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. 3, No. 2, 1975
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■ The Preparation of Some CH2NMe3-Substituted Bicyclo[3.2.1]octanes. The Rotameric Behaviour of the CH2NMe3-Substituent
Robert Van Cauwenberghe, Marc Anteunis,* and Christian Becu
*Laboratory for NMR Spectroscopy, Department of Chemistry, State University of Gent, Krijgslaan 271 (S.4bis), B-9000 Gent, Belgium
Abstract
The conformations of cis-2-CH2X-4-Me-3,6,8-trioxa-bicyclo[3,2,1]octane (X=Cl, NMe3) and cis-2-CH2NMe3-4-Me-3,8-dioxa-6-aza-bicyclo[3,2,1]octane are investigated by 1H-NMR spectroscopy. As a result of the imposed conformation of the five membered ring-moiety, the orientation of the side-chain is that with the C2-N+ adjacent O3-C2 bonds in an antiperiplanar relationship. This situation corroborates a previously proposed parallelity effect between p-O and C-N+.
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■ Observation of Regioselectivity in Cycloaddition Reaction of Oxabenzonorbornadiene with 1,3-Diphenylisobenzofuran
Tadashi Sasaki,* Ken Kanematsu, and Kinji Iizuka
*Institute of Applied Organic Chemistry, Faculty of Engineering, Nagoya University, Chikusa, Nagoya, Aichi 464-8601, Japan
Abstract
Cycloaddition reaction of oxabenzonorbornadiene with 1,3-diphenylisobenzofuran gave two 1:1 adducts accompanied with 1,4-diphenylnaphthalene. The structural elucidations of these adducts were accomplished by spectral inspections. The product distributions are observed to be dependent on the reaction temperatures.
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■ A New Synthesis of Alloxazine 5-Oxides
Fumio Yoneda,* Yoshiharu Sakuma, and Shigeru Matsumoto
*Faculty of Pharmaceutical Sciences, Kumamoto University, 5-1 Oe-hon-machi, Kumamoto 862-0973, Japan
Abstract
The condensation reaction of 4,6-dimethyloxadiazolo[3,4-d]pyrimidine-5,7(4H,6H)dione 1-oxide with anilines offers a new synthetic method for 1,3-dimethylalloxazine 5-oxides.
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■ Conversion of Δ4-3-Ketosteroids to Steroidal[3,4-b]furans and Steroidal[6,7-b]indoles
Maghar S. Manhas, John W. Brown, and Upendra K. Pandit*
*Organic Chemistry Laboratory, University of Amsterdam, Nieuwe Achtergracht 129, 1018 WS Amsterdam, The Netherlands
Abstract
Reactions of steroidal Δ3,5-dienamine 4 with ring substituted phenacyl bromides and ring substituted benzenodiazonium fluoborates, followed by Fischer-indole cyclization, lead to the formation of steroidal[3,4-b]furans (5a-g) and steroidal[6,7-b]indoles (7a-j), respectively.
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■ Chlorination of 1-Benzyl- or 1-Phenethyltetrahydroisoquinolines via a p-Quinol Acetate
Hiroshi Hara, Osamu Hoshino, and Bunsuke Umezawa*
*Faculty of Pharmaceutical Sciences, Science University of Tokyo, 2641 Yamazaki, Noda, Chiba 278-8510, Japan
Abstract
Reaction of p-quinol acetates derived from 1-benzyl- (Ib and Ic) or 1-phenethyl- (Id, Ie and If) tetrahydroisoquinolines with conc. Hydrochloric acid gave the corresponding 8-chloro derivatives in fair yields.
