Showing papers in "Chemical & Pharmaceutical Bulletin in 1977"
TL;DR: Shikonin, a naphthoquinone contained in the root of Lithospermum officinalis var.
Abstract: Shikonin, a naphthoquinone contained in the root of Lithospermum officinalis var. erythrorhizon MAX. and Macrotomia euchroma (ROYLE) PAULS (Boraginaceae), showed a high antitumor activity against the ascites cells of Sarcoma 180. Shikonin completely inhibited the tumor growth at a dose of 5-10 (mg/kg/day). At a higher dose (>15 mg/kg/day) shikonin showed'toxicity, whereas at a lower dose (1 mg/kg/day) it was inactive. Four shikonin derivatives and the chromatographic fractions of the plant extracts were also tested and they showed similar antitumor activities against S-180.
148 citations
TL;DR: In this article, the surface area of ground and intact M.C. was measured by adsorption methods of nitrogen gas and water vapor for both ground and ground samples, and the linear relationship between specific surface area by water vapor adsorptions and heat of wetting in water was obtained for ground samples.
Abstract: Microcrystalline cellulose (M.C.C.) having various ratios of crystal region to amorphous one obtained by grinding. Crystallinity was determined for M.C.C. and ground M.C.C. by X ray diffraction method (powder method) using Hermans'theory. Crystallinity was also determined by infrared measurement in converting hydroxyl groups into deuteroxyl groups in amorphous region of M.C.C. Crystallinities by both methods showed linear relationship for the samples. Specific surface area was measured by adsorption methods of nitrogen gas and water vapor for M.C.C. and ground samples. The same value of 1 m2/g was given by nitrogen gas adsorption for M.C.C. and ground samples. In water vapor adsorption ground samples increased in surface area with grinding time from 150 m2/g of intact M.C.C. to 360 m2/g of 32 hr ground M.C.C. This is due to the conversion of crystal into amorphous state by mechanical force. The linear relationships between specific surface area by water vapor adsorption and heat of wetting in water was obtained for ground samples. Porosity in compression and hardness of tablet was measured for ground samples. It was found that intact M.C.C. showed larger porosity in compression and higher tablet hardness than ground M.C.C.
124 citations
TL;DR: In this paper, the authors isolated three new sweet glycosides, named rebaudioside-C, -D, and -E, from leaves of Stevia rebaudiana BERTONI (Compositae).
Abstract: From leaves of Stevia rebaudiana BERTONI (Compositae), there were isolated three new sweet glycosides, named rebaudioside-C, -D, and -E. Application of 13C NMR spectroscopy as well as chemical evidences led to assign the structure V in Chart 1 to rebaudioside-C.
84 citations
TL;DR: The L-antipodes of N α-benzoyl and Nα-carbobenzoxy derivatives were shown to be the useful fluorogenic substrates for the sensitive determinations of trypsin and papain.
Abstract: L-Arginine-4-methylcoumaryl-7-amide 2 and its derivatives, which contain 7-amino-4-methylcoumarin 1 as a key fluorescence amine, were synthesized. The L-antipodes of Nα-benzoyl and Nα-carbobenzoxy derivatives were shown to be the useful fluorogenic substrates for the sensitive determinations of trypsin and papain.
65 citations
63 citations
TL;DR: 7-L-leucyl-4-methyl-coumarinylamide (hydrochloride) was prepared and shown to be a useful fluorogenic substrate for the assay of aminopeptidase.
Abstract: 7-Amino-4-methylcoumarin (2) was proposed as a candidate key fluorogenic amine. Thus 7-L-leucyl-4-methyl-coumarinylamide (hydrochloride) (1) was prepared and shown to be a useful fluorogenic substrate for the assay of aminopeptidase.
62 citations
58 citations
TL;DR: In this paper, the structure of rebaudiosides-D (4) and -E (5) was determined from 13C NMR evidences as well as the results of chemical and enzymatic hydrolysis.
