Regular Issue

Vol. 63, No. 3, 2004

18 data found. 1 - 18 listed
Communication | Regular issue | Vol 63, No. 3, 2004, pp. 505 - 508
Published online: 16th January, 2004
DOI: 10.3987/COM-03-9962
Dodecasubstituted Porphyrins — An Easily Accessible Type of Dendritic Porphyrins with Tunable Properties

Claudia Ryppa and Mathias O. Senge*

*Institut für Chemie, Universität Potsdam, Karl-Liebknecht-Strasse 24-25, D-14476 Golm, Germany


Dodecasubstituted dendritic porphyrins with nonplanar macrocycles were synthesized by a convergent approach via Lindsey condensation reactions in good yields.

PDF (46KB)
Communication | Regular issue | Vol 63, No. 3, 2004, pp. 509 - 517
Published online: 19th January, 2004
DOI: 10.3987/COM-03-9963
Acylated Peonidin 3-Rutinoside-5-glucosides from Commercial Petunia Cultivars with Pink Flowers

Fumi Tatsuzawa, Yukiko Toya, Hitoshi Watanabe, Yuji Hirayama, Koichi Shinoda, Ritsuko Hara, Hiroko Seki, and Toshio Ando*

*Faculty of Horticulture, Chiba University, 648 Matsudo, Matsudo City, Chiba 271-8510, Japan


Two new acylated peonidin glycosides and three known acylated or non-acylated peonidin glycosides were identified in the flowers of 17 commercial pink petunias: peonidin 3-O-[6-O-(4-O-(4-O-(6-O-(trans-caffeoyl)-β-D-glucopyranosyl)-trans-p-coumaroyl)-α-L-rhamnopyranosyl)-β-D-glucopyranoside]-5-O-[β-D-glucopyranoside], peonidin 3-O-[6-O-(4-O-(4-O-(β-D-glucopyranosyl)- trans-p-coumaroyl)-α-L-rhamnopyranosyl)-β-D-glucopyranoside]-5-O-[β-D- glucopyranoside], peonidin 3-p-coumaroylrutinoside-5-glucoside, peonidin 3-caffeoylrutinoside-5-glucoside, and peonidin 3-rutinoside-5-glucoside.

PDF (148KB)
Paper | Regular issue | Vol 63, No. 3, 2004, pp. 519 - 527
Published online: 9th January, 2004
DOI: 10.3987/COM-03-9947
Synthesis and Spectroscopic Differentiation of 2- and 4-Alkoxythiotetronic Acids

Gautham Shenoy, Pilho Kim, Michael Goodwin, Quynh-Anh Nguyen, Clifton E. Barry, 3rd, and Cynthia S. Dowd*

*Tuberculosis Research Section, National Institute of Allergy and Infectious Diseases, Rockville, MD 20852, U.S.A.


O-Alkylation of thiotetronic acids gives a mixture of 2- and 4-position enol ether products. Comparison of the physical data revealed that UV spectroscopy was the most reliable method of distinguishing between these related ethers. We have determined that 4-position ethers have a distinct absorption between 235-240 nm, while 2-position ethers have two absorbance peaks, one between 205-220 nm and the other between 305-310 nm. This report describes the synthesis and unambiguous characterization of 2- and 4-methoxy-3,5-dimethylthiotetronic acids. The UV absorption properties of several other pairs of thiotetronic acid ethers confirm that these differences are general features that provide a simple method for distinguishing between 2- and 4-substituted isomers.

PDF (132KB)
Paper | Regular issue | Vol 63, No. 3, 2004, pp. 529 - 537
Published online: 16th January, 2004
DOI: 10.3987/COM-03-9948
Synthesis and Cytotoxic Evaluation of Certain Tricyclic Benzo[g]quinolin-4(1H)-one and Benzo[g]quinoline-4,9,10-trione Derivatives

Shu-Lin Hsu, Yeh-Long Chen, and Cherng-Chyi Tzeng*

*Faculty of Medicinal and Applied Chemistry, College of Life Science, Kaohsiung Medical University, Kaohsiung City, Taiwan, R.O.C.


