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Shigeru KUROSAWA, Emiko TAWARA, Naoki KAMO, Fumihiko OHTA, Toshiaki HO ...
1990 Volume 38 Issue 5 Pages
1117-1120
Published: May 25, 1990
Released on J-STAGE: March 31, 2008
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A method for immunoassay of CRP (C-reactive protein) was developed using a piezoelectric quartz crystal. Previous immunoassays using a piezoelectric crystal have required the formation of a thin film on the crystal, to which an antibody is afflxed. The occurrence of antigen-antibody reaction increases the weight attached to the crystal surface, which causes a reduction in the oscillation frequency. In our method, the frequency reduction was observed using antibody-bearing latex without any film. One possible mechanism of the frequency change is that the crystal acts as a sensing apparatus for viscosity or density change in the solution due to aggregation of latex particles. The detection limit was almost the same as that for latex photometric immunoassay (LPIA). The present method has been designated as latex piezoelectric immunoassay (LPEIA).
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Kazuo IGUCHI, Akira SAHASHI, Yasuji YAMADA, Junichi KOHNO
1990 Volume 38 Issue 5 Pages
1121-1123
Published: May 25, 1990
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A new sesquiterpenoid hydroquinone 2 and three new sesquiterpenoid quinones 4, 5 and 6 were isolated from the Okinawan marine sponge, Dysidea sp., together with the known hydroquinone 1 and its corresponding quinone 3. The structures of these compounds were elucidated on the basis of spectroscopic data and chemical reactions.
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Takeshi IMANISHI, Masayuki YAMASHITA, Yoshimi HIROKAWA, Tetsuaki TANAK ...
1990 Volume 38 Issue 5 Pages
1124-1128
Published: May 25, 1990
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Improved synthetic routes to (±)-pentalenene (1) and (±)-9-epipentalenene (6) were developed. Intramolecular alkylation of a tricyclic halo ester (7), obtained from 3, by treatment with lithium hexamethyldisilazide in tetrahydrofuran gave 14 and 15 in a ratio of 74 : 26. Compound 14 was successfully converted into the key intermediate (16) for (±)-1. On the other hand, catalytic hydrogenation of 8 afforded 20, a key intermediate for (±)-6, along with 16 (20 : 16=86 : 14).
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Hajime KATAYAMA, Noriyuki TAKATSU, Haruko KITANO, Yukari SHIMAYA
1990 Volume 38 Issue 5 Pages
1129-1135
Published: May 25, 1990
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Acid-catalyzed intramolecular cycloaddition of 2-allylphenylhydrazones is an effective method for the preparation of 2, 3, 3a, 4-tetrahydro-1H-pyrazolo[1, 5-α]indole derivatives.
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Hiroyuki HAYAKAWA, Fumi TAKAI, Hiromichi TANAKA, Tadashi MIYASAKA, Ken ...
1990 Volume 38 Issue 5 Pages
1136-1139
Published: May 25, 1990
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Displacement of a hydroxyl group in pyrimidine nucleosides having a vicinal diol system by a fluorine atom was investigated by using diethylaminosulfur trifluoride (DAST). Though participation of the base moiety often thwarts the desired introduction of a fluorine atom, it was found that appropriate modification of the base and/or sugar moieties allowed the desired fluorodehydroxylation to occur, giving 5'-, 3'-β-, and 2'-α-fluorinated uracilnucleosides in good yields.
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Tatsuo YAMAUCHI, Fumiko ABE
1990 Volume 38 Issue 5 Pages
1140-1142
Published: May 25, 1990
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2'-O-Acetyl-β-D-thevetosides and β-D-glucosyl(1→4)-2'-O-acetyl-β-D-thevetosides of oleandrigenin and digitoxigenin were isolated along with D-cymarosides, D-thevetosides and D-digitalosides from the roots and the stems of Adenium obesum ROEM. et SCHULT. 4-O-β-D-Glucopyranosyl-D-cymaritol was isolated from the polar fraction.
