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MASAJI KOSHIOKA, YOSHIO TAKINO
1978 Volume 26 Issue 5 Pages
1343-1347
Published: May 25, 1978
Released on J-STAGE: March 31, 2008
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A method of the quantitative estimation of anthraquinones in Ketsumeishi was established and the change of anthraquinone contents in the seeds of Cassia obtusifolia L. and C. tora L. with various grade of maturity and ageing was studied. Also, the quantitative estimations of anthraquinones in Ketsumeishi samples obtained from various places were made. The absorbance of the alkaline extract after treatment with 5% sodium hydroxide solution containing 2% ammonia was measured at 520 nm, using 1, 8-dihydroxyanthraquinone as a standard. The optimum time for measurement was between 60 and 180 min after the completion of alkaline extraction and the optimum time for hydrolysis was 75 min. The recovery rate in the standard addition test was 97.0%. In the progress of maturity of the seed, the amount of free anthraquinones decreased and the amount of bound anthraquinones increased gradually, although the total amount was constant. The contents of both free and bound anthraquinones of fresh seeds were lower than those of the seeds preserved for 1 to 9 years. In Ketsumeishi samples, the contents of free anthraquinones were 0.01-0.04%, those of bound anthraquinones 1.01-1.29%, and the total contents varied from 1.04 to 1.31%. It was suggested that the crude drugs obtained from different places might be classified into two groups according to the contents of anthraquinones.
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HIROMU SAKURAI, SHIGERU SHIMOMURA, KENJI FUKUZAWA, KAZUHIKO ISHIZU
1978 Volume 26 Issue 5 Pages
1348-1352
Published: May 25, 1978
Released on J-STAGE: March 31, 2008
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The model system consisting of α-mercaptopropionylglycine (α-MPG), hemin and pyridine exhibited similar absorption and electron paramagnetic resonance spectra to cytochrome P-450. In the presence of an excess amount of pyridine, a low-spin state of heme iron was observed at both 293 and 77°K. A transition of the high-spin state of Fe (III) at 293°K to the low-spin state was detected at 77°K in the presence of trace amount of pyridine. When pyridine was omitted from the system, the high-spin state was produced. Under exposure of CO of this model system, the characteristic absorption band of 450 nm was observed, which is typical with cytochrome P-450. Two types of spectral change were obtained when aminopyrine (type I) or aniline (type II) was added to α-MPG-hemin. Spectral dissociation constant K
s of aniline with model system was compared with the reported value with a biological system. It was also discussed that the hydroxylating ability with model and liver microsomal systems.
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HARUHISA UEDA, TSUNEJI NAGAI
1978 Volume 26 Issue 5 Pages
1353-1356
Published: May 25, 1978
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The adsorption of sulphonylureas by carbon black from aqueous solution was investigated in detail regarding the hydrophobic interaction. The adsorption isotherms obtained were well described with Langmuir equation. The adsorbed amount decreased with the increase in pH of buffer solution between 6 and 9, showing that pH had influence on the hydrophobic and hydrophilic balance of the molecule. The adsorbed amount increased with the increase in concentration of buffer solution at pH 7.0, showing that the concentration of buffer solution had influence on water molecules of carbon black surface. The decrease in adsorbed amount with addition of urea demonstrated that the adsorption of sulphonylureas proceeded on the hydrophobic interaction. The adsorbed amount of sulphonylureas by carbon black decreased with temperature, showing the entropy change of adsorption of sulphonylureas by carbon black from aqueous solution was apparently positive.
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YASUFUMI SAWADA, MASAHIRO HAYASHI, SHOJI AWAZU, MANABU HANANO
1978 Volume 26 Issue 5 Pages
1357-1363
Published: May 25, 1978
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The in vivo and in vitro fates of 8-hydroxyquinoline (8-OH), 5-chloro-8-hydroxyquinoline (MC), 5, 7-dichloro-8-hydroxyquinoline (DC), and 5-chloro-8-hydroxy-7-iodoquinoline (CF) in rat was studied. The results obtained were as follows. (1) These compounds were metabolized to glucuronides and sulfates after intravenous administration. Glucuronides were excreted in bile and urine, but sulfates were excreted exclusively in urine. Unmetabolized forms were almost not excreted. (2) Glucuronides were more excreted in bile as the molecular weights increased by halogen substituents. And glucuronides having the higher affinities to plasma protein and 15% liver 100000 g supernatant fraction were more excreted in bile. (3) Although sulfates were well hydrolyzed as glucuronides in the body, sulfates (especially, CF sulfate) resisted enzymatic hydrolysis in vitro by mitochondria-lysosomal and microsomal enzymes in both liver and kidney in contrast to susceptibilities of glucuronides to them. (4) The conjugates were hydrolyzed by Cu
2+, Fe
3+, Zn
2+, and Mg
2+. Especially in the presence of Cu
2+ or Fe
3+, DC sulfate and CF sulfate which were extremely stable in thh enzymatic hydrolysis were unstable. Accordingly, the effects of the metal ions as well as the hydrolytic enzymes were suggested for the hydrolysis of the conjugates in the body.
