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. 12, No. 5, 1979
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■ Reaction at C-9 of Acridine Derivatives. Part XVI. Kinetics of Condensation of 9-Chloroacridine with Some Phenols
Andrzej Ledóchowski,* Antoni Kunikowski, Ewa Zylkiewicz, and Maria Drzewicka
*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 kinetics of reactions of 9-chloroacridine with p-chlorophenol, phenol and p-cresol in CCl4 at 25 - 60°C was found to be approximate to the second order equation under the conditions used. The most reactive was p-chlorophenol, less phenol and even a little less p-cresol. The reaction occurs through the intermediate, i.e., a hydrogen bonded complex, 9-chloroacridine.phenol, formed in the first reversible reaction step (equations (3) and (4)). The different reactivities observed for variously substituted phenols are due to different strengths of hydrogen bonds formed by them with the acridine nucleus decreasing in this way the electron density at C-9 atom.
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■ Synthesis of Tricyclic Arylspiro Compounds as Potential Antileukemic and Anticonvulsant Agents
Magid A. Abou-Gharbia* and Peter H. Doukas
*Department of Medical Chemistry, School of Pharmacy, Temple University, 3307 North Broad Street, Philadelphia, Pennsylvania 19140, U.S.A.
Abstract
Spiroaziridines, carboxanilides and spirosuccinimides were prepared as part of a study concerned with the relationships between chemical structure and biological activity.
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■ Primary and Secondary Photochemistry of α-Tropolone Methyl Ether
O. L. Chapman,* M. A. Hems, J. D. Lassila, and C. Kreil
*Department of Chemistry, University of California, One Shields Avenue, Davis, CA 95616-5295, U.S.A.
Abstract
The photoisomerization of α-tropolone methyl ether to 1-methoxybicyclo[3.2.0]hepta-3,6-dien-2-one proceeds via the S1 state. Irradiation of 1-methoxybicyclo[3.2.0]hepta-3,6-dien-2-one gives 6-methoxybicyclo[3.2.0]hepta-3,6-dien-2-one and 7-methoxybicyclo[3.2.0]hepta-3,6-dien-2-one. The 6-methoxy product is formed via α-cleavage in the T1 state. The 7-methoxy product is formed in a process involving a deep-seated skeletal rearrangement. The first step in this rearrangement involves formation of cis,cis-2-methoxybicyclo[2.1.0]pent-2-en-5-yl ketene from the S1 state of 1-methoxybicyclo[3.2.0]hepta-3,6-dien-2-one. The ketene intermediate is converted to 7-methoxybicylo[3.2.0]hepta-3,6-dien-2-one by a facile Cope rearrangement which proceeds rapidly above 233K.
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■ Mechanism of Photodetosylation of N-Tosyl-1,2,3,4-tetrahydroisoquinolines Involving Electron Transfer in the Excited State
Tatsuo Hamada, Atsushi Nishida, and Osamu Yonemitsu*
*Faculty of Pharmaceutical Sciences, Hokkaido University, Kita 12 Nishi 6, Kita-ku, Sapporo, Hokkaido 060-0812, Japan
Abstract
Umezawa and Hoshino reported that on irradiation N-tosyl-6,7-dimethoxy-1,2,3,4-tetrahydroisoquinolines (1) gave the detosylated, 3,4-dihydroisoquinolines (2) accompanied by the corresponding 1,2,3,4-tetrahydroisoquinolines (3) and aromatized isoquinolines (4), while in the presence of NaBH4 only 3 was isolated in high yield. The mechanism of this photodetosylation has now been elucidated. Thus, the reaction was initiated by the formation of exciplex or the electron transfer between the excited dimethoxybenzene group and the tosyl group followed by the formation of a biradical (7) and an N-radical (9), which readily changed to 2. Oxidation-reduction of 7 and 9 probably gave 3 and 4. In the presence of NaBH4, both 7 and 9 were reduced to 3. Experiments using deuterated compounds revealed that the routes via 7 and 9 acted almost equally in the photodetosylation.
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■ The Substitutent Effect and Assignment of the 13C-NMR Spectra of Some 2-Substituted 1,3-Diazazulenes
Hitoshi Takeshita* and Hiroaki Mametsuka
*Instituete of Advanced Material Study, Kyushu University, 6-1, Kasuga-koen, Kasuga 816-8580, Japan
Abstract
The 13C-NMR spectral signals of 1,3-diazazulene derivatives were unequivocally assigned by aids of 2H and 15N labellings. Variation of the C-2 substituents caused no appreciable effect on the chemical shifts of C-5 and C-9.
