Showing papers in "Chemical & Pharmaceutical Bulletin in 1980"
207 citations
TL;DR: In this paper, the CMR spectra of all positional isomers of mono-O-myristoyl-α- and β-D-glucopyranoses in pyridine-d5 are reported and discussed in connection with the anomalies of 1α and 1β-O -acyl derivatives.
Abstract: CMR spectra of all positional isomers of mono-O-myristoyl-α- and β-D-glucopyranoses in pyridine-d5 are reported and discussed in connection with the anomalies of 1α- and 1β-O-acyl derivatives. Calculation of the chemical shifts of some dimyristates using the acylation shifts obtained from monomyristate (Table III) gave values in agreement with the observed values for each compound, confirming the additivity of the acylation shift parameters. The effects of the solvent and the nature of the acyl moiety on the acylation shifts also examined using twenty samples, and it was concluded that the acylation shift parameters are independent of the solvent (s) and the kind (s) of acyl group (s), so that the above shift values obtained for the myristoyl group can be regarded as a universal set of additive parameters for usual di- and tri-acyl derivatives. This additivity rule of parameters was successfully applied to the structure elucidation of two naturally occurring acylglucose derivatives, tuliposide-A and spirarin. The previously reported data for various glucosyl γ-nitropropanoates in acetone-d5 are compared with the values calculated from the above parameters, again showing fair agreement.
170 citations
TL;DR: The amorphous form showed better tablet-forming properties than the crystalline form and a good linear relation was observed between the maximum amount of water absorbed and the degree of crystallinity at 100% or 89% RH at 30°.
Abstract: An X-ray diffraction method for determination of the degree of crystallinity of indomethacin was established, and the transition rate of indomethacin from amorphous to crystalline form was investigated. The transition of the amorphous form to crystalline form at 20°, 30°and 40°followed first-order kinetics and the Arrhenius plot showed good linearity. The amorphous form was shown to change to form I at 100% relative humidity (RH), to form I or II at 89% RH and to form I at 79% and 69% RH at 30°. The transition rate of the amorphous form to form II at 100% RH was larger than that at 89% RH. A good linear relation was observed between the maximum amount of water absorbed (log scale) and the degree of crystallinity at 100% or 89% RH at 30°. The dissolution rate of the amorphous form was higher than those of forms I and II. The amorphous form showed better tablet-forming properties than the crystalline form.
123 citations
TL;DR: It was found that nifedipine was absorbed, metabolized, and excreted rapidly, and that the main metabolite was M-I, which is a new major metabolite found in both dog and human urine.
Abstract: The urinary metabolites of nifedipine in a dog were isolated and identified by chromatographic and spectrometric techniques. A new major metabolite, 2, 6-dimethyl-4-(2-nitrophenyl)-5-methoxycarbonylpyridine-3-carboxylic acid (M-I), was found in both dog and human urine. A highly sensitive and specific method is described for the determination of nifedipine, M-I, and a previously reported metabolite. The method for analysis of nifedipine is based on the oxidation of nifedipine to its pyridine analog, benzene extraction, and determination by electron-capture gas chromatography. The method for analysis of the metabolites is based on ethyl acetate extraction of the acidified specimen, derivatization of M-I to its methyl ester, and determination by electron-capture gas chromatography. Quantitative determination was possible down to 5 ng/ml of nifedipine using 1 ml samples of biological specimens. This method was used to measure plasma levels of nifedipine and its metabolites in dogs, and urinary excretion by humans after oral administration of a nifedipine preparation. It was found that nifedipine was absorbed, metabolized, and excreted rapidly, and that the main metabolite was M-I.
104 citations
TL;DR: In this paper, two triterpene glycosides, momordicosides A and B, were isolated from the seeds of Momordica charantia L. (Cucurbitaceae).
Abstract: Two triterpene glycosides, momordicosides A and B, were isolated from the seeds of Momordica charantia L. (Cucurbitaceae). Their structures were determined on the basis of spectral and chemical evidence and by X-ray analysis as the 3-O-β-gentiobioside and 3-O-β-D-xylopyranosyl (1→4)-[β-D-glucopyranosyl(1→6)]-β-D-glucopyranoside, respectively, of cucurbit-5-ene-3β, 22(S), 23(R), 24(R), 25-pentaol.
