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. 11, 1977
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■ 1,4(2H,5H)-Dioxoimidazo[1,5,4-h,i]indazoline: A New Heterocyclic Ring System
Roy L. Williams,* Anna Ciereszko, Fran Morandini, and Gretchen Williams
*Department of Chemical Sciences, Old Dominion University, Norfolk, Virginia 23508, U.S.A.
Abstract
Thermolysis or photolysis of isatoic acid azide (3) in non-nucleophilic solvents gives rise to a novel rearrangement product which has been described as the 1,4(2H,5H)-dioxoimidazo[1,5,4-h,j]indazoline (8).
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■ Photolysis of Amino-substitutd 1,4-Naphthoquinones
Mitsuo Akiba,* Masao Okuyama, Yoshiyuki Kosugi, and Toyozo Takada
*School of Pharmacy, Tokyo University of Pharmacy and Life Science, 1432-1 Horinouchi, Hachioji, Tokyo 192-0392, Japan
Abstract
Photolysis of pyrrolidino- (3a), piperidino- (3b), and morpholino-1,4-naphthoquinone (3c) has been studied in non-polar and polar solvents, Besides the corresponding dehydro compounds (4), a number of products with degradation of the side ring via an oxazoline (16) and the zwitter ion intermediate (17) were obtained.
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■ Rections of 1-Methylthiabenzene 1-Oxides and 1-Methyl-2-azathiabenzene 1-Oxides with Acetylenedicarboxylate
Motsuaki Watanabe, Kouji Matsuno, Toshio Kinoshita, and Sunao Furukawa*
*Faculty of Pharmaceutical Sciences, Nagasaki University, 1-14, Bunkyo-machi, Nagasaki 852-8521, Japan
Abstract
1-Methylthiabenzene 1-oxide (3a) and 1-methyl-2-azathiabenzene 1-oxide (3b) were synthesized by the reaction of dimethyloxosulfonium methylide and dimethylsulfoximine with ketenethioacetal (2) in the presence of base catalyst. 1-Methylthiabenzene 1-oxides (5a, 5b) and 1-methyl-2-azathiabenzene 1-oxides (5c, 5d) were treated with acetylenedicarboxylate (6) for comparison of chemical reactivities. Biscycloheptatriene derivative (7), 1,3-addition product, was obtained from the former and phthalate derivatives (10a, 10b), 1,4-addition products, from the later as major products.
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■ Studies with Reissert Compounds. Part VI. Change of Pathway Occasioned by Phase Transfer Catalysis: Suppression of N-Acyl Pseudo-base Formation in Favour of a Reissert Reaction
Barrie C. Uff* and Ronald S. Budhram
*Department of Chemistry, Loughborough University of Technology, Loughborough, Leicestershire, LE11 3TU, U.K.
Abstract
Treatment of phthalazine with p-chlorobenzoyl chloride and potassium cyanide in a two-phase system gives an 1-acyl pseudo-base (3, R = 4-ClC6H4). Addition of a phase transfer catalyst to the medium changes the reaction pathway to give a Reissert compound (4, R = 4-ClC6H4) as major product with only a trace of N-acyl pseudo-base. The same change is observed with 5-nitroisoquinoline and a variety of acid chlorides. Inclusion of a phase transfer catalyst also increases the yields of Reissert compounds in reactions in which N-acyl pseudo-bases are not involved.
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■ Chemistry of 8-Azasteroids I. A New Route to 8-Azagonan Derivatives
Csaba Szántay,* András Vedres, and Gábor Tóth
*Institute for Organic Chemistry, Technical University Budapest, H-1521 Budapest, P.O. Box 91Gellért tér 4, Hungary
Abstract
When isoquinoline derivative 1 was reacted with unsaturated ketones 2 or 3, the 8-azagonan ring system was formed in good yield. The stereostructure of diastereoisomers formed has been elucidated.