Abstract: From the leaves of Stevia rebaudiana BERTONI, additional two sweet glucosides, named rebaudiosides-D (4) and -E (5) were isolated. On the basis of 13C NMR evidences as well as the results of chemical and enzymatic hydrolysis, the structures of 4 and 5 were assigned to be β-sophorosyl ester of steviol-13-O-[β-D-glucopyranosyl (1-2)] [β-D-glucopyranosyl-(1-3)]-β-D-glucopyranoside and β-sophorosyl ester of steviol-13-O-β-sophoroside, respectively. In connection with the structure determination, β-sophorosyl ester of ent-kaur-16-en-19-oic acid was prepared and the 13C chemical shift and the coupling constant of its ester anomeric carbon were discussed. The formulation of 4 and 5 was finally substantiated by their preparation from the known compounds.
56 citations
TL;DR: The isolation and characterization of the cardiotonic steroid constituents in the skin of the Japanese toad, Bufo vulgaris formosus BOULENGER, has been carried out and three new types of bufotoxins in which the succinoysl, adipoyl, and pimeloyl groups are displaced for the suberoyl residue of the so-called"bufotoxin, "were separated and identified.
Abstract: The isolation and characterization of the cardiotonic steroid constituents in the skin of the Japanese toad, Bufo vulgaris formosus BOULENGER, has been carried out. Three new types of bufotoxins in which the succinoyl, adipoyl, and pimeloyl groups are displaced for the suberoyl residue of the so-called"bufotoxin, "were separated and identified. In addition, the occurrence of bufogenin 3-sulfates and analogous conjugates of cardenolide named cardenobufotoxin was also demonstrated. The ethanolic extract of the skin obtained from 1800 toads was separated by chromatography on Amberlite XAD-2 resin, silica gel, and Sephadex LH-20, followed by highperformance liquid chromatography to provide new cardiotonic steroid conjugates. The structures of these substances were elucidated to be resibufogenin 3-succinoylarginine ester (Id), gamabufotalitoxin homologs (IIg, IIk, IIn, IIp), bufalitoxin homologs (IIIc, IIIe, IIIg, IIIi), cinobufotoxin homologs (IVc, IVe, IVg, IVl), arenobufotoxin (Vd), cinobufotalitoxin (VIb), cardenobufotoxins (VIIId, VIIIf), bufogenin 3-sulfates (IIq, IIIj, Ve, VIId), and sarmentogenin 3-sulfate (VIIIg) by degradative and synthetic means.
55 citations
TL;DR: From leaves of Panax japonicus C.A. MEYYR, ginsenoside-F17 and three new dammarane type saponins named chikusetsusaponins-L5 (I), -L10 (II) and -L9a (III) were isolated as mentioned in this paper.
Abstract: From leaves of Panax japonicus C.A. MEYYR, ginsenoside-F17) and three new dammarane type saponins named chikusetsusaponins-L5 (I), -L10 (II) and -L9a (III) were isolated. The structures of I, II and III were elucidated mainly by mass, 13C-nuclear magnetic resonance and 1H-nuclear magnetic resonance spectroscopy including partially relaxed Fourier transform method.
51 citations
TL;DR: Remarkable enhanced absorption of heparin was found by the administration of monoolein-bile salts mixed micelles solution in the small intestine and the large intestine of rats, suggesting that monoo Klein mixed micella was greatly useful as a safe adjuvant to potentiate absorption ofHeparin.
Abstract: Remarkable enhanced absorption of heparin was found by the administration of monoolein-bile salts mixed micelles solution in the small intestine and the large intestine of rats This result suggested that monoolein mixed micelles was greatly useful as a safe adjuvant to potentiate absorption of heparin
TL;DR: In this paper, two naphthalene glycosides, I, mp 150-152°, [α] D-119.0°, C22H24O12·3 1/2H2O were isolated together with 6-hydroxymusizin 8-O-β-D-glucopyranoside which was found to be identical with the one isolated from aphid Aphis nerii.
