Regular Issue

Vol. 45, No. 6, 1997

18 data found. 1 - 18 listed
Communication | Regular issue | Vol 45, No. 6, 1997, pp. 1047 - 1050
Published online:
DOI: 10.3987/COM-97-7775
New Crystalline N-(Coumarin-4-yl)-L-pyroglutamic Acid. The First Synthesis and Application to 1H NMR Optical Purity Determination of Alcohols and Amines

Kazuo Nagasawa,* Ritsuko Okazaki, Asami Yamashita, Keiichi Ito, and Kohji Wada

*Hokkaido College of Pharmacy, 7-1 Katsuraoka-cho, Otaru 047-02, Japan


Condensation of 3-phenylsulfonyl-4-chlorocoumarin with tert-butyl L-pyroglutamate potassium salt followed by desulfonylation and ester-cleavage yielded the novel crystalline N-(coumain-4-yl)-L-pyroglutamic acid [CPYRO-OH], which being evidenced to be a versatile and reliable 1H nmr optical purity determination agent for chiral alcohols and amines.

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Communication | Regular issue | Vol 45, No. 6, 1997, pp. 1051 - 1054
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DOI: 10.3987/COM-97-7780
1,3-Bis(1,3-dithiol-2-ylidene)-1,3-dihydrobenzo[c]heterophenes. New Fused Heteocycle-extended Donors and Their Conducting TCNQ-Complexes

Kazuko Takahashi* and Toshihiro Ise

*Department of Chemistry, Graduate School of Science, Tohoku University, Sendai 980-8578, Japan


A series of new fused-heterocycle-extended donors have been synthesized by convenient and short-step reactions. Of these benzo[c]furoquinonoid-extended one has the lowest oxidation potential. TCNQ complexes of these donors exhibit fairly high conductivities even when measured on compressed pellets.

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Communication | Regular issue | Vol 45, No. 6, 1997, pp. 1055 - 1058
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DOI: 10.3987/COM-97-7785
A Consice Synthesis of Novel Aromatic Analogs of Artemisinin

Mankil Jung* and Seokjoon Lee

*Department of Chemistry, Yonsei University, Seoul 120-749, Korea


Aromatic analogs of deoxoartemisinin were prepared from artemisinic acid via photooxygenative cyclization as a key step.

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Paper | Regular issue | Vol 45, No. 6, 1997, pp. 1059 - 1067
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DOI: 10.3987/COM-96-7727
Activated Manganese Dioxide as an Oxidizing Agent for the Conversion of N-Methylphenanthrolinium Salts to N-Methylphenanthrolones

Martin R. Johnson,* Dwayne Bell, and Lucy Shanaman

*Department of Chemistry, The George Washington University, Washington, DC 20052, U.S.A.


Activated manganese dioxide (MnO2) in dry THF was studied for the transformation of N-alkylpyridinium salts to N-alkyl-2-pyridones. Only cations of fused ring pyridines (1,10-phenanthroline, quinoline, etc.) were investigated. Nearly quantitative conversion to 1-methyl-1,10-phenanthrol-2-one was achieved under optimum conditions. Oxidative cleavage of ring methyl groups when present also led to pyridones, in some cases producing a 4-pyridone. Different counteranions gave mixed results. Overall, activated MnO2 is an effective alternavie to aqueous ferricyanide for the conversion of fused ring pyridinium salts to the corresponding 2-pyridones.

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Paper | Regular issue | Vol 45, No. 6, 1997, pp. 1069 - 1079
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DOI: 10.3987/COM-97-7741
Chromenes and Chromanones. Part IV.The Birch Reduction of 2,2-Dimethyl-4-chromanone and Its 7-Substituted Analogues

Miroslaw Aniol and Czeslaw Wawrzenczyk*

*Institute of Fundamental Chemistry, Agricultural University at Siedlce, Norwida 25, 50-375 Wroclaw, Poland


2,2-Dimethyl-4-chromanone (1a), 2,2,7-trimethyl-4-chromanone (1b) and 7-methoxy-2,2-dimethyl-4-chromanone (1c) have been reduced by sodium or lithium in liquid ammonia with the presence or without of proton donor. The bicyclic or phenolic products were obtained. Products with reduced benzen ring only were also observed. The possible mechanisms of reductions are considered.

