Regular Issue

Vol. 63, No. 10, 2004

21 data found. 1 - 21 listed
Communication | Regular issue | Vol 63, No. 10, 2004, pp. 2199 - 2202
Published online: 17th August, 2004
DOI: 10.3987/COM-04-10119
Novel 3-Aminothieno[2,3-b]pyridine Synthesis via a Silicon-directed Anionic Cyclization

Jason S. Parnes* and Mercedes Delgado

*Department of Medicinal Chemistry, Signal Pharmaceuticals, LLC, 4550 Towne Center Ct., San Diego, CA 92121, U.S.A.


A novel strategy yielding a 3-aminothiophene is described herein. This specifically relies upon an α-thiomethylsilane directing deprotonation, thereafter cyclization of the resultant anion into a pendant nitrile forms the necessary 3-aminothiophene ring.

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Communication | Regular issue | Vol 63, No. 10, 2004, pp. 2203 - 2206
Published online: 20th August, 2004
DOI: 10.3987/COM-04-10152
Alkatrienyl Sulfoxides and Sulfones. Part. VI. Cheletropic Addition of Sulfur Dioxide to 1- and 3-Vinylallenyl Sulfoxides and Sulfones

Valerij Ch. Christov* and Ivaylo K. Ivanov

*Department of Chemistry, University of Shumen, BG-9700 Shumen, Bulgaria


The reaction of 1- and 3-vinylallenyl sulfoxides and sulfones with sulfur dioxide in 1,2-dichloroethane at reflux proceeds as a cheletropic addition leading to the formation of 2-isopropylidene-3-sulfinyl(sulfonyl)- or 2-sulfinyl- (sulfonyl)methylidene-substituted 2,5-dihydrothiophene 1,1-dioxides in very good yields.

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Communication | Regular issue | Vol 63, No. 10, 2004, pp. 2207 - 2210
Published online: 17th August, 2004
DOI: 10.3987/COM-04-10173
Synthesis and Properties of Pyrazino[2,3-g]quinoxaline Derivatives: Blue and Green Fluorescent Materials with Electron Affinity

Katsuhiko Ono,* Yutaka Okazaki, Masakazu Ohkita, Katsuhiro Saito,* and Yoshiro Yamashita

*Department of Life and Material Engineering, Nagoya Institute of Technology, Gokiso, Showa, Nagoya 466-8555, Japan


The title compounds have been synthesized and their optical and electronic properties were surveyed in comparison to those of [1,2,5]thiadiazolo[3,4-g]quinoxaline and benzo[1,2-c:4,5-c’]bis([1,2,5]thiadiazole) derivatives. They are blue or green fluorophores with electron affinity due to the fused pyrazine rings. Substitution of the fused pyrazine ring for the fused 1,2,5-thiadiazole one led to red shifts of ca. 50 nm in the fluorescence spectra. The substitution also resulted in an increase of electron affinity in the 14π-electron systems. Using a series of these compounds, red-green-blue (RGB) fluorescent emission was achieved.

Communication | Regular issue | Vol 63, No. 10, 2004, pp. 2211 - 2215
Published online: 23rd August, 2004
DOI: 10.3987/COM-04-10188
Absolute Stereostructures of Acylated Khellactone-Type Coumarins from Angelica furcijuga

Toshio Morikawa, Hisashi Matsuda, Teruki Ohgushi, Norihisa Nishida, Tomoko Ishiwada, and Masayuki Yoshikawa

*Kyoto Pharmaceutical University, Misasagi, Yamashina-ku, Kyoto 607-8412, Japan


Two new acylated khellactone-type coumarin hyuganoside I (1) and hyuganin F (2) were isolated from the leaves of Angelica furcijuga. Their absolute stereostructures were determined on the basis of chemical and physicochemical evidence. Furthermore, the absolute stereostructures of the acyl moieties in hyuganins A (3) and C (4) and isoepoxypteryxin (5) were elucidated.

