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. 51, No. 10, 1999
Published online:
■ Conversion of Allyl Aryl Selenides into Selenochroman Derivatives
Hitoshi Abe,* Natsuko Koshiba, Akira Yamasaki, and Takashi Harayama*
*Faculty of Pharmaceutical Science, Okayama University, 1-1-1 Tsushima-naka, Okayama 700-8530, Japan
Abstract
Several allyl aryl selenides were prepared and examined their reactions with aluminum bromide to give selenochroman derivatives in high to moderate yields. A plausible mechanism of this reaction is also discussed.
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■ Products from a Novel Reaction of Di- hydropyrazines with Vichinaldiamines
Tadatoshi Yamaguchi,* Shigeru Ito, Yukiko Iwase, Kenji Watanabe, and Kazunobu Harano
*Department of Hygiene, Miyazaki Medical college, Kiyotake-cho, Miyazaki 889-1692, Japan
Abstract
Dihydropyrazines such as 2,3-dihydro-5,6-dimethylpyrazine reacted with 1,2-diamines like ethylenediamine to form cis-tetraazadecalins (TADs) as crystalline products. The NMR spectra of the products in CDCl3 or CD3CN at -20 ~ -60°C exhibited the signals due to TAD. However, the NMR spectra at room temperature showed that the TAD had dissociated into its parent materials. Seven TADs were obtained by only a mixing operation at a low temperature.
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■ 4-Alkylcarbonylmethylideneisoquinolines. A Synthetic and Mechanistic Study
Isabel Moreno, Raul SanMartin, Imanol Tellitu,and Esther Domínguez*
*Kimika Organikoa Saila, Zientzi Fakultatea, Euskal Herriko Unibertsitatea, Vasco, P.O. Box 644, 48080-Bilbao, Basque Country, Spain
Abstract
An efficient preparation of 4-alkylcarbonylmethylideneisoquinoline derivatives via a modification of Jones oxidation and alkene acylation conditions is reported. In addition, evidence on the mechanism involved in the formation of 12-alkylbenzo[c]phenanthridines from 3-aryl-4-methylideneisoquinolines is presented.
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■ Chemistry of Indoles Carrying a Basic Function. Part IV. Synthesis of D-Nor- ergoline and Ergoline Ring by Stobbe Reaction
István Moldvai, Eszter Temesvári-Major, Eszter Gács-Baitz, Orsolya Egyed, Ágnes Gömöry, László Nyulászi, and Csaba Szántay*
*Institute of Chemistry, Chemical Research Center, Hungarian Academy of Sciences, H-1525 Budpest , P.O. Box 17, Hungary
Abstract
Starting from Uhle’s ketone (2), pentacyclic lactone derivatives with D-norergoline ring (13 and 14) have been prepared by an unusual intramolecular Stobbe reaction of a succinic diester derivative (3a). The preparation of ergoline ring (1) itself was also achieved through modification of the reaction conditions.
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■ New Synthesis of Benzo[a]phenazines Based on Acid Promoted Ring Opening of the Benzotriazole Moiety
Alan R. Katritzky,* Abd El Rachman Ferwanah, Yasuhisa Matsukawa, Peter J. Steel, and Sergey N. Denisenko
*Center for Heterocyclic Compounds, Department of Chemistry, University of Florida, P. O. Box 117200, Gainesville, FL 32611-7200, U.S.A.
Abstract
Syntheses of benzo[a]phenazines (6a-d) have been accomplished based on an acid promoted tandem benzotriazole ring-opening / ammonia extrusion procedure. Compounds (6a-d) are thus accessible directly from 3-(benzotriazol-1-yl)-1,4-diaryl-1-buten-4-ols (3a-d) in one-pot reaction sequences or from the intermediate 3,4-dihydronaphthalenes (4a-c). This constitutes a new type of benzotriazole ring transformation.
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■ Synthesis of a Novel 7,14β-Ethano-bridged Opiate
Han Yu, Lijuan Wang, Judith L. Flippen-Anderson, Xinrong Tian, Andrew Coop, and Kenner C. Rice*
*Laboratory of Medicinal Chemistry, National Institute of Diabetes Digestive and Kidney Diseases, National Institute of Health, Bldg.8, Rm. B1-23 Betheda, MD 20892-0815, U.S.A.
Abstract
A novel 7, 14β-ethano-bridged opiate (1) was prepared from the known 14-alkenylcodeinone (3) in two steps. Selective reduction of the enone double bond of 3 followed by ozonolysis led to an aldehyde intermediate, which was cyclized in situ through an intramolecular aldol condensation to give the rigid hexacyclic derivative (1).