90 citations
TL;DR: In this paper, the 13C-NMR spectra of 61 flavone derivatives were measured in dimethyl sulfoxide and the parameters (α and β values) and correction factor (ο value) necessary for calculating their carbon shifts were deduced.
Abstract: The 13C-NMR spectra of 61 flavone derivatives were measured in dimethyl sulfoxide. By consideration of the chemical shifts of skeletal carbons, the parameters (α and β values) and correction factor (ο value) necessary for calculating their carbon shifts were deduced. The skeletal carbons of polysubstituted flavones and flavonols could easily be assigned by the use of these values and SCS of OMe or OH. The 13C-NMR spectra were confirmed to give useful information that could not be obtained from other spectral data. The data were applied for the structure elucidation of unknown polysubstituted flavones.
90 citations
TL;DR: In this article, a systematic separation of a saponin fraction of the root of Bupleurum falcatum L. furnished seven new saponins, i.e., five monoacetylsaikosaponins (15-18, 20) and saikoshaponins-e (19) and -f (21), besides the known SAIKOSaponins -a, -b2, −b4, -c, and -d. The structures of these new SAIKO-saponins were determined by means of carbon-
Abstract: A systematic separation of a saponin fraction of the root of Bupleurum falcatum L. furnished seven new saponins, i.e., five monoacetylsaikosaponins (15-18, 20) and saikosaponins-e (19) and -f (21), besides the known saikosaponins-a, -b2, -b4, -c, and -d. α-Spinasteryl β-D-glucoside (22) was also isolated. The structures of these new saponins were determined by means of carbon-13 nuclear magnetic resonance spectroscopy.
89 citations
TL;DR: The results suggest that hederagenin and crude saponin, as well as the other agents used, show some degree of anti-inflammatory activity, especially in the case of Sapindus mukorossi GAERTN.
Abstract: The anti-inflammatory activities of hederagenin and crude saponin isolated from Sapindus mukorossi GAERTN were investigated utilizing carrageenin-induced edema, granuloma pouch and adjuvant arthritis in rats. The effects of these agents on vascular permeability and acetic acid-induced writhing in mice were also examined. In some experiments, the results were compared with those obtained with saikogenin A, crude platycodin, platycodigenin and oleanolic acid. Anti-inflammatory activity on carrageenin edema was observed with i. p. and p. o. administered crude saponin, while hederagenin and the other agents used showed activity only when administered i. p. Hederagenin, 100 and 200 mg/kg p. o. per day for 7 days, showed no significant inhibitory effect on granuloma and exudate formations in rats, while crude saponin, 100 and 200 mg/kg p. o., showed significant effects. Crude saponin, 200 mg/kg p. o. per day for 21 days, significantly inhibited the development of hind paw edema associated with adjuvant arthritis in rats, but hederagenin, 50-200 mg/kg p. o., did not. Crude saponin, 400 mg/kg p. o., inhibited the increase in vascular permeability and the number of writhings induced by acetic acid in mice. The results suggest that hederagenin and crude saponin, as well as the other agents used, show some degree of anti-inflammatory activity, especially in the case of saponin.
82 citations
TL;DR: Heterocyclic condensed 1, 8-naphthyridine derivatives exhibited the highest activities among these compounds against many gram-negative bacteria, including Ps.