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Paper | Regular issue | Vol 45, No. 6, 1997, pp. 1081 - 1095
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DOI: 10.3987/COM-97-7753
Synthesis and Structural Investigation of Some Cyclic Ketene Acetals. Detection of an Unexpected Proton Transfer in (3-Benzylthiazolidin-2-ylidene)acetamide

Csaba Szántay Jr.,* István Szabadkai, Kálmán Harsányi, and Ferenc Trischler

*Chemical Works of Gedeon Richter Ltd., Spectroscopic Research Division, Budapest 10, P. O. Box 27, H-1475 Budapest, Hungary


The thiazolidines (2) and (3) were synthesized. Some of these compounds exhibit unexpected chemical behavior; e.g in the case of (3-benzylthiozolidin-2-ylidene)acetamide (3b), NMR investigations revealed the presence of chemical exchange involving C(6)-H and the NH2 protons.

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Paper | Regular issue | Vol 45, No. 6, 1997, pp. 1097 - 1110
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DOI: 10.3987/COM-97-7770
Synthesis of N-(1-Aziridinyl)-6-fluoro-1,4-dihydro-4-oxoquinoline-3-carboxylic Acids

Sándor Bátori,* Géza Tímári, András Messmer, Benjámin Podányi, Lelle Vasvári-Debreczy, and István Hermecz

*CHINOIN Pharmaceutical and Chemical Works Ltd., P. O. Box 110, H-1325 Budapest, Hungary


A series of N-(1-aziridinyl)quinoline-3-carboxylic acid derivatives (e.g. 11a-f, 20a-g, 21a-d) have been synthesized by insertion reaction of nitrenes (e.g. ethyl 7-chloro-6-fluoro-1-nitreno-1,4-dihydro-4-oxoquinoline-3-carboxylate (9)) into double bond of different olefins (e.g. styrene (10a), see Schemes 2 and 4). The nitrenes were formed in situ by oxidation of N-aminoquinolin-4(1H)-one derivatives (8, 18a,b) using Pb(OAc)4 as oxidizing agent.

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Paper | Regular issue | Vol 45, No. 6, 1997, pp. 1111 - 1119
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DOI: 10.3987/COM-97-7782
Asymmetric Synthesis of (S)-1-(5-Hydroxy-2-methoxybenzyl)-7-hydroxy-6-methoxy-2-methyl-1,2,3,4-tetrahydroisoquinoline (So-called "Dehassiline")

Keiko Takaba, Jun Haginaka, Jun-ichi Kunitomo,* and Tetsuro Shingu

*Faculty of Pharmaceutical Science, Mukogawa-Women's University, 11-68 Koushien Kyuban-Cho, Nishinomiya, Hyogo 663-8179, Japan


Optically active, (S)-1-(5-hydroxy-2-methoxybenzyl)-7-hydroxy-6-methoxy-2-methyl-1,2,3,4-tetrahydroisoquinoline (so-called "dehassiline") (1) was synthesized via highly stereoselctive reduction of the 3,4-dihydroisoquinolinium ion possessing a chiral auxiliary by Polniaszek’s method. The synthetic compound (1) was shown to be different from natural dehassiline, the structure of which should be revised.

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Paper | Regular issue | Vol 45, No. 6, 1997, pp. 1121 - 1129
Published online:
DOI: 10.3987/COM-97-7803
Use of the Triflamide Group for Friedel-Crafts Acylation of N-(β-Phenethyl)amino Acids to 3-Benzazepine Derivatives

Masami Kawase,* Noboru Motohashi, Masayuki Niwa, and Masakatsu Nozaki

*Faculty of Pharmaceutical Sciences, Josai University, 1-1 Keyakidai, Sakado, Saitama 350-0295, Japan


Triflamides of N-(β-phenethyl)amino acids (1) were treated with P2O5 under the Friedel-Crafts acylation conditions to give the 3-benzazepines in good yields. N-(β-Phenethyl)-N-triflylvaline (1f) and phenylglycine (1g) were efficiently prepared from the corresponding N-triflylamino acids and β-phenethyl alcohol via the Mitsunobu reaction.

