HETEROCYCLES
An International Journal for Reviews and Communications in Heterocyclic ChemistryWeb Edition ISSN: 1881-0942
Published online by The Japan Institute of Heterocyclic Chemistry
Special Issue
Tetsuji Kametani's Special Issues, Vol. 15, No. 2, 1981
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■ Photocontrol of Chiral Recognition by Capped Cyclodextrin
Akihiko Ueno, Rumiko Saka, Keiko Takahashi, and Tetsuo Osa*
*Pharmaceutical Institute, Tohoku University, Aramaki, Aoba-ku, Sendai 980-8578, Japan
Abstract
Azobenzene-capped β-cyclodextrin (1) exhibits chiral recognition in binding optical isomers of some guest molecules with stereoselectivity which inverts by photoirradiation.
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■ The Effect of Solvents and/or Alkali Cations of Absorption Spectra of Iron (III) Crowned Porphyrin
Nagao Kobayashi and Tetsuo Osa*
*Pharmaceutical Institute, Tohoku University, Aramaki, Aoba-ku, Sendai 980-8578, Japan
Abstract
Iron(III) meso-tetraphenylporphyrin derivative with four crown ether moieties (I) was synthesized. It showed remarkable solubility in various solvents and spectral dependencies on solvents and/or alkali cations, attributed to the crown ether moieties in the structure.
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■ A New Synthesis of Pyrimido[4,5-b]quinoline-2,4-(1H,3H)-diones by Reaction of 6-Arylamino-1,3-dimethyluracils with Carbon Disufide
Yoshinori Tominaga, Hiroto Okuda, Mutushi Tochiki, Yoshiro Matsuda, and Goro Kobayashi*
*Faculty of Pharmaceutical Sciences, Nagasaki University, 1-14, Bunkyo-machi, Nagasaki 852-8521, Japan
Abstract
Reaction of 6-arylaminouracils (I) with carbon disulfide in the presence of sodium hydroxide and subsequent methylation with dimethyl sulfate gave the corresponding 1,3-dimethyl-5-methylthiopyrimido[4,5-b]quinoline-2,4(1H,3H)-diones (II). Raney-nickel desulfurization of II afforded the corresponding 1,3-dimethylpyrimido[4,5-b]quinoline-2,4(1H,3H)-diones (1,3-dimethyl-5-deazaalloxazines) (VII) in good yields.
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■ Polarographic Reduction of Substituted Piperidinobenzamidrazones. Structure-Reactivity Relationships
Ahmad S. Shawali,* Sayed S. Abdel Rehim, Mohamed A. Negied and Cyril Párkányi*
*Department of Chemistry, Faculty of Science, University of Cairo, Giza, Egypt
Abstract
Polarogaphic reduction of a series of substituted piperidino benzamidrazones, 2a-2h, along with the unsubstituted benzamidrazone 3 has heen investigated in 40% (vol.) ethanolic Britton-Robinson buffers. For the sake of comparison, also the polarographic reduction of benzaldehyde phenylhydrazone 4, benzaldehyde p-nitrophenylhydarazone 5, and benzamidine 6 has been studied under similar conditions. The assignment of the waves and the reduction scheme are outlined. The E1/2 values of the polarographic waves were correlated with the Hammett substituent constants.
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■ Substituent Effects on Acidities and Tautomeric Structures of 1-Aryl-3-ethoxycarbonyl-4-pyrazolones and Their 5-Arylazo Derivatives
Ahmad S. Shawali,* Hamdi M. Hassaneen, and Mokntar A. Hanna
*Department of Chemistry, Faculty of Science, University of Cairo, Giza, Egypt
Abstract
Two series of 1-aryl-3-ethoxycarbonyl-4-hydroxypyrazoles (1) and 1-(m-chlorophenyl)-3-ethoxycarbonyl-4-hydroxy-5-arylazopyrazoles (2) have been prepared and their acidities determined spectrophotometrically at 25°C and ionic strength of 0.1 in 60 vol.% ethanol-water medium. The pKa data were correlated with the simple and extended Hammett equations. The regression lines are: pKa(1) =9.34 - 0.794 δX ; pKa(1) = 9.78 - 0.794 δXC6H4 ; PKa(2) = 7.49 - 1.158 δX ; and PKa(2) = 7.49 -1.245 δI,X - 1.075 δR,X. It is concluded that such linear relations exclude the presence of the keto tautomers (1A) and (2A) in equilibrium with the hydroxy tautomers (1B) and (2B) respectively, in agreement with the spectral data of the compounds investigated. The electrical effect, E, of value 0.86 determined for series (2) indicates that such compounds exist in the cis-chelated hydroxyazo structure (2B).
