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. 26, No. 1, 1987
Published online:
■ Demethylations of Methoxypyridazines with Amines
Hiromu Nagashima, Hirohisa Oda, Takahisa Hayakawa, and Kenji Kaji
*Gifu Pharmaceutical University, 6-1 Mitahora-higashi 5-chome, Gifu 502-8585, Japan
Abstract
When various pyridazines possessing the chlorine and methoxy group at 3, 4 and 5-position were treated with 10 eq. of primary and secondary amines, demethylation was observed. Demethylation of 2-methyl-methoxy-3(2H)-pyridazinones was also investigated.
Published online:
■ Extensive Hydrate Formation of 5-Nitrofurfural in Neutral Aqueous Solutions: Implications for Its Reactivity
Ruud W. Busker, Gerard M. J. Beijersbergen van Henegouwen, and Kees Erkelens
*Division of Medicinal Chemistry, Center for Bio-Pharmaceutical Science, Gorlaeus Laboratories, Leiden University, P.O.Box 9502, Einsteinweg 55, 2300 RA Leiden, The Netherlands
Abstract
In neutral aqueous solutions up to 56% of nitrofurfural was found to be in the geminal diol form. This was concluded from NMR experiments with nitrofurfural in DNSO-d6 with increasing amounts of D20 In DMSO nitrofurfural reacts faster with hydrazine than p-nitrobenzaldehyde does; in water the reverse holds. The decreased reactivity of nitrofurfural in water is caused by the large extent of hydration.
Published online:
■ Kuafumine, a Novel Cytotoxic Oxoaporphine Alkaloid from Fissistigma glausescens
Yang-Chang Wu, Sheng-Teh Lu, Tian-Shung Wu, and Kuo-Hsiung Lee
*Department of Applied Chemiastry, Providence College of Arta and Science, Shalu 43309, Taichung Hsien, Taiwan, R.O.C.
Abstract
The structure of kuafumine, a new oxoaporphine alkaloid isolated from Fissistigma glaucescens was established as formula 1. This alkaloid showed potent cytotoxiclty to KB cell (ED50 = 0.2 mcg/ml) in vitro.
Published online:
■ Chemical Behavior of Isolated Thiamin Ylide in Neutral Aqueous Solutiion — A New Mechanism of Interconversion of Thiamin and Thiamin Thiolate
Hirihiko Sugimoto and Kentaro Hirai
*Shionogi Research Laboratories, Shionogi & Co. Ltd., Fukushima-ku, Osaka 553-0002, Japan
Abstract
The isolated thiamin ylide (TY) was found to he converted into thiamin thiolate (TH+TS-, 3) in neutral aqueous solution. The formation of the ion-pair can best be explained by the disproportionation of the ylide into the yellow form (TH+YF-, 4) followed by ring-opening by the attack of water to pyrimido[4,5-d]pyrimidine ring of the yellow form. These results suggested a new mechanism for the interconversion between thiamin (TH+CI-) and thiamin thiolate (Na+TS-).
Published online:
■ A New C20-Diterpene Alkaloid, Spirasine III and the Interconversion of Oxazolidine Ring
Fang Sun, Xiao-Tian Liang,* and De-quan Yu
*Institute of Materia Medica, Chinese Academy of Medica lSceince, Nan-wei Road, Beijing 100050, China
Abstract
The structure of spirasine III (1) , a new C20-diterpene alkaloid isolated from Spiraea japonica, was established on the basis of chemical and spectroscopic evidence and confirmed by x-ray crystallography. The interconversion of the epimeric forms of the oxazolidine ring was determined by NMR.
Published online:
■ Novel Intramolecular Nitrogen to Carbon Double Migration
Shekhar Munavalli, Fu-Lian Hsu, and Edward J. Poziomek
*Reearch Directorate, Development and Engineering Center, U.S. Army Chemical Research, Aberdeen Proving Ground, Maryland 21010-5423, U.S.A.
Abstract
Steric hindrance gives rise to an unusual nitrogen to carbon migration when 2-amino-6-methylpyridine is reacted with di-iodomethane at 140-150°C.
