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. 8, 1986
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■ Nitriles in Heterocyclic Synthesis: New Approaches for Synthesis of Pyrazoles, Izoxazoles and Pyrimidines
Nadia S. Ibrahim,* Ebtisam A. A. Hafez, and Raafat M. Mohareb
*Department of Chemistry, Faculty of Science, University of Cairo, Giza, Egypt
Abstract
A variery of pyrazoles and aminoisoxazole were prepared from reaction of N-benzylidene cyanoethanoic hydrazide derivatives with hydrazines and hydroxylamine. A novel pyrimidine synthesis from reaction of ethyl cyanoacetate with the hydrazide is reported.
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■ 6α/6β-Hydroxy-3-O-methylepimaritidine, Two New Alkaloids from Narcissus tazetta L. var. chinensis Roem
Guang-En Ma,* Hui-Yin Li, Chun-E Lu, Xue-Ming Yang, and Shan-Hai Hong
*Shanghai Institute of Material Media, Chinese Academy of Science, 319, Yue-yang Road, Shanghai, 200031, China
Abstract
Two new alkaloids, 6α/6β-hydroxy-3-O-methylepimaritidine (3-epipapyramine) (4 and 5) were isolated from the bulbs of Narcissus tazetta L. var. chinensis Roem. together with four known alkaloids, maritidine, 3-O-methylmaritidine, epigalanthamine and lycoramine. The structures of 4 and 5 were determined on the basis of their IR, UV, CD, 1H-NMR and MS fragments.
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■ Dechlorination of Chloropyrazine N-Oxides
Yasuo Akita, Akira Inoue, Yohko Mori, and Akihiro Ohta*
*Tokyo University of Pharmacy and Life Science, 1432-1 Horinouchi, Hachioji, Tokyo 192-0392, Japan
Abstract
By heating chloropyrazine N-oxides with palladium catalysts and potassium acetate in N,N-dimethylformamide under a hydrogen stream, the chlorine atom was readily removed without deoxygenation of the N-oxide group.
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■ Synthesis of the Enantiomers of 7,8-Dimethoxy-7,8-2-phenyl-1,2,4,5-tetrahydro-3-benzazepine
Jürg R. Pfister*
*Institute of Organic Chemistry, Syntex Research, Palo Alto, California 94304, U.S.A.
Abstract
The chiral 2-phenyltetrahydro-3-benzazepines (R)-8 and (S)-8 were prepared from optically active O-acetylmandeloyl chlorides utilizing a ring closure/ring opening strategy.
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■ Four New C20-Diterpene Alkaloids, Spirasine I, Spirasine II, Spirasine VII and Spirasine VIII from Spiraea japonica
Fang Sun, Xiao-tian Liang,* and De-quan Yu
*Institute of Materia Medica, Chinese Academy of MedicalSceince, Nan-wei Road, Beijing 100050, China
Abstract
The structures of spirasine I (1), spirasine II (2), spirasine VII (3) and spirasine VIII (4), new C20-diterpene alkaloids isolated from Spiraea japonica, were established on the basis of chemical and spectroscopic evidence and confirmed by X-ray crystallography.
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■ Regiospecific Cyclization of 3-Carbomethoxyindole-1-propanoic Acid onto 7-Position of the Indole Nucleus
Shin-ichi Nakatsuka,* Osamu Asano, and Toshio Goto
*Faculty of Agriculture, Gifu University, 1-1 Yanagito, Gifu, Gifu 501-1193, Japan
Abstract
Intramolecular cycilzation of 3-carbomethoxyindole-1-propanoic acid (3) occurred not onto 2-position but onto 7-position to afford pyrrolo[3,2,1-ij]quinoline derivative 5.
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■ Effects of Hetero Atom Substituents in the Decomposition of Pyrazolines: Abnormal Behavior of Methoxy Group Compared with Arylthio or Arylseleno Group
Masashi Hamaguchi,* Toshiya Furusawa, and Toshikazu Nagai
*Institute of Chemistry, College of General Educatin, Osaka University, Toyonaka, Osaka 560-8531, Japan
Abstract
Quantitative hydrogen migration was observed on the thermal decomposition of 4-methoxy-substituted pyrazolines with two electron-withdrawing groups at C(3) except some trans-5-alkyl-4-methoxypyrazolines accompanied with methoxy migration.