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■ Studies on the Biomimetic Control of the Coupling Position in the Oxidative Ary-Aryl Coupling Reactions of the Bridged Ether Derivatives of O-Methylnorbelladine
Masayuki Murase, Tetsuya Takeya, and Seisho Tobinaga*
*Showa College of Pharmaceutical Sciences, 3-3165, Higashi-tamagawagakuen, Machida, Tokyo 194-8543, Japan
Abstract
Oxidative aryl-aryl coupling reactions of the bridged ether derivatives (10a, 10b) of O-methylnorbelladine were investigated mimicking the enzymatic control of the reaction sites. Oxidation of (10b) by VOF3 gave a para-metha coupling product (12), and (10a) afforded an ortho-metha coupling product (14) and a dimer (15).
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■ The Preparation and Rearrangement of 1-Prenylindoles and 3-Prenylindolenines
Kenneth J. Baird, Michael F. Grundon, David M. Harrison, and M. Gerard Magee
*School of Physical Sciences, New University of Ulster, Coleraine Northern Ireland, U.K.
Abstract
The preparation of 3-alkyl-3-prenylindolenines was explored by rearrangement of 1-prenylindoles and by allylation of 2-(methylthio)indoles. Reaction of the 3-formylindole (6) with trifluoracetic acid gave first the addition product (7) and then the pyridinoindole (8); the esters (11) and (14) were formed similarly from the tryptophan derivative (10) and the 2-(methylthio)indolenine (13), respectively. Successive reaction of the indolenine (13) with lithium aluminium hydride and manganese dioxide gave 3-(3,3-dimethylallyl)-3-methylindolenine (18) in good yield.
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■ Reductive Transformation of a Hydroxyiodoketone of 8-Azabicyclo[3.2.1]octane into 7-Azabicyclo[2.2.1]heptane with Lithium Aluminium Hydride
Shalom Sarel* and Edmund Dykman
*Department of Pharmaceutical Chemistry, The Hebrew University, P.O.Box 12065 Jerusalem, Isarel, Israel
Abstract
1α,4β-Diodo-2α-acetoxytropan-3-one (2) and 1α-iodo-2α-acetoxytropan-3-one (3),which comprise 64% of products emerging from the lead tetraacetate oxidation of tropan-3α-ol in presence of iodine, were subjected to lithium aluminium hydride reduction. The expected 2.3-dihydroxytropane was not obtained. Instead, a diol which was not prone to periodate oxidation, containing one primary and one secondary alcoholic groups was obtained. It was assigned the 1-hydroxymethyl-2α-hydroxy-7-methyl-7-azabicylo[2.2.1]heptane structure (8), on the basis of spectroscopic evidences (ir, nmr and mass spectrometry) and some chemical transformations [formations of a cyclic sulfite (9), an epichlorohydrin (11) and 1-methyl-2α-hydroxy-7-methyl-7-azabicyclo[2.2.1]heptane (12)]. The reaction is understood as an initial β-elimination process, triggered by the delivery of hydride ion to the carbonyl function in the sequence 3 → 21 → 22, yielding a highly reactive enolate aldehyde (22) which is prone to an immediate internal aldol condensation (22) → (23) →← (24), affording the observed diol (8) on further reduction of the aldehydie group by LiAIH4. The reductive deiodination of (3) into 2α-acetoxytropine (2b) or into 2α-hydroxytropan-3-one (25) was smoothly achieved by means of hydrogenation over Raney Nickel on mild basic conditions.
Unlike the tropane derivatives (1, 26-28) which under electron impact enter into two distinctly different modes of fragmentation, the 7-azabicyclo[2.2.1]heptane framework in (8)-(12) characteristically favor one mode by which carbon-2 and carbon-3 are lost and the methylene pyrrolenium ion emerges as the most prominent ion in their spectra.
