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. 29, No. 5, 1989
Published online:
■ Formation of Thiocyanates by Ring Cleavage from 2-Imino-5,6-dihydro-4H-1,3-thiazine
Mitsuhiro Ichinari and Yoshio Hayase
*Aburahi Laboratories, Shionogi & Co. Ltd., Gotanda, Koka-cho, Koka-gun, Shiga 520-3423, Japan
Abstract
The reaction of 2-imino-5,6-dihydro-4H-1,3-thiazine with diethyl chlorophosphate, diethyl chlorothiophosphate and p-toluenesulfonyl chloride in the presence of base gave N-propylthiocyanate derivatives of diethyl phosphoramide, diethyl phosphorothioamide and p-toluenesulfonamide, respectively, in goad yield.
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■ A Simple Synthesis of Amphimedine
Rolf H. Prager* and Chris Tsopelas
*School of Physical Sciences, The Flinders University of South Australia, Bedford Park, South Australia 5042, Australia
Abstract
Amphimedine may be synthesised in six simple steps from the readily amilable arafluorenone (2).
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■ The Directed Lithiation of Isogramine and Subsequent Reactions with Electrophiles in the Preparation of 2-Substitutes Isogramine Derivatives
Dennis J. Hlasta* and Malcolm R. Bell
*Sterling Research Group, Rensselaer, New York 12144, U.S.A.
Abstract
Isogramine (1) undergoes 2-lithiation on reaction with n-butyllithium under very practical and straightforward reaction conditions. This 2-lithio species (2) reacts with aromatic carbonyl compounds to afford in good yields 2-substituted isogramines(3).
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■ Ring Construction of Bicyclic-β-lactam by Use of Palladium Catalyzed Carbonylation
Miwako Mori,* Yukako Higuchi, Katsuji Kagechika, and Masakatsu Shibasaki*
*Faculty of Pharmaceutical Sciences, Hokkaido University, Kita 12 Nishi 6, Kita-ku, Sapporo, Hokkaido 060-0812, Japan
Abstract
Palladium catalyzed carbonylation Into vlnyl halide 10 afforded carbacepham 11 in good yield. The introduction of methoxycarbonyl group at C-4 position of carbacepham was achieved by conversion of methoxy group introduced by anodic oxidation in MeCN-MeOH to carboxyl group.
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■ A New and Convenient Synthesis of Macarpine and Dihydromacrpine from Oxychelirubine
Miyoji Hanaoka,* Won Jea Cho, Shuji Yoshida, Tsukasa Fueki, and Chisato Mukai
*Faculty of Pharmaceutical Scicences, Kanazawa University, 13-1 Takara-machi, Kanazawa 920-0934, Japan
Abstract
A novel and biomimetic conversion of oxychelirubine (8) to macarpine (1) and dihydromacarpine (12) was achieved by regioselective iodination and subsequent methoxylation.
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■ Bicornin, A New Hydrolyzable Tannin from Trapa bicronis, and Revised Structure of Alnusiin
Takashi Yoshida, Kazufumi Yazaki, M. Usman Memon, Izumi Maruyama, Kenji Kurokawa, and Takuo Okuda*
*Faculty of Pharmaceutical Sciences, Okayama University, 1-1-1 Tsushima-naka, Okayama 700-8530, Japan
Abstract
Previously proposed structure (1) for alnusiin, a hydrolyzable tannin isolated from Alnus sieboldiana, has been revised to 2, based on the 1H-13C long-range shift correlation spectroscopy. Bicornin (10), a new tannin was isolated from Trapa bicornis and its structure related to alnusiin was determined.
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■ Synthesis of (—)-3-Butyl-4-hydroxyphthalide
Yoshimitsu Ogawa,* Kunio Hosaka, Masao Chin (Chen Zhengxiong) and Hiroshi Mitsuhashi
*Research Institute for Biology and Chemistry, Tsumura & Co., 3586 Yoshiwara, Ami-machi, Inashiki-gun, Ibaraki 300-1192, Japan
Abstract
(-)-3-Butyl-4-hydroxyphthalide 1 was first synthesized enantioselectively by using a chiral aryllithium reagent and its absolute stereochemistry at C-3 was determined to be S-configuration.
