Regular Issue

Vol. 43, No. 3, 1996

24 data found. 1 - 24 listed
Communication | Regular issue | Vol 43, No. 3, 1996, pp. 509 - 512
Published online:
DOI: 10.3987/COM-95-7311
Azolium Salts as Effective Catalysts for Benzoin Condensation and Related Reactions

Akira Miyashita,* Yumiko Suzuki, Motoi Kobayashi, Naomi Kuriyama, and Takeo Higashino

*School of Pharmaceutical Sciences, University of Shizuoka, 52-1 Yada, Shizuoka 422, Japan


A catalytic ability of several azolium salts for benzoin condensation, the benzoylation of 4-chloro-1-phenyl-1H-pyrazolo[3,4-d]pyrimidine, and oxidative aroylation was examined. We found that azolium salts having an imidazolium moiety, such as 1,4-dimethyl-1,2,4-triazolium iodide (3), and 2-methylpyrido[1,2-c]- (4), dipyrido[1,2-c:2’,1’-e]- (5), naphtho[1,2-c]- (10), and phenanthro[9,10-c]imidazolium iodide (11) can be used as effective catalysts for benzoin condensation and related reactions.

PDF (145KB)
Communication | Regular issue | Vol 43, No. 3, 1996, pp. 513 - 517
Published online:
DOI: 10.3987/COM-95-7327
Synthesis of 3-Amino-4-indolyl-2-piperidones: Tryptophan-derived Pseudodipeptides

Ricardo Rodríguez, Anna Diez, Mario Rubiralta,* and Ernest Giralt

*Laboratori de Química Orgànica, Facultat de Farmàcia, Universitat de Barcelona, 08028 Barcelona, Spain


(αR,3R*,4R*)-N-(2-Acetoxy-1-phenylethyl)-3-allyloxycarbonylamino-4-(1-benzyl-3-indolyl)-2-piperidone (1), a pseudodipeptide which contains a conformationally restricted analogue of tryptophan has been synthesized from anhydride (2) and (R)-(-)-phenylglycinol (3).

PDF (130KB)
Communication | Regular issue | Vol 43, No. 3, 1996, pp. 519 - 522
Published online:
DOI: 10.3987/COM-95-7345
Synthesis and Characterization of Novel Photoreactive Naltrexone Analogs as Isomeric Carbene-generating Probes for Opioid Receptors

Yasumaru Hatanaka,* Norio Nakamura, Miwa Wakabayashi, Toshiyuki Fujioka, and Tohru Kikuchi

*Research Institute for Wakan-Yaku, Toyama Medical and Pharmaceutical University, Toyama 930-01, Japan


A convenient synthesis of m- and p-CF3-diazirinylbenzoic acid was developed. A pair of novel photoaffinity probes bearing these diazirines on a naltrexyl framework bind reversibly with high affinity at μ-, δ, and κ-receptors.

PDF (120KB)
Communication | Regular issue | Vol 43, No. 3, 1996, pp. 523 - 526
Published online:
DOI: 10.3987/COM-95-7349
Isolation of New TC Conformational Humulene 2,3; 6,7-Diepoxide

Kiyoharu Hayano,* Takao Shinjo, and Katsura Mochizuki

*Chemistry Laboratory, Hokkaido College of Education, Ainosato, Sapporo 002, Japan


The epoxidation of (2E,9E)-6,7-epoxy-3,7,11,11-tetramethylcycloundeca-2,9-diene (1) with m-CPBA gave a new TC and known CT diepoxides, (9E)-(2R*,3R*,6R*,7R*)-2,3;6,7-diepoxy-3,7,11,11-tetramethylcycloundec-9-ene (3) and (9E)-(2S*,3S*,6R*,7R*)-2,3;6,7-diepoxy-3,7,11,11-tetramethylcycloundec-9-ene (2), respectively, in the ratio of 2:3=91.5:8.5. The conformation of 3 was determined by X-ray crystallography (C15H24O2: monoclinic space group P21/n with a=13.735(4) Å, b=15.910(3) Å, c=6.553(2) Å, β=100.90(2)°, Z=4).