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■ N-Substituent Effect of 4-Amino-3-penten-2-one in the Reaction with Phenylhydrazine
Choji Kashima,* Shunichi Shirai, and Yasuhiro Yamamoto
*Department of Chemistry, University of Tsukuba, 1-1-1 Ten-nodai, Tsukuba-shi, Ibaraki, 305-8571, Japan
Abstract
The reaction rates of p-substituted 4-amino-3-penten-2-ones with phenylhydrazine were not comparable to the value of superdelocalizability for a nucleophile, but for an electrophile. From this result, the rate determing step was speculated to be the protonation on a substrate. The electron-donating group on nitrogen atom accelerated the reaction of 3-amino-2-en-1-ones with nucleophiles, especially in the presence of acid.
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■ Formation of Primary Adducts in 1,3-Dipolar Cycloaddition of Disubstituted Cycloimmonium Ylides with 1,2,3-Triphenylcyclopropene
Kiyoshi Matsumoto* and Takane Uchida
*Graduate School of Human and Environmental Studies, Kyoto University, Yoshida-Nihonmatsu-cho, Sakyo-ku, Kyoto 606-8501, Japan
Abstract
Pyridazinium, phthalazinium, 3-cyanopyridinium and 4-cyanopyridinium dicyanomethylides and isoquinolinium bis-(methoxycarbonyl)methylide underwent cycloaddition with triphenylcyclopropene to give the corresponding primary adducts (3 or 4). In the latter two cases, the indolizines (5a and 5e) were also isolated.
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■ Intramolecular Cycloaddition of 2-(2-Allylphenoxy)pyrimidines
Teruomi Jojima,* Hideo Takeshiba, and Takao Kinoto
*Agroscience Research Laboratories, Sankyo Co., Ltd., 1041 Yasu, Yasu-cho, Yasu-gun, Shiga 520-2342, Japan
Abstract
Novel ring fused heterocycles, 3, 10a-(11-azaetheno)-3,4,4a,10a-tetrahydro-[1]benzopyrano[2,3-b]pyridines were synthesized by the reaction of 2-chloropyrimidines with 2-allylphenols in the presence of a base. These compounds were formed by the intramolecular cycloaddition of initially formed 2-(2-allylphenoxy)pyrimidines.
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■ Synthetic Studies on β-Lactam Antibiotics III. Synthesis of New Bicyclic β-Lactam Ring System, 12-Oxo-4,8-dithia-1-azabicyclo[8.2.0]dodec-2-enes
Tetsuji Kametani,* Shuichi Yokohama, Yuichi Shiratori, Fumio Satoh, Masataka Ihara, and Keiichiro Fukumoto
*Pharmaceutical Institute, Tohoku University, Aobayama, Sendai 980-8578, Japan
Abstract
N-(α-Ethoxycarbonyl-β,β-diethoxyethyl)-3-phenyl-4-styryl-2-azetidinone (2) was converted to 2-ethoxycarbonyl-12-oxo-11-phenyl-4,8-dithia-1-azabicyclo[8.2.0]dodec-2-ene (11) by the following reactions, namely ozonolysis, reduction, tosylation, thioacetalisation and halogenation. Similarly, 2-ethoxycarbonyl-12-oxo-4,8-dithia-1-azabicyclo[8.2.0]dodec-2-ene (12) was synthesised from N-(α-ethoxycarbonyl-β,β-diethoxyethyl)-4-styryl-3-thiophenoxy-2-azetidinone (3).
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■ Synthesis of 4H-1,4-Benzothiazine Derivatives through Condensation of o-Aminothiophenol with α-Cyano-α-methylthioacetophenones
Shinzo Kano,* Yoko Yuasa, Toshihiro Ono, and Shiroshi Shibuya
*School of Pharmacy, Tokyo University of Pharmacy and Life Science, 1432-1 Horinouchi, Hachioji, Tokyo 192-0392, Japan
Abstract
Condensation of methylthioacetonitrile with methyl benzoates in THF at room temperature yielded the corresponding α-cyano-α-methylthioacetophenones (2a-2e). These α-substituted acetophenones were heated with o-aminophenol in DMSO at 110°C for 10 hr to give 2-cyano-3-phenyl-4H-1,4-benzothiazines (5a-5e).