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■ A New Synthesis of Benzo[a]quinolizines Related to Ipecac Alkaloids
Ichiya Ninomiya,* Toshiko Kiguchi, and Yukiko Tada
*Kobe Women’s College of Pharmacy, Motoyamakita, Higashinad, Kobe, Hyogo 658, Japan
Abstract
Acylation of 1-methyl-3,4-dihydroisoquinoline with substituted acryloyl chlorides followed by photocyclization provided a useful synthetic route for benzo[a]quinolizines (6 - 9).
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■ Molecular Structure of 3β-Acetoxyatractylon
Haruo Ogura,* Kimio Furuhata, Nobuyasu Tanaka, Yoshinori Harada, Yoichi Iitaka, Yoichi Nishikawa, Yohya Watanabe, Takako Sato, and Ichiro Yasuda
*School of Pharmaceutical Sciences, Kitasato University, 5-9-1, Shirokane, Minato-ku, Tokyo 108-8641, Japan
Abstract
The structure of a sesquiterpene 3β-acetoxyatractylon (I) obtained from Atractylodes lancea was confirmed by means of an X-ray crystal structure analysis. The crystal is the orthorhombic, space group P212121, and the structure was solved by MULTAN with final R-value 0.062.
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■ Structure of Casedine
Tuticorin R. Govindachari, Bantwal R. Pai,* Hosbett Suguna, and Manakkal S. Premila
*Department of Chemistry, Presidency College, Madras 600005, India
Abstract
A reinvestigation of the spectral data of the synthetic 1-hydroxy-2,10,11-trimethoxyberbine and natural caseadine shows that their nmr spectra are almost identical with very minor differences; so are their ir spectra in solution except for an additional band at 720 cm-1 in the natural product. These minor differences could not be due to structural or stereochemical differences but perhaps due to some impurity in the natural sample.
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■ A Facile Synthesis of Substituted Pyrimidines by Ring Transformation of 1,3-Oxazin-4-ones
Yutaka Yamamoto* and Yutaka Azuma
*Faculty of Pharmaceutical Sciences, Tohoku Pharmaceutical University, 4-4-1 Komatsushima, Aoba-ku, Sendai 981-8558, Japan
Abstract
Treatment of 6-methyl-2-phenyl-4H-1,3-oxazin-4-one (1) and 2-benzyl-2-ethoxy-6-methyl-3,4-dihydro-2H-1,3-oxazin-4-one (2) with thioamides led to conversion into the corresponding 2,6-disubstituted 5-acetyl-4-hydroxypyrimidines 3a-e and 4a,b, respectively.
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■ Ketonic Character of Alkyl 3-Hydroxypyrrole-2-carboxylates: The First Entry into 2,3-Unsubstituted 4-Oxo-2-pyrrolines
Takefumi Momose,* Tetsuaki Tanaka, and Takashi Yokoto
*Faculty of Pharmaceutical Sciences, Toyama Medical and Pharmaceutical University, 2630 Sugitani, Toyama, Toyama 930-0194, Japan
Abstract
A general synthetic route to 4,5-unsubstituted 3-hydroxypyrrole-2-carboxylates (IV) has been developed, and their marked β-keto ester nature has been demonstrated on alkylation and Michael addition leading to 2,3-unsubstituted 4-oxo-2-pyrrolines.
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■ 4-Oxo-2-pyrrolines Carrying No Substituents on the Ring Carbon: Substituent Effects in the Tautomerism between 4-Oxo-2-pyrrolines and 3-Hydroxypyrroles
Takefumi Momose,* Tetsuaki Tanaka, and Takashi Yokota
*Faculty of Pharmaceutical Sciences, Toyama Medical and Pharmaceutical University, 2630 Sugitani, Toyama, Toyama 930-0194, Japan
Abstract
Syntheses of 4-oxo-2-pyrrolines having no substituents on the ring carbon were accomplished, and the substituent effects governing the tautomerism between hydroxypyrroles and pyrrolinones were investigated in a series of 3-hydroxypyrroles synthesized.
