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. 6, No. 4, 1977
Published online:
■ Reaction of Pyrisinium and Isoquinolinium N-Imines with Ketenethihoacetals
Hiroshi Fujito, Yoshinori Tominaga, Yoshiro Matsuda, and Goro Kobayashi*
*Faculty of Pharmaceutical Sciences, Nagasaki University, 1-14, Bunkyo-machi, Nagasaki 852-8521, Japan
Abstract
Pyridinium and isoquinolinium N-vinylimine and azaindolizine derivatives were synthesized by a reaction of pyridinium and isoquinolinium N-imine with ketenethioacetals.
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■ Rearrangement of 9-Alkyltheophyllines to the 7-Alkyl amalogues
John H. Lister*
*John Curtin School of Medical Research, Canberra City 2601, Australia
Abstract
Under thermal conditions 9-benzyltheophylline (1) with either benzyl bromide or hydrobromic acid undergoes rearrangement in dimethylformamide to the 7-benzyl isomer (3).
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■ Convenient Synthesis of S-Containing Heterobicycles
Shiro Ikegami,* Jun-ichi Ohishi, and Yasuo Shimizu
*Faculty of Pharmaceutical Sciences, Teikyo University, 1091-1, Sagamiko, Kanagawa 199-0195, Japan
Abstract
6-exo-Chloro-2-thiabicyclo[2.2.l]heptane and its 1-methyl analog, and 4-exo-chloro-6-thiabicyclo[3.2.1]octane are synthesized by the intramolecular cyclization of sulfenyl chlorides formed in situ from the reaction of the corresponding cycloalkenyl disulfides with chlorine.
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■ A New Synthesis of (±)-7-Epideoxynupharidine and (±)-1-Epi-7-epideoxynupharidine
Shingo Yasuda, Miyoji Hanaoka, and Yoshio Arata*
*Faculty of Pharmaceutical Scicences, Kanazawa University, 13-1 Takara-machi, Kanazawa 920-0934, Japan
Abstract
The Mannich reaction of the amino-ketone (VIII) with 3-furylaldehyde followed by the isomerization afforded stereoselectively the trans-quinolizidine (X), the Wolff-Kishner reduction of which provided (±)-7-epi- and (±)-1-epi-7-epideoxynupharidine (I and II).
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■ Nitrous Acid Deamination of (R)-β-Aminoadipic Acid
Toshio Wakabayashi* and Yoshinori Kato
*Bio-Medical Research, Teijin Institute, Asahigaoka 4-3-2, Hino, Tokyo 191, Japan
Abstract
Intramolecular participation by carboxyl group in diazotization processes has received much attention. The deamination of (R)-β-aminoadipic acid in aqueous nitrous acid affords (S)-carboxymethylbutanolide (2) with 69% net inversion.
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■ Thalipine, a New Aporphine-benzylisoquinoline Alkaloid
M. Shamma,* J. L. Moniot, and P. Chinnasamy
*Department of Chemistry, The Pennsylvania State University, York Campus, P1031 Edgecomb Avenue, York, Pennsylvania 17403, U.S.A.
Abstract
(+)-Thalipine (1) has been obtained from Thalictrum polygamum Muhl. Like most other alkaloids of this plant, it is derived biogenetically from (+)-reticuline without recourse to O-demethylation.
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■ Alkaloids of Thalictrum. XIX. Revolutopine and Thelipine, New Arophinebenzylisoquinoline Dimers from Thalictrum revolutum
Jinn Wu, Jack L. Beal, Wu-Nan Wu, and Raymond W. Deskotch*
*Division of Pharmacognosy and Natural Products Chemistry, College of Pharmacy, The Ohio State University, Columbus, Ohio 43210, U.S.A.
Abstract
Revolutopine and thalipine, new alkaloids from the tops of Thalictrum revolutum have been assigned the aporphine-benzylisoquinoline structures 1 and 2 on the basis of physical and chemical evidence.
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■ 2-Substituted Acenaphtho[1,2-d]oxazoles
Otohiko Tsuge* and Masahiro Koga
*Research Institute of Industrial Science, Faculty of Engineering, Kyushu University, 6-1, Kasuga-koen, Kasuga 816-8580, Japan
Abstract
Irradiation of 2-diazoacenaphthenone (1) in nitriles such as acetonitrile, propionitrile, benzonitrile, p-tolunitrile, and acrylonitrile afforded the corresponding 2-substituted acenaphtho[l,2-d]oxazoles (3). In pyrolysis of 1 in benzonitrile 2-phenyloxazole derivative 3c was formed, together with traces of 2,2’-diacenaphthylidene-1,1’-dione.
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■ Biotransformation of Reticuline into Morphinandienone, Aporphine, and Protoberbaerine Alkaloids with Rat Liver Enzyme
Tetsuji Kametani,* Yohko Ohta, Makoto Takemura, Masataka Ihara, and Keiichiro Fukumoto
*Pharmaceutical Institute, Tohoku University, Aobayama, Sendai 980-8578, Japan
Abstract
(±)-Reticuline (1a) was biotransformed into morphinandienone alkaloid, pallidine (4a), and aporphine alkaloid, isoboldine (5a) in addition to protoberberine alkaloids, coreximine (3a) and scoulerine (2a). The transformation was stimulated by the presence of the following cofactors, NAD, NADP or NADPH. Deuterium labelled experiment revealed that the N-methyl group of (±)-reticuline was not intactly incorporated into protoberberines.
