Chemical and Pharmaceutical Bulletin
Online ISSN : 1347-5223
Print ISSN : 0009-2363
ISSN-L : 0009-2363
50 巻, 10 号
選択された号の論文の27件中1~27を表示しています
Regular Articles
  • Chia-Ying Li, Tian-Shung Wu
    原稿種別: Regular Article
    専門分野: [not specified]
    2002 年 50 巻 10 号 p. 1305-1309
    発行日: 2002年
    公開日: 2002/10/01
    ジャーナル フリー
    Five new naturally occurring monoterpenoids, crocusatins-A (1), -B (2a), -C (3), -D (4a) -E (5), a new lactate, sodium (2S)-(O-hydroxyphenyl)lactate (6), and eighteen known compounds were isolated and characterized from the pollen of Crocus sativus L. The tyrosinase inhibitory activities of these compounds were also discussed.
  • Qiao-Hong Chen, Feng-Peng Wang
    原稿種別: Regular Article
    専門分野: [not specified]
    2002 年 50 巻 10 号 p. 1310-1317
    発行日: 2002年
    公開日: 2002/10/01
    ジャーナル フリー
    After a series of optimization for the reaction conditions (reagents, reaction temperature, etc.), treatment of the sulfonates 4, 8, 13 and 15 with 8% NaOH (room temperature, 24 h) via a semipinacol rearrangement afforded the corresponding C-nor compounds 5, 9, 12 and 16, as the major of a pair of epimer at C-16, to an excellent extent, in 95%, 92%, 100% and 90% yield, respectively. The 12,13-seco compounds 21 and 22 (23) were obtained in 20% and 60% yield, respectively, by treating 5 with Br2–glacial HOAc (room temperature, 24 h). Treatment of the C-nor compounds 5 or 6, 16 or 17, and 28 from 10 with SOCl2–anhydrous benzene (room temperature, overnight) afforded the 12,13-seco compounds 24, 26 and 30 in 70% or 100%, 40% and 66% yield, respectively. When treatment of the C-nor compound 29 from 9 under same conditions gave the 12,13-seco products 30, 31 and 32 in 33%, 26% and 20% yield. When treating 21 or 24, and 26 with 5% KOH in EtOH afforded the 12,13-seco compounds 25 and 27 quantitatively, respectively. The compound 31 converted to 30 quantitatively by treatment with Na2CO3 in MeOH. All of the new compounds were isolated and fully characterized.
  • Taisuke Itaya, Tae Kanai
    原稿種別: Regular Article
    専門分野: [not specified]
    2002 年 50 巻 10 号 p. 1318-1326
    発行日: 2002年
    公開日: 2002/10/01
    ジャーナル フリー
    The first synthesis of (αS,βS)-β-hydroxy-α-[(methoxycarbonyl)amino]-4,6-dimethyl-9-oxo-3-β-D-ribofuranosyl-4,9-dihydro-3H-imidazo[1,2-a]purine-7-butanoic acid methyl ester [(αS,βS)-11] has been achieved by OsO4 oxidation of [S-(E)]-4-[4,6-dimethyl-9-oxo-3-[2,3,5-tris-O-(tert-butyldimethylsilyl)-β-D-ribofuranosyl]-4,9-dihydro-3H-imidazo[1,2-a]purin-7-yl]-2-[(methoxycarbonyl)amino]-3-butenoic acid methyl ester (13) followed by successive γ-deoxygenation through the cyclocarbonates, separation from the (αS,βR)-isomer by means of flash chromatography, and deprotection. On the other hand, the minor nucleoside of rat liver tRNAPhe was isolated on a scale of 100 μg by partial digestion of unfractionated tRNA (1 g) with nuclease P1, followed by reverse-phase column chromatography, complete digestion with nuclease P1/alkaline phosphatase, and reverse-phase HPLC. Comparison of this nucleoside with the synthetic one has unambiguously established its structure to be (αS,βS)-11.
  • Takashi Iida, Masahiro Hikosaka, Genta Kakiyama, Keisuke Shiraishi, Cl ...