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Paper | Regular issue | Vol 63, No. 10, 2004, pp. 2217 - 2224
Published online: 7th September, 2004
DOI: 10.3987/COM-02-9485
1,3-Dipolar Cycloaddition Reactions to Galanthamine Nitrone: An Entry to 4a,5,9,10-Tetrahydro-6H,14aH-benzofuro[3a,3,2-ef]isoxazolo[3,2-a][2]benzazepines

Margit Hemetsberger, Matthias Treu, Christian Hametner, Ulrich Jordis, Kurt Mereiter, and Johannes Fröhlich*

*Institute of Applied Synthetic Chemistry, Vienna University of Technology, Getreidemarkt 9, A-1060 Vienna, Austria


Starting with galanthamine nitrone as the 1,3-dipole derivatives of the novel 4a,5,9,10-tetrahydro-6H,14aH-benzofuro[3a,3,2-ef]isoxazolo[3,2-a][2]benzaz-epi-ne ring system have been prepared by cycloaddition.

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Paper | Regular issue | Vol 63, No. 10, 2004, pp. 2225 - 2229
Published online: 17th August, 2004
DOI: 10.3987/COM-04-10125
Three Component Synthesis of Some γ-Spiroiminolactones under Microwave-assisted Solvent-free Conditions

Javad Azizian,* Ali R. Karimi, Ali A. Mohammadi, and Mohammad R. Mohammadizadeh

*Department of Chemistry, Faculty of Science, Shahid Beheshti University, P. O. Box 19395-4716, Tehran, Iran


Series of some γ-spiroiminolactone derivatives were synthesized through microwave-assisted, three component reaction of isocyanides, dialkyl acetylenedicarboxylates and indenoquinoxalin-11-ones in DMF or in a solvent-less operation on solid support montmorillonite K10.

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Paper | Regular issue | Vol 63, No. 10, 2004, pp. 2231 - 2241
Published online: 20th August, 2004
DOI: 10.3987/COM-04-10128
Kinetics of the Thermal Decomposition of Substituted Cyclic Organic Peroxides in Toluene Solution: Substituent Effects on the Reaction Rates and the Activation Parameters of the Unimolecular Reactions

Adriana I. Cañizo,* Gladys N. Eyler, Carmen M. Mateo, Elida E. Alvarez, and Rosa K. Nesprías

*Department of Chemistry Engineering, Engineering Faculty, National University of the Center of Buenos Aires Province, del Valle Avenue N° 5737 (B7400JWI) Olavarria, Buenos Aires, Argentine


Thermal decomposition reactions of substituted cyclic organic di- and triperoxides have been carried out in toluene solution in order to investigate substituent effects on homolytic scission of the O-O bond in those compounds. A comparative analysis of the reactivities at 145 °C and the activation parameters for unimolecular reactions of molecules of this type were interpreted in terms of substituent effects and ring size. An isokinetic relationship was established to validate the existence of a genuine substituent effect for the unimolecular homolysis reaction of the substances considered. Cyclic organic peroxides of very high reactivity and sterically hindered deviated from correlation’s. It appears to be possible to determine whether a peroxy group is part of a six or nine membered ring on the basis of the activation parameters values.

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Paper | Regular issue | Vol 63, No. 10, 2004, pp. 2243 - 2267
Published online: 7th September, 2004
DOI: 10.3987/COM-04-10137
Synthesis, Oxidation and Dehydrogenation of Cyclic N,O- and N,S-Acetals. Part 1. Transformation of N,S-Acetals: 3-Acyl-1,3,4-thiadiazolines

László Somogyi

*Department of Organic Chemistry, University of Debrecen, P.O.Box 20, H-4010 Debrecen, Hungary


Aldehyde and ketone thiosemicarbazones are synthesized and cyclized into 3-acyl-1,3,4-thiadiazolines under acylating conditions. Reactions of the 2-monosubstituted heterocycles with oxidizing and dehydrogenating agents (KMnO4 or for the first time with CAN, DDQ, IBDA) lead to the formation of thiadiazoles. CAN oxidation of 2,2-disubstituted 3-acyl-1,3,4-thiadiazolines regenerates the parent ketones efficiently.