Abstract: From the Japanese rhubarb, "Shinshu Daio, " two new naphthalene glycosides, I, mp 150-152°, [α] D-119.0°, C20H24O9·H2O and II, [α] D-102.0°, C22H24O12·3 1/2H2O were isolated together with 6-hydroxymusizin 8-O-β-D-glucopyranoside which was found to be identical with the one isolated from aphid, Aphis nerii. By the chemical and spectral evidences, the structures of I and II were characterized to be torachrysone 8-O-β-D-glucopyranoside and torachrysone 8-O-β-D-(6'-O-oxalyl)-glucopyranoside, respectively.
TL;DR: The effects of sodium dipropylacetate on the metabolisms of γ-aminobutyric acid (GABA) and biogenic amines in the rat brain have been investigated and the mechanism of anticonvulsant activity of DPA is suggestive.
Abstract: The effects of sodium dipropylacetate (DPA) on the metabolisms of γ-aminobutyric acid (GABA) and biogenic amines in the rat brain have been investigated. The results obtained are as follows, which are suggestive of the mechanism of anticonvulsant activity of DPA. 1) The level of GABA in the brain was elevated after oral administration (400 mg/kg). At the peak time (0.5 hr), about 45% increase was observed and the elevation of GABA content wsa maintained for 4 hr after administration. 2) In the brain slices, DPA elevated GABA content and suppressed the oxygen consumption at 6 mM. 3) DPA had weak inhibitory effects on GABA metabolizing enzymes in brain homogenate. 4) The concentrations of 5-hydroxyindoleacetic acid and tryptophan in the brain were elevated after oral administration of DPA (400 mg/kg). These effects might be caused by the increase of free tryptophan in the serum followed by accelerated incorporation of tryptophan into the brain and the elevated turnover rate of 5-hydroxytryptamine in the brain. 5) DPA elevated the content of dopamine, but the level of norepinephrine was not affected. The changes of thess biogenic substances were coincident with the appearance of the anticanvulsant activity of DPA.
TL;DR: In this paper, the half-life times of a series of maleimide derivatives including the practical fluorescent thiol reagents such as N-[p-(2-benzimidazolyl) phenyl] maleimides, N-(1-anilinonaphthyl-4)-maleimide and N-(7-dimethylamino-4-methyl-3-coumarinyl)maleimides were compared and their stabilities in aqueons media were discussed.
Abstract: p-Substituted phenylmaleimides were synthesized and their hydrolytic rates were measured by dual-wavelength method. Hammett plot for the hydrolysis of p-substituted phenylmaleimide yields a straight line of p=0.35 with relative coefficiency r=0.99. The half-life times of a series of maleimide derivatives including the practical fluorescent thiol reagents such as N-[p-(2-benzimidazolyl) phenyl] maleimide, N-(1-anilinonaphthyl-4)-maleimide and N-(7-dimethylamino-4-methyl-3-coumarinyl) maleimide were compared and their stabilities in aqueons media were discussed.
TL;DR: These new cephalosporins exhibited excellent activities against a wide variety of bacteria including those which are resistant to β-lactamase susceptible cep Halosporin currently available.
Abstract: Syn-and anti-isomers of 7-[2-(2-aminothiazol-4-yl)-2-methoxyiminoacetamido]-cephalosporins were synthesized selectively. These new cephalosporins exhibited excellent activities against a wide variety of bacteria including those which are resistant to β-lactamase susceptible cephalosporins currently available. The syn-isomers showed higher activities than the anti-isomers.
TL;DR: This is the first example of the isolation of propyl cannabinoid acid from Cannabis, and these structures were elucidated on the basis of chemical and spectral data.
Abstract: Four new cannabinoid acids, tetrahydrocannabivarinic acid, cannabidivarinic acid, cannabichromevarinic acid and cannabigerovarinic acid were isolated from Thai Cannabis, 'Meao variant'and these structures were elucidated on the basis of chemical and spectral data. This is the first example of the isolation of propyl cannabinoid acid from Cannabis.