Abstract: In order to search for compounds with higher activity than thiazolo [5, 4-b], imidazo-[4, 5-b] and triazolo [4, 5-b] [1, 8] naphthyridine derivatives against Ps. aeruginosa, we synthesized some heterocyclic condensed 1, 8-naphthyridine derivatives by using bifunctional 6, 7-disubstituted 1, 8-naphthyridine as a starting material. Thiadiazolo [5, 4-b] and oxazolo [5, 4-b] [1, 8] naphthyridine derivatives (3) and (5) were prepared by hydrolysis of the 6-amino-7-chloro-3-ester (1) with sodium hydroxide or sodium hydrosulfide, followed by cyclization with acetic anhydride or sodium nitrite. Pyrazolo [3, 4-b] and isothiazolo [5, 4-b] [1, 8] naphthyridine derivatives (12) and (14) were synthesized by ring cyclization of the 7-chloro-6-formyl-3-ester (10) with methyl hydrazine or ethanolic ammonia in the presence of sulfur, followed by hydrolysis. Thieno and furo [2, 3-b] [1, 8] naphthyridine derivatives (20) and (31) were prepared through a series of reaction steps, e.g. diazotization, reduction of the nitrile ester (7) or (24), ring cyclization by means of ethyl mercaptoacetate or ethyl bromomalonate, hydrolysis and decarboxylation. The compounds obtained were tested for antimicrobial activities in vitro. 8-Ethyl-5, 8-dihydro-5-oxothieno [2, 3-b] [1, 8] naphthyridine-6-carboxylic acid (20) exhibited the highest activities among these compounds against many gram-negative bacteria, including Ps. aeruginosa, and against gram-positive bacteria.
81 citations
TL;DR: Three triterpenoid prosapogenins tentatively named CP0 (I), CP2a (VI) and CP3a (VIII) have been isolated from the alkaline hydrolysate of the crude saponin obtained from the root of Clematis chinensis OSBECK as mentioned in this paper.
Abstract: Three triterpenoid prosapogenins tentatively named CP0 (I), CP2a (VI) and CP3a (VIII) have been isolated from the alkaline hydrolysate of the crude saponin obtained from the root of Clematis chinensis OSBECK. On the basis of chemical and physicochemical evidence, they were characterized as follows : I, hederagenin 23-O-α-L-arabinopyranoside ; VI, hederagenin 23-O-β-D-glucopyranoside ; VIII, olean-12-ene-28-oic acid-3β, 24-diol (4-epihederagenin) 3-O-α-L-rhamnopyranosyl-(1→2)-α-L-arabinopyranoside. I and VI are the first examples of 23-O-glycosides of oleanane-type triterpenes to be isolated from nature. Six less polar genuine saponins were isolated and they appeared to be identical with prosapogenins CP4, CP6, CP7, CP8, CP9 and CP10, 1, 4) on the basis of the results of high performance thin-layer chromatography (HPTLC).
66 citations
TL;DR: The seasonal variations of skin temperature, skin pH, evaporative water loss (EWL) and skin surface lipid values were determined in the forearm skin of 24 healthy Japanese adults at four different periods over one year and significant correlations were observed between skin temperature and EWL, total lipid and squalene values.
Abstract: The seasonal variations of skin temperature, skin pH, evaporative water loss (EWL) and skin surface lipid values were determined in the forearm skin of 24 healthy Japanese adults at four different periods over one year. The results provide new information on the changing systemic patterns of the four skin parameters. It was found that EWL, total lipid and squalene values in July were approximately 2-3 times those in January. On the other hand, the skin pH was significantly lower in July than in January, April or October. However, the extents of change of skin pH and cholesterol values were less than those of EWL, squalene and total lipid values on the basis of statistical analysis. Furthermore, significant correlations were observed between skin temperature and EWL, total lipid and squalene values. On the other hand, significant inverse correlations were found between skin pH and skin temperature and EWL values. On the basis of these results, the dependence of sebaceous lipids on skin temperature and the contribution of eccrine sweating to the skin pH are discussed.
TL;DR: In this paper, a combination system consisting of boron trifluoride etherate and dimethyl sulfide has been used for the selective removal of the benzyl protecting group in a molecule having a Michael acceptor or carbonyl group.
Abstract: A new combination system consisting of boron trifluoride etherate and dimethyl sulfide has proved to be useful especially for the selective removal of the benzyl protecting group in a molecule having a Michael acceptor or carbonyl group (s).
TL;DR: Since the traditional usage of an Oriental medicine "mao", consisting of Ephedra herbs, suggests that it may possess antiinflammatory activity, a crude drug preparation, the aerial part of E. intermedia, was subjected to bioassay for anti inflammatory activity and methanol extract was found to be active.