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Paper | Regular issue | Vol 63, No. 10, 2004, pp. 2269 - 2285
Published online: 27th August, 2004
DOI: 10.3987/COM-04-10151
2-(1,3,5-Dithiazinan-5-yl)ethanol Heterocycles, Structure and Reactivity

Juan Carlos Gálvez-Ruiz, Javier C. Jean-Gaspar, Indira G. Castellanos-Arzola, Rosalinda Contreras, and Angelina Flores-Parra*

*Chemistry Department , Centro de Investigación y de Estudios Avanzados del I.P.N., A.P. 14-740, C.P. 07000 México, D.F., Mexico


Treatment of 2-(1,3,5-dithiazinan-5-yl)ethanol (1), 2-(1,3,5-dithiazinan-5-yl)-1-phenylethanol (2), 2-(1,3,5-dithiazinan-5-yl)-1-methylethanol (3) and 2-(1,3,5-dithiazinan-5-yl)-2-methyl-1-phenylethanol (4) with TsCl and NEt3 in CH2Cl2 afforded the corresponding 3-tosyl-1,3-oxazolidine derivatives (5-8), whereas tosylation of 1-4 in the presence of NHMe3Cl gave the corresponding O-tosyl-2-(1,3,5-dithiazinan-5-yl)ethanol derivatives (11-14). The direct preparation of 5 and 7 from formaldehyde and N-tosylethanolamine (9) or N-tosyl-2-propanolamine was not successful. Reactions of 1 or 3 with benzylamine furnish 1,3,5-tribenzyl-1,3,5-triazinane. Heating of 1 and 2 affords the corresponding 1,3,5-tri(2-hydroxyethyl)-1,3,5-triazinanes. X-Ray diffraction studies of compounds (1-9 and 11) are reported.

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Paper | Regular issue | Vol 63, No. 10, 2004, pp. 2287 - 2307
Published online: 20th August, 2004
DOI: 10.3987/COM-04-10158
New Preparative Route to Hetaryldienes and Azadienes

Ildikó Nagy, György Hajós,* and Zsuzsanna Riedl

*Chemical Research Center, Hungarian Academy of Sciences, H-1525 Budpest, P.O. Box 17, Hungary


Tetrazolylacroleins easily available via a four step pathway from 2-aminopyridines proved to be suitable starting compounds for preparation of new tetrazolyldiene systems. Reaction with reagents containing active methylene group gave a series of new dienes, whereas hydroxylamines yielded nitrones. The new dienes underwent cyclizations with electron withdrawn dienophiles to yield tetrazolyl substituted new polycycles, and the nitrones gave fused isoxazolines. The electron demand of the tetrazolyldienes in cycloadditions was interpreted by calculation of frontier orbital energy levels.

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Paper | Regular issue | Vol 63, No. 10, 2004, pp. 2309 - 2318
Published online: 23rd August, 2004
DOI: 10.3987/COM-04-10169
An Efficient Synthesis of Benzene Fused Six-, Seven- and Eight-membered Rings Containing Nitrogen and Sulfur by Benzyne Ring Closure Reaction

Chandrani Mukherjee and Ed Biehl*

*Department of Chemistry, Southern Methodist University, Dallas, TX 75275, U.S.A.


3,4-Dihydro-2-H-benzo[1,4]thiazines (3a—c), 2,3,4,5-tetrahydro[b]-[1,4]thiazapines (3d—f) and 2,3,4,5-tetrahydro-2H-benzo[b][1,4]thiazocines (3g—i) were prepared by the cyclization of the respective 2-bromophenylsulfanyl derivatives of ethylamine (1a—c), propylamine (2d—f) and butylamine (2g—i).

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Paper | Regular issue | Vol 63, No. 10, 2004, pp. 2319 - 2328
Published online: 7th September, 2004
DOI: 10.3987/COM-04-10174
A New Synthesis of Thiazole Derivatives via Ring Transformation of 6-Imino-6H-1,3-thiazine Hydroperchlorates

Detlef Briel

*Institut für Pharmazie, Pharmazeutische Chemie, der Universität Leipzig, Brüderstr. 34, D-04103 Leipzig, Germany


2-Arylthiazoles (8) with a cyanoacetate moiety in position 4 were synthesized by a new ring transformation reaction. Therefore 2-aryl-6-imino-6H-1,3-thiazinecarboxylic ester hydroperchlorates (3) were converted into 2-arylthiazoles (8) by reaction with acceptor substituted halomethanes (e.g. chloroacetonitrile, chloroacetic acid ester or phenacyl bromide). Using 2-(2-hydroxyphenyl)-6H-1,3-thiazinecarboxylicacid ester hydroperchlorate (3c) as the starting compound the benzoxazine (11a) was obtained. Starting from 2-(4-chlorophenyl)-6H-1,3-thiazinecarboxylicacid ester hydroperchlorate (3b) the thiazolo[5,4-c]pyridine (9e) was the final product.