TL;DR: The main tannin of Geranium thunbergii has been isolated as yellow crystals, and named geraniin this paper, which is shown by the proton nuclear magnetic resonance spectra to be a corilagin derivative esterified at O-2 and O-4 of D-glucopyranose in the molecule.
Abstract: The main tannin of Geranium thunbergii has been isolated as yellow crystals, and named geraniin. Geraniin gave upon hydrolysis in boiling water, gallic acid, hexahydroxydiphenic acid, ellagic acid, and corilagin, and is shown by the proton nuclear magnetic resonance spectra to be a corilagin derivative esterified at O-2 and O-4 of D-glucopyranose in the molecule. Upon condensation with o-phenylenediamine, geraniin yielded a phenazine derivative, named phenazine A (X), which was transformed into phenazine B (XI) upon prolonged reaction. These two phenazine derivatives gave phenazine C (XII) by further prolonged reaction, or by hydrolysis of X or XI in boiling water. Corilagin was also isolated from the hydrolysis products mixture. The structure of phenazine C was proved by identification of its hydrolyzed product XV with synthetic specimen which was prepared via hydrogenolysis of dimethyl dimethoxytetrabenzyloxydiphenoate. These data along with the PMR spectra show that the structure of geraniin to be I. The carbon nuclear magnetic resonance spectra of geraniin indicate partial hydration to form geminal diol at the cyclohexenetrione moiety.
TL;DR: In this article, an efficient synthesis of 2, 2-dimethylchromenes was developed to pursue chemical structure-biological activity studies of insect antijuvenile hormones.
Abstract: An efficient synthesis of 2, 2-dimethylchromenes was developed to pursue chemical structure-biological activity studies of insect antijuvenile hormones. The combination of Michael condensation and cyclodehydration with polyphosphoric acid gave nearly quantitative yields of alkoxy 2, 2-dimethylchromanones which were reduced and dehydrated in one flask, to yield the respective 2, 2-dimethylchromenes. By these methods several AJH analogs were prepared which possessed greater biological activity than the natural precocenes.
TL;DR: 2'-protected nucleosides, partially protected trinucleoside diphosphates, CpA (o-nitrobenzyl)-pA and CpCpA are candidates as suitable substrates of ribonucleic acid (RNA) ligase.
Abstract: Previously 2'-O-(o-nitrobenzyl) uridine was synthesized via 2', 3'-O-(stannylene) uridine and used in the synthesis of UpA and UpU. 2'-O-(o-Nitrobenzyl) derivatives of cytidine and adenosine were synthesized with o-nitrobenzyl bromide in the presence of sodium hydride. 3'-O-(o-Nitrobenzyl) cytidine was also isolated. Using these 2'-protected nucleosides, partially protected trinucleoside diphosphates, CpA (o-nitrobenzyl)-pA and CpCpA (o-nitrobenzyl) were synthesized using a diester method or a triester method. These oligomers are candidates as suitable substrates of ribonucleic acid (RNA) ligase. Removal of the o-nitrobenzyl group was effected by irradiation with ultraviolet spectrum (UV) light (wavelength longer than 280 nm) and the completely deblocked oligonucleotides were characterized by enzymatic hydrolysis.
TL;DR: The occurrences of the stilbene glycosides (I, II) and III in commercial Chinese rhubarbs were examined by thin-layer chromatography, which revealed that almost all kinds of rhubarb contained II and III while I appeared in the limited ones.
Abstract: A new stilbene glycoside (I), mp 258°, [α] D-86.0°, C27H26O12·1/2H2O, together with 3, 5, 4'-trihydroxystilbene 4'-O-β-D-glucopyranoside (II) and d-catechin (III), was isolated from the Japanese rhubarb, "Shinshu Daio", and the structure of I was established to be 3, 5, 4'-trihydroxystilbene 4'-O-β-D-(6''-O-galloyl)-glucopyranoside on the bases of chemical and spectral evidence. The occurrences of the stilbene glycosides (I, II) and III in commercial Chinese rhubarbs were examined by thin-layer chromatography, which revealed that almost all kinds of rhubarbs contained II and III while I appeared in the limited ones.