Published online:
■ Enneaphylline, Sarcophilline and Norsarcocapnidine, New Phenolic Cularines from Sarcocapnos Plants
Luis Castedo, Domingo Domínguez, Susana López, Angel Rodriguez de Lera, Emilia Tojo, and Carmen Villaverde
*Departamento de Química Orgánica, Sección de Alcaloides del C.S.I.C, Facultad de Química, Universidad de Santiago, 15706 Santiago de Compostela, Spain
Abstract
Three new phenolic cularines have been isolated from Sarcocapnos species. Their structures have been elucidated by spectroscopic studies, chemical correlations and total synthesis.
Published online:
■ Electrocyclization of 4-Azidocoumarins Leading to Benzopyrano[3,4-d]-1,2,3-triazol-4-ones
Keiichi Ito and Junko Hariya
*Hokkaido College of Pharmacy, 7-1 Katsuraoka-cho, Otaru 047-02, Japan
Abstract
4-Azidocoumarins 2 as the stable heteroaromatic azides possessing a vinyl azide structure suffered 1,5-dipolar electrocyclization induced by t-butoxide leading to the formation of benzopyrano[3,4-d]-l,2,3-triazol-4-ones 3.
Published online:
■ Intramolecular Cyclisation Using Methyl(bismethilthio)sulphonium Salts. Part 5. Synthesis of Functionalized 4,5-Dihydro-3,1-benzoxazepines
Giuseppe Capozzi, Rosaria Ottana‘, and Giovanni Romeo
*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
The reaction of methyl (bismethylthio) sulphonium herachloroantimonate 1 with N-( 2-allylphenyl) benzamide 2 gives the 4-methylthiomethyl-4,5-dihydro-3,1-benzoxazepine 4. Other electrophilic reagents reacts with 2 to give exclusively or preferentially products of addition to the allytic double bond.
Published online:
■ Trichilinin, a New Hexacyclic Limonoid from Trichilia roka
Munehiro Nakatani, Takashi Iwashita, Kosei Mizukawa, and Tsunao Hase
*Department of Chemistry and Bioscience, Faculty of Science, Kagoshima University, 1-21-35 Korimoto, Kagoshima 890-0065, Japan
Abstract
A new limonoid, trichilinin, has been isolated from the root bark of Trichilia roka and its structure established by NMR and CD studies. It appears to be a biogenetic precursor of salannin.
Published online:
■ Intramolecular Diels-Alder Cycloaddition of Isoxazole Derivatives Catalyzed by Brönsted Acids
Alberto Brandi and Patrizio Nuti
*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
Isoxazoles 3c-e undergo intramolecular Diels-Alder cycloaddition at 200°C only in CBCl3 solution or in toluene with CF3COOH catslysis.
Published online:
■ Cycloadditions of Ethyl 2-Amino-1-azaazulene-3-carboxylate with Dimethyl Acetylenedicarboxylate
Noritaka Abe
*Department of Chemistry, Faculty of Science, Yamaguchi University, 1677-1 Yoshida, Yamaguchi 753-8512, Japan
Abstract
Reaction of ethyl 2-amino-1-azaazulene-3-carboxylate with dimethyl acetylenedicarboxylate gave two 1:1-adducts (3 and 4), two 1:2-adducts (5 and 6), and a 1:3-adduct (7). Reaction mechanism is discussed.
Published online:
■ Reactions of 2-Acetyl-3-methylquinoxaline 1,4-Dioxide and Its Derivatives
Katsuhide Matoba, Takashi Terada, Masaru Sugiura, and Takao Yamazaki
*Faculty of Pharmaceutical Sciences, Toyama Medical and Pharmaceutical University, 2630 Sugitani, Toyama, Toyama 930-0194, Japan
Abstract
2-Cinnamoyl-3-methylquinoxaline 1,4-dioxide(2) was inert to hydrochloric acid in refluxing ethanol. When a xylene solution of 2-acetyl-3-methylquinoxaline 1,4-dioxide(1-dioxide) was refluxed overnight, the dioxide was reduced mainly to 1-4-oxide and the oxidative products from xylene were also obtained. 2-Cinnamoyl-3-methylguinoxaline 4-oxide(4a) and 3-methyl-4-oxido-2-quinoxalyl 4-phenyl-1,3-butadienyl ketone(4b)were quantitativelycyclized into 4-methyl-3-oxo-1-phenyl- and 4-methyl-3-oxo-1-styryl- 3H-pyrrolo[1,2-a]quinoxalin-l0-ium chloride(6a and 6b), respectively, when the ethanolic solution were refluxed in the presence of hydrochloric acid.