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■ A Novel Total Synthesis of (±)-Ajmalicine
Takeaki Naito, Noriko Kojima, Okiko Miyata, and Ichiya Ninomiya*
*Kobe Women’s College of Pharmacy, Motoyamakita, Higashinad, Kobe, Hyogo 658, Japan
Abstract
A common key intermediate (9) for the synthesis of (±)-ajmalicine was prepared in 11 steps from harmalane (2) with 30% overall yield.
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■ A New Route to 1-Acyl-5-oxoperhydroazocine Core Using 1,2,3,5,6,7-Hexahydropyrrolizinium Perchlorates
Seiji Miyano,* Nobuko Mibu, Michiko Irie, and Kunihiro Sumoto
*Faculty of Pharmaceutical Sciences, Fukuoka University, 8-19-1 Nanakuma, Jonan-ku, Fukuoka 814-0180, Japan
Abstract
A convenient simple method for the synthesis of 1-substituted 5-oxoperhydroazocines (1) is described. The method consists of N-acylation of 5-oxoperhydroazocine which is one of the tautomers of the pseudobase (3) generated by the treatment of 1,2,3,5,6,7-hexahydropyrrolizinium perchlorate with aqueous alkali.
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■ Directed beta-Lithiation of 2-Substituted Indoles — A New Synthetic Route to 2,3-Substituted Indoles
David A. Johnson and Gordon W. Gribble*
*Department of Chemistry, Dartmouth College, Hanover, New Hampshire 03775, U.S.A.
Abstract
Treatment of several N-protected 2-substituted indoles with n-butyllithium at -78°C leads toC-3 lithiation, presumably via coordination with the C-2 substituent. Depending on the exact system, the 3-lithioindole can either be trapped with electrophiles or suffer ring-opening to an alkyne.
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■ Phosphono Nucleoside. 2. Synthesis of 1’-Deoxy-1’-phosphono-1-β-D-fructofuranosyluracil and 1’,3’-Dideoxy-1’-phosphono-1-β-D-fructofuranosyluracil
Toshio Tatsuoka,* Kayoko Imao, and Kenji Suzuki
*Suntory Institute for Biochemical Research, Suntory Co. Ltd., 1-1-1, Wakayamadai, Shimamotocho, Mishimagun, Osaka 618-0024, Japan
Abstract
New phosphono nucleosides, phosphono methyl derivatives of arabinofuranosyl- and of deoxyribofuranosyluracil, substituted at C-1’ position were synthesized.
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■ Diels-Alder Reaction of 3-(2-Pyridylsulfinyl)acrylates — The Enhancement of the Reactivity and the Diastereoaelectivity by the Introduction of Electron-withdrawing Substitutents on thr Pyridine Ring
Hiromitusu Takayama, Kazuya Hayashi, Yoshio Takeuchi, and Toru Koizumi*
*Faculty of Pharmaceutical Sciences, Toyama Medical and Pharmaceutical University, 2630 Sugitani, Toyama, Toyama 930-0194, Japan
Abstract
The introduction of nitro or trifluoromethyl group at C3 position on pyridine ring enhanced the reactivity and the diastereoselectivity of 3-(2-pyridylsulfinyl)acrylate in the Diels-Alder reaction with furan.
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■ Kazinol P, a Novel Isoprenylated Spiro-compound from Broussonetia kazinoki Sieb.
Susumu Kato, Yoshio Hano, Toshio Fukai, Yasumi Kosuge, and Taro Nomura*
*Faculty of Pharmaceutical Sciences, Toho University, 2-2-1, Miyama, Funabashi, Chiba 274-8510, Japan
Abstract
A novel isoprenylated spiro-compound named kazinol P (1) was isolated from a benzene extract of the root bark of Broussonetia kazinoki Sieb. (Japanese name “Himekozo”, Moraceae). The structure was shown to be 1 on the basis of spectral evidence. Kazinol P is regarded biogenetically as a variation of a flavan and/or a 1,3-diphenylpropane derivative, such as kazinol E (2) and kazinol C (6).
