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. 24, No. 10, 1986
Published online:
■ A New Cytotoxic Alkaloid Thalifalandine
Long-Ze Lin, Shu-Fang Li, Xiang He, Guo-Qiang Song, and Zhong-Liang Chen*
*Shanghai Institute of Material Medica, Chinese Academy of Science, 354 Finglin Lu, Shanghai 200032, China
Abstract
The new dimeric aporphine-benzylisoquinoline alkaloid thalifalandine (1) from Thalictrum faberi has shown the marked antitumor activity in vitro. Its structure was confirmed by chemical transformation and spectral analysis.
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■ Anomalous Witting Reaction of Aldonic Thioamide Derivatives. A New Mode of Thiazole Ring Formation
László Somogyi,* Pál Herczegh, and Gyula Batta
*Reseaech Group of Antibiotics, Hungarian Academy of Sciences, H-4010 Debrecen, Hungary
Abstract
A new mode of thiazole ring formation and an unexpected acetoxy group elimination were observed as a result of the reaction of N-acetyl-per-O-acetylhexonic thioamides (1b and 2b) with ethoxycarbonylmethylenetriphenylphosphorane affording ethyl 2-(1’,5’-diacetoxy-penta-1’,3’-Z,E-dien-1’-yl)-4-methylthiazole-5-carboxylate (6).
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■ Synthesis of a Novel Class of Condensed 1,2-Thiazine-S-oxides. Cycloaddition Reaction of N-Aryl-4H-5,7a-epoxyisoindolines with N-Sulphinylaniline
Dipak Ranjan Borthakur, Dipak Prajapati, and Jagir Singh Sandhu*
*Division of Drug and Pharmaceutical Chemistry, Regional Research Laboratory, Jorhat 785 006, Assam, India
Abstract
N-Sulphinylanilins (2) reacts readily with N-aryl-4H-5,7a-epoxyisoindolines (1) to give a novel class of condensed 1,2-thiazine-S-oxides (3) in good yields.
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■ Models for "Fat" Nucleosides and Nucleotides: Syntheses of "Fat" Xanthine (fX), "Fat" Guanine (fG), and "Fat" Hypoxanthene (fHx) Analogues of the imidazo[4,5-e][1,4]diazepine System
Ramachandra S. Hosmane,* Anila Bhan, and Michael E. Rauser
*Labratorl for Chamical Dynamics, Department of Chemistry, University of Maryland Baltimore County, Catonsville, Maryland 21228, U.S.A.
Abstract
Synthetic analogues af xanthine, guanine, and hypoxanthine, possessing the skeletal structure of imidazo[4,5-e][1,4]diazepine, are reported.
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■ Photocycloaddition of Diethyl Acetylenedicarboxylate to 2-Phenyl-4H-1,3-benzothiazine Derivatives
Marija Sindler-Kulyk,* Alojz Dumbovic, Dunja Arzic, Biserka Metelko, and Lajosz Fodor
*Organic Chemistry Department, Faculty of Technology, University of Zagreb, Marulicev trg 20, 41000 Zagreb, Croatia
Abstract
Upon irradiation in the presence of diethyl acetylenedicarboxylate 6,7-dimethoxy-2-phenyl-4H-1,3-benzothiazine gives two main products: benzonitrile (X) and 2,3-carbethoxy-4,5-dimethoxy-7-methylbenzothiophene (XI). We report herein the first photochemical reaction of a 4H-1,3-benzothiazine derivative.
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■ Gracinine, a New C-19 Diterpenoid Alkaloid from Delphinium gracile DC
Antonio G. González, Rafael Díaz Acosta, José A. Gavín, and Gabriel de la Fuente*
*Instituto de Productos Naturales y Agrobiologia de Canrias, C. S. I. C./ Unversidad de La Laguna, P.O. Box 195, 38206- La Laguna, Tenerife, Spain
Abstract
Gracinine, a new C-19 diterpenoid alkaloid bearing a C-12 functionality, was isolated from Delphinium gracile DC, together with the known bases gadesine, dihydrogadesine and nudicaulidine. The structure of the new compound was established by means of 1H- and 13C-nmr spectroscopy.