Published online:
■ Synthesis and Cycloaddition Reaction of 2a,5-Diazacyclohept[cd]indebes: Formation of Cyclohept[ef]-6-azacycl[3.2.2.]azine System
Noritaka Abe
*Department of Chemistry, Faculty of Science, Yamaguchi University, 1677-1 Yoshida, Yamaguchi 753-8512, Japan
Abstract
Reaction of 8-amino-3-phenyl-1-azaazulene wlth phenacyl bromide gave 1,4- and 1,3-diphenyl-2a,5-diazacyclohept[cd]indenes. Cycloaddition of the former with dimethyl acetylenedicarboxylate gave cyciohept[ef]-6-azacycl[3.2.2]azine derivative.
Published online:
■ The Synthesis of 5- and 7-Acetylindole Derivatives. I. The Photochemical Rearrangement of 1-Acetylindoline
Masao Akagi and Kazuko Ozaki
*Osaka University of Pharmaceutical Sciences, 4-20-1 Nasahara, Takatsuki, Osaka 569-1094, Japan
Abstract
5- and 7-Acetyl substituted indole derivatives have been prepared via intramolecular photorearrangement of acyl radical and intermolecular electrophilic acylation of 1-acetylindoline.
Published online:
■ Efficient Synthesis of Indoloquinone Derivations by Several Oxidative Derivatib\ves of 6-Methylindole
Shin-ichi Nakatsuka, Kazuo Ueda, Osamu Asano, and Toshio Goto
*Laboratory of Organic Chemistry, Faculty of Agricultures, Nagoya University, Chikusa, Nagoya, Aichi 464-8601, Japan
Abstract
Indoloquinone 3 was efficiently synthesized from simple 6-methyindole by several oxidation steps.
Published online:
■ Side-chain Substitution of 6-Methylellipticine Approach to a New Class of Ellipticine Derivatives
Albert Langendoen, Gerrit-Jan Koomen, and Upendra K. Pandit
*Organic Chemistry Department, University of Amsterdam, Nieuwe Achtergracht 129, 1018 WS Amsterdam, The Netherlands
Abstract
Reaction of 6-methylellipticne with lithium diisopropylamide results in deprotonation of the C11-CH3 group, generating an anion which reacts with formaldehyde to give the corresponding hydroxymethyl derivative. The latter has been converted into its riboside, glucoside and galactoside.
Published online:
■ An N-Acyliminium Route to the 8-Azabicyclo[3.2.1]octane (Tropane) and the 9-Azabicyclo[4.2.1]nonane Ring System Synthesis of (±)-Anatoxin-A
Peter M. Esch, Henk Hiemstra, Wim J. Klaver, and W. Nico Speckamp
*Organic Chemistry Department, University of Amsterdam, Nieuwe Achtergracht 129, 1018 WS Amsterdam, The Netherlands
Abstract
Propargyl and ally 1 silanes 20-22, readily prepared from succinimide, cyclize on dissolution in formid acid to azabicycles 23-25 in excellent yields.
Published online:
■ Indolizino[3,4,5,6-cde]quinoxaline
Katsuhide Matoba, Masaru Sugiura, Takashi Terada, and Takao Yamazaki
*Faculty of Pharmaceutical Sciences, Toyama Medical and Pharmaceutical University, 2630 Sugitani, Toyama, Toyama 930-0194, Japan
Abstract
4-Methyl-3-oxo-1-styrylpyrrolo[1,2-a]quinoxalin-10-ium chloride (4) and 3-hydroxy-4-methyl-1-styrylpyrrolo[1,2-a]quinoxaline(3a) hydrochloride were cyclized exclusively to 2-hydroxy-3-methyl-8-phenylindolizino-[3,4,5,6-cde]quinoxaline(6a) and its 8,9-dihydro compound (5a), respectively, by the irradiation of high pressure mercury lamp.