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■ Acylation of Acyclic Enamines with an Excessive Amount of Pyridinecarbonyl Chlorides
Takeaki Naito and Ichiya Ninomiya*
*Kobe Women’s College of Pharmacy, Motoyamakita, Higashinad, Kobe, Hyogo 658, Japan
Abstract
Acylation of the acyclic enamines (1a and d) and (6a) with an excessive amount of isonicotinoyl or nicotinoyl chloride provided a simple preparation of the spiranes (2, 3, and 7) or the 1,6-naphthyridines (4 and 5) respectively, of which the latter has an analogous structure of nalidixic acid, a powerful antibacterial agent.
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■ Dipyridine Crown Ethers.Synthesis and Conformational Aspects of a Tetraazadithia-18-crown-6 Analog
George R.Newkome* and Dalip K.Kohli
*Department of Chemistry, Louisiana State University, Baton Rouge, Louisiana 70803-1804, U.S.A.
Abstract
The synthesis and conformational analysis by VTNMR of a bis-dipyridylthia-18-crown-6-ether (4) are described. The energy barrier of inversion ΔG is 10.4 kcal/mol and measures a transverse isomerization inversion process.
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■ Synthesis and Antitumor Activity of Platinum Complexes with Cyclic Thioamides
Sigeaki Fujieda,* Esuzu Tabata, Akiko Hatano, and Tetsuo Osa
*Pharmaceutical Institute, Tohoku University, Aobayama, Sendai 980-8578, Japan
Abstract
Platinum(lI) complexes with 2-mercaptopyridine, 2-thiouracil, and ethylenethiourea have been synthesized. Some of them showed antitumor activity against Sarcoma 180 in mice.
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■ Palladium-promoted Formation of Azepines from 1-Aminohexatrienyl System
Sumiko Hatano, Masumi Saruwatari, Kazuaki Isomura, and Hiroshi Taniguchi*
*Department of Applied Chemistry, Faculty of Engineering, Kyushu University, 6-10-1 Hakozaki, Higashi-ku, Fukuoka 812-8581, Japan
Abstract
Treatment of ethyl α-amino-β-(3-alkenylbenzofuran-2-yl)acrylate (1-aminohexatrienyl system) with PdCl2(PhCN)2 in the presence of Na2CO3 caused a selective cyclization of the amino group to the terminal carbon of the alkenyl group forming azepines.
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■ Thermal Decomposition of 1,3-Dipolar Cycloadducts of Pyridazine N-Acetylimines and Tetrachlorocyclopropene
Akio Ohsawa, Ikuo Wada, and Hiroshi Igeta*
*School of Pharmaceutical Sciences, Showa University, 1-5-8 Hatanodai, Shinagawa-ku, Tokyo 142-8555, Japan
Abstract
Thermolysis of 6-acetyl-4b,5,5,5a-tetrachloro-4a,4b,5a,6-tetrahydro-5H-cyclopropa[3,4]pyrazolo[1,5-b]pyridazines afforded 2-chloro-3-(dichloromethyl)pyrazolo[1,5-b]pyridazines which were converted to various types of pyrarolo[1,5-b]pyridazines.
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■ New Syntheses of a Pteridine
Sadao Nishigaki, Kiyoko Fukami, Misuzu Ichiba, Hashime Kanazawa, Keiko Matsuyama, Shinobu Ogusu, Keitaro Senga,* Fumio Yoneda, Ryosuke Koga, and Toyoko Ueno
*Pharmaceutical Institute, School of Medicine, Keio University, Shinanomachi 35, Shinjuku, Tokyo 160-0016, Japan
Abstract
The reaction of 6-amino-1,3-dimethyl-5-phenylazouracil (I), 6-amino-1,3-dimethyl-5-nitrosouracil (II), or 6-hydrazino-1,3-dimethyl-5-nitrosouracil (III) with dimethyl acetylenedicarboxylate offers new synthetic route to a pteridine [6,7-bis(methoxycarbonyl)-1,3-dimethyllumazine: IV].