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SHIGEKO OZAKI, MASAICHIRO MASUI
1978 Volume 26 Issue 5 Pages
1364-1369
Published: May 25, 1978
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The anodic oxidation of p-substituted phenylhydroxylamines (p-X-PHA's) was studied in acetonitrile. These p-X-PHA's generally showed three or four oxidation waves at a glassy-carbon electrode. On electrolyses, p-X-PHA's except for X=H gave the corresponding nitroso compounds (p-X-NB's) and azoxybenzenes (pp'-X-AB's), while p-X-PHA (X=H) gave only nitrosobenzene. A reaction mechanism that pp'-X-AB's are formed not only by the condensation of the corresponding p-X-NB's and p-X-PHA'S, but by the reaction of p-X-PHA cation radicals with p-X-PHA's or by the coupling of two phenyl nitroxides is proposed.
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KAORI TAKIKAWA, MASAHIRO NAKANO, TAKAICHI ARITA
1978 Volume 26 Issue 5 Pages
1370-1374
Published: May 25, 1978
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The spectra of iodine in the presence of iodide, iodic acid, and polyvinylpyrrolidone (PVP) were obtained. Large effects of PVP concentrations on the spectra were observed. Changes in iodine spectra in the presence of N-methyl-2-pyrrolidone and N, N-diethyl-propionamide in various solvents indicated charge-transfer type interaction in less polar solvents. The spectra of the aqueous iodine solution were more affected by the addition of PVP with a smaller degree of polymerization. Kinetic studies of hydrolysis of iodine in the absence and presence of PVP indicated that PVP accelerates hydrolysis of iodine except for the initial period. The possible mechanism of accelerated hydrolysis of iodine in the presence of PVP is complexation of triiodide ion with PVP and subsequent shifts in the hydrolysis equilibrium of iodine.
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YOSHIO ITO, YOSHIKI HAMADA
1978 Volume 26 Issue 5 Pages
1375-1383
Published: May 25, 1978
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Syntheses of 10H-pyrido [3, 2-b] [1, 4] and 5H-pyrido [3, 4-b] [1, 4] benzoxazine (1 and 3) were carried out by the cyclization reaction of 2-and 4-(2'-hydroxyanilino)-3-nitropyridines (7 and 9) in dimethylformamide in the presence of sodium hydroxide. This method is an improvement over the past reports that this kind of anilino compounds are difficult to undergo intramolecular cyclization because they have an intramolecular hydrogen bonding properties. 3-Substituted (methyl, chloro, bromo, nitro), 7-nitro, and 8-methyl derivatives of 10H-pyrido [3, 2-b] [1, 4] benzoxazine (1a-1f) were synthesized in a high yield by the application of this method. The anilino compound was obtained by the selective condensation of 2-chloro-3-nitro-5-substituted pyridine and o-aminophenol in ethanol in the presence of copper and sodium hydroxide. However, 5H-pyrido [2, 3-b] [1, 4] benzoxazine (4) was not obtained from 3-(2'-nitroanilino)-2-pyridone (10) in this sodium hydroxide-dimethylformamide system, while 5H-pyrido [2, 3-b] [1, 4] and 10H-pyrido [4, 3-b] [1, 4] benzoxazine (4 and 2) were synthesized by the cyclization of 2- and 4-(2'-bromophenoxy)-3-(N-formylamino) pyridines (13 and 17), respectively, in xylene in the presence of copper and potassium carbonate.
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HIROAKI TAGAWA, KATSUJIRO UENO
1978 Volume 26 Issue 5 Pages
1384-1393
Published: May 25, 1978
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In order to search for new antiinflammatory agents, several acetic acid derivatives of sulfur containing tricyclic compounds were prepared. Initially, 4, 10-dihydro-10-oxobenzo [b] thieno [2, 3-e] thiepin (3) and 4, 10-dihydro-4-oxobenzo [b] thieno [2, 3-e] thiepin (19) were prepared by cyclization of 3-(phenylthiomethyl) thiophene-2-carboxylic acid (2) and 2-(phenylthiomethyl) thiophene-3-carboxylic acid (18), respectively, with polyphosphoric acid (PPA). The oxepin (5) corresponding to 3 was prepared by cyclization of the acid chloride of 3-(phenoxymethyl) thiophene-2-carboxylic acid (4) with aluminum chloride. However, cyclization of 2-(phenoxymethyl) thiophene-3-carboxylic acid (20) did not give the oxepin (21) corresponding to 19 but the rearranged compound, 4, 10-dihydro-4-oxobenzo [b] thieno [2, 3-e] oxepin (22). A similar rearrangement took place in the reaction of 4 with PPA yielding 4, 10-dihydro-10-oxobenzo [b] thieno [3, 2-e] oxepin (7). Furthermore, the acetic acid derivatives of 3, 5 and 19 were prepared by methods similar to those used for the syntheses of unsubstituted tricyclic rings. These acetic acid derivatives exhibited good antiinflammatory activities, details of which will be reported elsewhere.
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TARO NOMURA, TOSHIO FUKAI, SACHIKO YAMADA, MASA KATAYANAGI
1978 Volume 26 Issue 5 Pages
1394-1402
Published: May 25, 1978
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From the benzene extract of the root bark of the cultivated mulberry tree (a variety of Morus alba L.), three new prenylflavones, morusin, cyclomorusin, and compound A were isolated. Their structures were shown to be I, II, and III, respectively.