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■ Theoretical Studies of Psychotropic Drugs. Questioning the Importance of Flex-angle in Drug Efficacy
Kenny Lipkowitz,* Anthony Burkett, and Jo Landwer
*Department of Chemistry, Indiana-Purdue University, PO Box 647, Indianapolis, IN 46223, U.S.A.
Abstract
MNDO calculations indicate that hetero-substituted 9,10-dihydroanthracenes are inherently planar molecules. Ring puckering is a very low energy process that can arise from intramolecular effects, e.g. peri-and/or transannular interactions as well as from intermolecular interactions like crystal packing forces. It is concluded that the angle of flexure, determined crystallographically and used as a descriptor of drug activity in several important CNS drugs, should be used with caution or not be used at all.
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■ Reaction of 2-Bromo-2,3-dihydro-1H-pyrazolo[1,2-a]indazolium Bromides with Alkaline Solution
Yasuo Fujimura,* Yoshiharu Nawata, and Masatomo Hamana
*Central Research Laboratories, Chugai Pharmaceutical Company, Ltd., Takada 3-41-8, Toshima-ku, Tokyo 171, Japan
Abstract
Treatment of 2-bromo-2,3-dihydro-1H-pyrazolo[1,2-a]indazolium bromides (1a-c) with alkaline solution initially affords 9H-pyrazolo[1,2-a]indazolium bromides (2a-c), which are further convertible by dehydrobromination into pyrazolo[1,2-a]indazoles (3a-c). The 9-position of 3 is susceptible to attack by oxygen and acetyl cation.
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■ Junosmarin, a New Khellactone Ester from Citrus junos Tanaka
Motoharu Ju-ichi,* Mami Inoue, Rika Tsuda, Naomi Shibukawa, and Hiroshi Furukawa
*Faculty of Pharmaceutical Science, Mukogawa-Women‘s University, 11-68 Koushien Kyuban-Cho, Nishinomiya, Hyogo 663-8179, Japan
Abstract
A new (-)-trans-khellactone ester, junosmarin, was isolated from the root bark of Citrus junos (Rutaceae) and the structure was assigned as 1 on the basis of spectral data and synthesis of its acetate 5.
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■ Two New Spirobenzylisoquinoline Alkaloids from Ripicapnos afrivana (Lam.) Pomel
Luis Castedo,* Domingo Domínguez, José Manuel Novo, Amelia Peralta, José Manuel Saá, and Rafael Suau
*Facultad de Química y Sección de Alcaloides, Deparamento de Química Orgánica, C. S. I. C., Santiago de Compostela, Spain
Abstract
Two new spirobenzylisoquinolines, (+)-isoparfumine and (+)-africanine, have been isolated from Rupicapnos africana (Lam.) Pomel and identified spectroscopically.
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■ Tandem Reductive Amination and Michael Addition. Synthesis of Optically Active Pyrrolidine Nucleus
Seiki Saito, Shingo Matsumoto, Shuji Sato, Masami Inaba, and Toshio Moriwake*
*Department of Applied Chemistry, Faculty of Engineering, Okayama University, 3-1-1 Tsushima-naka, Okayama 700-8530, Japan
Abstract
Reductive amination of ethyl (E)-(4S)-4-methoxymethoxy-6-oxo-2-hexenoate, derived from (S)-malic acid, with glycine ethyl ester was relayed intramolecularly by Michael-type addition, which has led, in one pot, to N-substituted (2R,3S)-2-ethoxycarbonylmethyl-3-hydroxypyrrolidine skeleton, a promising precursor for optically active necine bases such as (+)-heliotridine.
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■ Methyl Group at 1-Position of Stabilized Indoles as a Protective Group
Shin-ichi Nakatsuka,* Osamu Asano, and Toshio Goto
*Laboratory of Organic Chemistry, Faculty of Agricultures, Nagoya University, Chikusa, Nagoya, Aichi 464-8601, Japan
Abstract
Methyl group at 1-position of indoie derivative 2 was removed by oxidation with benzoyl peroxide and subsequent hydrolysis.