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Paper | Regular issue | Vol 63, No. 10, 2004, pp. 2329 - 2340
Published online: 23rd August, 2004
DOI: 10.3987/COM-04-10181
Synthesis of 1-Methyl-3-methylthio- and 1-Methyl-3-methylsulfinyl-4-substituted 2-(1H)-Quinolinones

Elwira Chrobak and Andrzej Maslankiewicz*

*Department of Organic Chemistry, The Medical University of Silesia, Jagiellonska 4, 41-200 Sosnowiec, Poland


Treatment of 4-substituted (X=Cl, OCH3, SCH3) quinolinium salts (2) in aqueous-DMSO solution with K3[Fe(CN)6] / NaOH system led to the respective 2-quinolinones (3) (60-69 %) which were accompanied by 1-methyl-
3-methylthio-4-quinolinone (8) (ca. 20%). 3-Methylthio substituent in quinolines (1), 4-quinolinethione (5) and 2-quinolinones (3) underwent S-oxidation to a sulfinyl group when the compounds (1), (3) and (5) were treated with nitrating mixture (-5 °C, 1 mol. eqv. of HNO3), but with an excess of nitric acid 2-quinolinones (3) were transformed to the respective 3-methylsulfinyl-6-nitro derivatives (7). The reaction of 4-chloroquinolines (1a), (3a) (at 140-160 °C) and (4a) (at 0 °C) with dimethylamine gave high yield of the 4-dimethylamino derivatives (1d), (3d) and (4d), respectively.

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Paper | Regular issue | Vol 63, No. 10, 2004, pp. 2341 - 2348
Published online: 31st August, 2004
DOI: 10.3987/COM-04-10182
Synthesis of 2-Chloro-8-(2-pyridyl)-1-azaazulene and Its Metal Complexes

Noritaka Abe,* Eri Hashimoto, Hiroyuki Fujii, Yoshiko Murakami, Shoji Tagashira, and Akikazu Kakehi

*Department of Chemistry, Faculty of Science, Yamaguchi University, Yamaguchi 753-8512, Japan


Reaction of 2-chloro-1-azaazulenes with 2-pyridyllithium followed by dehydrogenation by chloranil gave 8-(2-pyridyl) -1-azaazulene (2). Formation of metal complexes (M = Cu, Fe, Pd) of 2 was achieved. The reaction of 2 with Cu(I) gave 1:1-complex (3) and 2:1-complex (4). Complex (3) was deduced to have a polymeric chain structure with the copper center is +1. The ESR spectrum study of 4 showed that the copper center is +2. The structure of 4 was decided by X-Ray structural analysis and it is shown that the complex takes a trigonal bi-pyramidal structure.

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Paper | Regular issue | Vol 63, No. 10, 2004, pp. 2349 - 2354
Published online: 27th August, 2004
DOI: 10.3987/COM-04-10183
Synthesis of (-)-Tuliparin B Utilizing 2-Bromo-1-alkenes Conveniently Synthesized from the 3-O-Substituted 1,2-Dibromoalkane System by Regioselective Elimination

Tadaaki Ohgiya and Shigeru Nishiyama*

*Department of Chemistry, Faculty of Science and Technology, Keio University, Hiyoshi 3-14-1, Kohoku-ku, Yokohama 223-8522, Japan


Synthesis of (—)-tulipalin B with a variety of biological properties including cutaneous allergenic activity, was accomplished by using the 2-bromo-1-alkenes synthesized by the regioselective HBr elimination reaction of 3-acyloxy-1,2-dibromoalkanes.

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Paper | Regular issue | Vol 63, No. 10, 2004, pp. 2355 - 2362
Published online: 27th August, 2004
DOI: 10.3987/COM-04-10196
Synthesis of Cribrostatin 6

Shinsuke Nakahara* and Akinori Kubo

*Meiji Pharmaceutical University, 2-552-1, Noshio, Kiyose, Tokyo 204-8588, Japan


The first synthesis of cribrostatin 6 (1), a dark blue cancer cell growth inhibiter was achieved in ten-steps from 2,4-diethoxy-3-methylphenol (8), utilizing a catalytic hydrogenation which induces an intramolecular transfer reaction.

