Regular Issue

Vol. 12, No. 5, 1979

15 data found. 1 - 15 listed
Communication | Regular issue | Vol 12, No. 5, 1979, pp. 631 - 636
Published online:
DOI: 10.3987/R-1979-05-0631
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


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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Communication | Regular issue | Vol 12, No. 5, 1979, pp. 637 - 640
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DOI: 10.3987/R-1979-05-0637
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.


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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Communication | Regular issue | Vol 12, No. 5, 1979, pp. 641 - 645
Published online:
DOI: 10.3987/R-1979-05-0641
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.


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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Communication | Regular issue | Vol 12, No. 5, 1979, pp. 647 - 652
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DOI: 10.3987/R-1979-05-0647
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


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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Communication | Regular issue | Vol 12, No. 5, 1979, pp. 653 - 656
Published online:
DOI: 10.3987/R-1979-05-0653
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


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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Communication | Regular issue | Vol 12, No. 5, 1979, pp. 657 - 660
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DOI: 10.3987/R-1979-05-0657
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


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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Communication | Regular issue | Vol 12, No. 5, 1979, pp. 661 - 664
Published online:
DOI: 10.3987/R-1979-05-0661
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


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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Communication | Regular issue | Vol 12, No. 5, 1979, pp. 665 - 668
Published online:
DOI: 10.3987/R-1979-05-0665
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


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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Communication | Regular issue | Vol 12, No. 5, 1979, pp. 669 - 679
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DOI: 10.3987/R-1979-05-0669
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


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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Communication | Regular issue | Vol 12, No. 5, 1979, pp. 681 - 684
Published online:
DOI: 10.3987/R-1979-05-0681
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


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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Communication | Regular issue | Vol 12, No. 5, 1979, pp. 685 - 689
Published online:
DOI: 10.3987/R-1979-05-0685
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


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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Report | Regular issue | Vol 12, No. 5, 1979, pp. 691 - 694
Published online:
DOI: 10.3987/R-1979-05-0691
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


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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Report | Regular issue | Vol 12, No. 5, 1979, pp. 695 - 697
Published online:
DOI: 10.3987/R-1979-05-0695
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


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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Report | Regular issue | Vol 12, No. 5, 1979, pp. 699 - 700
Published online:
DOI: 10.3987/R-1979-05-0699
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


A simple and efficient γ-lactone formation relating to prostaglandin synthesis is described.

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Report | Regular issue | Vol 12, No. 5, 1979, pp. 701 - 702
Published online:
DOI: 10.3987/R-1979-05-0701
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


The title ring system was obtained from the condensation of 3-aminothieno[3,2-e]pyrazolo[4,3-c]pyridine with the appropriate reagents.

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15 data found. 1 - 15 listed