    原稿種別: Regular Article
    専門分野: [not specified]
    2002 年 50 巻 10 号 p. 1327-1334
    発行日: 2002年
    公開日: 2002/10/01
    ジャーナル フリー
    Epimeric 3α,7α,16- and 3α,7α,15-trihydroxy-5β-cholan-24-oic acids and some related compounds were synthesized from chenodeoxycholic acid (CDCA) and ursodeoxycholic acid (UDCA), respectively. The key reaction involved one-step remote oxyfunctionalization of unactivated methine carbons at C-17 of CDCA and at C-14 of UDCA as their methyl ester-peracetate derivatives with dimethyldioxirane (DMDO). After dehydration of the resulting 17α- and 14α-hydroxy derivatives with POCl3 or conc. H2SO4, the respective Δ16- and Δ14-unsaturated products were subjected to hydration via hydroboration followed by oxidation to yield the 3,7,16- and 3,7,15-triketones, respectively. Stereoselective reduction of the respective triketones with tert-butylamine-borane complex afforded the epimeric 3α,7α,16- or 3α,7α,15-trihydroxy derivatives exclusively. A facile formation of the corresponding ε-lactones between the side chain carboxyl group at C-24 and the 16α- (or 16β-) hydroxyl group in bile acids is also clarified.
  • Claire Jarry, Jean-Christophe Leroux, Jonathan Haeck, Cyril Chaput
    原稿種別: Regular Article
    専門分野: [not specified]
    2002 年 50 巻 10 号 p. 1335-1340
    発行日: 2002年
    公開日: 2002/10/01
    ジャーナル フリー
    The effects of steam sterilization and γ-irradiation on chitosan and thermogelling chitosan-β-glycerophosphate (GP) solutions containing polyol additives were investigated. The selected polyols were triethylene glycol, glycerol, sorbitol, glucose and poly(ethylene glycol) (PEG). They were incorporated to chitosan solutions prior to sterilization in a proportion ranging from 1 to 5% (w/v). The solutions were characterized with respect to their viscosity, thermogelling properties, compressive stress relaxation behavior and chitosan degradation. All polyols reduced the autoclaving-induced viscosity loss and had a positive impact on the solution thermogelling properties and compressive performance of the gels. Steam sterilization in the presence of glucose resulted in a substantial increase in the solution viscosity and gel strength. This was associated with a strong discoloration suggesting chemical alteration of the system. PEG was the most effective agent in preventing hydrolytic degradation of chitosan chains. Gamma-irradiation strongly decreased the chitosan solution viscosity regardless of the presence of additives, even when sterilization was carried out at −80 °C. Moreover, the thermogelling properties were dramatically altered, and thus, γ-irradiation would not be an appropriate method to sterilize chitosan solutions. In conclusion, polyols are potentially useful additive to maximise the viscoelastic and mechanical properties of chitosan-GP after steam sterilization.
  • Yu Jin, Junpei Yamanaka, Shizuko Sato, Isamu Miyata, Chikako Yomota, M ...
    原稿種別: Regular Article
    専門分野: [not specified]
    2002 年 50 巻 10 号 p. 1341-1348
    発行日: 2002年
    公開日: 2002/10/01
    ジャーナル フリー
    Hyaluronate-hydroxyethyl acrylate blend gel (HA-PHEA) were prepared to modify the brittleness of hyaluronate gel (HA) and the characteristics of HA-PHEA gel were compared with those of HA and polyhydroxyethyl acrylate (PHEA) gels. These gels were high in water content and transparent. HA-PHEA gel was improved in viscoelastic properties due to the elasticity and the high affinity with water of PHEA, and the drying-swelling cycles became reversible. The effective charge densities θ of the gels estimated from membrane potentials were −0.002, −0.008 and 0 mol dm−3 for HA-PHEA, HA and PHEA gels. Effects of electro- static and nonelectrostatic interactions on absorptions and releases were studied using sodium benzoate (NaBA) as an anionic solute, and methylene blue (MB), chlorpromazine (CPHCl) and benzethonium chloride (BZTCl) as cationic solutes, in which CPHCl and BZTCl are cationic amphiphilic solutes. The releases of MB, CPHCl and BZTCl from HA-PHEA and HA gels were suppressed comparing with those of NaBA. By adding salts, the releases of MB and CPHCl were enhanced but those of BZTCl were suppressed due to enhancement of the intra- and intermicelle formation. In the releases of the cationic solutes from HA-PHEA gel, electrostatic and nonelectrostatic interactions with HA were found to play important roles. Behaviors of the releases from HA-PHEA gel were found to possess the features of HA gel.