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Chihiro ITO, Tian-Sheng WU, Hiroshi FURUKAWA
1990 Volume 38 Issue 5 Pages
1143-1146
Published: May 25, 1990
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Seven new binary carbazole alkaloids, named murrastifoline-A (1), -B (2), -C (3), and -D (4) and chrestifoline-A (5), -B (6), and -C (7), were isolated from root bark of Murraya euchrestifolia HAYATA (Rutaceae) collected in Taiwan and their structures were elucidated by means of spectral methods.
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Akira MIYASHITA, Hideaki MATSUDA, Chihoko IIJIMA, Takeo HIGASHINO
1990 Volume 38 Issue 5 Pages
1147-1152
Published: May 25, 1990
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When a mixture of 4-chloro-1-phenyl-1H-pyrazolo[3, 4-d]pyrimidine (9), aromatic aldehyde (5), sodium hydride, and a catalytic amount of 1, 3-dimethylbenzimidazolium iodide (4) in tetrahydrofuran was refluxed, the nucleophilic aroylation occurred, resulting in the formation of the aryl 1-phenyl-1H-pyrazolo[3, 4-d]pyrimidin-4-yl ketones (11).Similar reaction of 4-chloro-1-methyl-1H-pyrazolo[3, 4-d]pyrimidine (10) gave the corresponding aryl 1-methyl-1H-pyrazolo[3, 4-d]pyrimidin-4-yl ketones (12) in moderate yields. Use of dimethylformamide or dimethyl sulfoxide in the above reaction reduced the necessary reaction time and reaction temperature. A plausible reaction pathway for the formation of the ketones 11 and 12 involving the catalytic action of 4 is proposed.
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Ryuichiro TANAKA, Tsuneatsu NAGAO, Hikaru OKABE, Tatsuo YAMAUCHI
1990 Volume 38 Issue 5 Pages
1153-1157
Published: May 25, 1990
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Five echinocystic acid glucuronide saponins, aster saponins Ha, Hb, Hc, Hd and foetidissimoside A (=kirengesho-masaponin I), were isolated from the ground part of Aster tataricus L. f. (Compositae) as their methyl esters, and their structures were determined based on spectral evidence and chemical degradation. These saponins have a common prosapogenin structure, echinocystic acid-3-O-glucopyranosiduronic acid, and differ in the structures of the 28-O-linked sugar moieties.Aster saponin Ha is a 28-[α-L-arabinopyranosyl]ester, Hb, a 28-[O-α-L-rhamnopyranosyl-(1→2)-α-L-arabinopyranosyl] ester Hc, a 28-[O-β-D-xylopyranosyl-(1→3)-O-β-D-xylopyranosyl-(1→4)-O-α-L-rhamnopyranosyl-(1→2)-α-L-arabinopyranosyl] ester and Hd, a 28-[O-β-D-xylopyranosyl-(1→3)-O-β-D-sylopyranosyl-(1→4)-[O-β-D-apiofuranosyl-(1→3)]-O-α-L-rhamnopyranosyl-(1→2)-α-L-arabinopyranosyl] ester of the prosapogenin.
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Machiko ONO, Reiko TODORIKI, Ichiro ARAYA, Shinzo TAMURA
1990 Volume 38 Issue 5 Pages
1158-1164
Published: May 25, 1990
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Acid hydrolysis of unsymmetrical N
1, N
2-disubstituted acetamidine and formamidine was examined kinetically in aqueous dioxane solution. The reaction afforded the more basic amine and the N-acyl derivative of the less basic amine. Increasing the dioxane content in the solvent increased the reaction rate. The reaction can be rationalized in terms of specific acid-general base catalysis.
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Shiroh FUTAKI, Takeshi YAGAMI, Takashi TAIKE, Toyoko OGAWA, Tadashi AK ...
1990 Volume 38 Issue 5 Pages
1165-1169
Published: May 25, 1990
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A new system for the facile reduction of Met(O) in protected peptides (dimethylformamide-sulfur trioxide complex/iodide ion) was introduced. Met(O) in protected Met-enkephalins and protected leucosulfakinins were reduced to Met within 1h by this system, and the reducing ability of this new system seemed comparable to or greater than that of the formerly reported dimethylformamide-sulfur trioxide complex/ethanedithiol system. The methylsulfinylbenzyl protecting group of Tyr was also reduced to a methylthiobenzyl group by this system.