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■ Benzyne Reaction of 1-Halogenophenethyl-3H-2-benzazepine
Shinzo Kano,* Toshihisa Ogawa, Tsutomu Yokomatsu, Youko Takahagi, Eiji Komiyama, and Shiroshi Shibuya
*School of Pharmacy, Tokyo University of Pharmacy and Life Science, 1432-1 Horinouchi, Hachioji, Tokyo 192-0392, Japan
Abstract
5,6,7,8,13,14-Hexahydro-13,14-methanodibenzo[b,f]azecines were obtained by the reaction of 1,2,4,5-tetrahydro-1-(2-bromo-4,5-dimethoxyphenethyl)-2-methyl-3H-2-benzazepines with sodium methylsulfinylmethanide.
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■ Fused Thieno[3,2-d]-v-triazine-4(3H)-ones
Stewart W. Schneller* and Fred W. Clough
*Department of Chemistry, University of South Florida, Tampa, Florida 33620, U.S.A.
Abstract
A convenient preparation of benzo[b]thieno[3,2-d]-v-triazine-4(3H)-one, pyrido[3’,2’:4,5]thieno[3,2-d]-v-triazine-4(3H)-one, and pyrazino[2’,3’:4,5]thieno[3,2-d]-v-triazine-4(3H)-one as representatives of fused tricyclic thieno[3,2-d]-v-triazines is reported.
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■ Biotransformnation of (±)-Reticuline into (±)-Coreximine with Rat Liver
Tetsuji Kametani,* Makoto Takemura, Keiichi Takahashi, Masataka Ihara, and Keiichiro Fukumoto
*Pharmaceutical Institute, Tohoku University, Aobayama, Sendai 980-8578, Japan
Abstract
The biotransformation of (±)-reticuline (1) inta (±)-coreximine (2) in the rat and with homogenised rat liver was demonstrated by tracer experiments with (±)-[N-14CH3]reticuline (1).
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■ Total Synthesis of (±)-Orientalidine
Tetsuji Kametani,* Akira Ujiie, Masataka Ihara, and Keiichiro Fukumoto
*Pharmaceutical Institute, Tohoku University, Aobayama, Sendai 980-8578, Japan
Abstract
The total synthesis of (±)-orientalidine (1) was accomplished by treatment of (±)-demethylmecambridine (2) with methylene chloride and sodium hydride in dimethylformamide. A synthesis of the tetrahydroprotoberberine (7) containing the 1,3-dioxane system is also described.
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■ Reduction of 3-Hydroxy-3-(3-hydroxyiminobutyl)oxindoles with Sodium Borohydride in the Presence and in the Absence of Cobalt Ion
Noboru Shoji, Yoshikazu Kondo, and Tsunematsu Takemoto*
*Pharmaceutical Institute, Tohoku University, Aobayama, Sendai 980-8578, Japan
Abstract
Reduction of 3-hydroxy-3-(3-hydroxyiminobutyl)oxindole (II) and its 1-methyl analog (I) with sodium borohydride afforded the corresponding pyrido[2,3-b]indoles. On the other hand, reduction of I with sodium borohydride in the presence of cobalt ion gave 3-hydroxy-3-(3-hydroxybutyl)-1-methyloxindole (VIII).
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■ Transformation of the Spiroisoquinoline to the Benzindanoazepine
Tetsuji Kametani,* Shoji Hirata, Satoshi Hibino, Hideo Nemoto, Masataka Ihara, and Keiichiro Fukumoto
*Pharmaceutical Institute, Tohoku University, Aobayama, Sendai 980-8578, Japan
Abstract
The spiroisoquinolines (5), (8), (11), and (14) were transformed to the benzindanoazepines (6,7), (9,10), (12,13), and (15,16), in high yield, respectively, under the reductive condition using zinc and acetic acid.