Published online:
■ Studies on the Synthesis of Optically Active Azalactams
Haruo Matsuyama, Michio Kobayashi, and Harry H. Wasserman
*Department of Chemistry, Faculty of Science, Tokyo Metropolitan University, Hachioji, Tokyo 192-0397, Japan
Abstract
The optically active nine-membered azalactam, (S)-(-)- 1,5-diaza-4-phenylcyclononan-2-one has been prepared starting with optically active (S)-(-)-β-phenyl-β-alanine methyl ester and 2-methoxypyrroline. Other studies with chiral esters of transcinnamic acid and piperidazine are reported.
Published online:
■ A New Approach to C-9 Hydroxylation of N(6)-Substituted Ellipticine
Albert Langendoen, Gerrit-Jan Koomen, and Upendra K. Pandit
*Organic Chemistry Department, University of Amsterdam, Nieuwe Achtergracht 129, 1018 WS Amsterdam, The Netherlands
Abstract
6-Methylellipticlne is converted to the corresponding 9-hydroxy derivative via a reaction sequence involving selective C-9 formylation followed by a Baeyer Villiger rearrangement.
Published online:
■ Reaction of L-Tryptophan with Alkyl Isocyanates
Miguel F. Braña, Mercedes Garrido, Maria L. López Rodríguez, and M. José Marcillo
*Departamento de Química Orgánica I., Facultad de Química, Universidad Complutense de Madrid, Ciudad Universitaria, E-28040 Madrid, Spain
Abstract
L-Tryptophan reacts with alkyl isocyanates to give the corresponding hydantoins 2,4-7. Alternatively, the reactions with ethyl, propyl and lsopropyl isocyanates in acetone provide the corresponding 2-[(3-alkyl-4,4-dimethyl-2-oxo)-1,3-diazetidinyl]-3 -(3-indoly) prpionic acids 3, 8 and 9.
Published online:
■ Cycloaddition Reactions of Ehtenesulfonic Acid Derivatives with Nitrones
Josette Chanet-Ray, Roger Vessière, and Abdellah Zéroual
*Laboratoire de Chomie Organique 2, Ecole Nationale Supérieure de Chimie de Clermont-Ferrand, Université de Clermont II, B. P. 45, 63170 Aubière, France
Abstract
The reaction of several derivatives of ethenesulfonic acid (CX2=CX-SO2 R ; X = H, Br ; R = F, NEt2) with different nitrones have been investigated. Regiospecific cycloadditions are observed, the reactions lead to 4-substituted isoxarolidines whatever is the nitrone involved. These results confirm Houk’s predictions, according to which the amount of 4-substituted adduct increases with the electrophilic character of the substituted alkenes.
Published online:
■ Regional and Steric Course of Thermal Reactions in Some Rhoeadine Alkaloid N-Oxides
Hasso Rönsch and Alfred Preiß
*Institute of Plant Biochemistry, The Academy of Science of the German Democratic Republic, Weinberg 3, Halle/S., DDR-4050, Germany
Abstract
The thermal behavior of a typical series of rhoeadine alkaloid N-oxides, 2a, 2b, 6b, and 7b, derived from alpinigenine (1a) or its B/D-cis analog 5a is greatly dominated by the Meisenheimer-type of rearmngement with the regiospecific formation of the benzoxazocine congeners 3a, 3b, and 8 of these alkaloids. Alternatively, Cope elimination has been possible under more extreme reaction conditions when the side product 4 was isolated in addition to 3a. In each case of rearrangement there was full retention of configuration. The N-epimeric 0-methyl-cis-alpinigenine N-oxides A (6b) and B (7b) serving as starting materials, as well as the hemiacetals corresponding them, have been discuaaed in terms of their chirality at nitrogen and C-14.
Published online:
■ A Convenient Two-step Synthesis of 3-Allylcoumarins and Their Benzoderivatives
Raghao S. Mali, Santosh G. Tilve, Suresh N. Yeola, and Anita R. Manekar
*Department of Chemstry, University of Poona, India
Abstract
A convenient, high yield, two step synthesis of 3-allylcoumarine and their benzo dsriuatives is described fmm 2-hydroxybenzaldehydes. The benzaldehydes (2a-j) on reaction with phosphorane 3 provide E-ethyl-α-allylcinmates (4a-j) in high yields. These esters (4a-j) on themal or photochemiml cyclisation give 3-allylcoumarines (6a-j) .