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■ Nucleotides, XIII: Phosphorylations of Adenosine and 2’-Deoxyadenosine by Phosphorochloridates
Ramamurthy Charubala and Wolfgang Pfleiderer*
*Fakultät für Chemie, Universität Konstanz, Posttach 5560, D-7750 Konstantz, Germany
Abstract
Phosphorylations of adenosine and 2’-deoxyadenosine by various phosphorylating agents such as diphenylphosphorochloridate have been achieved at positions 3’, 5’ and N6 using appropriate starting materials for unambiguous synthesis. There is a gradual reactivity of the different functions in these molecules with a preference of the 5’-OH-group followed by the 6-amino group and the 3’-OH-function in the third place. The various phosphotriesters and phosphoramidate diesters have been characterized by physical means and their properties are discussed.
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■ α-Halo Ketones IX. A New Furan-forming Reaction
E. W. Warnhoff* and F. W. Yerhoff
*Department of Chemistry, University of Western Ontario, London, Ontario, N6A5B7, Canada
Abstract
Some α-halo ketones react with 2-naphthol in the presence of strong acids to give naphtho[2,1-b]furans. A hydroxyallylic cation may be an intermediate in the reaction.
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■ Synthesis of Optically Active(5R,3S)-1-Deoxa-1-thia Analogues of Clavulanic Acid from Penicillanic Acid Derivatives
Maurizio Foglio, Giovanni Franceschi,* Guido Serra-Errante, Marzia Ballabio, and Federi-co Arcamone
*Farmitalia Carlo Erba S.p.A, Ricerca & Sviluppo Chimico, Via dei Gracchi,35 20146 Milan, Italy
Abstract
A novel synthesis of the chiral 1-thiaclavulanic skeleton consisting in the trapping reaction of penicillinate-S-oxide and glutinic acid dimethylester followed by demolition of the N-appendage and rebuilding of the thiazolidine ring is reported. Stereochemical assignements of the products are also discussed.
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■ Steroid Alkaloids of Fresh Bulbs of Fritillaria thunbergii Mig.and of Crude Drug “Bai-Mo” Prepared Therefrom
Junichi Kitajima, Naoki Noda, Yoshiteru Ida, Kazumoto Miyahara, and Toshio Kawasaki*
*Faculty of Pharmaceutical Sciences, Kyushu University, 3-1-1 Maidashi, Higashi-ku, Fukuoka 812-8582, Japan
Abstract
A new minor alkaloid FR-5 was isolated, besides verticine (I) and verticinone (II), from the fresh bulbs of Fritillaria thunbergii Miq., and the structure was determined as III. The crude drug “Bai-mo”, which was prepared from the above bulbs by treatment with lime followed by bleaching in the sun, provided two alkaloids F-3 and -4, together with I and II, in the free state, and additional two F-5 and -6 in the form of their acetates. They were assigned the structures VIII, IX, X and XI, which correspond, respectively, to an oxidation product of I, II and III.
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■ Diastereoselective Synthesis of Chroman-Sulfoxides
Jaap M. Akkerman, Henk de Koning,* and Henderikus O. Huisman
*Laboratory of Organic Chemistry, University of Amsterdam, Nieuwe Achtergracht 129,1018 WS Amsterdam, The Netherlands
Abstract
Intramolecular addition of a phenolic hydroxy function to an α,β-unsaturated chiral sulfoxide led to the formation of a chiral chroman-sulfoxide in 22% optical yield. Subsequent conversions provided an α-tocopherol synthon in 12% enantiomeric excess.
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■ Synthesis of 5H-1,2,3-Dithiazole, a Novel Heterocycle
Renji Okazaki, Kaoru Inoue, and Naoki Inamoto*
*Department of Chemistry, Faculty of Science, University of Tokyo, 7-3-1 Hongo, Bunkyo-ku, Tokyo 113-0033
Abstract
The reaction of β-ketoenamines with disulfur dichloride afforded 5H-1,2,3-dithiazoles probably via cyclization of intermediate N-thiosulfinylamine. Implication of this reaction with the Herz reaction is also mentioned.