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■ Studies on Aconitum Species. VIII. Components of "Kako-Bushi-Matsu"
Takao Mori, Takatomi Ohsawa, Mitsuo Murayama, Hideo Bando, Koji Wada, and Takashi Amiya*
*
*Hokkaido College of Pharmacy, 7-1 Katsuraoka-cho, Otaru 047-02, Japan
Abstract
Seventeen C19-diterpenoid alkaloids were isolated from the processed aconite, “Kako-bushi-mats”. Structures of those compounds were determined on the basis of their spectral and chemical data. It was demonstrated that 15-keto-pyro type compounds 10, 11, and 15-20 were induced by heating of aconitine mesaconitine, jesaconitine, and hypaconitine present in the raw aconite roots.
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■ Meso-tetrakis[2.2]paracyclophanylporphyrin: Unusual Stereoisomerism of a Porphyrin Derivative
Leszek Czuchajowski,* Stefan Goszczynski, and Antoni K. Wisor
*Department of Chemistry, University of Idaho, 301 Renfrew Hall, Moscow, ID 83844-2343, U.S.A.
Abstract
The hindered rotation about four direct bonds between the [2.2]paracyclophanyl substituents and the meso carbon centers of porphyrin in the title compound results in the appearance of many stereoisomers, some of them representing the type of stereoisomerism which had never been encountered before in porphyrin chemistry.
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■ Novel Exchange Reaction of 2-Imino or 2-Thiono Derivatives of 1,3-Thiazines and 1,3-Oxazines with p-Toluenesulfonyl Isocynate
Mitsuhiro Ichinari and Yoshio Hayase
*Aburahi Laboratories, Shionogi & Co. Ltd., Gotanda, Koka-cho, Koka-gun, Shiga 520-3423, Japan
Abstract
The reaction of 2-arylimino-1,3-thiazine with p-toluenesulfonyl isocyanate led to the formation of 2-(p-toluenesulfonyl)imino-1,3-thiazine. A similar reaction carried out with 1,3-thiazine-2-thione and 1,3-oxazine-2-thione gave 2-(p-toluenesulfonyl)imino-1,3-thiazine or 1,3-oxazine, respectively.
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■ Synthesis of Heterocyclic Compounds Isosterically Related to Pyrazolo[4,3-c]quinolines as Benzodiazepine Receptor Ligands
Hirohisa Shindo,* Toshio Fujishita, Takashi Sasatani, Nobuo Chomei, and Susumu Takada
*Shionogi Research Laboratories, Shionogi & Co. Ltd., Fukushima-ku, Osaka 553-0002, Japan
Abstract
Fused pyridine and pyrimidine derivatives have been synthesized which are isosterically related to pyrazolo[4,3-c]quinolines with the high affinity to the benzodiazepine receptor.
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■ Novel Reactions of Carbon Suboxide. IX. Synthesis of 2H-Pyran-2-one Derivatives
Leonardo Bonsignore, Salvadore Cabiddu,* Giuseppe Loy, and Daniela Secci
*Bristol-Myers Squibb Pharmaceutical Group, 100 Industrial Blvd., Candiac, QC J5R 1J1, Canada
Abstract
Trimethylsilyl enol ethers of aldehydes and acycilc or cyclic ketones react with carbon suboxide to give substituted 4-[(trimethylsilyl]oxy]-2H-pyran-2-ones in good yields, which were treated with water to afford the corresponding 4-hydroxy-2~-pyran-2-ones.