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Takehiro SANO, Yoshie HORIGUCHI, Suetaka KAMBE, Kazuhiko TANAKA, Jun'i ...
1990 Volume 38 Issue 5 Pages
1170-1175
Published: May 25, 1990
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Thermolysis of the 7-vinyl derivative of 1-aryl-5-ethoxycarbonyl-2-azabicyclo[3.2.0]heptane-3, 4-dione caused two different types of skeletal rearrangement depending on the stereochemistry of the 7-vinyl group. The exo-isomer (2) gave the hydroindole (4) by the 1, 3-shift of a C
1-C
7 bond to the vinyl group (path A reaction), while the endo-isomer (3) gave the 7-azabicyclo[4.2.1]nonane (5) by the Cope rearrangement (path B reaction). The product on thermolysis of the corresponding imidate also depends on the stereochemistry of the 7-vinyl group. The endo-isomer (13) gave the Cope product (12), while the exo-isomer (14) gave the dihydropyridone (16), which is produced by the 1, 3-shift of the C
1-C
7 bond to the C
3 position followed by cheletropic loss of CO from the intermediary 2-azanorbornene (path C reaction). The validity of path C was proved by isolation of the 2-azanorbornenes (21 and 22) formed by thermolysis of the 7-vinyl-4-acetoxy imidate (20).
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Machiko ONO, Kazuhide HAYAKAWA, Shinzo TAMURA
1990 Volume 38 Issue 5 Pages
1176-1181
Published: May 25, 1990
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In the hydrolysis of N
1-benzoyl-N
1, N
2-diphenylacetamidine (1) in carboxylate buffer solutions, nucleophilic attack of the catalytic acid was proved to take place at the amide carbonyl carbon (pathway d) and presumably also at the amidine central carbon (pathway e) in parallel to the normal hydrolysis processes. Mixed acid anhydride and N
1, N
2-diphenylacetamidine were formed by pathway d, and the former reacted with aniline formed by further hydrolysis of the latter to give two N-acylanilines. In parallel with this process, the mixed anhydride reacts with water to give two carboxylic acids. In this case, carboxylic acid acts as a nucleophilic catalyst.The reaction of 1 and p-methoxybenzoic acid under anhydrous conditions gave products derived from the attack of p-methoxybenzoate ion at both amide carbonyl and amidine central carbons.Hydrolysis of N
1-benzoyl-N-
1, N
2-diphenylformamidine (7) in acetate buffer solution proceeded mainly through the ordinary hydrolysis pathway. Formation of a small amount of acetanilide implies that the reaction proceeds through pathway d or e to a small extent.In hydrolysis of N
1-tosyl-N
1, N
2-di(p-methylphenyl)acetamidine (6b) in glycolate buffer solution, a small amount of N-(acetoxyacetyl)-p-toluidine was formed together with the ordinary hydrolysis products. This implies that the reaction proceeds through pathway e to a small extent.
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Kazunobu HARANO, Takashi AOKI, Masashi ETO, Takuzo HISANO
1990 Volume 38 Issue 5 Pages
1182-1191
Published: May 25, 1990
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Pericyclic reactions of 5-methoxycarbonyl-2-pyrone (Ic) with nonconjugated dienes (IIa-j) were investigated. The diene (Ic) reacted readily with IIa-j to give [4+2]π cycloadducts (IIIa-j) that lost carbon dioxide to afford intramolecular double Diels-Alder (DDA) adducts (V). The structures of these adducts were determined from spectral evidence. The reactivity of the addends and the regiochemistry of the primary adducts are discussed on the basis of modified neglect of diatomic overlap (MNDO) calculation data. The relative stability of the twistene- and isotwistene- type compounds and the conformation of some isotwistene-type compounds are discussed on the basis of the molecular mechanics (MM2) calculation data.
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Yoshiaki KISO, Makoto YOSHIDA, Tooru KIMURA, Yoichi FUJIWARA, Masanori ...