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■ Metalation of Pyrazinethiocarboxamides. Metalation of Diazines XXVI
Corinne Fruit, Alain Turck, Nelly Plé, and Guy Quéguiner*
*Laboratoire de Chimie Organique Fine et Hétérocyclique(UPRES-A 6014), IRCOF, INSA, Université de Rouen, Place Emilae Blondel, BP 08,76131 Mont-Saint-Aignan Cedex, France
Abstract
Some new pyrazinethiocarboxamides were synthesized and metalated with LTMP in tetrahydrofuran. The reaction of these lithio derivatives with various electrophiles gave access to a large range of 2,5-disubstituted pyrazines. This unexpected regioselectivity was established by application of gradient enhanced HMBC sequence for the observation of long range 1H-15N heteronuclear couplings at natural abundance.
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■ Rotameric Properties of Novel N-Acyl and N-Acyloxy Dimeric 4-Phenyl-1,4-dihydropyridines Derived from Developed Solid-State Synthesis
Andreas Hilgeroth,* Ute Baumeister, and Frank Heinemann
*Institute of Pharmaceutical Chemistry, Department of Pharmacy, Martin-Luther-University Halle-Wittenberg, Wolfgang-Langenbeck-Str. 4, 06120 Halle, Germany
Abstract
Novel N-acyl and N-acyloxy dimeric 4-phenyl-1,4-dihydropyridines are given by solid-state photodimerization of their monomeric educts in excellent yields. The existence of rotamers was demonstrated by 1H NMR spectroscopical measurement at certain temperatures and additionally supported by X-Ray crystal structure analysis of centrosymmetrical cage-dimeric N-acetyl-3,5-dimethoxycarbonyl-4-phenyl-1,4-dihydropyridine (3b). Topochemical investigations by X-Ray crystal structure analysis prove the formation of anti-dimeric N-Boc-3,5-dimethoxycarbonyl-4-phenyl-1,4-dihydropyridine (4e) to be controlled by the nearest distance of potentially reacting double bonds with 3.667(3) Å.
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■ A Synthesis of 4-Quinolone-3-carboxylic Acids via Pyrolysis of N-Aryldioxopyrrolines
Kunihiko Mohri,* Akihiko Kanie, Yoshie Horiguchi, and Kimiaki Isobe
*Showa College of Pharmaceutical Sciences, 3-3165, Higashi-tamagawagakuen, Machida, Tokyo 194-8543, Japan
Abstract
A synthesis of 4-quinolone-3-carboxylic acids (8) was achieved by pyrolysis of 4,5-dimethoxycarbonyl-1-aryl-1H-pyrrole-2,3-diones (3) followed by selective de-methoxycarbonylation of the resulting 2,3-dimethoxycarbonyl-4-quinolones (4) in excellent overall yields.
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■ Reaction of Quinoline N-Oxides with Alkyl- and Aryllithiums in the Presence of Oxidant
Yoshinobu Tagawa, Manami Nomura, Hiroyuki Yamashita, Yoshinobu Goto,* and Masatomo Hamana
*Faculty of Pharmaceutical Sciences, Fukuoka University, Nakamura, Jonan-ku, Fukuoka, 814-0180, Japan
Abstract
Quinoline and some 4-substituted quinoline 1-oxides react with alkyl- and aryllithiums in the presence of an oxidant to afford 2-alkyl- and 2-arylquinoline 1-oxides in generally good yields. Among oxidants used, 9-fluorenone is most effective. On the other hand, quinaldine 1-oxide undergoes a base-induced electrophilic reaction with n-BuLi and 9-fluorenone to give 2-[(9-hydroxyfluoren-9-yl)methyl]quinoline 1-oxide.
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■ Synthesis of Furo[2,3-c]quinolin-4(5H)-ones
Krishna C. Majumdar,* Anup K. Kundu, and Paritosh Biswas
*Department of Chemistry, University of Kalyani, Kalyani-741 235, W. B., India
Abstract
A number of 1-aryloxymethyl-3H-pyrano[2,3-c]quinolin-5(6H)-ones (4a-d, 4f-i) on heating in N,N-diethylaniline for 8 h underwent an unusual ring contraction to give 1-aryloxymethyl-2-methylfuro[2,3-c]quinolin-4(5H)-ones(5a-d, 5f-i) in 66-79 % yields.
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■ Thermal Ring Contraction of 3H-1,4-Benzodiazepines into Quinazolines
Mamoru Kaname, Takashi Tsuchiya, and Haruki Sashida*
*Faculty of Pharmaceutical Sciences, Hokuriku University, 3-Ho, Kanagawa machi, Kanazawa 920-1181, Japan
Abstract
The thermolysis of the 5-methoxy- (11a-c) and 5-diethylamino-3H-1,4-benzodiazepines (14a-c) resulted in a ring transformation to give the 4-methoxy- (12a-c) and 4-diethylaminoquinazolines (15a-c), respectively. The mechanism of this ring contraction is also described.