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■ Convenient Preparation of Iridodial by Reduction of Nepetalactone. Corroboration for the Role of Iridodil as an Indole Alkaloid Precursor in a Catharanthus roseus Cell Suspension
John Balsevich* and Greg Bishop
*Plant Biothchnology Institute, National Research Council of Canada, Saskatoon, Saskatchewan, S7N, OW9, Canada
Abstract
Iridodial of high isomeric purity was effectiveiy prepared by reduction of nepetalactone with sodium borohydride in tert-butanol. Nepetalactone, in turn was readily obtained by steam distillation of the aerial parts of Nepeta cataria. Feeding of deuterium-labelled iridodial prepared as above and deuterium-labelled material prepared by acid-promoted cyclization of 10-oxocitronellal, to a Catharanthus roseus cell suspention culture, afforded the alkaloid, ajmalicine, which was specifically labelled with deuterium to the extent of 76% and 36%, respectively.
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■ Synthesis of 3-Carboethixy-4-oxo-4H-pyrimido[1’,2’:1,5][1,2,4]triazolo[3,4-b]benzoxazole and 5H-Pyrido[3",2":5’,6’]pyrimido[1’,2’:1,5][1,2,4]triazolo[3,4-b]benzoxazole-5-one: Novel Heterocycles
Thallapalli Ramalingam,* Madugula Sree Rama Murty, and Pralhad Balvantrao Sattur
*Regional Research Laboratory, Hyderabad 500 007, India
Abstract
Reaction of 3-amino-1, 2, 4-triazolo[3,4-b]benzoxazole 2 with diethyl ethoxymethylenemalonate and 2-chloropyridine-3-carboxylic acid chloride afforded 3-carboethoxy-4-oxo-4H-pyrido[1’,2’:1,5][1,2,4]triazolo[3,4-b]benzoxazole 4 and 5H-pyrido[3”,2”:5’,6’]pyrimido[1’,2’:1,5][1,2,4]triazolo[3,4-b]benzoxazole-5-one 6 respectively, new ring systems.
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■ The Structure and Nmr Spectra of Some Diels-Alder Adducts of Nitrosobenzene, p-Nitrosotoluene and 1-Chloro-1-nitrosocyclohexane
Henryk Labaziewicz* and Karl R. Lindfors
*Department of Chemistry, Central Michigan University, Mt. Pleaasant, MI 48859, U.S.A.
Abstract
The products of the following Diels-Alder reactions have been investigated: (i) nitrosobenzene with 2-phenyl-1,3-butadiene, isoprene. piperylene, 2,3-dimethyl-1,3-butadiene, 2-methyl-3-phenyl-1,3-butadiene and 2,4-hexadiene; (ii) p-nitrosotoluene with 2,4-hexadiene: (iii) 1-chloro-1-nitrosocyclohexane with 2-methyl-3-phenyl-1,3-butadiene and 1-phenyl-1,3-pentadiene. The 4-methyl and 4-phenyl isomers are formed in relatively larger quantities in the diene reaction of isoprene and 2-phenyl-1,3-butadiene with nitrosobenzene, while the 4-methyl-5-phenyl isomer is the major product from the reaction of 2-methyl-3-phenyl-1,3-butadiene with 1-chloro-1-nitrosocyclohexane.
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■ Alkylation and Arylation of Pyrazines by Organoboron Compounds
Akihiro Ohta,* Ryoichi Itoh, Yasunobu Kaneko, Haruo Koike, and Kayo Yuasa
*Tokyo University of Pharmacy and Life Science, 1432-1 Horinouchi, Hachioji, Tokyo 192-0392, Japan
Abstract
By palladium-catalyzed cross-coupling reactions of chloropyrazines with organoboron compounds prepared from Grignard reagents, various alkyl and aryl groups were successfully introduced into the pyrazine ring.
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■ Oxidation Studies on β-Lactam Antibiotics: 2β-Heteroarylthiomethyloanems
Rajeshwar Singh,* Maya P. Singh, and Ronald G. Micetich
*SynPhar Laboratories Inc., 4290-91A Street, Edmonton, Alberta, T6E 5V2, Canada
Abstract
The structural determination (by 1H and 13C-nmr) of the various products obtained by the m-chloroperbenzoic acid oxidation of 2β-heteroarylthiomethyl penicillins is reported.
