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. 7, 1975
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■ A Simple Synthesis of Benzopyrans
Tetsuji Kametani,* Kazuo Kigasawa, Mineharu Hiiragi, Haruhide Ishimaru, and Nagatoshi Wagatsuma
*Pharmaceutical Institute, Tohoku University, Aobayama, Sendai 980-8578, Japan
Abstract
trans-2-(3-Hydroxyphenyl)cyclohexanol (4) was converted into 1,2,3,4,4a,10b-hexahydro-6-spirocyclohexano-6H-dibenzo[b,d]pyran-9-ol (8) either by phenolic cyclisation or by acid catalysis. The corresponding 6-methyl-6-phenylbenzopyran derivative (9) was also obtained from 4 by the same methods. This type of reaction was applied to the fecile synthesis of 3,4-dihydro-6-methoxy-1-methoxycarbonyl-1-methyl-1H-2-benzopyran (11) and the hexahydro-6H-dibenzo[b,d]pyrans (18, 19, 22, and 23).
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■ Synthesis of Hexa-O-methyl-6,6”-binaringenin and -biapigenin
Fa-ching Chen,* Yuh-meei Lin, Youe-kong Shue, and Tsong Ueng
*Department of Chemistry, National Taiwan University, Roosevelt Road Section 4, Taipei 106, Taiwan, R.O.C.
Abstract
A three-step synthesis of the title compounds starting from 4,4’-dibenzyloxy-2,2’,6,6’-tetramethoxybiphenyl (V) has been accomplished and the proposed structure of 6,6”-binaringenin for succedaneaflavanone is confirmed.
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■ A Novel Reaction of 3-Ethoxycarbonyl-2-methylthiothiazolo[2,3-a]isoquinolinium Sulfate with Active Methyl Compounds
Kazumichi Mizuyama, Yoko Matsuo, Yoshinori Tominaga, Yoshiro Matsuda, and Goro Kobayashi*
*Faculty of Pharmaceutical Sciences, Nagasaki University, 1-14, Bunkyo-machi, Nagasaki 852-8521, Japan
Abstract
The reaction of 3-ethoxycarbonyl-2-methylthiothiazolo[2,3-a]isoquinolinium sulfate with active methyl compounds (nitromethane, acetophenone) in the presence of base produced ethyl 2-methylthio-1-nitropyrrolo[2,1-a]isoquinoline-3-carboxylate (II) and ethyl 2-methylthiopyrrolo[2,1-a]isoquinoline-3-carboxylate (III).
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■ The “Hilbert-Johnson” Reaction of 3,5-Diethoxy-1,2,4-thiadiazole
Gerrit-Jan Koomen and Upendra K. Pandit*
*Organic Chemistry Laboratory, University of Amsterdam, Nieuwe Achtergracht 129, 1018 WS Amsterdam, The Netherlands
Abstract
Alkylation of 3,5-diethoxy-1,2,4-thiadiazole via a Hilbert-Johnson type reaction results in the formation of N(2)-substituted derivatives.
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■ 1,4-Addition Reactions of 4-(m-Nitrobenzylidene)-3,5-dimethylisopyrazole
Takushi Kurihara,* Emi Araya, and Toshiko Sakaguchi
*Faculty of Pharmaceutical Science, Osaka University of Pharmaceutical Sciences, 4-20-1 Nasahara, Takatsuki, Osaka 569-1094, Japan
Abstract
Reactions of 4-(m-nitrobenzylidene)-3,5-dimethylisopyrazole (II) with hydrochloric acid in methanol, acetic anhydride, acetic acid, benzoyl chloride and dimethyl sulfate gave the 1,4-addition products (III, IV, V, VIII, and IX) in fairly good yields.
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■ Studies of Medium-membered Heterocyclic Compounds. II. Reaction of 5-Benzyl-4,6-dihydro-3,7-diaryl-1,2,5-triazepines with Halogenation-reagents
Otohiko Tsuge* and Kichinosuke Kamata
*Research Institute of Industrial Science, Faculty of Engineering, Kyushu University, 6-1, Kasuga-koen, Kasuga 816-8580, Japan
Abstract
Treatment of 5-benzyl-4,6-dihydro-3,7-diaryl-1,2,5-triazepine (6a or 6b) with bromination-reagents afforded either 1-benzyl-4-arylimidazole (7a or 7b) or 3,6-diarylpyridazine (2a or 2b) as the main product, depending on the reaction conditions. On the other hand, 6a reacted with sulfuryl chloride to give 4-benzylamino-3,6-diphenylpyridazine (8), while the reaction of 6 with chlorine gas afforded 5-chloropyridazine derivative (9), which was easily obtained by further chlorination of 8. Although the reaction course for the formation of 2 is not clear, the products 7 and 8 can be accounted for by the pathway via triazanorcaradiene (10).