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TAKAYASU KITAGAWA, SATOSHI MIZUKAMI, EIZO HIRAI
1978 Volume 26 Issue 5 Pages
1403-1414
Published: May 25, 1978
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Lactim-lactam tautomerism of 5-substituted 4-hydroxy-2-methylpyrimidines (R ; H, CH
3, OCH
3 and COOC
2H
5) was examined in MeOH, n-BuOH and n-hexane. All the compounds existed mainly in the lactam form (4(3H)-pyrimidone, IIb) in the alcohols. No substituent effect at 5-position on the tautomerism in the alcohols was observed. In n-hexane, 5-H and 5-CH
3 derivatives also existed mainly in the lactam form, IIb. 5-Carbethoxy-4-hydroxy-2-methylpyrimidine (4), however, existed mainly in the lactim form (4-pyrimidinol, I). The lactim form of 4 in n-hexane was changed into the lactam form, IIb, on addition of MeOH and n-BuOH to the solution. The conversion to the lactam form may be explained as a result of an association of two molecules of alcohol to 4, i. e., [chemical formula] The association was investigated quantitatively by ultraviolet spectrophotometry : K
1=1483±29 (MeOH-association) and K
1=1279±19 (n-BuOH-association). the tautomeric equilibrium constant (K
t ; K
t=[IIb]/[I]) in pure n-hexane was estimated to be less than 0.02.
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TAKAYASU KITAGAWA, KUMIKO MATSUMOTO, EIZO HIRAI
1978 Volume 26 Issue 5 Pages
1415-1425
Published: May 25, 1978
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Lactim-lactam tautomerism of 5-carbethoxy-4-hydroxy-2-methylpyrimidine (1) was examined in the ethereal solvents (ethyl ether, n-propyl ether, isopropyl ether, n-butyl ether and p-dioxane). Compound 1 existed as a mixture of the lactim form (4-pyrimidinol, I) and the lactam form (4(3H)-pyrimidone, IIb) in the ethers, except p-dioxane. In p-dioxane, 1 existed mainly in the lactam form, IIb. A method was deviced to estimate spectrophotometrically the tautomeric equilibrium constant (K
t ; K
t=[IIb]/[I]). The lactim form decreased with increasing the polarity of the solvent, 9.0% (IIb, 91.0%) in isopropyl ether ; 10.5% (IIb, 89.5%) in n-propyl ether and 14.7% (IIb, 85.3%) in n-butyl ether. The lactim-lactam tautomerism of 2-hydroxynicotinic acid esters (ester R ; CH
3 (5), n-C
8H
17 (5')) and 4-hydroxynicotinic acid esters (ester R ; CH
3 (8), n-C
8H
17 (8')) was also examined because of a structural resemblance to 1. Compound 5 existed as a mixture of the lactim form (2-pyridinol) and the lactam form (2(1H)-pyridone) in the ethers. The lactim form of 5 existed in amounts, 10-70% (lactam form ; 30-90%). Compound 8 existed mainly in the lactim form (4-pyridinol) in all the ethers. The presence of the lactim form may be resulted form an intramolecular hydrogen bonding of these compounds.
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TAKAYASU KITAGAWA, KUMIKO MATSUMOTO, EIZO HIRAI
1978 Volume 26 Issue 5 Pages
1426-1430
Published: May 25, 1978
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The lactim form, I, one of the tautomers of 5-carbethoxy-4-hydroxy-2-methylpyrimidine (1), in n-hexane was changed into the lactam form, IIb (4(3H)-pyrimidone) on addition of the ethereal solvents (ethyl ether, n-propyl ether, isopropyl ether, n-butyl ether and p-dioxane). The lactam form, IIb, increased with increasing the concentration of the etheriin n-hexane. The following association equilibria were examined. [chemical formula] The over-all association constant which was defined as K
0 (K
0=([I]+[IIb])[S]/[I']+[IIb']) was estimated. The K
0 values increased in that order : p-dioxane <isopropyl ether <ethyl ether <n-propyl ether <n-butyl ether.
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TARO NOMURA, TOSHIO FUKAI, SACHIKO YAMADA, MASA KATAYANAGI
1978 Volume 26 Issue 5 Pages
1431-1436
Published: May 25, 1978
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When a solution of morusin (I) was exposed to bright sunshine or irradiated with a high-prssure mercury lamp, morusin hydroperoxide (III) was obtained in a high yield. This reaction did not occur in the dark. The reaction was dependent on the solvent and proceeded in chloroform or benzene solution whereas the starting material was recovered unchanged in methanol, ethanol or tert-butyl alcohol solution. Both of the free hydroxyl group at C
2' and the isolated double bond of the γ, γ-dimethylallyl group attached to the 3-position of flavone were found to be required for this photooxidation. Reduction of III gave compound A (II) which had been isolated from the root bark of Morus alba L. On the basis of these findings, the structure of morusin hydroperoxide was shown to be III.