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■ Cyclodextrin-Nitrophenol Systems Studied by Polarography
Tetsuo Osa,* Tomokazu Matsue, and Masamichi Fujihara
*Graduate School of Pharmaceutical Sciences, Tohoku University, Aramaki, Aoba-ku, sendai 980-8578, Japan
Abstract
The effects of added α- and β-cyclodextrins on the half-wave potentials and the diffusion coefficients of o-, m-, and p-nitrophenols were examined, and a new polarographic method for determining the dissociation constants of cyclodextrin-substrate complexes was proposed. The dissociation constants of p-nitrophenol-cyclodextrin complexes obtained by polarographic method are in good agreement with those determined by spectrophotometric method. This polarographic method is applicable to many electroactive compound-cyclodextrin complexes whose dissociation constants can hardly be determined by spectrophotometric method.
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■ The Rections and Syntheses with Organometallic Compounds. VIII. The Total Synthesis of Sendaverine by Use of the Palladium Catalyzed Insertion of Carbon Monoxide
Miwako Mori, Katsumi Chiba, and Yoshio Ban*
*Faculty of Pharmaceutical Sciences, Hokkaido University, Kita 12 Nishi 6, Kita-ku, Sapporo, Hokkaido 060-0812, Japan
Abstract
The alkaloid, sendaverine (3), which was isolated from Corydalis aurea Willd. was synthesized from the 2-bromophenethylamine derivative (10) as an extension of the synthetic method of benzolactams by palladium catalyzed insertion of carbon monoxide.
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■ Oxidative Cyclization of Morusin with Manganese Dioxide
Taro Nomura,* Toshio Fukai, and Masa Katayanagi
*School of Pharmaceutical Sciences, Toho University, 2-2-1, Miyama, Funabashi, Chiba 274-8510, Japan
Abstract
Oxidative cyclization of morusin (I) by using one-electron transfer oxidizing agents (manganese dioxide, silver oxide) afforded morusin hydroperoxide (II). A similar reaction was carried out in the presence of 2,4,6-tri-tert-butylphenol, a radical quencher, to give compounds (V-VIII) coupled with the 2,4,6-tri-tert-butylphenoxy radical. On the basis of above results, the possible mechanism of this oxidative cyclization was discussed. In addition, cyclomorusin (III) and XI were obtained from I with manganese dioxide in a nitrogen atmosphere.
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■ Application of Enamine Photocyclization to a Total Synthesis of (±)-Cryptaustoline
Ichiya Ninomiya,* Junko Yasui, and Toshiko Kiguchi
*Kobe Women’s College of Pharmacy, Motoyamakita, Higashinad, Kobe, Hyogo 658, Japan
Abstract
(±)-Cryptaustoline (1) was synthesised by the route including enamine photocyclisation.
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■ A Convenient Photoosynthsis of Aziridino-pyrrolo[1,2-a]benz[f]indoloquinones as Model Mitomycins in a One-pot Reaction
Mitsuo Akiba* and Toyozo Takada
*School of Pharmacy, Tokyo University of Pharmacy and Life Science, 1432-1 Horinouchi, Hachioji, Tokyo 192-0392, Japan
Abstract
The aziridinopyrrolo[1,2-a]benz[f]indoloquinones (4b) were photosynthesized as model mitomycins from 2-chloro-3-ethoxycarbonylcyanomethyl-1,4-naphthoquinone (1b) and 6-(4-bromophenyl)-3,6-diazabicyclo[3.1.0]hexane in a one-pot reaction.
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■ Preparation of 3,4,5-Trisubstituted Pyrazoles from 2,2-Dioxoketene-S,S-acetals
Edward C. Taylor* and W. Ronald Purdum
*Department of Chemistry, Princeton University , Princeton, New Jersey 08544, U.S.A.
Abstract
2,2-Dioxoketene-S,S-acetals (5 - 7) react with hydrazine to give 5-methylthiopyrazoles (8 - 10) rather than diazafulvenes (A). Nucleophilic displacement of the 5-methylthio (or the derived 5-methylsulfonyl) substituent in these pyrazoles was not possible.