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■ Cycloaddition of Benzothiazolium N-Phenacylide with Olefinic Dipolarophiles
Otohiko Tsuge,* Hiroshi Shimoharada, and Michiko Noguchi
*Graduate School of Engineering, Kyushu University, 6-10-1 Hakozaki, Higashi-ku, Fukuoka 812-8581, Japan
Abstract
Benzothiazolium N-phenacylide, generated in situ from 3-phenacylbenzothiazolium bromide and triethylamine, reacted with maleic anhydride, N-(p-methoxyphenyl)maleimide, dimethyl maleate, and fumrate to give the corresponding tetrahydropyrrolo[2,1-b]benzothiazole derivatives, all of which were stable on treatment with triethylamine, in good yields respectively. With maleonitrile the sole cycloadduct was formed, whereas fumaronitrile gave a mixture of two stereoisomeric cycloadducts. In some cases, dimer and/or hydrated compound of ylide were formed as by-products. On treatment with triethylamine epimerization and ring-transformation of cycloadducts obtained from both the dinitriles were observed.
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■ Change of Selectivity in Modified Cyclodextrin Catalyst
I. Tabushi, Y. Kuroda and Y. Sakata
*Department of Synthetic Chemistry, Kyoto University, Yoshida, Sakyou-ku, Kyoto 606-8501, Japan
Abstract
β-Cyclodextrin having a hydroxamate functional group was newly prepared and its catalytic activity for hydrolysis of a series of mono- or dinitrophenyl acetates was estimated. Relative enhancement of catalytic hydrolysis, kcat(CD-hydroxamate)/kcat(CD), was very sensitive to the substrate structure, e.g., lacation of substituent nitro group(s), being 230, for p-nitro; 130, 2,3-dinitro; 66, 3,4-dinitro; and 36 for 2,5-dinitro. The reaction mechanism was discussed.
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■ Synthesis of Nicotianamine and a Related Compound,Derivatives of Azetidine-2-carboxylic Acid
Shinji Fushiya, Shuichi Nakatsuyama, Yoshikazu Sato, and Shigeo Nozoe*
*Pharmaceutical Institute, Tohoku University, Aramaki, Aoba-ku, Sendai 980-8578, Japan
Abstract
The synthesis of nicotianamine (1) and a related compound (2) — amino acid derivatives having the azetidine ring — was achieved by reductive coupling of L-aspartic-β-semialdehyde derivatives with L-azetidine-2-carboxylic acid methyl ester.
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■ Synethetic Studies of Withanolides. Part 3. Some Approaches for the Side-Chain Lactone Synthesis by Means of γ-Coupling of Lithium Dienolates with the Steroidal 22-Aldehydes
Masaji Ishiguro, Masao Hirayama, Hiromitsu Saito, Akira Kajikawa, and Nobuo Ikekawa*
*Faculty of Engineering, Tokyo Institute of Technology, 2-12-1,Oh-Okayama, Meguro-ku, Tokyo 152-8552, Japan
Abstract
γ-Coupling of the lithium dienolates 5a-d with the steroidal 22-aldehydes 1-4 was investigated. Condensation of 5a with the (20R)-20-methoxymethyloxy-22-al 4 followed by lactonization gave the (20R,22R)-20-hydroxy-δ-lactone 13 which had the identical structure with withanolide D side-chain moiety, while the reaction of 5a with the 20-deoxy-22-al 1 gave the 22S-δ-lactone 6 which had the opposite stereochemistry at the 22-position to that of deoxywithaferin A. Attempts to invert the 22S-compounds 6 and 11 were unsuccessful. Lactonization of the 5,22,24-trienoic acid 14 gave predominantly the unsaturated γ-lactones.
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■ A Facile Method for the Synthesis of Azuleno[2,1-b]furan and Azuleno-[2,1-b]pyrrole Derivatives and Their Some Properties
Tadayoshi Morita,* Teruo Nkadate, and Kahei Takase*
*Department of Chemistry, Faculty of Science, Tohoku University, Aoba-ku, Ssendai 980-8578, Japan
Abstract
Azuleno[2,1-b]-furan and -pyrrole derivatives have been synthesized by the reaction of 2-acetoxy- and 2-acetamido-3-iodoazulene derivatives with cuprous phenylacetylide.