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TAICHI OHMOTO, TAMOTSU NIKAIDO, MASA IKUSE
1978 Volume 26 Issue 5 Pages
1437-1442
Published: May 25, 1978
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A new triterpene 3-epiocotillol II was isolated along with sinapic acid, apige hydroxyhopanone, ocotillol II, and betulafolientriol oxide I from pollen grains of silver birch (Betula platyphylla SUKATCHEV var. japonica HARA) and the structure was clarified from chemical and spectral data. Presence of formic acid and other organic acids in the pollen grains were confirmed and analyzed quantitatively.
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HIROYUKI OBASE, HIDEKO TATSUNO, KATSUTOSHI GOTO, KOKI SHIGENOBU, YUTAK ...
1978 Volume 26 Issue 5 Pages
1443-1452
Published: May 25, 1978
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Some propanolamine derivatives were synthesized and their β-adrenergic blocking activities were determined. Among the compounds tested, all compounds with benzothiazole nucleus were found to have potent β-adrenergic blocking activity, and those with other nuclei failed to produce substantial β-blocking activity with one exception. Three compounds with benzothiazole nucleus were more potent than sotalol in their β-blocking activity, and the other two were equipotent to sotalol. One with benzotriazole nucleus had about the same β-blocking activity as sotalol.
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TARO NOMURA, TOSHIO FUKAI, MASA KATAYANAGI
1978 Volume 26 Issue 5 Pages
1453-1458
Published: May 25, 1978
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The structures of four new flavone derivatives, kuwanon A, B, C and oxydihydromorusin were isolated from the benzene extract of the root bark of the cultivated mulberry tree (a variety of Morus alba L.), and were shown to be I, II, III and IV, respectively, on the basis of spectroscopic and chemical evidences. Photooxidative cyclization did not occur with I but with II leading to the formation of a hydroperoxide possessing a dihydrooxepin ring. III was cyclized on photooxidation as II and was converted to morusin (V) by treating with DDQ. On hydration with methanolic hydrochloric acid, V was converted to IV.
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MASATOSHI YAMATO, JUNICHI UENISHI, KUNIKO HASHIGAKI
1978 Volume 26 Issue 5 Pages
1459-1464
Published: May 25, 1978
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Selfcondensation of diethyl acetonedicarboxylate (DADC) using the various catalysts was examined. The analyses of the condensation products of DADC were undertaken by GC and GC-MS. A correlation between the kind of catalysts used and products formed was revealed. Formation of ethyl 4-carboxyorsellinate (5) and diethyl 3, 5-dihydroxyhomophthalate (6) was newly proved in this reaction.
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KOICHI MIYANO, TAICHI KOSHIGOE, TAKEJI SAKASAI, HIROAKI HAMANO
1978 Volume 26 Issue 5 Pages
1465-1472
Published: May 25, 1978
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5-Haloalkyl or 5-branched alkyl picolinic acids, dopamine β-hydroxylase inhibitor were synthesized by the various methods. 2-Methyl-5-ethynyl pyridine (III) reacted with alkyl dihalide followed by hydrogenation to give 2-methyl-5-haloalkyl pyridine. III also reacted with ethylene oxide in the same manner to give 2-methyl-5-(4-hydroxybutyl)-pyridine, which was converted to halobutyl derivative. 2-Methylpyridine-5-aldehyde reacted with isoalkylidene phosphorane followed by hydrogenation to give 2-methyl-5-isoalkyl pyridines. These 2-methyl-5-(substituted alkyl) pyridines were oxidized via N-oxide and 2-acetoxymethyl compounds to 5-(substituted alkyl) picolinic acids.
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USHIHO MATSUMOTO, AKIRA KUNUGI, YUZO NAGASE
1978 Volume 26 Issue 5 Pages
1473-1479
Published: May 25, 1978
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Homogenate of the human term placenta was extracted consecutively with ethanol and methanol, and the extract was fractionated with ether-water system into free and conjugated corticosteroids. Fractions obtained by enzymic hydrolysis of conjugates and free fraction were submitted to reverse isotope dilution analysis and the kinds of corticosteroids present in each fraction were identified. Amount of these corticosteroids was determined by the double isotope derivative dilution method in which the carbonyl group in C-3 position alone is derived to thiosemicarbazone-
35S. Presence of the following corticosteroids was proved per 1 g (wet weight) of human term placental tissue : 0.136-1.176μg of free and 0.014-0.099 μg of conjugated 11-deoxycorticosterone, 0.040-0.668 μg of free and 0.079-0.273 μg of conjugated 11-dehydrocorticosterone, 0.026-0.078 μg of free and 0.023-0.037 μg of conjugated corticosterone, 0.016-0.050 μg of free and 0.014-0.031 μg of conjugated cortisone, 0.004-0.045 μg of free and 0.009-0.015 μg of conjugated cortisol, and 0.014 μg of free and 0.011 μg of conjugated aldosterone, with a larger amount than the above of progesterone (0.731-2.370 μg of free and 0.235-0.964 μg of conjugated). The use of the present method of determination allows separatory determination of free and conjugated corticosteroids, using about one-half of the placenta (250-280g). Quantitative distribution of corticosteroids in three placenta analyzed here showed a marked individual difference but in all the placental tissues analyzed, the content of 11-deoxycorticosterone and 11-dehydrocorticosterone was higher than that of the three kinds of 11-oxo-17α-hydroxycorticosteroid.