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■ A New Synthesis of 3,4-Diaminothiophenes
Yoshinori Tominaga, Hiroshi Fujito, Yoshiro Matsuda, and Goro Kobayashi*
*Faculty of Pharmaceutical Sciences, Nagasaki University, 1-14, Bunkyo-machi, Nagasaki 852-8521, Japan
Abstract
3,4-Diaminothiophenes were synthesized by the cleavage of pyridine ring in 3-aminothien-4-yl-pyridinium iodides, which were prepared by the reaction of 1-cyanomethylpyridinium chloride with carbon disulfide and alkylating agents in the presence of alkali, followed by the base-catalyzed interamolecular cyclization.
The reaction of 3,4-diaminothiophenes with 1,2-dicarbonyl derivatives gave thieno[3,4-b]pyrazines in a good yield.
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■ A Novel Ring Contraction of 4-Bromo-2,3-dihydrobenzo[b]thiepin-5(4H)-one
Mitsuhito Okitsu, Hiroshi Shimizu, Tadashi Kataoka, and Mikio Hori*
*Department of Pharmacognosy, Gifu College of Pharmacy, 6-1 Mitahora-higashi 5-chome, Gifu 502-8585, Japan
Abstract
The unexpected ring contraction of 4-bromo-2,3-dihydrobenzo[b]thiepin-5(4H)-one (I) to 3-oxo-2,3-dihydro[l]benzothiophen-2-spirocyclopropane (II) besides 2,3-dihydro[l]benzothieno[3,2-b]furan (III) is reported.
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■ Proton Magnetic Resonance Spectra of Some Alkylpyridine and Alkylpyrazine N-Oxides
Akihiro Ohta,* Yasuo Akita, and Chiseko Takagi
*Tokyo University of Pharmacy and Life Science, 1432-1 Horinouchi, Hachioji, Tokyo 192-0392, Japan
Abstract
In the PMR spectra of some 2-alkylpyridine 1-oxides and 2,5-dialkylpyrazine 1-oxides, except α-picoline 1-oxide and 2,5-dimethylpyrazine 1-oxide, the signals of the α-protons of the side chain at C-2 appeared in a lower field than those of the parent amines. It is concluded that this shift to the lower field is caused by the anisotropic effect of the N-O group.
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■ Derivatives of Morphie. VII. Constitution of a Presumed Isomer of 5-Benzyldihydrocodeinone
Surendra P. Bhatnagar and Ulrich Weiss*
*Laboratory of Chemical Diseases, National Institute of Diabetes and Digestive and Kidney, National Institute of Health, Bethesda, MD 20892, U.S.A.
Abstract
Work by Small et al. (1938) has shown that Zeisel-demethylation of 5-benzyldihydrocodeinone (1) yields an alkali-insoluble product (3) in addition to the expected, alkali-soluble 5-benzyldihydromorphinone (2). The hitherto unknown structure of the alkali-insoluble compound is now determined by spectroscopic methods, and it is shown to be a secondary product formed from (2) during the demethylation.
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■ The Partial Synthesis of Structural Analogs of Tubulosine
Françoise Sigaut-Titeux, Louisette Le Men-Oliver, and Jean Le Men*
*Facluté de Pharmacie, UPRES-A/CNRS 6013, Insitut des Biomoleculés, 51, rue Cognacq-Jay, F-51096 Reims Cedex, France
Abstract
The two couples of title derivatives 4, 5 and 6, 7 were obtained from the Pictet-Spengler condensation of homoveratrylarmine with dihydrocorynantheal 2 and corynantheidal 3, respectively. Their structure and absolute configuration were determined on the basis of their mass and NMR spectra, and of their CD curves.
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■ Synthesis of Xanthines by the Reaction of 6-Amino-5-arylazouracils or 5-Arylazobarbituric Acids with Alkylamines
Masatsugu Higuchi and Fumio Yoneda*
*Faculty of Pharmaceutical Sciences, Kumamoto University, 5-1 Oe-hon-machi, Kumamoto 862-0973, Japan
Abstract
Treatment of 6-amino-5-arylazouracils or 5-arylazobarbituric acids with alkylamines offers a convenient synthetic method of xanthines.
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■ Reissert Compounds Studies. XXIX. An Improved Synthesis of the Phthalazine Reissert Compound by Phase Transfer Catalysis
Debkumar Bhattacharjee and Frank D. Popp*
*Department of Chemistry, University of Missouri-Kansas City, Kansas City, Missouri 64110, U.S.A.