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Note | Regular issue | Vol 63, No. 10, 2004, pp. 2363 - 2370
Published online: 27th August, 2004
DOI: 10.3987/COM-04-10135
Two New C19-Diterpenoid Alkaloids from Aconitum nagarum var. lasiandrum

Hong Ji, Dong-Lin Chen, and Feng-Peng Wang*

*Department of Chemistry of Medicinal Natural Products, West China College of Pharmacy, Sichuan University, No. 17, Duan 3, Remin Nan Road, Chengdu 610041, China


Further investigation on the phytochemistry of the plant Aconitum nagarum var. lasiandrum led to isolate two C19-diterpenoid alkaloids, francheline (1) and lasianine (3). Their structures were established on the basis of the spectral data.

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Note | Regular issue | Vol 63, No. 10, 2004, pp. 2371 - 2377
Published online: 27th August, 2004
DOI: 10.3987/COM-04-10142
Effect of Sodium Naphthalenide, a Key Set Reagent, on 3-Substituted Indoles

Avijit Banerji*, Debasish Bandyopadhyay, and Bidyut Basak

*Centre of Advanced Studies on Natural Products, Department of Chemistry, Calcutta University, 92, A. P. C Road, Kolkata 700009, India


Action of the single electron transfer (SET) reagent sodium naphthalenide on 3-substituted indoles revealed that indoles with electron-donating substituents do not respond whereas indoles with electron-withdrawing substituents easily react, yielding several products depending upon the substituent.

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Note | Regular issue | Vol 63, No. 10, 2004, pp. 2379 - 2383
Published online: 17th August, 2004
DOI: 10.3987/COM-04-10153
Formation of Unnatural Cyclic Amino Acid Equivalent from the Simple Cyclic Hydrazine

Duk Keun An, Hye-Min Kim, Min Sung Kim, Seung Kyu Kang, Jae Du Ha, Sung Soo Kim, Joong-Kwon Choi, and Jin Hee Ahn*

*Medicinal Science Division, Korea Research Institute of Chemical Technology, Daejeon 305-600, Korea


An alternative method for the synthesis of unnatural cyclic amino acid equivalent from the simple cyclic hydrazine via oxidation and cyanation was developed.

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Note | Regular issue | Vol 63, No. 10, 2004, pp. 2385 - 2392
Published online: 20th August, 2004
DOI: 10.3987/COM-04-10178
Enantioselective Synthesis of (S)-3-(4-Thiazolyl)-2-tert-butoxycarbonylaminopropionic Acid: A Chiral Building Block for Renin Inhibitor

Yoshifumi Yuasa, Haruki Tsuruta, and Yoko Yuasa*

*School of Pharmacy, Tokyo University of Pharmacy and Life Science, 1432-1 Horinouchi, Hachioji, 192-0392, Tokyo, Japan


(S)-3-(4-Thiazolyl)-2-tert-butoxycarbonylaminopropionic acid (6), an important structural constituent of the renin inhibitor, has been synthesized from (Z)-3-(4-thiazolyl)-2-benzoylaminoprop-2-enoic acid (4b) by enantioselective hydrogenation using the Ru-(S)-p-tolyl-BINAP complex as the key step, and then followed by acid hydrolysis and tert-butoxycarbonylation.

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Review | Regular issue | Vol 63, No. 10, 2004, pp. 2393 - 2407
Published online: 30th July, 2004
DOI: 10.3987/REV-04-585
Transition Metal Complexes in Organic Synthesis, Part 73. Synthetic Routes to Naturally Occurring Furocarbazoles

Wolfgang Fröhner, Micha P. Krahl, Kethiri R. Reddy, and Hans-Joachim Knölker*

*Institut of Organic Chemistry, Technical University Dresden, Bergstrasse 66, 01069 Dresden, Germany


The isolation and the development of total syntheses of naturally occurring furocarbazole alkaloids are described. The diverse synthetic strategies which were elaborated by different research groups are discussed and compared.

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21 data found. 1 - 21 listed