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. 4, No. 12, 1976
Published online:
■ Syntheses of 1-Methyl-2-azathiabenzene 1-Oxide and 1-Methyl-4-azathiabenzene 1-Oxide Derivatives
Mitsuaki Watanabe, Michito Minohara, Kazuhisa Masuda, Toshio Kinoshita, and Sunao Furukawa*
*Faculty of Pharmaceutical Sciences, Nagasaki University, 1-14, Bunkyo-machi, Nagasaki 852-8521, Japan
Abstract
1-Methyl-2-azathiabenzene 1-oxide derivatives are synthesized by the reaction of dimethylsulfoximine and ketenethioacetal derivatives. Reaction of dimethyloxosulfonium methylide with cyanamide derivatives affords 1-methyl-4-azathiabenzene 1-oxide derivatives.
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■ Weak Bases of Laurelia nobea-zelandiae. A Cautionary Note on Oxoaporphine Nmr Assignments
Alejandro Urzúa and Bruce K. Cassels*
*Laboratorio Central de Química, Universidad Técnica del Estado, Santiago 2, Chile
Abstract
Liriodenine and its 10-methoxy derivative, for which the name oxolaureline is proposed, were isolated from the weak base fraction of Laurelia novae-zelandiae (Monimiaceae) bark. Examination of the nmr spectra of the latter alkaloid and some of its congeners shows that C11-H does not necessarily resonate downfield from C8-H, as has been generally assumed.
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■ Reactions of Papaverinol with Acids
Somsak Ruchirawat,* Ngarmpong Tongpenyai, Nujaree Prasitpan, and Pairote Prempree
*Department of Chemistry, Faculty of Science, Mahidol University, Rama 6 Road, Bangkok 10400, Thailand
Abstract
Reaction of papaverinol (I) with glacial acetic acid gave papaverine (II) and papaveraldine (III). However, reaction of papaverinol with 90% sulphuric acid gave a demethylation product (IVa) and another product (V) resulting from carbon-carbon bond cleavage.
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■ Reaction of Picolyl Ether with Dimethylformamide
Hiroshi Yamanaka* and Syoetsu Konno
*Pharmaceutical Institute, Tohoku University, Aobayama, Sendai 980-8578, Japan
Abstract
Reaction of 2- (I) and 4-ethoxymethylpyridine (VIII) with dimethylformamide in the presence of NaH afforded 2- (III) and 4-(1’-ethoxyvinyl)pyridine (IX). This type of reaction proceeded in 4-ethylpyridine to give 2,4-bis(2’-pyridyl)pentane (X).
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■ Synthesis of Adamantane Derivatives. 36. Synthesis of Some Bisadamantane Spiro Thiaheterocycles via Adamantanethione Adamanthylide
Tadashi Sasaki,* Shoji Eguchi, and Yoshiyuki Hirako
*Institute of Applied Organic Chemistry, Faculty of Engineering, Nagoya University, Chikusa, Nagoya, Aichi 464-8601, Japan
Abstract
Adamantanethione adamanthylide (2) generated by thermal nitrogen extrusion reaction of thiadiazine 1 afforded thiirane 3 in good yield, and the same thermolysis of 1 in the presence of appropriate 1,3-dipolarophiles afforded bisadamantane spiro thiaheterocycles 8-13 in 25-77% yields.
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■ Acidic Alumina- and BF3·OEt2-Induced Reactions of 1,2-Diphenyl-1-azaspiro[2.2]pentane
Otohiko Tsuge* and Hiroyuki Watanabe
*Research Institute of Industrial Science, Faculty of Engineering, Kyushu University, 6-1, Kasuga-koen, Kasuga 816-8580, Japan
Abstract
The acidic alumina-induced reaction of 1,2-diphenyl-1-azaspiro[2.2]pentane (1) afforded 3-phenylindoline-2-spirocyclopropane (2) and 1-anilino-1-hydroxybenzylcyclopropane (3). On treatment with diethyl azodicarboxylate 3 was converted to 2-benzoylquinoline (4). Under the influence of BF3·OEt2 1 gave 2 and a dimer of 1, 1,3,4,6-tetraphenylpiperidine-2,5-bispirocyclopropane (5).
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■ Acetyl-1,3,4-thiadiazolines from the Reaction of Thiosemicarbazones with Acetic Anhydride
Seiju Kubota,* Kazuichi Fujikane, Masayuki Uda, and Tamiya Yoshioka
*Faculty of Pharmaceutical Sciences, University of Tokushima, Sho-machi, Tokushima 770-8505, Japan
Abstract
N.m.r. spectroscopy showed that the compounds obtained by reaction of thiosemicarbazones (I) with acetic anhydride are 2-acetylamino-4-acetyl-1,3,4-thiadiazolines (II) and not N4,S-diacetyl-thiosemicarbazones (III) as thought previously.
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■ Synthesis of Hexa-O-methyl-6,8"-binaringenin
Fa-ching Chen,* Yuh-meei Lin, Sun-kwei Huang, and Tsong Ueng
*Department of Chemistry, National Taiwan University, Roosevelt Road Section 4, Taipei 106, Taiwan, R.O.C.
Abstract
A two-step synthesis of the title compound starting from 3,3’-diacetyl-2,4’-dihydroxy-2’,4,6,6’-tetranethoxybiphenyl has been accomplished and the proposed structure of 6,8”-binaringenin for rhusflavanone ie confirmed.
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■ A Convenient Synthesis of 1-Aroylisoquinolines
Somsak Ruchirawat,* Vanida Somchitman, Ngarmpong Tongpenyai, Werawat Lertwanawatana, Supalak Issarayangyuen, Nujaree Prasitpan, and Pairote Prempree
*Department of Chemistry, Faculty of Science, Mahidol University, Rama 6 Road, Bangkok 10400, Thailand
Abstract
1-Aroylisoquinolines could be conveniently prepared by the oxidation of 1-benzyl-3,4-dihydroisoquinolines or 1-benzylisoquinolines with oxygen and triton B in pyridine.
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■ "Push-pull-acetylenes" as Versatile Intermediates in Heterocyclic Synthesis
Hans-Joachim Gais and Klaus Hafner*
*Institut für Organische Chemie, Technische Hochschule Darmstadt, Petersenstrasse. 22 64287 Darmstadt, Germany
Abstract
Phosgene and oxalyl chloride add to “push-pull-acetylenes” (1) to give excellent yields of highly reactive adducts of type (3) and (4). A variety of specifically substituted heterocyclic compounds, like pyrazolo-oxazinones (6), pyrazoles (7), oxazinones (9), (10), (12) and (13) or furanones, e.g., (21) and (22) (Table 1), can be synthesized taking advantage of the bifunctionality of these adducts. From the acetylenes (1) and phenylhydrazine the isomeric pyrazoles (25) and (26) as well as pyrazolones (27) and (28) (Table 1) are obtained due to their ambident electrophilic reactivity.