Abstract
Treatment of phthalazine with benzoyl chloride and potassium cyanide gives in addition to the Reissert compound, the pseudo-base. Use of a phase transfer catalyst suppresses the formation of the pseudo-base.
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■ A New Synthesis of 6-Hydroxypteridine Derivatives
Keitaro Senga,* Kayoko Shimizu, and Sadao Nishigaki
*Pharmaceutical Institute, School of Medicine, Keio University, Shinanomachi 35, Shinjuku, Tokyo 160-0016, Japan
Abstract
Treatment of 6-amino-l,3-dimethyl-5-nitrosouracil with phenacylpyridinium halides in pyridine containing aqueous sodium hydroxide gave the corresponding 7-aryl-6-hydroxy-1,3-dimethyllumazines.
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■ Preparation of 3-Anilino-5-diazouracils and Their Conversion into Indolo[2,3-d]pyrimidines
Yoshiharu Sakuma and Fumio Yoneda*
*Faculty of Pharmaceutical Sciences, Kumamoto University, 5-1 Oe-hon-machi, Kumamoto 862-0973, Japan
Abstract
The diazotization of 5-amino-3-methyl-6-(N-substitutedanilino)uracils with sodium nitrite in acetic acid led to the formation of the corresponding stable 5-diazouracils, which were converted into 3-methyl-9-substituted indolo[2,3-d]pyrimidine-2,4(1H,3H)diones by both photolysis and thermolysis.
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■ A Novel Synthesis of v-Triazolo[4,5-d]pyrimidines
Keitaro Senga,* Misuzu Ichiba, and Sadao Nishigaki
*Pharmaceutical Institute, School of Medicine, Keio University, Shinanomachi 35, Shinjuku, Tokyo 160-0016, Japan
Abstract
Treatment of 6-azido-l,3-dimethyluracil with alkyl halides in dimethylformarnide containing potassium carbonate gave the corresponding 1-alkyl-4,6-dimethyl-v-triazolo[4,5-d]pyrimidine-5,7(4H,6H)-diones via 4,6-dimethyl-v-triazolo[4,5-d]pyrimidine-5,7(4H,6H)-dione.
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■ New Syntheses of Purines and Oxazolo[5,4-b]pyrimidines
Keitaro Senga,* Junko Sato, Kayoko Shimizu, and Sadao Nishigaki
*Pharmaceutical Institute, School of Medicine, Keio University, Shinanomachi 35, Shinjuku, Tokyo 160-0016, Japan
Abstract
Treatment of 6-amino-5-benzylideneamino-1,3-dimethyluracils and 5-benzylideneamino-1,3-dimethylbarbituric acids with N-bromosuccinimide in chloroform afforded the corresponding purines and oxazolo[5,4-d]pyrimidines respectively.
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■ Synthesis of 3-Arylfervenulins
Misuzu Ichiba, Sadao Nishigaki, and Keitaro Senga*
*Pharmaceutical Institute, School of Medicine, Keio University, Shinanomachi 35, Shinjuku, Tokyo 160-0016, Japan
Abstract
Treatment of 6-hydrazino-1,3-dimethyl-5-nitrosouracil with benzyl halides (or phenacyl halides) in dimethyl sulfoxide gave the corresponding 3-arylfervenulins.
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■ An Abnormal Formation of Oxazolo[5,4-d]pyrimidines from 6-(Benzylidine-1’-methylhydrazino)-1,3-dimethyluracils
Keitaro Senga,* Yukako Kanamori, and Sadao Nishigaki
*Pharmaceutical Institute, School of Medicine, Keio University, Shinanomachi 35, Shinjuku, Tokyo 160-0016, Japan
Abstract
Treatment of 6-(benzylidene-1’-methylhydrazino)-1,3-dimethyluracils with sodium nitrite in acetic acid gave the corresponding 2-aryl-5,7-dimethyloxazolo[5,4-d]pyrimidine-4,6(5H,7H)-diones.