Abstract: Since the traditional usage of an Oriental medicine "mao", consisting of Ephedra herbs, suggests that it may possess antiinflammatory activity, a crude drug preparation, the aerial part of E. intermedia, was subjected to bioassay for antiinflammatory activity by two methods. The methanol extract was found to be active. The extract was fractionated in monitoring the antiinflammatory activity, resulting in the isolation of (+)-pseudoephedrine as the active principle. The antiinflammatory effects of ephedrine analogs were determined by four assay methods ; pseudoephedrine exhibited the strongest activity in the Whittle method, the carrageenin paw edema method in mice, and the fertile egg method.
TL;DR: The 13C NMR spectra of thirteen dibenzocyclooctadiene lignans, isolated from the iruits of Schizandra chinensis BAILL (Schizandraceae), were analyzed and their carbon shifts assigned Several important chemical shift trends are described as mentioned in this paper.
Abstract: The 13C NMR spectra of thirteen dibenzocyclooctadiene lignans, isolated from the iruits of Schizandra chinensis BAILL (Schizandraceae), were analyzed and their carbon shifts assigned Several important chemical shift trends are described
TL;DR: (+)- and (-)-2-(N-benzyl-N-methylamino)ethyl methyl 2, 6-dimethyl-4-(m-nitrophenyl)-1, 4-dihydropyridine-3, 5-dicarboxylate (6) (nicardipine) were synthesized from (-)- and (+)- 1-ethoxymethyl-5-methoxycarbonyl-2, 6
Abstract: (+)- and (-)-2-(N-benzyl-N-methylamino)ethyl methyl 2, 6-dimethyl-4-(m-nitrophenyl)-1, 4-dihydropyridine-3, 5-dicarboxylate (6) (nicardipine) were synthesized from (-)- and (+)- 1-ethoxymethyl-5-methoxycarbonyl-2, 6-dimethyl-4-(m-nitrophenyl)-1, 4-dihydropyridine-3-carboxylic acid (3), respectively. Resolution of 3 was carried out using cinchonidine and cinchonine as resolving agents. The vertebral vasodilating activity of (+)-YC-93 (the hydrochloride of (+)-(6)) was about 3 times that of (-)-YC-93.
TL;DR: A thioanisole-trifluoroacetic acid (TFA) system was found to deprotect Tyr (Bzl) quantitatively at 25°within 3 hr by a push-pull mechanism without O-to-C rearrangements.
Abstract: A thioanisole-trifluoroacetic acid (TFA) system was found to deprotect Tyr (Bzl) quantitatively at 25°within 3 hr by a push-pull mechanism without O-to-C rearrangements. This new deblocking system did not completely deprotect Ser (Bzl) and Thr (Bzl), but deprotected Lys (Z) quantitatively.
TL;DR: Various TRH analogs were synthesized and pharmacologically tested and γ-butyrolactone-γ-carbonyl-His-Pro-NH2 was found to have potent central nervous actions in antagonizing pentobarbital sleep and in potentiating apomorphine-induced circling in mice, and only nominal TSH-releasing activity in rats.
Abstract: Various TRH analogs, γ-butyrolactone-γ-carbonyl-His-Pro-NHR, γ-butyrolactone-γ-carbonyl-N3-im-methyl-His-Pro-NHR, 2-ketopiperidine-6-carbonyl-His-Pro-NHR and 3-oxoperhydro-1, 4-thiazine-5-carbonyl-His-Pro-NHR (R=H, methyl, ethyl, n-propyl, n-butyl, n-amyl, n-hexyl, β-phenethyl) were synthesized and pharmacologically tested in the hope of separating the central nervous action from endocrine activity. Among them, γ-butyrolactone-γ-carbonyl-His-Pro-NH2 was found to have potent central nervous actions in antagonizing pentobarbital sleep and in potentiating apomorphine-induced circling in mice, and only nominal TSH-releasing activity in rats.
TL;DR: In this article, two new diterpenes were isolated from the rhizomes of Alpinia speciosa K. SCHUM and their structures were established by the spectral evidences as I and II.
Abstract: Two new diterpenes were isolated from the rhizomes of Alpinia speciosa K. SCHUM. (Zingiberaceae) and their structures were established by the spectral evidences as I and II. The latter has an unusual bisnorlabdane carbon skeleton. It is the first example that diterpenes were obtained from Alpinia genus.