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■ New Synthrtic Routes to Fully Unsaturated 1,4-Benzodiazepines from Quinolyl Azides
Haruki Sashida, Akira Fujii, Hiroyui Sawanishi, and Takashi Tsuchiya*
*School of Pharmacy, Hokuriku University, 3-Ho, Kanagawa machi, Kanazawa 920-1181, Japan
Abstract
Photolysis of 4-azidoquinolines (1) in the presence of methoxide ions resulted in ring-expansion to give the 1H-1,4-benzodiazepines (3), which were tautomerized to the 3H-isomers (4) by further treatment with sodium methoxide. Similarly, 3-azidoquinolines (9) afforded the 3H-1,4-benzodiazepines (11), which were converted to the 5H-isomers (14) by treatment with sodium methoxide.
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■ A Synthesis of 15,16-Dimethoxyerythirin-6-en-8-one
Yong Zhang, Shigeko Takeda, Takao Kitagawa, and Hiroshi Irie*
*Faculty of Pharmaceutical Sciences, Nagasaki University, 1-14, Bunkyo-machi, Nagasaki 852-8521, Japan
Abstract
A synthesis of 15,16-dimethoxyerythrin-6-en-8-one was accomplished using an intramolecular Wadsworth-Emmons reaction for constructing five-membered lactam, indicating a convenient method to the synthesis of the erythrinan skeleton.
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■ Synthesis of (±)-1β-Methoxy-9β,7β-epoxy-5α-methyl-trans-decalin
Ajoy K. Banerjee,* Carmen A. Peña, Hétor E. Hurtado S., and María G. Díaz
*Centro de Química, Instituto Venezolano de Investigaciones Científicas, I.V.I.C., Apartado 21827, Caracas 1020-A, Venezuela
Abstract
The ketal-ketone (14), prepared from dione (3), was converted to the olefin (16) which on reduction and methylation yielded the ketone (18). The alcohol (19), obtained by reduction with sodium and n-propanol, on oxidation with lead tetraacetate in benzene afforded the cyclic ether (1) which on treatment with trichloromethylsilane and sodium iodide followed by oxidation with Jones reagent produced the keto-ether (2). The α,β-unsaturated ketone (21), prepared from keto-ether (2), was subjected to cyanation, hydrolysis, esterification and deoxygenation respectively to obtain ester (23) whose conversion to lactone (24) followed by reduction, oxidation and esterification afforded the keto-ester (25). The olefinic material obtained from the keto-ester (25) was treated with silver chromate and iodine to obtain α-keto halogenated product and this on treatment with diphosphorous tetraiodide yielded the keto-ester (26).
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■ Asymmetric Synthesis of Cyclic Imino Acids via Chiral Shiff Bases
Jerzy Bajgrowicz, Abdelrhani El Achquar, Maris-Louise Roumestant, Chiristian Pigière, and Philippe Viallefont*
*U.S.T.L., Place E. Bataillon, 34060 Montpellier Cedex, France
Abstract
A new method of synthesis af cyclic imino acids is reported. Diastereoselective alkylation of schiff bases (derived from α-amino esters and (+) or (-) 2-hydroxypinan-3-one) with dihalogeno compounds, followed by hydrolytic cleavage and cyclisation affords the imino esters. Reactions are highly enantioselective, with one exception corresponding to steric crowding.
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■ Improved Procedures for Preparation of 2-Pyridones and 2-Hydroxymethylpyridines from Pyridine N-Oxides
Katsuhiro Konno,* Kimiko Hashimoto, Hatuhisa Shirahama, and Takeshi Matsumoto
*Faculty of Science, Hokkaido University, Kita 10 Nishi 8, Kita-ku, Sapporo, Hokkaido 060-0810, Japan
Abstract
2-Pyridones and 2-hydroxymethylpyridines were prepared from pyridine N-oxides by treatment with trifluoroacetic anhydride in dimethylformamide. The reaction proceeds at room temperature in satisfactory yields.