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■ Synthesis of 2-Methyl-4-phenyl-1,2,3,4-tetrahydroisoquinolin-4-ol Derivatives by a Novel Insertion of Aryl-Nickel Complexes
Masaru Kihara,* Akinori Nakanishi, and Shigeru Kobayashi
*Pharmaceutical Sciences, Graduate of School, University of Tokushima, Sho-machi, Tokushima 770-8505, Japan
Abstract
2-Methyl-4-phenyl-1,2,3,4-tetrahydroisoquinolin-4-ol derivatives (1a-j) as a new potentiator of noradrenaline were prepared by a novel intramolecular insertion of the aryl-nickel complexes of N-(2-halobenzyl) phenacylamines (2a-m).
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■ 1,3-Dipolar Cycloadditions with Methyl 4-Oxo- and 4-Hydroxy-2-butynoates. Synthesis of Functionalized Pyrazoles and Triazoles
Francisco Fariña,* Pilar Fernández, M. Teresa Fraile, M. Victoria Martín, and M. Rozario Martín
*Instituto de Química Orgánica General, C. S. I. C., Calle Juan de Cierva, 3, 28006 Madrid, Spain
Abstract
The 1,3-dipolar cycloadditions of acetylenic esters 1-3 with diazo compounds, sydnones and p-methoxyphenyl azide proceed in good yields and afford functionalized pyrazoles and triazoles. Cycloadditions with the acetal 1 occur with high regioselectivity, whereas the reactions with the alcohol 3 are less selective. The aldehyde 2 is more reactive than 1 or 3 and cycloadditions proceed with lower regioselectivity, normally in opposite sense with respect to 1.
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■ A Novel and Facile Synthesis of 5-Substituted 1,3-Dioxolane-2,4-diones Using Trichloromethyl Chloroformate
Kouhei Toyooka,* Yoshiyuki Takeuchi, and Seiju Kubota
*Pharmaceutical Sciences, Graduate of School, University of Tokushima, Sho-machi, Tokushima 770-8505, Japan
Abstract
5-Substituted 1,3-dioxolane-2,4-diones including the chiral derivatives were synthesized by the reaction of α-hydroxy carboxylic acids with trichloromethyl chloroformate.
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■ Substituted Spiro[pyrrolidine-5,2’-tricyclo[3.3.1.13,7]decane] Derivatives
Christpher G. Acker, George B. Mullen, Lesley A. Radov, Laura A. Trusso, Dietgard K. Kamp, and Vassil St. Georgiev*
*Department of Chemistry and Pharmacology, Divisional Research and Development, Fisons Pharmaceuticals, Rochester, New York 14623, U.S.A.
Abstract
The synthesis of a series of novel substituted spiro[pyrrolidine-5,2’-tricyclo[3.3.1.13,7]decane] derivatives 5-13 is described. When tested in the carrageenin-induced rat paw edema assay, several analogues elicited anti-inflammatory activity.
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■ Condensed Thienopyrimidines 3. Synthesis of Angular Annelated Oxazolo[2,3-b]thienopyrimidin-5-one Derivatives
Mitsuo Sugiyama, Toshiaki Sakamoto, and Hiroshi Fukumi*
*Medicinal Chemistry Research Laboratories, Sankyo Co., Ltd., 1-2-58 Hiromachi, Shinagawa-ku, Tokyo 140-8710, Japan
Abstract
Angular annelated trlcycllc oxazolothienopyrimidine derivatives, 1,2-dihydro-5H-oxazolo [2,3-b] thieno [3,2-d], [3,4-d]-, and [2,3-d] pyrimidin-5-one (2), were prepared and evaluated for gastric antisecretory activity in pylorus-ligated rats.