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■ A Facile Synthesis of 7-Phenylpyrido[3,4-d]pyridazine-1,4(2H,3H)-dione
Yoshiro Usui,* Yukio Hara, Norio Shimamoto, Shojiro Yurugi, and Toru Masuda
*Central Research Division, Takeda Chemical Industries, Ltd., 17-85 Jusohonmachi 2-chome, Yodogawa-ku, Osaka 532-8686, Japan
Abstract
1,4-Cycloaddition reactions of 4-phenyloxazole (IV) with a variety of maleic acid derivatives were undertaken. Maleimide derivatives were proved to be the most efficient dienophiles, affording 1,4-cycloadduct, 3-phenyl-7-oxa-2-aeabicyclo[2.2.1]hept-2-ene-5,6-dicarboximide derivatives (XII) in good yields.
Acid-catalyzed dehydration of XII, followed by the reaction of the resulting XIII with hydrazine, gave 7-phenylpyrido[3,4-d]pyridazine-l,4(2H,3H)-dione (II), which is the key compound for the synthesis of a potent diuretic, DS-511 (I). Structures of by-products formed in those reactions were elucidated.
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■ Photoreduction of Pyrimidine Nucleosides in the Presence of Sulfite Ion
Yoshikazu Kondo,* Fumihiko Yoshizaki, and Tsunematsu Takemoto
*Pharmaceutical Institute, Tohoku University, Aobayama, Sendai 980-8578, Japan
Abstract
Irradiation of aqueous solutions of uridine and thymidine at pH 9 with 2537 Å-light in the presence of bisulfite revealed complete disappearance of the uv absorption. Hydrolysis followed by purification on silica gel column chromatography gave the corresponding dihydropyrimidine bases. In this reaction of thymidine 2-oxo-4-methoxy-5-methylhexahydropyrimidine was obtained in addition to dihydrothymine. Excess bisulfite was unaffected to the resulting dihydropyrimidine nucleus.
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■ The Total Synthesis of (±)-Mappicine
Tetsuji Kametani,* Hiromitsu Takeda, Hideo Neoto, and Keiichiro Fukumoto
*Pharmaceutical Institute, Tohoku University, Aobayama, Sendai 980-8578, Japan
Abstract
Reduction of 7-methoxycarbonyl-8-methylindolizino[l ,2-b]quinolin-9(11H)-one (3), prepared from 7-methoxycarbonylindolizino[1,2-b]quinolin-9(11H)-one (2), gave the correspondmg alcohol (5), which was converted into (±)-mappicine (7) through the aldehyde (6).
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■ An Improved Synthesis of the Pyridocarbazole Indole Alkaloid Olivacine
James P. Kutney* and David S. Grierson
*Department of Chemisry, University of British Columbia, Vancouver 8, V5T 1W5, Canada
Abstract
An improved synthesis of the alkaloid olivacine (I) has been developed. Employing tryptophol (III) as starting material, the synthetic sequence provides, in three high-yielding steps, the important aldehyde intermediate X. The latter has been previously converted in an efficient manner to the desired alkaloid.
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■ A Total Synthesis of (±)-Yohimbine
Tetsuji Kametani,* Masahiro Kajiwara, Tamiko Takahashi, and Keiichiro Fukumoto
*Pharmaceutical Institute, Tohoku University, Aobayama, Sendai 980-8578, Japan
Abstract
A total synthesis of (±)-yohimbine (8) from 1,2,3,4,5,6,7,12b-octahydroindolo[2,3-a]quinolizin-2-one (5) has been achieved through 15,16-dehydroyohimbinone (6) and yohimbinone (7). Two kinds of novel syntheses of (5) are also reported.
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■ A Regioselective Synthesis of Pyrrolo- and Pyrido[2,3-d]pyrimidine-2,4-diones
Yasumitsu Tamura,* Toshiko Sakaguchi, Tomomi Kawasaki, and Yasuyuki Kita
*Faculty of Pharmaceutical Sciences, Osaka University, 1-6 Yamadaoka, Toyonaka, Osaka 560-0043, Japan
Abstract
Reaction of diacylethylene with 6-amino-1,3-dimethyluracil gives rise to either pyrrolo- or pyrido[2,3-d]pyrimidine-2,4-dione by the selection of reaction conditions.