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Paper | Regular issue | Vol 45, No. 6, 1997, pp. 1131 - 1142
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DOI: 10.3987/COM-97-7804
Cyclization of o-(3-Hydroxy-3-methylbutynyl)phenols with Boron Tribromide to 4-Bromo-2,2-dimethylchromenes and Their Electroreduction to 2,2-Dimethylchromenes

Masao Tsukayama,* Hideyuki Utsumi, Akira Kunugi, and Hiroshi Nozaki

*Department of Chemical Science and Technology, Faculty of Engineering, University of Tokushima, Minamijosanjima-cho, Tokushima 770-0814, Japan


Cyclization of o-(3-hydroxy-3-methylbutynyl)phenols (2) with boron tribromide gave easily 4-bromo-2,2-dimethylchromenes (3). Electrolytic reduction of 3 at a Hg-pool electrode afforded the corresponding 2,2-dimethylchromenes (6) in high yields.

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Paper | Regular issue | Vol 45, No. 6, 1997, pp. 1143 - 1150
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DOI: 10.3987/COM-97-7806
Reaction of Indole-2,3-dicarboxylic Anhydride with Grignard Reagents: Synthesis of 2-Acylindoles

Yasuyoshi Miki,* Hiroko Hachiken, and Ichigo Yoshikawa

*Faculty of Pharmaceutical Sciences, Kinki University, 3-4-1, Kowakae, Higashi-Osaka 577-8502, Japan


Reaction of indole-2,3-dicarboxylic anhydrode with methylmagnesium bromide and phenylmangesium bromide gave 2-acetyl- and 2-benzoyl-indole-3-carboxylic acids, but with tert-butylmagnesium chloride, 3-pivaloylindole-2-carboxylic acids were obtained as the main products. Treatment of 2-acylindole-3-carboxylic acids with copper chromite in quinoline or potassium hydroxide gave the corresponding 2-acylindoles.

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Paper | Regular issue | Vol 45, No. 6, 1997, pp. 1151 - 1159
Published online:
DOI: 10.3987/COM-97-7812
Total Syntheses of Naturally Occurring Bis(methylthio)silvatin and Its Three Stereoisomers

Yasuchika Yonezawa, Kanetaka Shimizu, Mayumi Uchiyama, Natsuki Kagawa, and Chung-gi Shin*

*Laboratory of Organic Chemistry, Faculty of Technology, Kanagawa University, 3-27-1 Rokkakubashi, Kanagawa-ku, Yokohama 221-8686, Japan


Total syntheses of naturally occurring bis(methylthio)silvatin and its three stereoisomers were achieved from 1,4-dimethyl-3-(p-hydroxy)benzyl-2,5-piperazinedione. The configurational structures of the four stereoisomers, thus obtained, were definitely determined by the comparisons of their mps, specific rotations and NMR spectra.

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Note | Regular issue | Vol 45, No. 6, 1997, pp. 1161 - 1167
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DOI: 10.3987/COM-96-7690
Electron Deficient Flavin as Catalyst for Baeyer-Villiger Reaction: Oxidation of Cyclobutanones to γ-Lactones Using Hydrogen Peroxide

Claudio Mazzini, Jacques Lebreton, and Roland Furstoss*

*Groupe Biocatalyse et Chimie Fine, ERS 157 associee au CNRS, Faculté des Sciences de Luminy, 163 Avenue de Luminy, 13288 Marseille Cedex 9, France


The use of an electron deficient isoalloxazine derivative as coenzyme model for the Baeyer-Villiger oxidation is described. This allows, in the presence of hydrogen peroxide, the catalytic oxidation of cyclobutanones into the corresponding γ-lactones with good excellent yields.

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Note | Regular issue | Vol 45, No. 6, 1997, pp. 1169 - 1172
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DOI: 10.3987/COM-97-7757
Structure of Marshdimerin and Bisosthenon-B, Two New Bicoumarins from the Roots of Marsh Grapefruit

Yuko Takemura, Yoshiko Isono, Yasue Arima, Motoharu Ju-ichi,* Mitsuo Omura, Chihiro Ito, and Hiroshi Furukawa

*Faculty of Pharmaceutical Science, Mukogawa-Women's University, 11-68 Koushien Kyuban-Cho, Nishinomiya, Hyogo 663-8179, Japan


The structures of two dimeric coumarins named marshdimerin (1) and bisosthenon-B (2) from the roots of Marsh grapefruit (Citrus paradisi Macf.) were elucidated on the basis of their spectral data.