PDF (92KB)
Communication | Regular issue | Vol 43, No. 3, 1996, pp. 527 - 530
Published online:
DOI: 10.3987/COM-95-7350
Cycloadditions of 1,5- and 1,7-Azulenequinones to Benzo[c]furan and Its 1,3-Diphenyl Derivative

Hitoshi Takeshita*, Yong Zhe Yan, Akira Mori, and Tetsuo Nozoe*

*Institute of Advanced Material Study, 86, Kyushu University, Kasuga-koen, Kasuga, Fukuoka 816, Japan


With 1,3-diphenylbenzo[c]furan (DIBF), 1,5-azulenequinone (5-AQ) gave a [2+4] cycloadduct and a [2+4]-[6+4] cycloadduct which were interconverted under mild conditions. This is the first observation of conjugated rearrangement of [2+4] mode to [6+4] mode with the second attack of cycloaddend or conjugated cycloreversion with the rearrangement. 1,7-Azulenequinone (7-AQ) formed two stereoisomeric 1:2-[2+4]-[6+4] cycloadducts. With benzo[c]furan, 5-AQ and 7-AQ afforded two and four stereoisomeric [2+4]-[6+4] cycloadducts, respectively.

PDF (118KB)
Communication | Regular issue | Vol 43, No. 3, 1996, pp. 531 - 534
Published online:
DOI: 10.3987/COM-95-7356
Synthesis of a Carbon-linked CMP-NANA Analog and Its Inhibitory Effects on GM3 and GD3 Synthases

Yasumaru Hatanaka*, Makoto Hashimoto, Kazuya I.-P. Jwa Hidari, Yutaka Sanai, Yoshitaka Nagai, and Yuichi Kanaoka

*Research Institute for Wakan-Yaku, Toyama Medical and Pharmaceutical University, Sugitani 2630, Toyama 930-01, Japan


A carbon-linked analog of cytidine monophospho-N-acetylneuraminic acid (CMP-NANA) was synthesized as the degradation resistant inhibitor for sialyltransferases. The compound is the first example of synthetic CMP-NANA analog that exhibited inhibitory effects on the activity of GM3 and GD3 synthases.

PDF (125KB)
Communication | Regular issue | Vol 43, No. 3, 1996, pp. 535 - 538
Published online:
DOI: 10.3987/COM-95-7361
Garciduols A and B, New Benzophenone-Xanthone Dimers, from Garcinia dulcis

Munekazu Iinuma*, Hideki Tosa, Tetsuro Ito, Toshiyuki Tanaka, and Soedarsono Riswan

*Department of Pharmacognosy, Gifu Pharmaceutical University, 5-6-1 Mitahora-higashi, Gifu 502, Japan


From the roots of Garcinia dulcis (Guttiferae), two new compounds, garciduols A and B, were isolated. The skeleton was a dimer composed of a xanthone and a benzophenone.

PDF (113KB)
Paper | Regular issue | Vol 43, No. 3, 1996, pp. 539 - 543
Published online:
DOI: 10.3987/COM-95-7215
An Easy and Efficient Microwave - assisted Method to Obtain 1-(4-Bromophenacyl)azoles in "Dry Media"

Eduardo Pérez, Eddy Sotelo, André Loupy,* Raul Mocelo, Margarita Suarez, Rolando Pérez, and Miguel Autié

*Laboratoire des Réactions Sélectives sur Supports, CNRS UA 478, Université Paris-Sud, 91405 Orsay, France


N-Alkylation of azoles with 4-bromophenacyl bromide has been carried out under microwave irradiation in solvent-free conditions. The results obtained showed high yields and selectivity. The specific "non-thermal" effect produced by microwave was demonstrated.

PDF (136KB)
Paper | Regular issue | Vol 43, No. 3, 1996, pp. 545 - 550
Published online:
DOI: 10.3987/COM-95-7285
Reduction and Carboxylation of 1-Chloromethyl-6,7-dimethoxy-3,4-dihydroisoquinolinium Salts. An Easy Entry to 1-Hydroxymethyl-1,2,3,4-tetrahydroisoquinoline Alkaloids

Rafael Suau,* Inmaculada Ruiz, Natalia Posadas, and María Valpuesta

*Departamento de Química Orgánica, Facultad de Ciencias, Universidad de Málaga, E-29071 Málaga, Spain


At 25 °C, the NaBH4/MeOH reduction of the title isoquinolinium salts gave the aziridine exclusively. At a low temperature (0°C) in the presence of CO2/K2CO3, the 2-oxazolidinone was obtained in almost quantitative yield. Controlled hydrolysis of the borane complex derived from the isoquinolinium salts also gave the cyclic carbamate. (±)-Calycotomine and its N-Me derivative were obtained in high yields.