TL;DR: From these results, it is concluded Co-BLM to be superior as a tumor scanning agent than BLM and other BLM metal chelates.
Abstract: Cobalt chelate of bleomycin (Co-BLM) was inert to ligand exchange reaction and showed absorption at 450 nm and 580 nm, which indicated cobalt is trivalent. Co-BLM was accumulated in tumor tissue much more than BLM and other BLM metal chelates. In urine of 67Ga-BLM or 111In-BLM injected mice, most of radioactivity was not bound to BLM. On the other hand, all the radioactivity was attributable to BLM bound 57Co in urine of 57Co-BLM injected mice. In tumor tissue homogenate, most of Co-BLM was present in cell nuclei, while BLM, CoCl2 and other BLM metal chelates distributed mainly in supernatant fractions. Co-BLM may bind to deoxyribonucleic acid (DNA) in tumor cell. From these results, we conclude Co-BLM to be superior as a tumor scanning agent than BLM and other BLM metal chelates.
TL;DR: In this article, a water-soluble polysaccharide from ascocarps of Cordyceps sinensis was purified by ethanol fractionation and gel filtration, and the results of periodate oxidation, Smith-type degradation, methylation analysis, partial acid hydrolysis, and 13C-NMR spectrometry were concluded that CS-I is a highly branched galactomannan.
Abstract: Water-soluble polysaccharide from ascocarps of Cordyceps sinensis was purified by ethanol fractionation and gel filtration. Purified polysaccharide, CS-I, [α] D-45.3°(c=1, H2O), gave D-galactose (phenylosazone, mp 185-187°) and D-mannose (phenyl-hydrazone, mp 199-200°) in a molar ratio of 1 : 1 by acid hydrolysis. From the results of periodate oxidation, Smith-type degradation, methylation analysis, partial acid hydrolysis, and 13C-NMR spectrometry, it is concluded that CS-I is a highly branched galactomannan which consists of mannan core and galactosyl oligomer containing branches. The mannan core mainly contains (1→2)-α-linked-D-mannopyranosyl residues, and the branches contain (1→3), (1→5), and (1→6)-linked-D-galactofuranosyl, (1→4)-linked-D-galactopyranosyl residues. The non-reducing ends are D-galactofuranose and D-manno-pyranose, and the branching points are D-mannopyranosyl residues.
TL;DR: A new chalcone, xanthoangelol was isolated from the roots of Angelica keiskei KOIDZUMI (Umbelliferae), and was elucidated as 2', 4', 4, 4-trihydroxy-3'-[(E)-3, 7-dimethyl-2, 6-octadienyl] chalecone.
Abstract: A new chalcone, xanthoangelol was isolated from the roots of Angelica keiskei KOIDZUMI (Umbelliferae), and was elucidated as 2', 4', 4-trihydroxy-3'-[(E)-3, 7-dimethyl-2, 6-octadienyl] chalcone.
TL;DR: In this article, the improvement of the transglycosylation from acylated pyrimidine nucleoside to purines was studied, where trimethylsilyl derivatives of exo-N-acyl purines were used as a glycosyl acceptor and trifluoromethanesulfonate as a catalyst.