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■ Synthesis of Parasorbic Acid, the Component of Sorbus aukuparia L.
Tsuguo Sato*
*Faculty of Pharmaceutical Sciences, Tohoku Pharmaceutical University, 4-4-1 Komatsushima, Aoba-ku, Sendai 981-8558, Japan
Abstract
Parasorbic acid ((5s)-(+)-hexen-5-olide) was synthesized from ethyl acetoacetate by utilizing its baker’s yeast reduction.
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■ The Reaction of Lithio-alkyk-isoxazoles with Acid Chlorides in the Presence of Cerium Trichloride. Direct Preparation of β-Keto-isoxazolyl Compounds
Nicholas R. Natale,* Steven G. Yocklovich, and Brenda M. Mallet
*Department of Chemistry, University of Idaho, 301 Renfrew Hall, Moscow, ID 83844-2343, U.S.A.
Abstract
Lithio-alkyl-isoxazoles react with acid chlorides in the presence of cerium trichloride to give β-keto-isoxazoles.
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■ Regiospecific Alkylation of 9-Benzyl-1,3-dimethyl-6-hydroxypyrimido[2,1-f]purine-2,4,8(1H,3H,9H)-trione
Daniel M. Solomon, David J. Conn, Shing-Chun Wong, and James J. Kaminski*
*Pharmaceutical Research Division, Schering-Plogh Research Institute, Bloomfield, NJ 07003, U.S.A.
Abstract
The sodium salt of 9-benzyl-1,3-dimethyl-6-hydroxypyrimido[2,1-f]purine-2,4,8(1H,3H,9H)-trione (1a) reacted with a series of alkyl halides in N,N-dimethylformamide to yield 7-carbon alkylated products (1b-1). No O-alkylated products were detected. Isolated yields (not optimized) were in the range of approximately 15-58% for activated halides; non-activated halides were substantially less reactive and gave lower yields. The effects of reaction parameters on reactivity and site of alkylation are discussed, and it is demonstrated that the observed regiospecificity is not the result of an equilibration process.
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■ Heterocycles 4: Synthesis of 2,2-Dimethyl-2H-pyrano[2,3-a]carbazoles
Desikachari Sowmithran and Karnam Jayarampillai Rajendra Prasad*
*Department of Chemistry, Indian Institute of Technology, Powai, Bombay 400 076, India
Abstract
Condensation of methyl 1-hydroxy-carbazolecarboxylates 1, 2 and 3 with 3,3-dimethylacrylic acid in presence of zinc chloride-phosphorous oxychloride (ZnCl2-POCl3) afforded corresponding 3,4-dihydro-2,2-dimethyl-4-oxo-2H-pyrans, 4,5 and 6 respectively. These on sodium borohydride (NaBH4) reduction followed by dehydration using p-toluenesulphonyl chloride-pyridine yielded 2,2-dimethyl-2H-pyrano[2,3-a]carbazoles, 10, 11 and 12 respectively.
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■ Novel Synthesis of Pyridopyrimidine Diones
Amin Farouk Fahmy, Mohamed Salah Kamel Youssef,* Mohamed Said Abdel Halim, Mamdouh Adly Hassan, and Jourgin Sauer
*Chemistry Department, Faculty of Science, Assiut University, Assiut 71516, Egypt
Abstract
N-(Phenylsulphonyloxy)quinolinimide (I) reacts with different nucleophiles to give II-VIII. It was proved that the nucleophilic attack occurs at the more electro-positive carbonyl group to give only one product in good yields.
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■ "Cross-coupling" of 2-Chlorobenzothiazole with Benzothiazolylalkylmagnesium Bromide: Synthesis of Bis(2-benzothiazolyl)alkanes
Francesco Babudri, Saverio Florio,* Giovanni Ingrosso, and Anna Maria Turco
*Laboratorio di Chimica Organica, C.d.L. in Scienze Biologiche, Università, via Monteroni, 73100 Lecee, Italy
Abstract
Bis(2-benzothiazolyl)alkanes have been prepared via cross-coupling of 2-chlorobenzothiazole with benzothiazolylalkylmagnesium bromide.