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■ The Synthesis of a Potential Intermediate to Apomitomycin
Tetsuji Kametani,* Yoshio Kigawa, Hideo Nemoto, Masataka Ihara, and Keiichiro Fukumoto
*Pharmaceutical Institute, Tohoku University, Aobayama, Sendai 980-8578, Japan
Abstract
Condensation of methyl α-bromo-(2-bromo-4,5-dimethoxyphenyl)acetate (10) with 2-thiopyrrolidone (11) and with trans-3-acetoxy-4-(N-ethoxycarbonyl-N-methylamino)-2-thiopyrrolidone (14) gave in high yields methyl (Z)-α-(2-bromo-4,5-dimethoxyphenyl)-α-pyrrolidine-2-ylideneacetate (12), and methyl α-[3-acetoxy-4-(N-ethoxycarbonyl-N-methylamino)pyrrolidine-2-ylidene]acetates (15) and (16), respectively. Treatment of compounds 12 and 15 or 16 with sodium hydride and cuprous bromide in dimethylformamide afforded, again in good yields, methyl 6,7-dimethoxy-1H-pyrrolo[1,2-a]indole-9-carboxylate (13) and methyl trans-1-acetoxy-2-[N-ethoxycarbonyl-N-methylamino]-6,7-dimethoxy-1H-pyrrolo[1,2-a]indole-9-carboxylate (17), respectively.
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■ A New Synthesis of 5-Aryl-5-deazaflavins [5-Arylpyrimido[4,5-b]quinoline-2,4(3H,10H)-diones]
Fumio Yoneda,* Toshiko Asano, Kinshiro Tsukuda, and Akira Koshiro
*Faculty of Pharmaceutical Sciences, Kumamoto University, 5-1 Oe-hon-machi, Kumamoto 862-0973, Japan
Abstract
The condensation of 6-(N-alkylanilino)-3-methyluracils with aryl aldehydes in the presence of polyphosphoric acid afforded the corresponding 5-aryl-3-methylpyrimido[4,5-b]quinoline-2,4(3H,10H)-diones (5-aryl-3-methyl-5-deazaflavins) in a single step and in high yields. These compounds were reduced to the corresponding 5-aryl-1,5-dihydro-5-deazaflavins by ethanolic potassium hydroxide.
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■ New Synthesis of Aminopropylbensenes and 1,2,3,4-Tetrahydroazocines from N-Substituted Tetrahydronicotinamides with Acetylenic Esters
R. Morrin Acheson and Giuseppe Paglietti*
*Instituto di Chimica Farmaceutica, University of Sassari, Via Muroni 23/a, 07100 Sassari, Italy
Abstract
Some N-substituted tetrahydronicotinamides (1) and dimethyl acetylenedicarboxylate (DMAD) gave the dienamines (3) through a known type of carboxamide elimination. However, these compounds further undergo cycloaddition to DMAD and via the intermediate (5) formed the aminopropylbenzenes (7-9) by a trans-elimination. In contrast (1b) with methyl propiolate, along with small amounts of dienamine (4) and aminopropylbenzene (10), gave in 40% yield the tetrahydroazocine (12), thus providing a new route to this class of heterocycles.
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■ An Efficient γ-Lactone Formation Relating to Prostaglandin Synthesis
Seiichi Takano,* Hiromitsu Iwata, and Kunio Ogasawara
*Pharmaceutical Institute, Tohoku University, Aobayama, Sendai 980-8578, Japan
Abstract
A simple and efficient γ-lactone formation relating to prostaglandin synthesis is described.
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■ A New Tetracyclic Heteroaromatic Ring System — Thieno[3”,2”:5’,6’]pyrido[3’,4’:3,4]pyrazolo[1,5-a]pyrimidine
Misbahul Ain Khan* and Alice Maria Coimbra Rolim
*Seção de Quimica, Instituto Militar de Engenharia, Urca, 20.000 Rio de Janeiro, RJ, Brazil
Abstract
The title ring system was obtained from the condensation of 3-aminothieno[3,2-e]pyrazolo[4,3-c]pyridine with the appropriate reagents.