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KEIJIRO SAMEJIMA, YOKO NAKAZAWA, ISAO MATSUNAGA
1978 Volume 26 Issue 5 Pages
1480-1485
Published: May 25, 1978
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Decarboxylated S-adenosyl-L-methionine and its nine analogs have been prepared by a modified method of Jamieson including alkylation of the appropriate aminoalkyl-adenosyl thioether with alkyl iodides in a mixture of formic and acetic acids in the presence of silver perchlorate. The use of silver perchlorate allowed various combinations of the thioether and the alkyl iodide, and prompted the reaction. The sulfonium compounds were obtained as a white hygroscopic powder in 99% ethanol after purification by silica gel column chromatography with a solvent system of butanol-acetic acid-water (1 : 1 : 1). The chemical and physical data of the sulfonium compounds supported a general structure containing 2 mol of sulfuric acid and 0.5 mol of ethanol. The nuclear magnetic resonance data showed the existence of sulfonium diastereoisomers.
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SHUNJI NARUTO, ATSUSUKE TERADA
1978 Volume 26 Issue 5 Pages
1486-1492
Published: May 25, 1978
Released on J-STAGE: March 31, 2008
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The optical resolution and the determination of the absolute configuration of the four possible stereoisomers of the anti-inflammatory agent, 2-(2-isopropylindan-5-yl) propionic acid (I), are described.
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NAOKI MITSUO, TAKEHISA KUNIEDA, TAKEO TAKIZAWA
1978 Volume 26 Issue 5 Pages
1493-1500
Published: May 25, 1978
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Enol phosphates (3), arising from reaction of vinylene carbonate-tetrachloromethane telomers (2) with phosphite, were readily converted by successive procedures involving hydrolytic cleavage of carbonate rings, acylation and introduction of ethylamine moieties, to the unnatural types of cephalin and lecithin analogues, which possessed saturated long (C
18 : 0) and short (C
8 : 0) chains. Two kinds of fatty acid residues were selectively introduced by monoacylation with acid anhydrides followed by treatment with acid chlorides. Use of phosphonite in place of phosphite gave the same type of enol phosphonate which may serve for phosphono-lipid preparation. Synthetic phospholipid analogues thus formed exisist in thermotropic and lyotropic liquid crystalline states within definite temperature range. Their phase transition temperatures and Craft points as well as the lipid-water binary phase diagrams were compared with those of the corresponding natural phospholipids.
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NAOKI MITSUO, TAKEHISA KUNIEDA, TAKEO TAKIZAWA
1978 Volume 26 Issue 5 Pages
1501-1504
Published: May 25, 1978
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Permeability properties of liposomal membranes composed of the synthetic unnatural type phospholipids (IIa-c, III, IV) are compared with those of the corresponding glyceride-type lecithins (Ia, Ib). Certain synthetic analogues (IIa, III and IV) can retain glucose in the liposomes in nearly same order as that in the saturated long-chain lecithinderived liposomes. Cholesterol fluidizing effect of the lecithin analogues was generally small compared with those of the corresponding lecithins, partly due to bulkiness of trichloromethyl group which may hinder the immobilization of cholesterol along the fatty acid chains. Interestingly, the liposomes derived from enol-type synthetic lipid (III) can regain the barrier ability at the temperatures above the transition temperature just as natural unsaturated-chain lecithins do.
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MASAHIRO NAKANO, MASAKAZU YAMAMOTO, TAKAICHI ARITA
1978 Volume 26 Issue 5 Pages
1505-1510
Published: May 25, 1978
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Interaction of nalidixic acid with aluminum ion was revealed by spectrophotometric study. Stoichiometry of the nalidixic acid-aluminum ion complex was estimated to be 3 to 1 by the method of continuous variations. The interaction was further supported by an increase in solubility of the drug with increasing concentration of aluminum ion, by a decrease in (carbon tetrachloride/acetate buffer, pH3.3) partition coefficient with increasing concentration of aluminum ion in the aqueous layer, and by a decrease in the permeation rate of the drug through a cellulose membrane in the presence of aluminum ion in the donor compartment. Interaction of nalidixate anion with magnesium and calcium ions was also shown spectrophotometrically.
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TETSUYA AONO, YOSHIAKI ARAKI, KUNIHIRO TANAKA, MASAYUKI IMANISHI, SHUN ...
1978 Volume 26 Issue 5 Pages
1511-1521
Published: May 25, 1978
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For elucidating the receptor site of antiinflammatory arylacetic acids, some modifications were made on 4-aroyl-1-indancarboxylic acids (Ia-d) which have potent antiinflammatory activities. Modifications were introduced on the characteristic parts of I and 1-methylated derivatives (VIII), tetralin analogs (XVIII) and benzyl analogs (XXX) of I were prepared. However, these compounds showed weaker activities than the parent compound I. The result suggests that 1-indancarboxylic acid is the pharmacologically effective derivative of arylacetic acid.