Published online:
■ Pentaazabicyclononanes
Joseph H. Boyer and Govindarajulu Kumar
*Department of Chemistry, University of New Orleans, New Orleans, LA 70148, U.S.A.
Abstract
The synthesis of 3-benzamido-6,8-dibenzoyl-1,3,5,6,8-pentaazabicyclo[3.2.2]- nonane 2 and 2,7-dibenzoyl-4-benzamido-1,2,4,6,7-pentaazabicyclo[4.2.1]nonane 3 provides the first examples of pentaazabicyclononanes.
Published online:
■ 1,3-Dipolar Cycloaddition of Pyrazolo[1,2-a]indazoles with Domethyl Acetylenedicarboxylate
Yasuo Fujimura,* Yoshiharu Nawata, and Masatomo Hamana
*Central Research Laboratories, Chugai Pharmaceutical Company, Ltd., Takada 3-41-8, Toshima-ku, Tokyo 171, Japan
Abstract
Pyrazolo[1,2-a]indazoles (3a and 3b) obtained from 9H-pyrazolo[1,2-a]indazolium bromides (2a and 2b) and sodium hydride readily react with dimethyl acetylenedicarboxylate to give 1,3-dipolar cycloadducts (4 and 8). Products 4 and 8 are hydrogenated to the 3,4-dihydro derivatives (6 and 10) and converted into their 4-alkoxy derivatives (5,7 and 9) with alcohols under acidic conditions.
Published online:
■ Synthesis of Diketonic Intermediates for the Total Syntheses of Dihydrojasmone, cis-Jasmone and dl-Muscone Starting from 1,n-Di(1-methyl-1H-imidazol-2-yl)-1,n-alkanedione
Shunsaku Ohta, Satoshi Hayakawa, Yoshimi Tamai, Teruyuki Yuasa, and Masao Okamoto
*Kyoto Pharmaceutical University, Misasagi, Yamashina, Kyoto 607-8414, Japan
Abstract
2,15-Dihydroxy-2,15-di(1-methyl-1H-imidazol-2-yl) hexadecane (3) was obtained by treating 1,14-(1-methyl-1H-imidazol-2-yl)-1,14-tetradecadione (2b) with an excess of CH3MgI, while 1,4-di (1-methyl-1H-imidazol-2-yl)-4-trimethylsilyloxy-2-pentanone (6; R1 = TMS) was obtained by the similar treatment of 1,4-(1-methyl-1H-imidazol-2-yl)-1,4-butadione (2a) followed by trimethylsilylation. These products (3 and 6) were convertible into the known diketonic intermediates for the synthesis of dl-muscone, dihydrojasmone and cis-jasmone.
Published online:
■ Photoreactions of Phthalimide-thietanes: Fission of the Thietane Ring and Formation of 1,2-Dithianes
Minoru Machida, Kazuaki Oda, Eiichi Yoshida, and Yuichi Kanaoka
*Faculty of Pharmaceutical Scicences, Higashinihonngakuen University, 1757 Kanazawa, Toubetu-cho, Ishikari-gun, Hokkaodo 061-0212, Japan
Abstract
Photolysis of N-methylmonothiophthalimide (1) in the presence of thletane (4) gave 1,2-dithiane (5) and 1,3-dithiane (6) . The formation of 1,2-dithianes in the photoreaction of 1 with styrene derivatives (2) is explained in terms of the
intermediacy of the phthalimide-thietanes. Photolysis of the thietane ring is also described.
Published online:
■ Synthesis and Characterization of a Novel 6-Heteroaryl-3,6-dihydro-2H-pyran-2-acetic Acid
Gerald E. Stokker and Steven M. Pitzenberger
*Department of Medicinal Chemistry, Merck Sharp and Dohme Research Laboratories, West Point, PA 19486, U.S.A.
Abstract
Cis and trans-6-[2-[3-(4-fluorophenyl)-1-(1-methylethyl)-1H-indol-2-yl]ethenyl]-3,4, 5,6-tetrahydro-4-hydroxy-2H-pyran-2dne (1b and 1a) rearrange under mildly acidic conditions giving only cis-6-[3-(4-fluorophenyl)-l-(l-methylethyl)-1H-indol-2-yl]-3,6-dihydro-2H-pyran-2-acetic acid (3). A mechanism is proposed for the acid catalyzed rearrangement.