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■ Synthesis of Limousamine, a 4-Hydroxylated Cularine
Angel Rodriguez de Lera, Carmen Villaverde, and Luis Castedo*
*Departamento de Química Orgánica, Universidad de Santiago and Sección de Alcaloides (C.S.I.C.), E-15706, Santiago de Compostela, Spain
Abstract
LTA treatment of cularidine 1c as described by Umezawa afforded a 2:3 mixture of limousamine 1a and its 4-epimer 1g, whose stereochemistry is discussed. DDQ oxidation of the O-methyl derivative 1h gave the first 3,4-dioxocularine alkaloid 9.
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■ A Simple Efficient Synthesis of a New, Versatile Tetrahydroisoquinoline-1,3-aminoalcohol Synthon
Jenó Kóbor, Ferenc Fülöp, and Gábor Bernáth*
*Institute of Pharmaceutical Chemistry,University of Szeged, H-6720 Szeged, Eötvös u. 6, Hungary
Abstract
Through the addition of 2 moles of formaldehyde to 1-methyl-6,7-dimethoxy- and 6,7-diethoxy-3,4-dihydroisoquinoline, the corresponding 1-[bis(hydroxymethyl)methyl]-6,7-dialkoxy-3,4-dihydroisoquinolines (3a,b) were prepared, which were then reduced to the 1,3,3’-trifunctional tetrahydroisoquinoline aminoalcohol synthons (5a,b).
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■ A Selective Synthesis of Unsymmetrical 1,1’-Methylenebisdiazoles by Solid-liquid Phase Transfer Catalysis
Sebastian Juliá, Carlos Martínez-Martorell, and José Elguero*
*Instituto de Química Médica, C. S. I. C., Calle Juan de Cierva, 3, 28006 Madrid, Spain
Abstract
1,1’-Methylenebisdiazoles Az1-CH2-Az2, Az1 and Az2 being two different diazoles, can be prepared selectively in three steps, through 1-hydroxymethyl- and 1-chloromethyldiazoles, by solid-liquid (S-L) phase transfer catalysis.
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■ Unusual Rearrangement Reaction of Quebrachamine Derivative Catalyzed by Cyanide Anion
Kiyoshi Yoshida, Sumihiro Nomura, Yoshihiko Nishibata, and Yoshio Ban*
*Faculty of Pharmaceutical Sciences, Toho University, 2-2-1, Miyama, Funabashi, Chiba 274-8510, Japan
Abstract
Cyanation of trimethylammonium salt 8 with potassium cyanide afforded 3-cyano derivatives 9a and 9b accompanied by a significant amount of unexpected rearrangement product 10. The structure of 10 was established by single X-ray crystallographic analysis.
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■ Synthesis of Imidazo[1,2-a]pyridine and Pyrido[1,2-a]pyrimidine Derivatives by the Addition and Cyclocondensation Reactions of Ketenaminals Containing Imidazolidine or Hexahydropyrimidine Ring with Esters of α,β-Unsaturated Acids
Zhi-tang Huang* and Zhi-rong Liu
*Institute of Chemistrym, Academia Sinica, Beijing, China
Abstract
Ketenaminals 1 react with methyl propiolate, methyl acrylate and dimethyl acetylenedicarboxylate to afford the fused imidazo[1,2-a]pyridines and pyrido[1,2-a]pyrimidines 3, 4 and 5, respectively. In some cases, the intermediate addition products 2 and 6b are isolated.
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■ Synthesis of Bi- and Tricyclic Mesonic [1,2,4,6]Thiatriazine-1,1,3-trioxides
Jae Sung Kang and Dong Young Oh*
*Department of Applied Chemistry, Korea Advanced Institute of Science and Technology, P.O.Box 150 Chong-Yang-ni, Seoul 131, Korea
Abstract
The reaction of N-substituted aminoheterocycles with chlorosulfonyl isocyanate (CSI) or pentachlorophenyl N-chlorosulfonylcarbamate (PCPCSC) affords bi- and tricyclic mesoionic [1,2,4,6]thiatriazine-1,1,3-trioxides in the presence of ethyldiisopropylamine.