PDF (172KB)
Paper | Regular issue | Vol 43, No. 3, 1996, pp. 551 - 554
Published online:
DOI: 10.3987/COM-95-7287
One Step Synthesis of Polyhydroxyflavanones from Hydroxyacetophenones and Hydroxybenzaldehydes

Wing Lai Chan,* Yong Cheng Lin, Wei Han Zhang, Pak Lai Tang, and Yau Shan Szeto

*Department of Applied Biology and Chemical Technology, The Hong Kong Polytechnic University, Hung Hom, Kowloon, Hong Kong


Polyhydroxyflavonones were synthesized in a one-step process by reacting the appropriate hydroxyacetophenones and hydroxybenzaldehydes in the presence of boric acid, in a mixed solvent system.

PDF (98KB)
Paper | Regular issue | Vol 43, No. 3, 1996, pp. 555 - 565
Published online:
DOI: 10.3987/COM-95-7292
A Convenient Synthesis of the Five-membered Lactams from D-Arabinose

Yaeko Konda,* Tomomi Machida, Michiko Akaiwa, Kazuyoshi Takeda, and Yoshihiro Harigaya

*School of Pharmaceutical Sciences, Kitasato University, Shirokane, Minato-ku, Tokyo 108, Japan


Synthesis of the five-membered lactams, (3S,4R,5S)-1-benzoyl- and (3S,4R,5S)-1-benzyloxycarbonyl-5-benzyloxymethyl-3,4-dibenzyloxypyrrolidin-2-ones (3a and 3b) which are the important intermediates for the unsaturated five membered amino acid moiety (2) in carzinophilin (1) was described. Lactams (3a and 3b) were synthesized from 2,3,5-tri-O-benzyl-D-arabinitol (6) by a convenient method in seven steps.

PDF (314KB)
Paper | Regular issue | Vol 43, No. 3, 1996, pp. 567 - 580
Published online:
DOI: 10.3987/COM-95-7294
Synthesis of Dipolar Ethyleneimidazolium Benzimidazolate Inner Salts and Their Transformation to 2-Vinylbenzimidazoles through a Type of β-Elimination Reaction

Ermitas Alcalde,* Maria Gisbert, and Lluïsa Pérez-Garcia

*Laboratorio de Chímica Oránica, Facultad de Fharmacia, Universidad de Barcelona, E-08028 Barcelona, Spain


The synthesis and spectroscopic properties of the fairly stable title inner salts (5) are reported. For several of the betaines (5), both the highly dipolar character due to the terminal rings and the nature of the spacer promoted a type of β-elimination reaction. Thus, formation of 2-vinylbenzimidazoles (7) from the corresponding betaines (5) proceeds in high yield under neutral and mild conditions. Following similar treatment, the 1-(2-benzimidazol-2-ylethyl)imidazolium salt (8b) undergo nucleophilic substitution reactions.

PDF (364KB)
Paper | Regular issue | Vol 43, No. 3, 1996, pp. 581 - 588
Published online:
DOI: 10.3987/COM-95-7296
Isoflavan Derivatives from Glycyrrhiza glabra (Licorice)

Takeshi Kinoshita,* Kiichiro Kajiyama, Yukio Hiraga, Kunio Takahashi, Yukiyoshi Tamura, and Kenji Mizutani

*Faculty of Pharmaceutical Sciences, Teikyo University, 1091-1 Suarashi, Sagamiko-machi, Tsukui-gun, Kanagawa 199-01, Japan


A new isoflavan was isolated from the root of Glycyrrhiza glabra (licorice; Fabaceae), and its structure was elucidated as 8-prenyl-phaseollinisoflavan on the basis of spectroscopic evidence. Five known isoflavans have also been isolated, and identified with glabridin, 4’-O-methylglabridin, hispaglabridins A, B and what was previously elucidated as "3’-methoxyglabridin". The structure of the latter compound was revised to 3’-hydroxy-4’-O-methylglabridin by an irradiation experiment and long range 13C-1H COSY spectral analysis.

PDF (297KB)
Paper | Regular issue | Vol 43, No. 3, 1996, pp. 589 - 599
Published online:
DOI: 10.3987/COM-95-7302
Synthesis of Novel Amphiphilic Compounds Containing Aza-12-crown-4 or D-Glucosamine and Their Ion Permeability

Akira Katoh,* Shin-ichi Ishida, Junko Ohkanda, and Masao Washizu

*Department of Industrial Chemistry, Faculty of Engineering, Seikei University, Musashino, Tokyo 180, Japan


New amphiphilic compounds (Types 1, 2, and 3) composed of triethylene glycol monomethyl ether, octanol, and aza-12-crown-4 or D-glucosamine were synthesized. Aza-15-crown-4 was connected to an amphiphlic alkyl chain by the -CO-N- linkage in Type 1 and by -CO-N- in Type 2, and D-glucosamine was connected to it by -CO-N- in Type 3. The ion permeability of these compounds was elucidated by means of the black lipid membrane method with an alternating current (a.c.). Only Type 2 compound showed significant transmembrane currents when incorporated into the lipid bilayer membrane in aqueous NaCl, KCl, and RbCl solutions.