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■ A Novel 1,2-Alkyl Migration of Trialkyl(4-pyrodyl)borates
Minoru Ishikura, Tsukasa Ohta, and Masanao Terashima*
*Faculty of Pharmaceutical Scicences, Higashinihonngakuen University, 1757 Kanazawa, Toubetu-cho, Ishikari-gun, Hokkaodo 061-0212, Japan
Abstract
The reaction of lithium trialkyl(4-pyridyl)borates with Lewis acids or acylating agents produced 4-alkylpyridines via 1,2-alkyl migration from boron to pyridine ring.
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■ Novel Approach to 1H-Benzo[f]pyrrolo[1,2-a]indole-5,10-diones
Eric O. M. Orlemans, Willem Verboom, and David N. Reinhoudt*
*Laboratory of Organic Chemistry, Twente University of Technology, Enschede, The Netherlands
Abstract
The Friedel-Crafts reaction product of 1,4-dimethoxynaphthalene (3) and (S)-1-(trifluoroacetyl)-2-pyrrolidinecarbonyl chloride (4) could be converted in two steps into the benzo[f]pyrrolo[1,2-a]indole 10 following two different pathways. Compound 10 could easily be dehydrated using acid to 11. Upon reduction of 10 to the corresponding hydroquinone 12, spontaneous dehydration occurred.
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■ Thermal Reactions of o-Aminophenols and Dimethyl Actylenedicarboxylate
Norio Kawahara,* Takako Shimamori, Tsuneo Itoh, and Haruo Ogura
*Hokkaido College of Pharmacy, 7-1 Katsuraoka-cho, Otaru 047-02, Japan
Abstract
o-Aminophenols reacted with dimethyl acetylenedicarboxylate (DMAD) in refluxing dioxane to give 1,4-benzoxazine derivatives and their isomers. Further, novel tricyclic compounds and benzoxazole derivative were prepared in this reaction.
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■ Interaction of 2,4-Dihydroxy-7-methoxy-1,4-benzoxazin-3-one (DIMBOA) with Alcoholic Solvents
Héctor R. Bravo and Hermann M. Niemeyer*
*Departamento de Química, Facultad de Ciencias, Unversidad de Chile, Casilla 653, Santiago, Chile
Abstract
Solubilities and IR spectra of DIMBOA in alcoholic solvents showed that the carbonyl group of DIMBOA is hydrogen-bonded to the solvent. Activation parameters of DIMBOA in the same solvents suggested that the decomposition of DIMBOA occurs through an isocyanate, in analogy with the reaction in aqueous and aprotic solvents.
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■ The Formation and Facile Conversion of Trityl Phenylcynomethane Nitronate
Joseph H. Boyer* and Thanikavelu Manimaran
*Department of Chemistry, University of New Orleans, New Orleans, LA 70148, U.S.A.
Abstract
Trityl chloride and silver phenylcyanomethane nitronate in toluene at -20°C gave trityl phenylcyanomethane nitronate 1, an unstable ester that rearranged and fragmented at 5-10°C to 1-triphenylmethoxy-4,5-diphenyl-1,2,3-triazole 6 with coproducts carbon dioxide, α,α’-bis(triphenylmethaneazo)stilbene 3, benzonitrile-N-oxide 4, and trityl isocyanate 5.
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■ Syntheses of Vinylogous 4H-Pyrones from 2,6-Dimethyl-4H-pyran-4-thione and Arenyl Bromomethyl Ketones
Katsuo Ohkata, Masao Imagawa, and Kin-ya Akiba*
*Department of Chemistry, Faculty of Science, Hiroshima University, 1-3-1 Kagamiyama, Higashi-Hiroshima, Hiroshima 739-8526, Japan
Abstract
2,6-Dimethyl-4H-pyran-4-ylideneacetophenones (5) were prepared by desulfurization of mercaptopyriliurn salts (4) with diazabicyclo[5.4.0]undecene (DBU) in moderate yield. The 1H NMR spectra in CDCl3 solution of 5 show the exclusive preference for s-cis conformation at the enone site.
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■ Synthesis of New Cyclophosphazenes Containing Polyoxuethylene Moieties
Luciana Corda, Carlo Anchisi, Gianni Podda,* Pietro Traldi, and Mario Gleria
*Istituto di Chimica Farmaceutica, Tossicologica ed Applicate, University of Cagliari, Via Ospedale 72, 09100 Cagliari, Italy
Abstract
Hexa-substituted cyclophosphazenes are formed by the reaction of hexachlorocyclophosphazenes with polyethylene glycols mono alkyl ether and employed as transfer catalysts in anion-promoted reactions.