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■ Convenient Synthesis of Cyclohexa[a]pyrrolo[2,1-b][3]benzazepine, a Cephalotaxus Alkaloid Analogue
Hitoshi Tanaka,* Mitsunobu Doi, Hiroshi Shimizu, and Hideo Etoh
*Faculty of Pharmacy, Meijo University, 150 Yagoto, Tempaku-ku, Nagoya, Aichi 468-8503, Japan
Abstract
Irradiation of N-(3-hydroxy-4-methoxyphenethyl)-3-(2-iodo-5-methoxyphenyl)propionamide (11) in methanol in the presence of sodium hydroxide furnished 3-hydroxy-2,12-dimethoxy-6,7,9,10-tetrahydrodibenz-[d,f]azecin-8(5H)-one (14) which was successfully led to cephalotaxine analogue (17) bearing pyrrolo[2,1-b][3]benzazepine skeleton by reduction with borane followed by Birch reduction and subsequent acidic treatment. The structure of 17 was established by means of X-ray crystallography.
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■ tert-Butyl 2-{1-[2-Aryl-4-oxothiazol-5- (4H)-ylidene]ethyl}diazene-1-carboxyl- ates: A New Class of 1,2-Diaza-1,3- butadienes
Orazio A. Attanasi, Paolino Filippone,* Barbara Guidi, Francesca R. Perrulli, and Stefania Santeusanio
*Istituto di Chimica Organica, Facolta di Scienze, Università di Urbino, Piazza della Repubblica 13, I-61029 Urbino, Italy
Abstract
The synthesis and reactions of tert-butyl 2-{1-[2-aryl-4-oxothiazol-5(4H)-ylidene]ethyl}diazene-1-carboxylates: a new class of 1,2-diaza-1,3-butadienes is reported.
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■ Substituent Effects in the Ring-Chain Tautomerism of 1,2-Diarylimidazolidines
Anikó Göblyös, László Lázár, Ferenc Evanics, and Ferenc Fülöp*
*Institute of Pharmaceutical Chemistry, Abert Szent-Györgyi Medical University, POB 121, H-6701 Szeged, Eötvös u. 6, Hungary
Abstract
1,2-Diaryl-substituted imidazolidines proved to be ring-chain tautomeric mixtures in CDCl3 at 300 K. Both 1- and 2-aryl groups exerted significant electronic effect on the tautomeric equilibria, which could be described by the equation log KX = ρσ+ + log KX=H.
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■ Diastereoselective Synthesis of trans- 4-Arylpiperidine-3-carboxylic Acid Derivatives from 4-Aryl-1,4-dihydropyridine
Kae-Shyang Shih, Chin-Wei Liu, Yu-Jung Hsieh, Shyh-Fong Chen, Hao Ku, Lee Tai Liu,* Ya-Chuan Lin, Hsiang-Ling Huang, and Chia-Lin Jeff Wang
*Deparatment of Medicinal Chemistry, Development Center for Biotechnology, Hsi-Chih Research Park 102, Lane 169, Kang Ning St, Hsi Chih 221, Taipei Hsien, Taiwan, R.O.C.
Abstract
A convenient procedure for the preparation of trans-3,4-disubstituted piperidines from 4-aryl-1,4-dihydropyridine is described. The diastereoselective synthesis of an unnatural amino acid, trans-4-arylpiperidine-3-carboxylic acid, and its derivatives is exemplified. The key steps include the construction of a trans-3,4-disubstituted piperidine moiety in compound (5), N-methyl carbamate of trans-4-aryl-piperidine-3-carboxylic acid, from 4-aryl-1,4-dihydropyridine-3-carboxylic acid methyl ester (2) via hydrogenation, reduction, and hydrolysis. Reduction of acid (5) with lithium aluminum hydride or with sodium borohydride provided the corresponding carbinol (7) or (8).
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■ Synthesis of Trifluoromethylpyrimidines from Fluorinated En-aminodiketones
Mustapha Soufyane, Sarah van den Broek, Layachi Khamliche, and Catherine Mirand*
*Laboratoire de Transformations et Synthèse de Substances Naturelles, UPRESA/CNRS 6013, Université de Reims-Champagne-Ardenne, Faculté de Pharmacie, 51, rue Cognacq-Jay, F-51096 Reims Cédex, France
Abstract
4-Trifluoromethylpyrimidines (2,7) were easily synthesized by reaction of enamino diketones (1,6) with N,N-dimethylguanidine, O-methylisourea or guanidine. The 4,6-bistrifluoromethylpyrimidine (11) was obtained from 10 and O-methylisourea. Hydrolysis of the 2-methoxypyrimidines (2c,7c,12) gave the 4-hydroxypyrimidones (3,8,13).