PDF (328KB)
Paper | Regular issue | Vol 43, No. 3, 1996, pp. 601 - 610
Published online:
DOI: 10.3987/COM-95-7320
An Alternative Method for Lactonization of β,γ-Enoic Acids and its Application to Verticillene-10-carboxylic Acid

Yoshihiro Yaguchi, Mitsuhiro Akiba, Makoto Harada, and Tadahiro Kato*

*Department of Chemistry, Faculty of Science, Science University of Tokyo, Kagurazaka 1-3, Shinjuku-ku, Tokyo 162, Japan


The reaction with iodine in refluxing acetic acid was found to be an alternative method for the lactonization of β,γ-enoic acids. Application of the method to verticillene-10-carboxylic acid (6) resulted in the formation of three γ-lactones (7, 12, and 13), 12 being an unexpected product.

PDF (199KB)
Paper | Regular issue | Vol 43, No. 3, 1996, pp. 611 - 617
Published online:
DOI: 10.3987/COM-95-7335
Some Base-catalyzed Reactions of NOR-Clerodane Derivatives and Their Antifeedant Activity

Chen Huan-Ming, Min Zhi-Da,* Munekazu Iinuma, and Toshiyuki Tanaka

*Department of Pharmacognosy, Gifu Pharmaceutical University, 5-6-1 Mitahora-higashi, Gifu 502, Japan


By base-catalyzed reaction of a nor-clerodane diterpene, teucvidin (1), several cis- (5, 6) and trans-clerodane derivatives (3, 7, 8) were obtained. Their structures including stereochemistry were established by spectroscopic means and X-ray analysis of 5, and by correlation to the known products. The formation of these compounds implied that a different kind of basic reagents had influence on the stereochemistry of reactive products. Among the compounds obtained, 7 showed the most potent antifeedant activity to larvae of Leucania separata.

PDF (204KB)
Paper | Regular issue | Vol 43, No. 3, 1996, pp. 619 - 624
Published online:
DOI: 10.3987/COM-95-7336
Dihydrobenzofurans via Dienone-Phenol Rearrangement of Spirooxetanes from Photoaddition of Quinones with Electron Donor Olefins

Takumi Oshima,* Yu-ichi Nakajima, and Toshikazu Nagai

*Department of Applied Chemistry, Faculty of Engineering, Osaka University, Toyonaka, Osaka 560, Japan


Photoaddition of electron donor olefins such as vinyl ethers and stilbene to variously methyl- and halogeno-substituted 1,4-benzoquinones resulted in the formation of dihydrobenzofurans via a dienone-phenol rearrangement of the primary product spirooxetanes.

PDF (196KB)
Paper | Regular issue | Vol 43, No. 3, 1996, pp. 625 - 631
Published online:
DOI: 10.3987/COM-95-7339
Ring Cleavage Reaction of Heterocyclic Ketones Based on Crossed Aldol Condensation

Hiroshi Suemune,* Jun Uchida, and Kiyoshi Sakai

*Faculty of Pharmaceutical Sciences, Kyushu University, Fukuoka 812-82, Japan


Ring cleavage reaction based on crossed aldol condensation using heterocyclic ketones such as 4-piperidone and nortropinone derivatives with benzaldehyde under acetalization conditions (BF3·Et2O/ethylene glycol) has been achieved.

PDF (193KB)
Paper | Regular issue | Vol 43, No. 3, 1996, pp. 633 - 640
Published online:
DOI: 10.3987/COM-95-7340
Reaction of 1-Hydroxyphthalimide Derivatives with Aluminum Chloride in Benzene

Kensaku Uto, Takeshi Sakamoto, Keita Matsumoto, and Yasuo Kikugawa*

*Faculty of Pharmaceutical Sciences, Josai University, 1-1 Keyakidai, Sakado, Saitama 350-02, Japan


The reaction of 1-hydroxyphthalimide derivatives with AlCl3 in benzene has been investigated. From 1-hydroxyphthalimide (1a) 2-hydroxy-3,3-diphenyl-2,3-dihydroisoindol-1-one (2) and 1,1-diphenyl-1H-benzo[d][1,2]oxazine-4-one (3) are obtained by initial attack of benzene on the imide carbonyl, assisted by the neighboring oxygen atom. Heating 2 with Lewis acid (AlCl3) in benzene results in ring expansion to afford 3, while heating 3 with protic acid (H2SO4) leads to ring contraction to give 2. From O-(2-phenethyl)- and O-benzoyl derivatives (1b and c), 1,2-diphenylethane (4) and benzophenone (5) are obtained, respectively, by the heterolytic cleavage of an C-O bond.