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Note | Regular issue | Vol 45, No. 6, 1997, pp. 1173 - 1181
Published online:
DOI: 10.3987/COM-97-7781
Thermal Rearrangement of cis-N-Alkyl-3-phenylaziridin-2-yl-phenyl Ketone Tosylhydrazones in Dimethoxyethane. Preparation of 5-Alkylamino-2-pyrazoline Derivatives

Motonobu Morioka, Masahiko Kato, Hiroshi Yoshida, and Tsuyoshi Ogata*

*Department of Applied Chemistry, Faculty of Engineering, Shizuoka University, 3-5-1 Johoku, Hamamatsu 432-8561, Shizuoka, Japan


Thermal rearrangement of cis-aziridinyl ketone tosylhydrazones (4) in refluxing dimethoxyethane produced 5-alkylamino-3,5-diphenyl-1-tosyl-2-pyrazolines (5) in good to excellent yields. The reaction of cis-1-isopropyl-3-phenyl-aziridin-2-yl phenyl ketone tosylhydrazone (4a) in refluxing chloroform in the presence of acetic acid yielded 3,5-diphenyl-1-tosyl-pyrazole (6a). Under the similar conditions, 5-isopropylamino-3,5-diphenyl-1-tosyl-2-pyrazoline (5a) was rearranged into 6a. The rearrangement from 4 to 5 was assumed to be initiated with ionic cleavage of the bond between ring nitrogen and C2 carbon.

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Note | Regular issue | Vol 45, No. 6, 1997, pp. 1183 - 1190
Published online:
DOI: 10.3987/COM-97-7792
Study of Tautomeric and Isomeric Behaviour of New 2-Arylhydrazono-1,4-benzothiazines

Petra Frohberg,* Ute Baumeister, Dieter Ströhl, and Henning Danz

*Institute of Pharmaceutical Chemistry, Martin-Luther-University Halle-Wittenberg, Wofgang-Langenbeck-Str. 4, 06120 Halle, Germany


Cyclization reactions of α-ketohydrazonyl chlorides such as methyl 6-arylhydrazono-6-chloro-5-oxohexanoates (2) and the 6-arylhydrazono-6-chloro-5-oxohexanoic acids (3) with o-aminothiophenol lead to 1,4-benzothiazine derivatives. The tautomeric and isomeric equilibria are discussed using 1H and 15N NMR as well as X-Ray diffraction analysis.

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Note | Regular issue | Vol 45, No. 6, 1997, pp. 1191 - 1195
Published online:
DOI: 10.3987/COM-97-7801
Alternative Synthesis of a Pyridone Alkaloid, Cerpegin

Keizo Matsuo,* Mariko Kobayashi, and Ken-ichi Sugimoto

*Faculty of Pharmaceutical Sciences, Kinki University, 3-4-1, Kowakae, Higashi-Osaka 577-8502, Japan


A new pyridone alkaloid, cerpegin was synthesized starting from (-)-carvone.

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Note | Regular issue | Vol 45, No. 6, 1997, pp. 1197 - 1202
Published online:
DOI: 10.3987/COM-97-7813
Diacylated Malvidin 3-Rutinoside-5-glucosides from the Flowers of Petunia guarapuavensis

Fumi Tatsuzawa, Maya Koshiishi, Etsuko Ohtani, Toshio Ando, Hitoshi Watanabe, Hisashi Kokubun, Masato Yokoi, Goro Hashimoto,* Hiroko Seki, Norio Satio, and Toshio Honda

*Faculty of Horticulture, Chiba University, Matsudo, Chiba, Japan


Two novel diacylanthocyanins were isolated from the flowers of Petunia guarapuavensis T. Ando et Hashim. and determined to be malvidin 3-O-[6-O-(4-O-(4-O-(6-O-(trans-caffeyl)-β-D-glucopyranosyl)-trans-p-coumaryl)-α-L-rhamnopyranosyl)-β-D-glucopyranoside]-5-O-[β-D-glucopyranoside] and 3-O-[6-O-(4-O-(4-O-(6-O-(trans-caffeyl)-β-D-glucopyranosyl)-trans-caffeyl)-α-L-rhamnopyranosyl)-β-D-glucopyranoside]-5-O-[β-D-glucopyranoside].

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18 data found. 1 - 18 listed