The present report describes the synthesis and evaluation of tricyclic benzo[g]quinoline-4(1H)-one derivatives (CAB type) in which an additional aromatic ring is linearly fused on the antibacterial quinolone-3-carboxylic acid to maintain a free carboxylic acid (increase water-solubility) and a coplanar tricyclic DNA-intercalating chromophore (improve antitumor activity). 1H-Benzo[g]quinoline-4,5,10-trione, 1-methyl-1H-benzo[g]quinoline-4,5,10-trione, and ethyl 1-methylbenzo[g]quinoline-4,5,10-trione-3-carboxylate exhibited significant cytotoxicity against all 60 cancer cells with mean GI50 values of 5.92, 7.75, and 2.52 μM respectively while 1-methylbenzo[g]quinoline-4,5,10-trione-3-carboxylic acid and 5-hydroxy-10-methoxy-1-methylbenzo[g]quinolin-4(1H)-one- 3-carboxylic acid were inactive, indicated free carboxylic acid at C-3 position is unfavorable. The results have also implied the importance of carbonyl moieties at C-5 and C-10 due to the inactiveness of reduced products, ethyl 5-hydroxy-10-methoxy-1-methylbenzo[g]quinolin-4(1H)-one-3-carboxylate and ethyl 10-benzyloxy-5-hydroxybenzo[g]quinolin-4(1H)-one-3-carboxylate.

PDF (117KB)
Paper | Regular issue | Vol 63, No. 3, 2004, pp. 539 - 565
Published online: 9th January, 2004
DOI: 10.3987/COM-03-9952
Synthetic Studies on Azaspiracid, a Novel Shellfish Poison: Attempts to Construct the ABCD Ring System

Yuichi Ishikawa 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 the ABCD ring system of azaspiracid (1) was attempted. Construction of the highly substituted tetrahydrofuran (9) via the Pd(0)-mediated cyclization, followed by spirocyclization afforded trispiro-ring (28), carrying an unnatural ring-junctions. The BCD ring system of 1 was successfully produced by using the bridge of a sulfur atom between the B and C ring to control the spiroacetal center of the C13 position. The stereostructures were unambiguously determined by the NOE experiments.

PDF (196KB)
Paper | Regular issue | Vol 63, No. 3, 2004, pp. 567 - 582
Published online: 16th January, 2004
DOI: 10.3987/COM-03-9956
Synthesis and Photochromic Properties of Methoxy Substituted 2,2-Diaryl-2H-naphtho[1,2-b]pyrans

Christopher D. Gabbutt, John D. Hepworth, B. Mark Heron,* David A. Thomas, Colin Kilner, and Steven M. Partington

*Department of Colour Chemistry, The University of Leeds, Leeds, LS2 9JT, U.K.


A series of methoxy-substituted 2,2-di(4-methoxyphenyl)-2H-naphtho[1,2-b]pyrans has been synthesised from 3-alkoxycarbonyl-1-naphthols and 1,1-di(4-methoxyphenyl)prop-2-yn-1-ol. The influence of the methoxy group on the wavelength of maximum absorption and the stability of the ring-opened naphthopyrans is discussed.

PDF (180KB)
Paper | Regular issue | Vol 63, No. 3, 2004, pp. 583 - 589
Published online: 19th January, 2004
DOI: 10.3987/COM-03-9957
Green Chemistry Approaches to the Synthesis of 5-Arylidenethiobarbituric Acids by a Condensation Reactions between Aromatic Aldehydes and Thiobarbituric Acid: Comparison of Water, Microwave Irradiation, and Grinding

Jun Lu,* Yingying Li, Yinjuan Bai, and Min Tian

*Department of Chemistry, Northwest University, Xi'an, Shaan'xi 710069, China


A general and practical green chemistry route to the synthesis of 5-arylidenethiobarbituric acids is described from aromatic aldehydes and thiobarbituric acid under three different sets of reaction conditions: water without catalyst conditions, microwave irradiation, and grinding method using NH4OAc as a catalyst at room temperature.