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■ A Convenient Synthesis of (Z)-3- (α-Cyano-α-alkoxycarbonylmethylene)-2-piperazinones and Their Derivatives
Yoichi Yamada,* Heinosuke Yasuda, and Masaaki Kasai
*Utsunomiya University, 350 Mine, Utsunomiya 321-8505, Japan
Abstract
(Z)-3-(α-Cyano-α-alkoxycarbonylmethylene)-2-piperazinone derivatives (3) and trans-(Z)-3-(α-cyano-α-alkoxycarbonylmethylene)-octahydro-2(1H)-quinoxalinone derivatives (5) possessing various alkoxycarbonyl groups are prepared directly from the reaction of dialkyl (E)-2,3-dicyanobutenedioates (1) with ethylenediamine (2) and with trans-1,2-diaminocyclohexane (4), respectively. Furthermore, cis-1,2-diaminocycloheptane (6) and meso-2,3-diaminobutane (8) were reacted with the diethyl ester 1b to give cis-(Z)-3-(α-cyano-α-ethoxycarbonyl-methylene)decahydro-2H-cycloheptapyrazin-2-one (7) and cis-(Z)-3-(α-cyano-α-ethoxycarbonylmethylene)-5,6-dimethyl-2-piperazinone (9), respectively. The structural studies of 3, 5, 7, and 9 were carried out by NMR experiments in some details.
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■ New Chiral 3-Naphthylaminomethylpyrroli- dines: An Unexpected Epimerisation Reaction
Cristiana Fava, Roberta Galeazzi, Giovanna Mobbili, and Mario Orena*
*Dipartimento di Scienze dei Materiali e della Terra, Università di Ancona, Via Brecce Bianche, I-60131 Ancona, Italy
Abstract
New enantiomerically pure 3-naphthylaminomethylpyrrolidines (8), (9), (14) and (15) were obtained through simple steps starting from chiral 4-ethenylpyrrolidin-2-ones (2) and (3). On the other hand, starting from pyrrolidine (16), an epimerisation reaction occurred, which was explained through formation of the bicyclic ammonium salt (18). Nucleophilic addition of Et2Zn to benzaldehyde, carried out in the presence of 8, gave (S)-1-phenyl-1-propanol in 28% e.e.
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■ A Facile and Convenient Synthetic Method for Fluorine-containing 1,2-Dihydropyrido[3,2-h]quinazolines and Pyrido[3,2-h]quinazolines
Etsuji Okada* and Norikado Tsukushi
*Department of Chemical Science andd Engineerring, Faculty of Engineering, Kobe University, Kobe 657-8501, Japan
Abstract
5,7-Bis(trifluoroacetyl)-8-quinolylamine (1) reacted with various aliphatic and aromatic aldehydes in the presence of aqueous ammonia to afford fluorine-containing 1,2-dihydropyrido[3,2-h]quinazolines (2) and pyrido[3,2-h]quinazoline-6-methanols (3) in moderate to high yields. Dehydrogenation of 2 with DDQ gave the corresponding pyrido[3,2-h]quinazolines (4) in excellent yields. Conversion of alcohols (3) into hydrates (4) with DDQ was also successful.
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■ Synthesis of 4-Benzyl-5-(2,6-dichloro- phenyl)-2-ethoxy-1,2,3,4-tetrahydro-1,4,6,2-oxadiazaphosphorine 2-Oxide
Wynona Johnson,* Alan Faux, and Gary Fallon
*CSIRO, Molecular Science, Praivate BAg 10, Clayton South MDC, Victoria, 3169, Australia
Abstract
A derivative of the novel heterocyclic ring system - 1,2,3,4-tetrahydro-1,4,6,2-oxadiazaphosphorine (1), was prepared by the cycloaddition of the nitrile oxide generated from hydroximoyl chloride (2) with aminomethylphosphonate (3). The structure was elucidated by NMR analysis and X-Ray crystallography. The stability of the new ring system was investigated.
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■ Acetylene-based Functionalized Dihydrofuranones and Related Biomimetic Assemblies
Boris A. Trofimov* and Anastasiya G. Mal'kina
*Siberian Branch, Institute of Chemistry, Russian Academy of Sciences, 1, Favorsky Street, Irkutsk, 664033, Russia
Abstract
There are overviewed new acetylene-based syntheses of functional dihydrofuran-2-ones and 2-iminodihydrofurans related to naturally occurring and biologically active compounds. Most of the products are synthesized by nucleophilic addition of water, alcohols, amines, azoles, thiols, azide and halogenide ions, etc., as well as multident and multifunctional nucleophiles (thiurea, benzimidazole-2-thione, benzoxazole-2-thione, etc.) to esters, amides or nitriles of α,β-acetylenic γ-hydroxy acids followed by cyclization of the adducts.