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. 31, No. 1, 1990
Published online:
■ A New Route to 1,2-Dithiole-3-thiones (Trithiones) by the Reaction of Enaminones with Carbon Disulfide
Yoshinori Tominaga,* Hajime Norisue, Chizuko Kamio, Toshiyuki Masunari, Yuji Miyashiro, and Akira Hosomi*
*Faculty of Pharmaceutical Sciences, Nagasaki University, 1-14, Bunkyo-machi, Nagasaki 852-8521, Japan
Abstract
Enaminones reacted with carbon disulfide in the presence of sodium hydroxide to give the corresponding 1,2-dithiole-3-thiones (trithiones) in 30-82% yields.
Published online:
■ A Stereocontrolled Synthesis of the 16-Membered Ring Macrolide Aglycones, Niddanolide, Carbonolide B, and Platenonolide W1
Noriyuki Nakajima, Kouichi Uoto, and Osamu Yonemitsu*
*Faculty of Pharmaceutical Sciences, Hokkaido University, Sapporo 060, Japan
Abstract
The aglycones of the 16-membered ring macrolide antibiotics, niddanolide, carbonolide B, and platenonolide W1, were synthesized via the Yamaguchi esterification of the C1-10 segment and the C11-C15 segment, prepared stereoselectively from n-glucosed, followed by an intramolecular Wittig-Horner type cyclization.
Published online:
■ New and Efficient Synthesis of 5,6,7,8-Tetrahydroindolizidines. Application to the Synthesis of Pharmacologically Relevant Chiral Aminoderivatives from L-Asparagine
Peter Gmeiner* and Holger Lerche
*Institut für Pharmazie und Lebensmittelchemie, Ludwig-Maximilins-Universität, Sophienstraße 10, 8000 München 2, Germany
Abstract
A convenient and high yielding cyclization reaction of N-pyrrolylbutyl triflates is shown. The method is applied to afford the potential DA agonists 3, enantiomerically pure from L-aspargine.
Published online:
■ A New Synthetic Approach to (+)-Galantinic Acid, Degradation Product from the Peptide Antibiotic Galantin I, via 4-Amino-3-hydroxypyranose
Shinzo Kano,* Tsutomu Yokomatsu, and Shiroshi Shibuya
*Tokyo College of Pharmacy, 1432-1 Horinouchi, Hachioji, Tokyo 192-0392, Japan
Abstract
5-Phenylthioxazolidin-2-ones, derived from L-serine, were subjected to photo-induced radical allylation to give the corresponding 4-substituted 4,5-trans-5-allyloxazolidin-2-ones. 4-Ethoxyethyl derivative (13c) was led to N-Boc galantinic acid methyl ester via N-Boc 4-amino-3-hydroxypyranose.
Published online:
■ A Convenient, One-Pot Azulene Synthesis from Cyclohepta[b]furan-2-ones and Vinyl Ether and Its Analogues. (II). Acetals as Reagent
Tetsuo Nozoe,* Hidetsugu Wakabayashi,* Sumio Ishikawa, Chi-Phi Wu, and Paw-Wang Yang*
*Department of Chemistry, Faculty of Science, Josai University, 1-1 Keyakidai, Sakado, Saitama 350-0295, Japan
Abstract
Variously functionalized azulene derivatives were synthesized in one-pot and by the reaction of cyclohepta[b]furan-2-ones with acetals of several aldehydes and ketones on heating at 160-190 °C in neat or aprotic solvent.
Published online:
■ Synthesis of 1,2,3,4,5,6-Hexahydro-8-hydroxy-2,6-epithio-3-benzazocine
Mikio Hori,* Hiroyuki Ozeki, Tatsunori Iwamura, Hiroshi Shimizu, Tadashi Kataoka, and Noriyuki Iwata
*Department of Pharmacognosy, Gifu College of Pharmacy, 6-1 Mitahora-higashi 5-chome, Gifu 502-8585, Japan
Abstract
In anticipation of diminishing narcotism of 1,2,3,4,5,6-hexahydro-8-hydroxy-2,6-methano-3-benzazocine opioids, the corresponding 2,6-epithio-3-benzazocines (2) have been synthesized by intramolecular cyclization of 1-(2-aminoethyl)-3,4-dihydro-1H-2-benzothiopyrans (9) with tert-butyl hypochlorite, and subsequent treatment of the 5-membered cyclic aminosulfonium slats (17) with NaOH.
Published online:
■ Studies on the Alkaloids from Aconitum barbetum var. hispidum Ledeb.