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■ The Formation of Azuleno[2,1-d]pyrimidine Derivatives by the Reactiohn of 2-Acetylimino-2H-cyclohepta[b]furan Derivatives with Active Methylene Compounds
Kahei Takase,* Tomoo Nakazawa, and Tetsuo Nozoe
*Department of Chemistry, Faculty of Science, Tohoku University, Aoba-ku, Ssendai 980-8578, Japan
Abstract
The reaction of 2-acetylimino-2H-cyclohepta[b]furan derivatives with some active methylene compounds directly gave azuleno[2,1-d]pyrimidine derivatives, which were also synthesized from 2-amino-1-carbamoylazulenes.
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■ 3-Hydroxypyrroles. IV. Ring-Enlargement of 3-Hydroxypyrrole-2-carboxylates
Takefumi Momose,* Tetsuaki Tanaka, Takashi Yokota, Norio Nagamoto, Hideko Kobayashi, and Sonoko Takano
*Faculty of Pharmaceutical Sciences, Osaka University, 1-6 Yamadaoka, Toyonaka, Osaka 560-0043, Japan
Abstract
3-Hydroxypyrrole-2-carboxylates (1) yielded ring-expanded compounds, 4-pyrimidinone derivatives (2 and 10), on nitrosation and on the reaction with p-nitrobenzenediazonium chloride, respectively.
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■ 13C-NMR Chemical Shifts and Coupling Constants JC-H of Six-membered Ring Systems Containing Sulfur-Sulfur Linkage
Toshikazu Takata, Kazuyuki Iida, and Shigeru Oae*
*Department of Chemistry, University of Tsukuba, 1-1-1 Ten-nodai, Tsukuba-shi, Ibaraki, 305-8571, Japan
Abstract
13C-NMR chemical shifts and coupling constants of methylene groups of several six-membered cyclic compounds having sulfur-sulfur linkage were measured. Some interesting NMR behaviours of a series of cyclic disulfides, thiolsulfinates and thiolsulfonates were observed and structural features of these compounds were investigeted.
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■ A New Synthesis 1,3-Thiazin-4-ones via 1,3-Oxazinium Salts from N-Acetoacetylcarboxamides
Yutaka Yamamoto,* Yutaka Azuma, and Shuhei Ohnishi
*Tohoku Pharmaceutical University, 4-4-1 Komatsushima, Aoba-ku, Sendai 981-8558, Japan
Abstract
In the formation of 1,3-oxazinium salts from N-acetoacetylcarboxamides (1), the effect of acids such as 70% perchloric acid (3a), 98% sulfuric acid (3b), 36% hydrochloric acid (3c), saturated hydrogen chloride-ethanol solution (3d), trifluoroacetic acid (3e), and acetic acid (3f) was examined by the established method leading to the pyrazole (5) via 1,3-oxazinium salt (2), and the order was as follows; 3a > 3b > 3e > 3d > 3c (3f was uneffective). The result was applied to synthesize 2-substituted 1,3-thiazine derivatives (7a-e, 8a,b) via 1,3-oxazinium salts from 1a-f and hydrogen sulfide in the presence of acetic anhydride in satisfactory yields.
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■ Variation of Skeletons of Antitumor Antibiotics I. Simple Synthesis of Naphtho[2,3-g]quinolines and a Naphtho[2,3-g]quinoxaline
Noriichi Oda, Kazuhiro Kobayashi, Taisei Ueda, and Isoo Ito*
*Faculty of Pharmaceutical Sciences, Nagoya City University, Tanabe-dori, Mizuho-ku, Nagoya 467-8603, Japan
Abstract
Simple synthesis of naphtho[2,3-g]quinolines (III,VI,IX) and a naphtho[2,3-g]quinoxaline (XII), which are a novel heterocyclic ring system, was carried out by the Diels-Alder reaction of 1,2-dimethylenecyclohexane (I) with quinoline-5,8-quinone (II,V,VIII) or quinoxaline-5,8-quinone (XI). Air oxidation of these adducts (III,VI,IX) in alcoholic alkaline solution gave tetrahydronaphtho[2,3-g]quinolines (IV,VII,X).