PDF (140KB)
Paper | Regular issue | Vol 63, No. 3, 2004, pp. 591 - 608
Published online: 26th December, 2003
DOI: 10.3987/COM-03-9961
Reaction of [1,4]Benzodioxinopyridazines with Sodium Methoxide and Amines

Etsuo Oishi,* Chitose Sugiyama, Ken-ichi Iwamoto, and Ikuo Kato

*Division of Environmental Health Sciences, Graduate of School of Nutritional & Environmental Sciences, University of Shizuoka, 52-1 Yada, Shizuoka 422-8526, Japan


The reaction of 1-chloro (3), 1-methylsulfonyl (7) [1,4]benzodioxino[2,3-d]pyridazine and 4-chloro[1,4]benzodioxino[2,3-c]pyridazine (4) with sodium methoxide afforded dioxin ring-opened pyridazines (1416) and ring-cyclized pyridazines (9, 10), while their reaction with amines [n-butylamine (8a), cyclohexylamine (8b), morpholine (8c), piperidine (8d), pyrrolidine (8e), hydrazine (8f) and aniline (8g)] afforded 1-substituted [1,4]benzodioxino[2,3-d]pyridazines (18), 4-substituted [1,4]benzodioxino[2,3-c]pyridazines (19) and/or 2-hydroxyphenoxypyridazines (2022).

PDF (119KB)
Paper | Regular issue | Vol 63, No. 3, 2004, pp. 609 - 629
Published online: 16th January, 2004
DOI: 10.3987/COM-03-9964
Synthesis of 5-Substituted Ethyl 3-Oxo-2H-pyrazolo[4,3-c]pyridine-7-carboxylates

David Bevk, Renata Jakse, Amalija Colobic, Ljubo Golic, Anton Meden, Jurij Svete,* and Branko Stanovnik*

*Faculty of Chemistry and Chemical Technology, University of Ljubljana, Askerceva 5, SI-1000 Ljubljana, Slovenia


Ethyl (2E)-3-dimethylamino-2-[(4Z)-4-dimethylaminomethylidene-5-oxo-1-phenyl-4,5-dihydro-1H-pyrazol-3-yl]propenoate (3) was transformed with N-nucleophiles into ethyl 3-oxo-2-phenyl-3,5-dihydro-2H-pyrazolo[4,3—c]pyridine-7-carboxylates (6, 7, 9, 12, and 14).

PDF (317KB)
Paper | Regular issue | Vol 63, No. 3, 2004, pp. 631 - 639
Published online: 19th January, 2004
DOI: 10.3987/COM-03-9965
Synthesis of Aromatic Ring Fused Pyrrole Derivatives by Palladium-catalyzed Annulation of o-Iodoarylamines with Allyl Acetate

Chang Sung Hong, Jae Yong Seo, Eul Kgun Yum,* and Nack-Do Sung

*Department of Chemistry, Chungnam National University, Yusung, Daejon 305-764, Korea


Indoles, azaindoles, and pyrroloquinolines were obtained by palladium-catalyzed annulation of o-iodoarylamines with allyl acetate under 5 mol % Pd(OAc)2, 1 equiv. LiCl, 3 equiv. K2CO3 , and 2 equiv. allyl acetate in DMF at 120°C.