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■ Dual Substituent Parameter Treatment of 13C Substituent Chemical Shifts in 5-Substitued 2-Thenylidenemalononitriles and Molecular Orbital Theoretical Analysis at the CNDO/2 Level
Sumana Datta, Asish De, Sankar Prasad Bhattacharyya,* Chitrani Medhi, and Ajit Kumar Chakraborty
*Theory Group, Department of Physical Chemistry, Indian Asociation for the Cultivation of Science, Jadavpur, Calcutta 700 032, India
Abstract
DSP treatment of 13C SCS among the members of the title compound indicated the dominance of the resonance effect at Cβ and the presence of both localized and extended polarization in the side chain. MO calculations at the CNDO/2 level corroborated the observed SCS trends.
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■ Synthesis of Novel N-Heteroatomic Cannabinol Analogues
Marie-Claude Bellassoud-Fargeau, Bernadette Graffe, Marie-Claude Sacquet, and Pierre Maitte*
*associé au CNRS, 4 Place Jussieu, Laboratoire de Chimie des Hétérocycles, Université P. et M. Curie, case courrier 43, 4 Place Jussieu, F-75252 Paris Cedex 05, France
Abstract
Cyclization of 2,2-dimethyl-3-pyrrolidinomethylene-5-hydroxy-7-pentyl-4-chromanone 2 with guanidine, formamidine, acetamidine and benzamidine hydrochlorides in the presence of 2 eq. of sodium ethoxide afforded novel 5H-[1]benzopyrano[4,3-d]pyrimidines 4a-d in good yields.
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■ New Syntheses of 1-Amino- and 1-(2-Aminoethyl)-2,6-dicyanopiperidines and Diazabicyclo Compounds by a Strecker Reaction Using Glutaraldehyde and Diamines, and Their Stereochemistry
Kazumasa Takahashi,* Akira Tachiki, Katsuyuki Ogura, and Hirotada Iida
*Deparment of Synthetic Chemistry, Faculty of Engineering, Chiba University, 1-33 Yayoi-cho, Inage-ku, Chiba 263-8522, Japan
Abstract
An efficient sequence proposed here involves a simple Strecker reaction of glutaraldehyde with hydrazine or 1,2-diaminoethane, which gives 1-amino- or 1-(2-aminoethyl)-2,6-dicyanopiperidines, 2-cyano-1,7-diazabicyclo[4.3.0]nonane, and 10-cyano-1,4-diazabicyclo[4.4.0]decan-5-one. Their stereochemistry is also elucidated. Moreover, treatment of l-amino-2,6-dicyanopiperidine and phthaloyl dichloride in the presence of 4-(N,N-dimethylamino)pyridine quantitatively gives 1-phthalimido-2,6-dicyanopiperidine.
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■ Andrachamine a New Alkaloid from Andrachne aspera
Viqar Uddin Ahmad* and M. Ajmal Nasir
*H. E. J. Postgraduate Institute of Chemistry, University of Karachi, Karachi-75270, Pakistan
Abstract
A new piperidine alkaloid andrachamine was isolated from the medicinal plant Andrachne aspera. Its structure was established by spectroscopic studies.
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■ Synthesis of 3,6-Disubstituted β-Carbolines Which Possess either Benzodiazepine Antagonist or Agonist Activity
Timothy J. Hagen, Filadelfo Guzman, Christopher Schultz, James M. Cook,* Phil Skolnick, and Harlan E. Shannon
*Department of Chemistry, University of Wisconsin-Milwaukee, Milwaukee, Wisconsin 53201, U.S.A.
Abstract
A series of 3-substituted and 3,6-disubstituted β-carbolines have been synthesized. These compounds have been screened in vitro in order to determine the size of substituents which benzodiazepine receptors will tolerate at positions -3 and -6 of the β-carboline nucleus. It has been found that the receptor will tolerate ester alkyl groups at position-3 as large as cyclohexyl 1g but not as large as adamantyl 5d. Moreover, N-aryl substituents as large as naphthobenzylamino 8b can be introduced at position-6 without significant loss of receptor binding affinity.