  • Hiroshi Imoto, Eikoh Imamiya, Yu Momose, Yasuo Sugiyama, Hiroyuki Kimu ...
    原稿種別: Regular Article
    専門分野: [not specified]
    2002 年 50 巻 10 号 p. 1349-1357
    発行日: 2002年
    公開日: 2002/10/01
    ジャーナル フリー
    A novel series of oxyiminoacetic acid derivatives were synthesized in an effort to develop a potent antidiabetic agent, which does not contain the 2,4-thiazolidinedione moiety. These compounds were evaluated for glucose and lipid lowering effects in genetically obese and diabetic KKAy mice. Several of the compounds showed strong antidiabetic activity, including functional potency at peroxisome proliferator-activated receptor (PPAR)-γ. (Z)-2-[4-[(5-Methyl-2-phenyl-1,3-oxazol-4-yl)methoxy]benzyloxyimino]-2-(4-phenoxyphenyl)acetic acid (25) significantly reduced plasma glucose (33%, p<0.01) and plasma triglycelide levels (43%, p<0.01) even at a dosage of 0.001% in diet. Pharmacokinetic analyses of 25 are also reported.
  • Tsutomu Nakanishi, Yuka Inatomi, Hiroko Murata, Naoki Iida, Akira Inad ...
    原稿種別: Regular Article
    専門分野: [not specified]
    2002 年 50 巻 10 号 p. 1358-1361
    発行日: 2002年
    公開日: 2002/10/01
    ジャーナル フリー
    Two new phenol glucosides termed juniperosides I (1) and II (2) were isolated, together with known two biflavones, cupressuflavone and amentoflavone and a diterpene, 3β-hydroxy sandaracopimaric acid, from leaves of Juniperus occidentalis HOOK. (Cupressaceae) collected in Oregon, U.S.A., and their structures were established as (1S)- and (1R)-1-(2′-hydroxy-6′-methylphenyl)ethanol 2′-O-β-D-glucopyranosides (1, 2), respectively, on the basis of spectral, chemical, and synthetic evidence. The glycosides 1 and 2, as well as the corresponding aglycones 1a and 2a, are apparently novel types of naturally occurring compounds; to our knowledge, isolation of these types of natural phenol derivatives has only rarely been reported from the vegetable kingdom.
  • Tadashi Shiraiwa, Masahiro Suzuki, Yoshio Sakai, Hisashi Nagasawa, Kaz ...
    原稿種別: Regular Article
    専門分野: [not specified]
    2002 年 50 巻 10 号 p. 1362-1366
    発行日: 2002年
    公開日: 2002/10/01
    ジャーナル フリー
    To synthesize optically active 2-amino-2-methyl-3-phenylpropanoic acid (1), (RS)-2-benzoylamino-2-benzyl-3-hydroxypropanoic acid [(RS)-2] was first optically resolved using cinchonidine as a resolving agent to yield optically pure (S)- and (R)-2 in yields of about 70%, based on half of the starting amount of (RS)-2. Next, the racemic structure of (RS)-2 was examined based on melting point, solubility, IR spectrum, and binary and ternary phase diagrams, with the aim of optical resolution by preferential crystallization of (RS)-2. Results indicated that the (RS)-2 exists as a conglomerate at room temperature, although it forms a racemic compound at the melting point. The optical resolution by preferential crystallization yielded (S)- and (R)-2 with optical purities of about 90%, which were fully purified by recrystallization. After O-tosylation of (S)- and (R)-2, reduction by zinc powder and sodium iodide gave (R)- and (S)-1, respectively.
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