TL;DR: The structure of chloranthalactone C (III) was determined by X-ray crystallographic analysis of a crystal of III in conjunction with the negative Cotton effect in the optical rotatory dispersion curve and negative circular dichroism curve of the ketoalcohol (XII) prepared from III.
Abstract: Six sesquiterpene lactones (I-VI) were isolated and characterized as constituents of Chloranthus japonicus (Chloranthaceae). The lactones chloranthalactone A-E (I-V) were found to be lindenane derivatives, and the lactone VI was identified as atractylenolide III. The structure of chloranthalactone C (III) was determined by X-ray crystallographic analysis of a crystal of III in conjunction with the negative Cotton effect in the optical rotatory dispersion (ORD) curve and negative circular dichroism curve of the ketoalcohol (XII) prepared from III. The stereostructures of chloranthalactone A and B (I and II) were deduced from the ORD curves of the degradation products (VII and X). The cytotoxicities of these lactones against mouse lymphosarcoma L-5178Y cells were determined in comparison with that of helenalin, and they were found to show moderate cytotoxic effects.
TL;DR: Two new indolic metabolites, fumitremorgin A and B, were isolated from the fungus Aspergillus fumigatus, and caused severe tremor and convulsion in experimental animals.
Abstract: Two new indolic metabolites, fumitremorgin A and B, were isolated from the fungus Aspergillus fumigatus. These two metabolites caused severe tremor and convulsion in experimental animals. The structure of fumitremorgin A, including the stereochemistry, was determined to be 1 mainly on the basis of the spectral data for the compound and some derivatives obtained from it. The stereochemical factors affecting the appearance of tremorogenic activity in fumitremorgin A and related compounds are discussed.
TL;DR: In this article, a new flavone derivative, containing condensed dihydrochalcone partial structure named kuwanon G, was isolated from the root barks of the cultivated mulberry tree (a variety of Morus alba L.).
Abstract: A new flavone derivative, containing condensed dihydrochalcone partial structure named kuwanon G, was isolated from the root barks of the cultivated mulberry tree (a variety of Morus alba L.). The structure was shown to be 1 on the basis of chemical and spectral data. The compound (1) to rabbit (1 mg/kg, i.v.) produced a significant hypotension.
TL;DR: A series of aryl-or aralky-substituted 2-amino-3, 4-dihydroquinazolines and related compounds were synthesized and showed inhibitory activity towards collagen-and ADP-induced aggregation of rat blood platelet in vitro and ex vivo.
Abstract: A series of aryl-or aralky-substituted 2-amino-3, 4-dihydroquinazolines and related compounds were synthesized. The compounds were evaluated for inhibitory activity towards collagen-and ADP-induced aggregation of rat blood platelet in vitro and ex vivo. A group of 3-benzyl-substituted derivatives had potent activity. The structure-activity relationships are discussed.
TL;DR: A representative mucilage, named Okra-mucilage F, has been isolated from the immature fruits of Abelmoschus esculentus MOENCH as discussed by the authors, and its molecular weight was estimated to be about 1700000.
Abstract: A representative mucilage, named Okra-mucilage F, has been isolated from the immature fruits of Abelmoschus esculentus MOENCH (=Hibiscus esculentus L. ; Okra). The final preparation was homogeneous as determined by ultracentrifugal analysis, cellulose acetate membrane electrophoresis, and gel chromatography. Its water solution gave an intrinsic viscosity value of 30.1. It was composed of partially acetylated acidic polysaccharide and protein in a ratio of approximately 8.1 : 1.0, and its molecular weight was estimated to be about 1700000. Analysis of component sugars, together with reduction and methylation, and partial degradation studies showed that the polysaccharide moiety in the mucilage possesses a main chain having the repeation structure (1→4)-O-α-(D-galactopyranosyluronic acid)-(1→2)-O-α-L-rhamnopyranose, and that half the L-rhamnose residues in the main chain have branches composed of 4-O-β-D-galactopyranosyl D-galactopyranose at position 4.