Aina Lao, Hongcheng Wang, Jun Uzawa, Yasuo Fujimoto,* and Makoto Kirisawa
*College of Pharmacy, Nihon University, 7-7-1 Narashinodai, Funabashi-shi, Chiba 274-8555, Japan
Abstract
A new C18-diterpenoid alkaloid, hispaconitine (1) and four known alkaloids, tuguaconitine (2), delsoline (3), 14-acetyldelcosine (4) and delcosine (5), have been isolated from the roots of Aconitum berbetum var. hispidum Ledeb. The structure of hispaconitine (1) was determined by 2D-nmr spectroscopic analyses.
Published online:
■ Studies in Spiroheterocycles: Part XXII: Synthesis of Novel Fluorine Containing Spiro[3H-indole-3,5’-(5H)pyrano[2,3-d]pyrimidine]-6’-carbonitriles and Ethyl Carboxylates
Krishna C. Joshi,* Renuka Jain, and Saroj Nishith
*Department of Chemistry, University of Rajasthan, Jaipur 302 004, India
Abstract
A number of novel fluorine containing spiro[3H-indole-3,5’-(5H)-pyrano[2,3-d]pyrimidine]-6’-carbonitriles and ethyl carboxylates have been synthesized by the Michael reaction of 3-dicyano- and carboethoxycyanomethylene-2-oxindole with phenylbarbituric acid. As the reaction offers two possibilities, the formation of the pereferred product has been discussed. Further, the spiro compounds have been subjected to acetylation and methylation.
Published online:
■ Synthesis of Methyl 4-(2,2-Dimethoxyethyl)-6-hydroxy-7-methoxyindole-2-carboxylate: A Potential Intermediate for the Synthesis of the Central and Right Parts of the Anticancer Antibiotic CC-1065
Luis Castedo, Carlos F. Marcos, María Ruiz, and Gabriel Tojo*
*Departamento de Química Orgánica, Facultad de Farmacia, Universidad de Santiago de Compostela, E-15706, Santiago de Compostela, Spain
Abstract
We describe an efficient synthesis of methyl 4-(2,2-diemthoxyethyl)-6-hydroxy-7-methoxyindole-2-carboxylate (5), a key inermediate for the synthesis of the cetnral and right parts of the antitumor agent CC-1065 (1) and of the inhibitors of cyclic adenosine-3’,5’-monophosphate phosphodiesterase PDE-I (2) and PDE-II (3).
Published online:
■ Chemistry of Silyl Thioketones. Part 6. Synthesis of 5-Membered Silyl-heterocycles via 1,3-Dipolar Cycloaddition to Aryl Silyl Thioketones
Bianca F. Bonini, Gaetano Maccagnani,* Germana Mazzanti, Ghamel Abdel-Lateef Achmed Atwa, Paolo Zani, and Gaetano Barbaro
*Dipartimento di Chimica Organica "A Mangini", Università degli Studi di Bologna, Viale Risorgimento, 4, I-40136 Bologna , Italy
Abstract
Aryl silyl thioketones react with 1,3-dipoles (nitriloxides, nitrilimine and nitrile ylide) to give regiospecifically silyl thiaheterocycles. These cycloadducts undergo desilylation leading either to ring fragmentation products or to the H-substituted heterocycles.
Published online:
■ Studies on Dipolar Cycloaddition Reactions. Synthesis of 3,4-Disubstituted 1-(2,4-Dichlorobenzamidoyl)azetidin-2-ones and Fused Δ2-Pyrazolines
Chandra Sekhar Sarma, Probin C. Gogoi, and Jibon C. S. Kataky*
*Regional Research Laboratory, Jorhat 785 006, Assam, India
Abstract
From the dipolar cycloaddition reactions of ketenes and aniles 2, the new azetidinones 3 and 4 were isolated. In addition the reaction between the nitrilimine 6 and cyclic olefins 7 gave new fused Δ2-pyrazolines 8, 9 and 10. The chemical behaviour and spectral data of the new compounds were determined.
Published online:
■ Fluorinated Analogues of the Imidazole Insect Growth Regulator KK-42
César Arbonés, Francisco J. Sánchez, Maria-Pilar Marco, Francisco Camps, and Angel Messeguer*
*Departmenr of Biological Chemistry, C.I.D. (CSIC), J. Giroba 18. 08034-Barcelona, Spain
Abstract
The preparation of compounds 1b, 1c and 1e, monofluoro and trifluoromethyl analogues of the imidazole KK-42 (1a) is reported. The synthetic sequence involves the formation of an imine between the appropriate fluoro aldehyde and benzylamine, followed by condensation with tosylmethyl isocyanide (TosMIC) in basic media. Each step has been thoroughly studied and the whole procedure has been optimized for the case of model imidazole 1a. It has been observed that when possible, the imine formation proceeds with a concomitant Z/E isomerization on the olefin moiety of the α,β-unsaturated system. Finally, data on the biological activity of the title compounds as ecdysone antagonists are also presented.
