloaddition reaction of 1-methylindazole with C-acetyl-N-phenylnitrilimine was performed. The cycloadduct could be used to synthetize 1,2,4-triazole derivatives.
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■ A Dichotomy in the Intramolecular Cycloaddition of Aza Analogs of Hexatriene. Thermolysis and Photolysis of 6-Benzylideneamino-5-dimethylaminomethyleneamino-1,3-dimethyluracils
Fumio Yoneda,* Masatsugu Kiguchi, and Mitsuko Kawamura
*Faculty of Pharmaceutical Sciences, Kumamoto University, 5-1 Oe-hon-machi, Kumamoto 862-0973, Japan
Abstract
The 5-dimethylaminomethylene derivatives (II) resulting from the condensation of the 6-amino-5-benzylideneamino-1,3-dimethyluracils (I) with dimethylformamide diethylacetal underwent intramolecular cycloaddition by thermolysis in sulfolane to yield the respective 1,3-dimethyllumazine derivatives (III), while the photolysis of II in alcohol led to the formation of theophylline via another type of cycloaddition.
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■ Preparation and Some Reactions of 2-Trimethylsilyloxyfurans
Eiichi Yoshii,* Toru Koizumi, Eitaro Kitatsuji, Toshiji Kawazoe, and Tomie Kaneko
*Faculty of Pharmaceutical Sciences, Toyama University, Gofuku 3190, Toyama 930-8555, Japan
Abstract
Synthetically useful 2-trimethylsilyloxyfurans were prepared by silylation of but-2-enolides. Some of their reactions — bromination, dichlorocarbene addition, and a Diels-Alder reaction — were also reported.
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■ Heterocycles. II. Photochemistry of 4-(3’,4’-Dimethyoxyphenylacetyl)-2-methylisocarbostyril and Its Enol Acetates
Masayuki Onda,* Yoshihiro Harigaya, and Tsutomu Suzuki
*School of Pharmaceutical Sciences, Kitasato University, 5-9-1, Shirokane, Minato-ku, Tokyo 108-8641, Japan
Abstract
Photolyses of the isocarbostyril (2) and its enol acetates (4) and (5) are examined. The former affords the C-nor-benzo[c]phenanthridine (3). The Z-isomer (4) of the enol acetate isomerizes to, the E-isomer (5) along with formation of the acetylene (6). Photolysis of the E-isomer (5) in the presence of iodine gives the 11-acetoxybenzo[c]phenanthridines (7) and (8). Structures for all photo-products are confirmed on the basis of their NMR spectra.
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■ Michael Additions of Indoles to 2-Oxoindolin-3-ylidene Ketones
Akinori Kubo,* Tatsuya Nakai, and Toshikazu Nozoye
*Meiji Pharmaceutical University, 2-522-1 Noshio, Kiyose, Tokyo 204-8588, Japan
Abstract
Michael-type additions to (E)-2-oxoindolin-3-ylidene ketones (1) and indoles (2) gave rise to C-1’ (3) and/or C-3 (4) adducts depending on the oxindolic N-substituents and the C-1’ adducts(3) were converted into new 9H-pyridazino[3,4-b]indole derivativeg (6).
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■ Synthesis of Cardic Steroid 3-Suberoylbradykinin Esters
Youichi Fujii, Kazutaka Shimada, and Toshio Nambara*
*Pharmaceutical Institute, Tohoku University, Aobayama, Sendai 980-8578, Japan
Abstract
The cardiac steroid 3-suberoylbradykinin esters which may possibly occur in the toad venom, were synthesized by the activated ester method. Digitoxigenin 3-hemisuberate and bufotalin 3-hemisuberate were converted by the DCC method to the p-nitrophenyl esters, which in turn were condensed with bradykinin in aqueous pyridine to yield the desired compounds (1c, 2c).
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■ A Novel Transformation of Tetrahydroberberine Methiodide to Allocyptopine by Photo-oxygenation
Miyoji Hanaoka,* Chisato Mukai, and Yoshio Arata
*Faculty of Pharmaceutical Scicences, Kanazawa University, 13-1 Takara-machi, Kanazawa 920-0934, Japan
Abstract
Allocryptopine (II) was synthesized from tetrahydroberberine methiodide (I) in one step by photo-oxygenation.
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■ Oxazolines XXIV: Chiral Oxazolines and Thiazolines from L-Serine and L-Cysteine. Their Potential Use in Asymmetric Synthesis
A. I. Meyers* and Charles E. Whitten
*Department of Chemistry, Colorado State University, Fort Collins, CO 80523-1872, U.S.A.
Abstract
The synthesis of S(+)-3-phenylheptanoic acid in >90% ee using a chiral oxazoline derived from L-serine is described.
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■ Reactions at C9 of Acridine Derivatives. XV. On the Mechanism of Hydrolysis of 1-Nitro-9-aminoacridines
Stanislaw Skonieczny* and Andrzej Ledochowski
*Laboratory of Chemistry and Biochemistry of Antitumour Compound, Institute of Organic and Food Chemistry and Technology, Techinical University of Gdansk, 80-952 Gdansk 6, Poland
Abstract
The hydrolysis rate constants for 1-nitro-9-aminoacridines are dissimilar to those for other 9-aminoacridines. These differences are discussed in terms of 9-iminoacridan ⇔ 9-aminoacridine tautomerism existing in aqueous solutions.
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■ Semisynthetic β-Lactam Antibiotics. III. Synthesis and Antibacterial Activity of α-(2-Imidazolinylamino)benzylpenicillin and -desacetoxycephalosporin
Mario Pinza,* Giuseppe LiBassi, Giampietro Broccali, and Giorgio Pifferi
*Laboratories for Biomedical Research, ISF, Trezzano s/N, Milan, Italy
Abstract
The preparation of the new β-lactam antibiotics α-(2-imidazolinylamino)benzyl-penicilline in (I) and -desacetoxyccphalosporin (II) via the appropriate phenylacetylchloride hydrochloride (VII) is reported. Their antibacterial activities against several micro-organisms have been determined in vitro.
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■ Pyrimidone Derivatives as Effective Acid Captors. A Method for the Preparation of Carboxamides
Edward Bald, Susumu Kobayashi, and Teruaki Mukaiyama*
*Faculty of Pharmaceutical Sciences, University of Tokyo, Hongo, Bunkyo-ku, Tokyo 113, Japan
Abstract
The equimolar reactions of carboxylic acids and amines with 1-methyl-2-chloropyridinium salt in the presence of 3,4-dihydro-9-methyl-2H-pyrido[1,2-a]pyrimidin-2-one(II) or 3,4-dihydro-3,9-dimethyl-2H-pyrido[1,2-a]pyrimidin-2-one (III) afforded the corresponding carboxamides in high yields.