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MITSUHIRO WAKIMASU, MASAHIKO FUJINO
1978 Volume 26 Issue 5 Pages
1522-1526
Published: May 25, 1978
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The nonacosapeptide corresponding to the proposed amino acid sequence of turkey glucagon was synthesized via the corresponding sulfoxide, [Met (O)
27]-turkey glucagon. For the synthesis of the protected nonacosapeptide six peptide fragments were prepared and the condensations of the fragments were achieved by the HONB-DCC method. Finally, all the protecting groups were removed by the treatment with anhydrous hydrogen fluoride-anisole to give [Met (O)
27]-turkey glucagon. The sulfoxide was then treated with aqueous thioglycolic acid to give turkey glucagon, which was successfully crystallized from dilute aqueous sodium chloride solution. The biological activity, lipolysis on rat adipocytes, of the synthetic turkey glucagon was as potent as that of mammalian glucagon.
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SEIKI TANADA, KEITO BOKI, KAZUOKI MATSUMOTO
1978 Volume 26 Issue 5 Pages
1527-1532
Published: May 25, 1978
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Adsorption of methyl sulfide and methyl disulfide as the offensive odor substances was measured by a gravimetric method to elucidate the mechanism of their adsorption on activated carbon, zeolite, and silicate. The mechanism of adsorption was discussed on the basis of the application of Dubinin-Astakhov equation (W=W
0exp (-[A/E)
n)] to the adsorption isotherms and the pore size distribution in the range of pore radius 7.5 to 300 Å. Dubinin-Astakhov equation was well applicable to the adsorption isotherm on activated carbon and the exponent n was 2. No straight line was found between log W and A
n (n=1-6) of adsorption isotherm on zeolite. A plot of log W against A (n=1) of adsorption isotherm on silica gel was found to be linear. It was confirmed that the adsorption of methyl sulfide and methyl disulfide on activated carbon and silica gel resulted in the volume filling of their micropores by the mechanism of capillary condensation, and that its adsorption was a physical adsorption. The amount of methyl sulfide and methyl disulfide adsorbed on the porous adsorbents was determined by their micropore volume of pore radius less than about 20 Å.
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TAKAO KUROSAWA, MASAHIKO TOHMA, YUJI OIKAWA, OSAMU YONEMITSU
1978 Volume 26 Issue 5 Pages
1533-1539
Published: May 25, 1978
Released on J-STAGE: March 31, 2008
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The thermal elimination of β-ketosulfoxides (3, 4, 5) derived easily from methyl 4-(3-methoxyphenyl) butyrate (1) gave 6-(3-methoxyphenyl) hex-1-en-3-one (6), which was condensed with 2-methylcyclopentane-1, 3-dione (8) to yield the triketone (7), one of key intermediates of Smith's estrone synthesis. Compound 7 was cyclized to the unsaturated diketone (9), which was converted to estrone methyl ether (13) by the established procedures. When the mixture of 3 (or 4) and 8 was heated, 7 was directly formed in a good yield. Moreover, heating of 5 and 8 gave 9, though in less satisfactory yield. The over-all yield of this simple and short cut synthesis of estrone methyl ether (13) from the starting material (1) was 34%, nearly twice of the original Smith method. This method also applied for the synthesis of 11α-methylequilenine methyl ether (20) and 11α-methylisoequilenine methyl ether (19) via the prior introduction of a methyl group to 3 yielding the β-ketosulfoxide (14) in 40% over-all yield.
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HIROSHI OGAWA, HARUAKI YAJIMA
1978 Volume 26 Issue 5 Pages
1540-1548
Published: May 25, 1978
Released on J-STAGE: March 31, 2008
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As a starting material for the total synthesis of duck glucagon, the C-terminal protected heptadecapeptide, Boc-Tyr-Leu-Asp (OBzl)-Thr-Arg (MBS)-Arg (MBS)-Ala-Gln-Asp-(OBzl)-Phe-Val-Gln-Trp-Leu-Met (O)-Ser-Thr-OH (position 13-29), was synthesized by successive azide condensation of 4 peptide fragments ; (position 13-14), (15-19), (20-23) and (24-29).
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HIROSHI OGAWA, MASANORI SUGIURA, HARUAKI YAJIMA, HIDEO SAKURAI, KINSUK ...
1978 Volume 26 Issue 5 Pages
1549-1557
Published: May 25, 1978
Released on J-STAGE: March 31, 2008
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The nonacosapeptide corresponding to the entire amino acid sequence of duck glucagon was synthesized using methanesulphonic acid as a deprotecting reagent at the final step of the synthesis. Synthetic duck glucagon was obtained in a crystalline form and exhibited the biological activity equivalent to that of porcine glucagon. However, the immunological property of synthetic duck glucagon was found to differ from the mammalian origin.