Abstract: Transglycosylation from acylated pyrimidine nucleoside to purines was originally developed by Miyaki, et al. To apply this method to the naturally occurring pyrimidine nucleosides having a labile sugar moiety, we studied the improvement of this reaction. As model compounds, tri-O-acetyl-3-benzoyluridine (1) and tetraacetylcytidine (2) were employed. Reaction conditions and yields were greatly improved by utilizing (1) trimethylsilyl derivatives of exo-N-acylpurines as a glycosyl acceptor, (2) trimethylsilyl trifluoromethanesulfonate as a catalyst in acetonitrile-dichloroethane. Because of the mild reaction conditions and high yield, this procedure may be regarded as a versatile method for transglycosylation, which was shown by the successful preparation of purine analogs of the polyoxin and octosyl acid nucleosides having labile amino-or anhydrosugar uronic acid.
TL;DR: In this paper, the structure of aloesaponol I and -IV was established to be 1oxo-4 (S, equatorial), 8, 9-trihydroxy-6-methyl-1, 2, 3, 4-tetrahydroanthracene and 1-oxo4 (quasi-equatorial) on the basis of chemical and spectral evidences.
Abstract: Phenolic constituents of young subterranean stems of Aloe saponaria HAW. were investigated to give aloesaponol III, -IV, chrysophanol, helminthosporin and 1, 4, 8-trihydroxy-2-methoxy-6-methyl-anthraquinone (isoxanthorin). The structures of aloesaponol III and -IV were established to be 1-oxo-4 (S, equatorial), 8, 9-trihydroxy-6-methyl-1, 2, 3, 4-tetrahydroanthracene and 1-oxo-4 (quasi-equatorial), 8, 9-trihydroxy-2-methoxy (equatorial)-6-methyl-1, 2, 3, 4-tetrahydroanthracene on the basis of chemical and spectral evidences. The application of the extended benzoate chirality rule was attempted to determine the absolute configuration of hydroxyl group in aloesaponol I and -III.
TL;DR: The first biogenetic-type asymmetric synthesis of natural (+)-maritidine from L-tyrosine is described in this paper, where an asymmetric cyclization of dienone was found highly selectively to give one diastereomer preferentially.
Abstract: A first biogenetic-type asymmetric synthesis of natural (+)-maritidine from L-tyrosine is described. Phenolic oxidative coupline of monophenol (10b) with thallium (III) trifluoroacetate afforded the corresponding spiro dienone (11b) in 66.5% yield. Asymmetric cyclization of dienone (14) was found to occur highly selectively to give one diastereomer (15) preferentially. Removal of the carboxamide group in 15 was effected by reductive decyanization of the intermediate amino nitrile (18) by sodium in liquid ammonia to (+)-epimaritidine (19), which was epimerized to the objective (+)-maritidine by the known method.
TL;DR: In this article, the four stereoisomers of 20, 22-dihydroxycholesterol 9, 10, 17 and 19 were synthesized from pregnenolone using a Grignard reaction on the [20S]-20-formyl-carbinol.
Abstract: The four stereoisomers of 20, 22-dihydroxycholesterol 9, 10, 17 and 19 were synthesized from pregnenolone. Vinylation of the 3, 5-cyclo derivative 1 of pregnenolone gave the [20S]-carbinol 2, which was then oxidized with m-chloroperbenzoic acid to afford the [22S]-22, 23-epoxide 3 and its [22R]-isomer 4 (7 : 2). Reaction of 3 and 4 with i-Bu2CuLi followed by acid treatment yielded 20R, 22S-dihydroxycholesterol 9 and its 20R, 22R-isomer 10, respectively. The latter triol 10 was more effectively prepared by a Grignard reaction on the [20S]-20-formyl-carbinol 14, which was derived from pregnenolone THP ether 12, through the 1, 3-dithiane derivative 13. Oxidation of 20-dehydrocholesterol acetate 16 with OsO4 gave stereoselectively the 20S, 22S-glycol 17 (R=Ac). Treatment 17 (R=Ac) with N-chlorosuccinimide-dimethylsulfide followed by reduction with LiAlH4 afforded 20S, 22R-dihydroxycholesterol 19 together with the 20S, 22S-isomer 17 (R=H) (3 : 2). Acid-catalyzed epoxide opening reactions of 20, 22-epoxycholesterols were also discussed.