Published online:
■ Synthesis of an Aminopyrazolidines Substituted Quinolone Acid
Kyoung Soon Kim* and Patrick C. Ryan
*Cancer and Infectious Diseases Research, The Upjohn Company, Kalamazoo, Michigan 49001, U.S.A.
Abstract
A synthesis of a new heterocycle, 2-methyl-4-(S)-Cbz-aminopyrazolidine (2), and the preparation of aminopyrazolidine substituted quinolone acid 1 are reported.
Published online:
■ Synthesis of an Aminoisoxazolidine Substituted Quinolone Acid
Kyoung Soon Kim*
*Cancer and Infectious Diseases Research, The Upjohn Company, Kalamazoo, Michigan 49001, U.S.A.
Abstract
New heterocycle aminoisoxazolidine 7 and tetrafluorobenzoic acid are synthesized for the synthesis of a quinolone antibacterial agent. The synthesis of a chiral aminoisoxazolidines substituted quinolone acid, U-82662A, is described.
Published online:
■ Synthesis of New Heterocyclic Ring Systems: Indeno[2,1-b]benzo[g]indolizine and indeno[1’,2’:5,4]pyrrolo[2,1-a]phthalazine
Francesco Campagna,* Angelo Carotti, Giovanni Casini, and Maria Macripò
*Dipartimento Farmaco-Chimico, Università di Bari, Via Amendola 173, 70126 Bari, Italy
Abstract
Some derivatives of the title heterocycles have been prepared by a "one step" synthesis from 2-hydroxy-2-acylmethylene-1,3-indandiones, tosyl chloride and isoquinoline or phthalazine. The synthesis of new indeno[2,1-b]indolizine derivatives performed by using pyridine as base is also reported.
Published online:
■ Synthesis of 2-t-Butyl-5-hydroxypyrimidine via Hydrolysis of 2-t-Butyl-5-halopyrimidines
Richard Garth Pews*
*Organic Chemicals and Polymers Laboratry, Central Research, The Dow Chemical Company, Midland, Michigan 48674, U.S.A.
Abstract
The hydrolysis of 2-t-butyl-5-halopyrimidine (halogen = bromine or chlorine) with sodium methoxide in methanol yields 2-t-butyl-5-hydroxypyrimidine. The side reaction product, 2-t-butylpyrimidine, is substantially reduced, especially in the case of the bromo derivative, with catalytic amounts of elemental sulfur.
Published online:
■ On the Multiplicity of Carbenes Conjugated with Pyrrole and Furan Moieties: Molecular Orbital Calculation and Reaction of 2-(1-Methyl)pyrrolylmethylene and 2-Furylmethylene with cis- and trans-Stilbenes
Katsuhiro Saito,* Takahiro Ushida, Hiroshi Fushihara,Yoshiro Yamashita, Shoji Tanaka, and Kensuke Takahashi
*Department of Applied Chemistry, Nagoya Institute of Technology, Gokiso-cho, Showa-ku, Nagoya 466-8555, Japan
Abstract
The reaction of 2-(1-methyl)pyrrolylmethylene and 2-furylmethylene with cis- and trans-stilbenes proceeded in a stereospecific manner to give the corresponding cyclopropane derivatives to show that the multiplicities of these carbenes are singlet. The molecular orbital calculation showed that these carbenes are triplet in their ground state and nucleophilic both in singlet and triplet states.
Published online:
■ Novel Synthetic Route to Pyridine-2(1H)-thiones: Unexpected Products of the Reaction of β-Phenethylidenemalononitriles with Arylmethylenecyanothioacetamides
Galal Eldin Hamza Elgemeie*
*Chemistry Department, Faculty of Science, Bani Suef, Egypt
Abstract
A novel synthesis of 3-cyanopyridine-2(1H)-thione derivatives utilizing arylmethylenecyanothioacetamides and β-phenethylidenemalononitriles as starting componets is described.
Published online:
■ A Novel One Pot Synthesis of 1,3,7-Triaryl-1,2,3,4-tetrahydro-4-oxo-5-phenyl-2-thioxo-5H-pyrano[2,3-d]pyrimidines
Vinod Kumar Ahluwalia,* Rachna Aggarwal, Mohammad Alauddin, Gurpreet Gill, and Chandra Has Khanduri
*Department of Chemistry, University of Delhi, Delhi-110 007, India
Abstract
A novel one pot synthesis of 1,3,7-triaryl-1,2,3,4-tetrahydro-4-oxo-5-phenyl-2-thioxo-5H-pyrano[2,3-d]pyrimidines has been described. It utilizes the reaction of different thiobarbituric acids with chalcones.