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MAMORU TANAKA, YASUHIRO ABE, KANJI TOKUYAMA
1978 Volume 26 Issue 5 Pages
1558-1569
Published: May 25, 1978
Released on J-STAGE: March 31, 2008
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The reaction of 2-formyl-3-methoxypropionitrile derivatives (I, II, III) with benzenes (VIa-h) in the presence of an acid catalyst gave cis isomers of 2-methoxymethylene-3-phenylpropionitriles (VIIa-h) via electrophilic substitution of allyl cation (IV). The aluminum chloride-catalyzed reaction of III with the benzenes afforded 2-methoxymethyl-3, 3-diphenylpropionitriles (XVa-c) via electrophilic substitution of oxocarbonium ion (V). The same reactions of carbomethoxy analogs of I, II, and III were carried out to provide trans isomers of methyl 2-methoxymethylene-3-phenylpropionates (XIa-e) and a small amount of the carbomethoxy analog (XVIc) of XVc. In these reactions indan-(VIIIa, XIIa, b), triphenylpropane-(IXa, XIIIc), and indene-(XIVa, b) derivatives were obtainable via successive intra- or intermolecular substitutions of benzenes at the 2-methoxymethylene groups of VII and XI. The compounds VII and XV were converted into 2-dimethoxymethyl-3-phenylpropionitriles (X) and 2-cyano-1, 1-diphenyl-1-propenes (XVII), respectively, by the treatment of sodium methoxide in methanol. Some heterocycles such as 3-cyano-2-methoxychroman (XIX), 3-cyano-2H-chromen (XXIII), and 3-cyanoquinoline (XXIV) were simply derived from I or III following the above methods.
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TAIGI CHUNG, HIDEKO ISHIHARA, SETSUZO TEJIMA
1978 Volume 26 Issue 5 Pages
1570-1575
Published: May 25, 1978
Released on J-STAGE: March 31, 2008
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Methanolysis and benzyl alcoholysis of β-cellobiosyl, or β-lactosyl, or β-maltosyl N, N-dimethyldithiocarbamate in the presence of mercuric chloride and cadmium carbonate were investigated. Methyl and benzyl glycosides formation proceeded in good yield under mild conditions, in which formation of α-anomer was always predominant over that of β-anomer : in methanolysis, the ratios of α-and β-anomers were about 4 : 1 and in benzyl alcoholysis, 2 : 1, respectively. Using this method methyl α-cellobioside, α-lactoside, and α-maltoside were synthesized. The procedure is a facile synthetic method for appropriate alkyl α-glycosides of reducing disaccharides.
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OSAMU NISHIMURA, CHIEKO KITADA, MASAHIKO FUJINO
1978 Volume 26 Issue 5 Pages
1576-1585
Published: May 25, 1978
Released on J-STAGE: March 31, 2008
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The S-p-methoxybenzyl, S-t-butyl and S-1-adamantyl groups of cysteine were smoothly cleaved with mercuric acetate in trifluoroacetic acid or mercuric trifluoroacetate in aqueous acetic acid. The treatment of the formed mercaptides with thiols regenerated cysteine derivatives. This new method was applied to the synthesis of biologically active polypeptides oxytocin and somatostatin.
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TOSHIAKI MORIMOTO, MINORU SEKIYA
1978 Volume 26 Issue 5 Pages
1586-1591
Published: May 25, 1978
Released on J-STAGE: March 31, 2008
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A reaction of β, β-dialkylenamines with trichloroacetic anhydride has been found to proceed with decarboxylation resulting in both β-trichloroacetylation and α-trichloromethylation. Mechanistically this reaction path involves an intermediate, β-trichloroacetylated iminium trichloroacetate, which suffers decarboxylation resulting in α-trichloromethylation. This course of the reaction was also stepwise processed by allowing to react with trichloroacetyl chloride, which was replaceable by p-nitrobenzoyl chloride, and succeedingly with trichloroacetate. The above reactions have provided a general method of synthesis of tertiary amines possessing both α-trichloromethyl and β-trichloroacetyl. Hydrolysis of these products is also described.
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TAKEFUMI MOMOSE, KENICHI KANAI, TAKESHI NAKAMURA
1978 Volume 26 Issue 5 Pages
1592-1597
Published: May 25, 1978
Released on J-STAGE: March 31, 2008
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The photochemistry of the β-apolignan (1) was investigated, and a specific rearrangement was found to occur on irradiation of 1. The photoproduct was identified as a tetrahydrocycloprop (a) indene (2b) based on an unambiguous synthesis of the dihydro product (3b) derived from its hydrogenolysis. Similar irradiation of taiwanin A gave two isomeric tetrahydrocycloprop (a) indenes (10a and 10b) via the cyclization into β-apolignans followed by their degenerate rearrangement. Consequently, this type of phototransformation was found to be a common feature of β-apolignans irrespective of ring substituents, and was characterized as a vinyl-aryl di-π-methane rearrangement. Mechanistic aspects of the rearrangement are briefly described.
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KEIJI SEKIGUCHI, MOTOHARU IWATSURU, KENICHI SHIROTANI
1978 Volume 26 Issue 5 Pages
1598-1603
Published: May 25, 1978
Released on J-STAGE: March 31, 2008
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It was confirmed that the particle size distributions could be effectively obtained by dissolution rate analysis. If the drug dissolves by a diffusion-controlled mechanism and the absorbance E of its solution obeys the Beer's law, the absorbance change with respect to time t will be proportional to the surface area S and be expressed as dE/dt=k'S, where k'is a constant. When a drug powder is composed of n uniform and spherical particles the following equation d
2E/dt
2=k'dS/dt=Kn (τ-t) will hold, where τ is the disappearance time of the particles and K is a constant. Any powder can be considered as a set of n
1, n
2‥‥particles having the diameter of D
1, D
2‥‥, and the equation can be transformed into d
2E/dt
2=K{n
1(τ
1-t)+n
2(τ
2-t)+n
3(τ
3-t)+‥‥}. Thus the size distribution of a powder on the number basis can be determined from the tangent on the d
2E/dt
2-time curve. The proposed method was applied to benzoic acid crystals and the results were compared with those from microscopic analysis, and the agreement was fairly good. The mechanical trituration effects on the sulfanilamide crystals were also studied by this procedure. Thus it was found that the method gave the effective diameter for dissolution and the results could be obtained in much shorter time as compared with the ordinary methods such as microscopic analysis.