PDF (185KB)
Paper | Regular issue | Vol 43, No. 3, 1996, pp. 641 - 651
Published online:
DOI: 10.3987/COM-95-7342
Synthesis and Behaviour of Furo[2,3,4-k,l]acridines and Furo[2,3,4-k,l]pyrano[3,2-h]acridines

Catherine Jolivet, Christian Rivalle, Alain Croisy, and Emile Bisagni*

*URA 1387 CNRS, Institut Curie, Section de Recherche, Bat 110-112, Centre Universitaire 91405 Orsay, France


From noracronycine and 1-hydroxy-3-methoxy-10-methylacridone, a [2,3,4-k,l] fused furan ring bearing an ethoxycarbonyl group was built up. Amidification of this ester function with N,N-dimethylaminoalkylamines allowed us to prepare watersoluble furo[2,3,4-k,l]pyrano[3,2-h]acridine and furo[2,3,4-k,l]acridine derivatives. In the course of attempts to saponify the ester function under aqueous sodium hydroxide basic conditions and to reduce it upon aluminium hydride, an abnormal ring opening reaction of the ethoxycarbonylated furan was ascertained.

PDF (351KB)
Paper | Regular issue | Vol 43, No. 3, 1996, pp. 653 - 664
Published online:
DOI: 10.3987/COM-95-7348
Quassinoids and Limonoids from Harrisonia perforata

Kunio Kamiuchi, Katsuyoshi Mitsunaga, Kazuo Koike, Yishan Ouyang, Taichi Ohmoto, and Tamotsu Nikaido*

*School of Pharmaceutical Sciences, Toho University, 2-2-1, Miyama, Funabashi, Chiba 274, Japan


Three new quassinoids, perforaquassins A, B and C, and a new limonoid, perforin A, were isolated from the bark of Harrisonia perforata (Simaroubaceae). Their structures were determined by spectral techniques.

PDF (281KB)
Paper | Regular issue | Vol 43, No. 3, 1996, pp. 665 - 674
Published online:
DOI: 10.3987/COM-95-7355
Synthesis and Biological Activity of Arthrographol and Related Compounds

Muneharu Miyake, Yoshiaki Hanaoka, Yasuo Fujimoto *, Yoshio Sato, Naoki Taketomo, Itsuro Yokota, and Yoshihiro Yoshiyama

*College of Pharmacy, Nihon University, Narashinodai 7-7-1, Funabashi, Chiba 274, Japan


(±)-Arthrographol (1a) and related compounds were synthesized and their inhibitory activities against 5-lipoxygenase were investigated. The 1’(Z)-isomer (1b) of arthrographol was found to be three times active than arthrographol itself.

PDF (325KB)
Paper | Regular issue | Vol 43, No. 3, 1996, pp. 675 - 683
Published online:
DOI: 10.3987/COM-95-7358
The Diastereoselective Synthesis of Oxacephams from 1,3-2H-Oxazines

Mostafa Hatam, Sabine Köpper, Jürgen Martens*

*Fachbereich Chemie, Universität Oldenburg, P. O. Box 2503, D-26111 Oldenburg, Germany


Various oxacephams are obtained from symmetrically and unsymmetrically 2,2,5,5-substituted 1,3-2H-oxazines by the Staudinger reaction. The annulation reaction proceeds diastereoselectively with both synthons, as unequivocally determined by nmr spectroscopical analysis.

PDF (280KB)
Paper | Regular issue | Vol 43, No. 3, 1996, pp. 685 - 690
Published online:
DOI: 10.3987/COM-95-7365
Laccarin, a New Alkaloid from the Mushroom, Laccaria vinaceoavellanea

Mamoru Matsuda, Tsuneyasu Kobayashi, Sachiko Nagao, Tomihisa Ohta*, and Shigeo Nozoe*

*Faculty of Pharmaceutical Sciences, Tohoku University, Aobayama, Aobaku, Sendai 980-77, Japan


A new alkaloid laccarin was isolated from the mushroom, Laccaria vinaceoavellanea, and the structure was determined on the basis of a spectroscopic analysis. Laccarin showed phosphodiesterase inhibitory activity.

PDF (136KB)
24 data found. 1 - 24 listed