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■ Photochemical Synthesis of Indolo[2,1-a]isoindole Derivatives by the Cyclization of N-(o-Tolyl)phthalimides
Yuichi Kanaoka,* Chieko Nagasawa, Hideo Nakai, Yasuhiko Sato, Hiroshi Ogiwara, and Tomishige Mizoguchi
*Faculty of Pharmaceutical Sciences, Hokkaido University, Sapporo 060-0812, Japan
Abstract
On irradiation, N-(o-tolyl)phthalimides 1 possessing a variety of substituents on the benzene rings afforded indolo[2,l-a]isoindole derivatives 2 (or 3) in most cases. Phthalimides with electron-donating groups on the A ring resisted to the cyclization. The photochemical behavior of 1 qualitatively parallels that of phenyl ketones.
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■ Compounds Related to Acridine. XII. Reaction of 1-(9-Acridinyl)-2-benzoylethylene and 9-Acridinylstyrylketone with Hydrazines
Akiyoshi Torii and Otohiko Tsuge*
*Research Institute of Industrial Science, Faculty of Engineering, Kyushu University, 6-1, Kasuga-koen, Kasuga 816-8580, Japan
Abstract
The reaction of 1-(9-acridinyl)-2-benzoylethylene (1) with hydrazine hydrate (3) gave pyrazoline 4, hydrazinohydrazone 6, or pyrazole 7, depending on the reaction conditions. On the other hand, 9-acridinylstyrylketone (2) reacted with 3 under mild conditions to yield a Michael type adduct 8 as the main product, accompanied with hydrazinohydrazone 9 and 7. On heating in ethanol 8 was dissociated into starting materials. The reaction of 1 with phenylhydrazines (10) gave the expected pyrazolines 11, which on oxidation with lead tetraacetate gave pyrazoles 12, while 2 reacted with 10a to afford a Michael type adduct 13, which on heating in ethanol converted into 2 and 10a.
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■ A New Synthetic Approach to the 1,4,2-Oxathiazole Ring System by the Action of Dimethyl Acetylenedicarboxylate on Arylthiohydroxamic Acids
Parthasarathi Rajagopalan* and Chandravadan N. Talaty
*CIBA-GEIGY Research Centre, Goregaon Bombay 400063, India
Abstract
The reaction of arylthiohydroxamic acids wlth dimethyl acetylenedicarboxylate yields, in one step, 3-Aryl-5-methoxycarbonyl-1,4,2-oxathiazoles.
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■ Synthesis of 2-Substituted 3-Methylbenzothiazolines by the Reaction of 3-Methylbenzothiazolium Iodide with Grignard Reagents
Kin-ya Akiba, Yoshio Ohara, Motoyuki Hisaoka, and Naoki Inamoto*
*Department of Chemistry, Scool of Science, University of Tokyo, 7-3-1 Hongo, Bunkyo-ku, Tokyo 113-0033
Abstract
2-Substituted 3-methylbenzothiazolines (2) were prepared by the reaction of 3-methylbenzothiazolium iodide (1) with Grignard reagents in high yields.
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■ Addition of Diethyl Mesoxalate to Benzofurane-2(3H)-one, 1-Benzothiophene-2(3H)-one and 2-Indolinone
Heinz Wolfers, Udo Kraatz, and Friedhelm Korte*
*Lehrstuhl für Ökologische Chemie, Technische Universität München, Lichtenbergstrasse 4, D-85747 Garching, Germany
Abstract
The condensation of a benzo-condensed lactone, thiolactone and lactam 1a-c with diethyl mesoxalate does not yield α-methylene derivatives but only hydroxy compounds 4a-c, which cannot be dehydrated further.
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■ Ultraviolet and Infrared Spectra of Alkaloids with a Cyclohexedienone or Cyclohexeone Ring
Svatava Dvorácková, Ladislav Hruban, Vladimír Preininger, and Frantisek Santavy*
*Chemical Institute, Medical Faculty, Palacky University, Hnevotínská 3, 77515 Olomouc, Czech Republic
Abstract
The ultraviolet and the infrared spectra (region between 1750-1600 cm-l) of proaporphine/homoproaporphine and promorphinane/homopromorphinane alkaloids with a keto group on the ring D, conjugated either with two (cyclohexadienone compounds) or with one (cyclohexenone compounds) double bond, are discussed. Furthermore, the effect of the enol ether in the α-, α,α’- or β-position to the keto group and that of the electron donating substituents of the ring A on the uv and the ir spectra have been studied.