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■ Synthesis of 2H-Pyrazolo[3,4-b]pyridines from 1,1,2,2-Tetracyanocyclopropanes
Masahiko Takahashi,* Toshiaki Orihara, Takanori Sasaki, Tetsuya Yamatera, Ken‘ichi Yamazaki, and Atomi Yoshida
*Department of Materials Sciences, Faculty of Engineering, Ibaraki University, 4-12-1 Nakanarusawamachi, Hitachi, Ibaraki 316-8511, Japan
Abstract
Reaction of 3-substituted 1,1,2,2-tetracyanocyclopropanes (1) with phenylhydrazine proceeded through the formation of pyrazole-4-spirocyclopropanes (4) followed by the ring opening of the cyclopropane ring to give 4-vinylpyrazoles (5), from which 2H-pyrazolo[3,4-b]pyridines (6) were obtained.
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■ Preparation of Chloro-α-truxillic Acids via 3-Methyl-4-nitro-5-styrylisoxazole Photodimers
Antonella Baracchi, Stefano Chimichi, Francesco De Sio, Donato Donati, Rodolfo Nesi, Piero Sarti-Fantoni,* and Tomas Torroba
*CNR, Centro di Studio Sulla Chimica e la Struttura dei Composti Eterociclici e lolo Applicazioni, c/o Dipartimento di Chimica Organica "Ugo Schiff", Università di Firenze, Via Gino Capponi 9, I-50121 Firenze, Italy
Abstract
Chloro-α-truxillic acids (3b-e) were prepared by oxidation of the photodimers (2b-e) of 3-methyl-4-nitro-5-chlorostyrylisoxazoles (1b-e).
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■ Synthesis of 4,5-Dihydro-1H-imidazoles from 1,5-Dihydro-2H-imidazoles Using ‘Nickel Boride’
Melvin R. Euerby, Amanda C. Oldroyd, and Roger D. Waigh*
*Department of Chemistry, University of Manchester, Oxford Road, Manchester, M13 9PL, U.K.
Abstract
In situ prepared ‘nickel boride’ generated from sodium borohydride and nickel (II) chloride cleanly transforms 1,5-dihydro-2H-imidazoles into 4,5-dihydro-1H-imidazoles in high yields by a double bond migration.
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■ The Preparation and Spectral Characterization of 2-Haloindoles, 3-Haloindoles, and 2,3-Dihaloindoles
Mary R. Brennan, Karen L. Erickson,* Frank S. Szmalc, Marilyn J. Tansey, and Janice M. Thornton
*Jeppson Laboratory, Clark University, Worcester, MA 01610, U.S.A.
Abstract
The preparation and properties of a series of 2- and 3-haloindoles and 2,3-dihaloindoles are described, and the mechanism of halogenation of 3-halo substituted indoles is briefly discussed.
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■ Synthesis and Phermacodynamic Investigation of New Isoguvacine Analogues with Benzoquinolizine Skeleton
Gábor Blaskó, Julianna Kardos, Eszter Baits-Gács, Miklós Simonyi, and Csaba Szántay*
*Central Research Institute for Chemistry, Hungarian Academy of Sciences, H-1025 Budapest, Pusztaszeri ut 59-67, P.O.Box 17, Hungary
Abstract
Stereoisomer hydroxy-esters 15 -19 as well as isoguvacine analogue 20 with benzo[a]quinolizine skeleton have been prepared via regioselective Dieckmann condensation of diester 9 followed by subsequent reduction and E2-elimination. Compounds 16 and 20 have shown a considerable in vitro activity at the GABA/benzodiazepine receptor complex.
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■ The Synthesis of 2,3’:2’,3"-, 2,3’:4’,3"-, 2,3’:5’,3"- and 2,2’:4’,3"-Terthienyls
Nimal Jayasuriya and Jacques Kagan*
*Department of Chemistry, University of Illinois at Chicago, 845 West Taylor St., Chicago, IL 60607-7061, U.S.A.
Abstract
The coupling of thienyl Grignard reagents with the appropriate bromobithiophenes in the presence of Ni(dppp)Cl2 gave the title compounds with yields ranging between 72 and 95%.