Published online:
■ Unexpected Reaction between DCC and Cephalosporanic Acid Sulphones
Marco Alpegiani, Pierluigi Gissolino, Emanuele Arlandini, Daniela Borghi, and Ettore Perrone
*Farmitalia Carlo Erba, R&D, Infectious Diseases Dep., Via dei Gracchi 35, 20146 Milano, Italy
Abstract
Cephalosporanic acid sulphones react with DCC to give a novel 4-spiroazetidinyl-Δ2-cephem structure with high stereoselectivity. The reaction, though general for cephem-4-carboxylic acids, is deeply affected by oxidation at sulphur; an external base was required for the 1-sulphide 3, and stereoselectivity was lost with the 1α-sulphoxide 9.
Published online:
■ Labrandine: A New Pentacyclic Proaporphine Alkaloid from Roemeria hybrida
Belkis Gözler*
*Department of Pharmaceutical Chemistry, Faculty of Pharmacy, Ege University, Izmir, Turkey
Abstract
The pentacyclic phenolic proaporphine (-)-labrandine (1) has been isolated from Turkish Roemeria hybrida (L.) DC. (Papaveraceae). O-Methylation furnished (-)-misramine (2) which is also present in the plant. Acetylation of 1 afforded (-)-2,10-deacetyllabrandine (3), and selective deacetylation of the latter provided (-)-10-acetyllabrandine (4).
Published online:
■ Pollycyclic N-Hetero Compounds. XXXI. Synthesis and Anti-platelet Aggregation Activity of 4-Substituted 5,6-Dihydrobenzo[h]quinazolines
Takashi Hirota,* Kenji Sasaki, Hiromi Ohtomo, Ayako Uehara, and Taiji Nakayama
*Faculty of Pharmaceutical Sciences, Okayama University, 1-1-1 Tsushima-naka, Okayama 700-8530, Japan
Abstract
4-Substituted 5,6-dihydrobenzo[h]quinazolines (IV) were synthesized by the reaction of 4-chloro-5,6-dihydrobenzo[h]quinazoline (II) with amines (III) and their inhibitory activity against platelet aggregation was investigated.
Published online:
■ Synthesis and Characterization of [8](3,6)Azepinophane and [8](3,6)Oxepinophanes
Kyosuke Satake,* Isao Umemoto, Kunihiro Usumoto, Masaru Kimura, Shiro Morosawa, Tsutomu Kumagai, and Toshio Mukai
*Department of Chemistry, Faculty of Science, Okayama University, 3-1-1 Tsushima-naka, Okayama 700-8530, Japan
Abstract
[8](3,6)Azepinophane (methyl 3,6-octano-1H-azepine-4-carboxylate) and [8](3,6)oxepinophane (3,6-octanoxepin) were synthesized from bicyclo[8.2.2]undecadiene, and structural features of them were also studied on the basis of their spectral data. The effect of the substituents at 3 and 6 positions on the structure of 1H-azepine ring was elucidated by comparison of several 3,6-dialkyl-1H-azepine derivatives with the title azepinophane.
Published online:
■ Synthesis and Reactivity of 2-(1,3-Dithian-2-yl)indoles. III. Influence of the Indole Protective N-Phenylsulfonyl Group
Mario Rubiralta,* Anna Diez, Ignashi Reig, Josep Castells, Jean-Luc Bettiol, David S. Grierson, and Henri-Philippe Husson
*Laboratory of Organic Chemistry, Faculty of Pharmacy, University of Barcelona, Av. de Joan XXIII, s/n, 08028 Barcelona, Spain
Abstract
Formation of the anion 2-(1,3-dithian-2-yl)indoles was shown to be possible when the indole nitrogen is protected by a p-methoxyphenylsulfonyl group. In contrast to the corresponding N-phenylsulfonylindole dithiane 1, the anion of dithiane 2 reacts efficiently with electrophiles. The influence of the indole protective group on the metallation of 2-bis(ethylthio)methyl-1-(phenylsulfonyl)indole (14) and the corresponding sulfoxide 24 with n-butyllithium is also reported.
Published online:
■ Bakuchicin, A New Simple Furanocoumarin from Psoralea corylifolia L.
Yoshikazu Kondo,* Atsushi Kato, Yoshiyuki Kubota, and Shigeo Nozoe
*Pharmaceutical Institute, Tohoku University, Aobayama, Sendai 980-8578, Japan
Abstract
A new simple furanocoumarine, bacuchicin, has been isolated from the hexane-extract of seeds of Psoralea corylifolia L. (Leguminosae) alone with stigmasterol, psoralen and bakuchiol. The structure of bakuchicin has been shown as 8-oxo-8H-furo[2,3-f][1]benzopyran (1) by spectral means.