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KOUKI KITAGAWA, YUKO BAN, TADASHI AKITA, TOMIO SEGAWA, YOSHIHIRO NAKAT ...
1978 Volume 26 Issue 5 Pages
1604-1607
Published: May 25, 1978
Released on J-STAGE: March 31, 2008
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A bovine hypothalamic peptide, substance P was synthesized alternatively by successive condensation of three subunits, N-terminal di-, middle hepta- and C-terminal dipeptides. Two newly synthesized peptides, PCA-Phe-Phe-Gly-Leu-Met-NH
2 and PCA-Gln-Phe-Phe-Gly-Leu-Met-NH
2 were both found to be approximately two times active than synthetic substance P, when the contractile activity was determined in isolated guinea-pig ileum.
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ZENICHI HORII, KEISHIRO NAGAO, SANGWON KIM
1978 Volume 26 Issue 5 Pages
1607-1610
Published: May 25, 1978
Released on J-STAGE: March 31, 2008
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The chemical investigation of Argentine bezoar showed the existence of cholesteryl esters of fatty acids (1), lithocholic acid, methyl cholate, methyl deoxycholate, methyl chenodeoxycholate, oleanolic acid, and ursolic acid besides the constituents already reported to be. The fatty acid compositions of 1, as well as of free fatty acids (2) were scrutinized using gas chromatography and mass chromatography by converting them into the corresponding mixtures of methyl esters (1e) and (2e). These analyses showed that the mixtures consisted of C
14 to C
18 fatty acid esters with varing degree of relative abundance, palmitate and stearate being the major components in each of the mixtures.
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SHIRO YOSHIZAKI, EIYU YO, JUNICHIRO OTSUBO
1978 Volume 26 Issue 5 Pages
1611-1614
Published: May 25, 1978
Released on J-STAGE: March 31, 2008
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A series of new sympathomimetic amines having a 3, 4-dihydrocarbostyril nucleus was synthesized. These compounds have two weakly acidic hydrogen atoms in locations similar to those of the hydroxyl groups of adrenergic agents containing catechol. One threo-isomer 1i-threo was synthesized by inversion of the corresponding erythro-isomer by the S
Ni reaction.
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TADAMASA TERAI, MASAAKI KATAI, NOBUYUKI HAMANAKA, TAKESHI MATSUMOTO, H ...
1978 Volume 26 Issue 5 Pages
1615-1619
Published: May 25, 1978
Released on J-STAGE: March 31, 2008
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Treatment of grayanotoxin (G) III with CH
3CHO in the presence of anhydrous CuSO
4 afforded a diethylidene compound (2). Oxidation of 2 (CrO
3) and subsequent ozonolysis and hydrolysis (KOH-MeOH) gave G-V (4) in 34% overall yield. Direct ozonolysis of 2 produced rhodojaponin (R) IV (8) in 68% yield. Δ
2-Diethylidene compoud (10) was oxidized to 11, which on ozonolysis-hydrolysis furnished R-III (12) in 9.2% overall yield.
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TOSHIKO SATAKE, TAKAO MURAKAMI, YASUHISA SAIKI, CHIUMING CHEN
1978 Volume 26 Issue 5 Pages
1619-1622
Published: May 25, 1978
Released on J-STAGE: March 31, 2008
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Aus den oberirdischen Teilen von Pteris vittata L. wurden zwei neue Lignanglykoside, d. h., cis-Dihydro-dehydro-diconiferylalkohol-9-O-β-D-Glukosid (I) und Lariciresinol-9-O-β-D-Glukosid (III) isoliert und identifiziert.
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TADATOSHI YAMAGUCHI, KENICHI ICHIKI, HISAO SONE, MINORU MAEDA, MASAHAR ...
1978 Volume 26 Issue 5 Pages
1623-1626
Published: May 25, 1978
Released on J-STAGE: March 31, 2008
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5-Iodomethyl-3, 5-dimethyl-oxazolidine-2, 4-dione-
131I (6) and 5-iodomethyl-5-methyloxazolidine-2, 4-dione-
131I (13) were synthesized to evaluate their potential utility as pancreatic scanning agents.
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TSUTOMU MOMOSE
1978 Volume 26 Issue 5 Pages
1627-1628
Published: May 25, 1978
Released on J-STAGE: March 31, 2008
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Aliphatic and aromatic acids and 2-nitrophenylhydrazine hydrochloride were coupled in aqueous ethanol with dicyclohexylcarbodiimide as a coupling agent in the presence of pyridine and thiourea. The resultant hydrazide solution was made alkaline to develop a violet color, and heated at 60°to decolorize the brown blank color. This colorimetric method of determination is suitable for aqueous and aqueous ethanol samples of carboxylic acids.
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