PDF (171KB)
Paper | Regular issue | Vol 63, No. 3, 2004, pp. 641 - 653
Published online: 9th January, 2004
DOI: 10.3987/COM-03-9967
Leptosins O-S, Cytotoxic Metabolites of a Strain of Leptosphaeria Sp. Isolated from a Marine Alga

Takeshi Yamada, Chika Iwamoto, Naoko Yamagaki, Takako Yamanouchi, Katsuhiko Minoura, Sanji Hagishita, and Atsushi Numata*

*Osaka University of Pharmaceutical Sciences, 4-20-1 Nasahara, Takatsuki, Osaka 569-1094, Japan


Leptosins O (1), P (2), Q (3), R (4) and S (5) have been isolated from a strain of Leptosphaeria sp. originally separated from the marine alga Sargassum tortile. Their absolute stereostructures have been elucidated on the basis of spectroscopic analyses of their acetate derivatives (610) using various 1D and 2D NMR techniques and some chemical transformations. The NMR and NOE spectral analyses of 610 revealed that they exist in a single conformer of B type in CDCl3. Among these metabolites, leptosins O (1) and P (2) exhibited significant cytotoxicity against cultured P388 cells

PDF (264KB)
Paper | Regular issue | Vol 63, No. 3, 2004, pp. 655 - 661
Published online: 16th January, 2004
DOI: 10.3987/COM-03-9968
Syntheses of 1,2,3,4,6,7,12,12b-Octahydroindolo[2,3-a]quinolizine and Harmicine Using a Chiral 1-Allyl-1,2,3,4-tetrahydro-β-carboline as the Starting Material

Takashi Itoh, Michiko Miyazaki, Kazuhiro Nagata, Shigeru Nakamura, and Akio Ohsawa*

*School of Pharmaceutical Sciences, Showa University, 1-5-8 Hatanodai, Shinagawa-ku, Tokyo 142-8555, Japan


Total syntheses of (S)-1,2,3,4,6,7,12,12b-octahydroindolo[2,3-a]quinolizine and (S)-harmicine were carried out using chiral 1-allyl-1,2,3,4-tetrahydro-β-carboline as the starting material.

PDF (328KB)
Paper | Regular issue | Vol 63, No. 3, 2004, pp. 663 - 670
Published online: 9th January, 2004
DOI: 10.3987/COM-03-9971
Density Functional Theory Study of the Preferred Conformation of Geissoschizine

Juriffah Ariffin, Hiromitsu Takayama, Mariko Kitajima, Norio Aimi,* and Chikara Kaneko

*Graduate School of Pharmaceutical Sciences, Chiba University, 1-33 Yayoi-cho, Inage-ku, Chiba 263-8522, Japan


Density functional theory (DFT) study of the hitherto proposed structures of geissoschizine (1) has proved that the structure (1a) having hydrogen bond between the enol hydroxyl and Nb functions with a trans-quinolizidine-type C/D ring and twistboat D ring (proposed by van Tamelen and Wright) is the most stable one. A strong contribution of the zwitterionic species (1a') to 1a is suggested together with the reasons why 1a' was not found as a local minimum. Calculations of 1H- and 13C- NMR chemical shifts based on this structure also support its structure.

PDF (89KB)
Note | Regular issue | Vol 63, No. 3, 2004, pp. 671 - 679
Published online: 16th January, 2004
DOI: 10.3987/COM-03-9930
Synthesis and Characterization of Potential Photolabeling Probes for Studying the Antiviral Mechanisms of EICAR

Qiongyou Wu, Jinqiao Wan, Yi Xia, Jiehua Zhou, Fanqi Qu, and Ling Peng*

*AFMB CNRS UMR 6098, Département de Chimie, Université Aix-Marseille II, 163, avenue de Luminy, 13288 Marseille, France


The designed photolabeling probes: 5-diazonium-1-β-D-ribofuranosyl-1H-imidazole-4-carboxamide (1) and 5-azido-1-β-D-ribofuranosyl-1H-imidazole-4-carboxamide (2) were synthesized via a short and convenient synthetic route, namely by diazotizing AICAR and subsequently performing substitution with NaN3. Although 1 was not stable even at low temperatures, 2 showed a rapid and clean photochemical reaction, which suggests that it may be a valuable tool for use in photolabeling studies.