TL;DR: After oral administration of fluorescein to rabbits and human subjects, the urinary metabolites were examined and two new metabolites, fluorescin and fluorescencein monoglucuronide, were identified in addition to the main metabolite.
Abstract: After oral administration of fluorescein to rabbits and human subjects, the urinary metabolites were examined. Two new metabolites, fluorescin and fluorescin monoglucuronide, were identified in addition to the main metabolite, fluorescein monoglucuronide. In both conjugates, glucuronic acid was found to be linked to a phenolic OH group iva an ether bond.
TL;DR: In this article, a cycloaddition of primary aliphatic nitro compounds with acid chlorides in N, N-dimethylacetamide led to the formation of nitrile oxides, which cyclized in situ with olefinic dipolarophiles in a 1, 3-dipolar cycloadding mode to afford 2-isoxazoline derivatives.
Abstract: O-Acylation of primary aliphatic nitro compounds with acid chlorides in N, N-dimethylacetamide led to the formation of nitrile oxides, which cyclized in situ with olefinic dipolarophiles in a 1, 3-dipolar cycloaddition mode to afford 2-isoxazoline derivatives. Optimum reaction conditions were investigated, and the use of several types of dipolarophiles, such as acetylenes, Schiff bases, aromatic nitriles, and ketones, in this cycloaddition resulted in the formation of the corresponding cycloadducts, namely isoxazoles, 1, 2, 4-oxadiazolines, 1, 2, 4-oxadiazoles, and 1, 4, 2-dioxazoles, respectively, in reasonable yields.
TL;DR: Compounds 4a, 11a and 12a and their β-carboxypropionyl and ο-phthaloyl esters were studied pharmacologically, and showed antiulcerogenic, antiallergic and antiinflammatory activities.
Abstract: 18β-Olean-12-ene-3β, 30-diol (deoxoglycyrrhetol) (4a) was prepared with a view to eliminating pseudoaldosteronism, a side-effect of glycyrrhetinic acid (1b), which is the sapogenin of Licorice saponin, glycyrrhizin (1a), while maintaining or enhancing the therapeutic activities.On reduction of the 11-keto and 30-carboxyl groups of 1b with NaAlH2- (OCH2CH2OCH3) 2, olean-12-ene-3β, 11β, 30-triol (9) and olean-12-ene-3β, 11α, 30-triol (10) were obtained. On catalytic hydrogenation of 9 and 10 with Pd-C as a catalyst, 4a was formed in an overall yield of 80%. On treatment with conc. HCl, 9 yielded 18β-olean-9 (11), 12-diene-3β, 30-diol (11a), while 10 yielded olean-11, 13 (18) -diene-3β, 30-diol (12a). Mono-and di-β-carboxy-propionyl and mono-and di-ο-pbthaloyl esters of 4a, lla and 12a were prepared to increase the hydrophilic character.The competitive inhibition of 5β, Δ4-reductase of corticosteroids in the liver which is caused by lb to induce pseudoaldosteronism was not observed in the case of 4a. Compounds 4a, 11a and 12a and their β-carboxypropionyl and ο-phthaloyl esters were studied pharmacologically, and showed antiulcerogenic, antiallergic and antiinflammatory activities.
TL;DR: In this article, the hydrogen donating capabilities of antioxidants, such as butylated hydroryanisole (BHA), BHT, dl-α-tocopherol (Toc), sesamol and ethyl protocatechuic acid (EP), were investigated.
Abstract: The hydrogen donating capabilities of antioxidants, such as butylated hydroryanisole (BHA), butylated hydroxytoluene (BHT), dl-α-tocopherol (Toc), sesamol and ethyl protocatechuic acid (EP), to a stable free radical, 2, 2-diphenyl-1-picrylhydrazyl (DPPH), were investigated. Toc, sesamol and EP donated two hydrogen atoms, BHA donated 0.75-1.2 hydrogen atoms, and BHT donated much less hydrogen. A synergistic effect on hydrogen donation to DPPH was observed with the combinations of Toc+BHT and BHA+BHT. The synergistic effect observed in the reaction between BHA+BHT and DPPH might arise from the regeneration of BHA from its oxidized intermediate, with the loss of BHT.