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■ Photochemical Reactions of 2-Benzylidenehydrazinopyrimidines
Teruaki Tsujikawa* and Motomi Tatsuta
*Central Research Division, Takeda Chemical Industries, Ltd., 17-85 Jusohonmachi 2-chome, Yodogawa-ku, Osaka 532-8686, Japan
Abstract
Under a nitrogen atmosphere, anti-isomers of 2-benzylidenehydrazinopyrimidines easily underwent isomerization to their syn-isomers by irradiation with an ultraviolet light over a benzene solution, but in thb presence of oxygen, photosensitized auto-oxidation occurred to afford 3-aryl-1,2,4-triazolo[4,3-a]pyrimidines. When irradiated in the same manner, 2-benzylidenehydrazino-1,3,5-triazine derivative decomposed into benzaldehyde and 2-hydroxy-1,3,5-triazine.
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■ A Synthesis of Flavins by the Reaction of 6-(N-Alkylanilino)-5-nitrouracils with Diethyl Azodicarboxylate in the Presence of Base
Fumio Yoneda* and Yoshiharu Sakuma
*Faculty of Pharmaceutical Sciences, Kumamoto University, 5-1 Oe-hon-machi, Kumamoto 862-0973, Japan
Abstract
The treatment of 6-(N-alkylanilino)-5-nitrouracils with diethyl azodicarboxylate (DAD) in the presence of bases gave the corresponding isoalloxazines (flavins).
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■ Studies on the Synthesis of Bisindole Alkaloids. IX. The Synthesis of Novel Vindoline Derivatives
James P. Kutney,* Ka Kong Chan, William B. Evans, Yutaka Fujise, Toshio Honda, Frederick Karl Klein, and Joao Pedro de Souza
*Department of Chemisry, University of British Columbia, Vancouver 8, V5T 1W5, Canada
Abstract
A detailed study involving the degradation of vindoline (1) provides a series of novel vindoline derivatives which are important intermediates in the synthesis of bisindole alkaloids.
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■ Studies on the Synthesis of Bisindole Alkaloids. X. The Synthesis of Novel Vinblastine Derivatives
James P. Kutney,* William B. Evans, and Toshio Honda
*Department of Chemisry, University of British Columbia, Vancouver 8, V5T 1W5, Canada
Abstract
The coupling of catharanthine-Nb-oxide with various novel vindoline derivatives provides a series of novel vinblastine derivatives. These compounds provide an opportunity to evaluate the importance of the functionality in the dihydroindole unit of the bisindole system in terms of anti-tumor activity.
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■ Pteridines. Part XLII. Synthesis of Some Banzo[g]pteridines. A Novel Aromatization Reaction
Edward C. Taylor* and John V. Berrier
*Department of Chemistry, Princeton University , Princeton, New Jersey 08544, U.S.A.
Abstract
Condensation of 6-chloro-2-oximinocyclohexanone with aminomalononitrile gave 2-amino-3-cyano-5-chloro-5,6,7,8-tetrahydroqinoxaline 1-oxide (1), which upon heating in acetic acid underwent a novel aromatization reaction, with loss of HCl and H2O, to give 2-amino-3-cyanoquinoxaline (3). An analogous aromatization reaction was observed with 3-amino-2-cyano-5,6-dihydrobenzo(h)quinoxaline 1-oxide (9), which gave 3-amino-2-cyanobenzo(h)quinoxaline (10) upon heating with a trace of HCl or H2SO4. These o-aminonitriles were then converted to variously substituted fused pteridine derivatives by conventional cyclization techniques.
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■ Electro-oxidation of 1-Phenethylisoquinolines
Ahmad Najafi and Malcolm Sainsbury*
*School of Chemistry, University of Bath, Bath, Avon. BA2 7AY, U.K.
Abstract
An examination of methoxylated derivatives of 1-phenethylisoquinoline has shown that the mode of eleotrochemical oxidation undergone by such compounds is different to that exhibited by analogous 1-benzylisoquinolines: in particular, intramolecular cyclisation through C-C bond formation is not observed.
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■ Neopelline. A Partial Synthesis of 8-Acetyl-14-benzoylneoline
S. William Pelletier,* J. Bhattacharayya, and Naresh V. Mody
*Department of Chemistry, Institute for Natural Products Research, The University of Georgia, Chemistry Building, Athens, Georgia 30602-2556, U.S.A.
Abstract
A synthesis of 8-acetyl-14-benzoylneoline has been effected in five steps from the known alkaloid, delphisine. On the basis of the reported data for “neopelline”, the suggested structure of 8-acetyl-14-benzoylneoline is in error and the existence of “neopelline” in nature is doubtful.
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■ Reaction of N-Benzenesulfonyl-9-azabicyclo[3.3.1]nona-2,6-diene with Diborane: Failure of Cyclic Hydroboration in the Intramolecularly Faces Diene System
Takefumi Momose* and Shohgo Atarashi
*Faculty of Pharmaceutical Sciences, Toyama Medical and Pharmaceutical University, 2630 Sugitani, Toyama, Toyama 930-0194, Japan
Abstract
Hydroboration of N-benzenesulfonyl-9-azabicyclo[3.3.1] nona-2,6-diene gave 2,6-diols and exo,exo-2,7-diol in the ratio of ca. 2.3 : 1, but neither exo,exo-3,7-diol nor the products derived from a boraadamantane were formed. A marked site-selectivity in the hydroxylation was discussed in terms of inductive or spatial effects of the N-substituent.
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■ Pseudobase Formation from Quaternary Pyridinium, Quinolinium and Isoquinolinium Cations
Vilím Simánek* and Vladimír Preininger
*Institute of Medical Chemistry, Palacky University, 3, Hnevotínská, 775 15 Olomouc, Czech Republic
Abstract
A review of recent studies of addition reactions of the hydroxide ion with some quaternary aromatic nitrogen compounds has been presented.