PDF (187KB)
Note | Regular issue | Vol 63, No. 3, 2004, pp. 681 - 690
Published online: 19th January, 2004
DOI: 10.3987/COM-03-9959
Diastereoselective Synthesis of Substituted 2-Phenyltetrahydropyrans as Useful Precursors of Aryl C-Glycosides via Selenoetherification

Michelangelo Gruttadauria,* Carmela Aprile, Paolo Lo Meo, Serena Riela, and Renato Noto

*Department of Organic Chemistry "E. Paternò", University of Palermo, Viale delle Scienze, Parco d'Orleans II, 90128 Palermo, Italy


The cyclization of several substituted 5-phenyl-pent-4-en-1-ols with selenium electrophiles along some mechanistic considerations is discussed. In particular, an efficient diastereoselective synthesis of a 2,3,5,6-tetrasubstitued tetrahydropyran is reported. These findings open an interesting approach: the use of chiral selenium electrophiles for cyclization of chiral substrates. The cyclized products are useful starting material for the synthesis of D- or L-aryl C-glycosides.

PDF (127KB)
Note | Regular issue | Vol 63, No. 3, 2004, pp. 691 - 697
Published online: 23rd January, 2004
DOI: 10.3987/COM-03-9966
Quassinoid Xylosides, Javanicosides G and H, from Seeds of Brucea javanica

Ik Hwi Kim, Yukio Hitotsuyanagi, and Koichi Takeya*

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


Two new quassinoid xylosides, javanicosides G and H, were isolated from the seeds of Brucea javanica (L.) Merr. (Simaroubaceae). Their structures were elucidated by the analysis of spectral data and chemical evidence.

PDF (142KB)
Note | Regular issue | Vol 63, No. 3, 2004, pp. 699 - 706
Published online: 16th January, 2004
DOI: 10.3987/COM-03-9972
Practical Synthesis of DQ-113, a New Quinolone Antibacterial Agent, by Using the Intramolecular Horner-Wadsworth-Emmons Reaction

Hiroaki Inagaki, Toshiyuki Takeda, Rie N. Miyauchi, Katsuhiro Kawakami, Hisashi Takahashi, and Makoto Takemura*

*Medicinal Chemistry Research Laboratory, Daiichi Pharmaceutical Co., Ltd., 16-13, Kita-Kasai 1-Chome, Edsogawa-ku, Tokyo 134-8630, Japan


A practical route was developed for synthesizing the C-7 substituent of DQ-113 (6, 5-amino-7-[(3S,4R)-4-(1-aminocycloprop-1-yl)-3-fluoropyrrolidin-1-yl]-6-fluoro-1-[(1R,2S)-2-fluorocyclopropan-1-yl]-1,4-dihydro- 8-methyl-4-oxoquinolin-3-carboxylic acid), a new quinolone antibacterial agent for serious infections caused by Gram-positive pathogens. The key step was the intramolecular Horner-Wadsworth-Emmons reaction. In addition, the yield of the final aromatic nucleophilic substitution reaction was improved.

PDF (138KB)
Note | Regular issue | Vol 63, No. 3, 2004, pp. 707 - 713
Published online: 16th January, 2004
DOI: 10.3987/COM-03-9975
A Convenient Synthesis of Trifluoromethylpyridazines from 3-Hydrazono-1,1,1-trifluoroalkan-2-ones

Yasuhiro Kamitori* and Tomoko Sekiyama

*Department of Chemical Science and Engineering, Faculty of Engineering, Kobe University, Kobe 657-8501, Japan


3-Hydrazono-1,1,1-trifluoroalkan-2-ones readily obtained from aldehyde dialkylhydrazones reacted with acetylacetone to afford the corresponding 4-acetyl-3-methyl-5-trifluoromethylpyrizazines in good yields. The reaction with ethyl acetoacetate also gave the corresponding pyridazines. These reactions proceeded successfully in the absence of any catalyst.

PDF (55KB)
18 data found. 1 - 18 listed