1990 Volume 38 Issue 5 Pages
1192-1199
Published: May 25, 1990
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The hexadodecapeptide corresponding to the entire amino acid sequence of porcine brain natriuretic peptide (pBNP) was synthesized by assembling four segments in solution, followed by HF deprotection and subsequent oxidation to establish and intramolecular disulfide bridge. The synthesis using the newly developed S-trimethylacetamido-methylcysteine [Cys(Tacm)] derivative gave a better yield than that using the S-2, 4, 6-trimethylbenzylcysteine [Cys(Tmb)] derivative. The chick rectum relaxant activity of the synthetic pBNP was 2.9 times more potent than that of α-rat atrial natriuretic peptide (α-rANP).
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Tozo FUJII, Masashi OHBA, Takeshi TACHINAMI, Hisae MIYAJIMA
1990 Volume 38 Issue 5 Pages
1200-1204
Published: May 25, 1990
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The first total synthesis of ochropposinine (1), a Neisosperma and Ochrosia alkaloid, has been accomplished in the form of a racemic modification by means of an initial coupling of the lactim ether (±)-3 with 5 and succeeding steps proceeding through the intermediates (±)-7, (±)-8, (±)-9, (±)-10, and (±)-11. A parallel synthetic route starting with (+)-3 produced the chiral target molecule (-)-1 via the intermediates (+)-7, (+)-8, (+)-9, 10, and (-)-11. As a result, the absolute configuration of ochropposinine has been unequivocally established to be that represented by formula (-)-1.
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Eisuke SATO, Yoshiya IKEDA, Yuichi KANAOKA
1990 Volume 38 Issue 5 Pages
1205-1210
Published: May 25, 1990
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Photolyses of quinoline-2-thiones (1A, B), isoquinoline-1-thione (14A), and phthalazine-1-thiones (14B-D) in the presence of olefins (2) afforded photoaddition products such as substituted quinolines, isoquinolines, phthalazines, and novel tricyclic products, probably by way of thietanes formed by photoaddition of olefins to the C=S bond.
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Takashi YOSHIDA, Tong CHOU, Aya NITTA, Ken-ichi MIYAMOTO, Ryozo KOSHIU ...
1990 Volume 38 Issue 5 Pages
1211-1217
Published: May 25, 1990
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Three new dimeric hydrolyzable tannins, woodfordins A, B and C, along with seven known hydrolyzable tannins, including oenothein B, a dimer exhibiting marked host-mediated antitumor activity, were isolted from in Indonesian curde drug, Sidowayah [dried flowers of Woodfordia fruticosa (L.) KURZ (Lythraceae)]. The structures of the new tannins were elucidated based on chemical and spectral evidence. Woodfordin C, having a macro-ring structure, was also found to exhibit a significant antitumor activity.
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Jer-Huei LIN, Gen-ichiro NONAKA, Itsuo NISHIOKA
1990 Volume 38 Issue 5 Pages
1218-1223
Published: May 25, 1990
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A chemical examination of the tannins in the leaves of Macaranga tanarius (L.) MUELL. et ARG. (Euphorbiaceae) has led to the isolation of seven new hydrolyzable tannins (22-28), together with twenty-one known tannins (1-21). On the basis of chemical and spectroscopic evidence, the structures of compounds 22-28 were established as 1, 4-di-O- galloyl-α-D-glucopyranose (22), 3, 4-di-O-galloyl-D-glucopyranose (23), galloylpunicafolin (24), galloylgeraniin (25), 1-O- galloyl-3-O-brevifolincarboxyl-β-D-glucopyranose (26), 1, 2, 4-tri-O-galloyl-3, 6-(S)-hexahydroxydiphenoyl-β-D-glucopyranose (macaranganin) (27) and 1, 2, 4-tri-O-galloyl-3, 6-(R)-dehydrohexahydroxydiphenoyl-β-D-glucopyranose (tanarinin) (28).
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Tsutomu HATANO, Taeko YASUHARA, Rieko YOSHIHARA, Isao AGATA, Tadataka ...
1990 Volume 38 Issue 5 Pages
1224-1229
Published: May 25, 1990
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The inhibitory effects of hydrolyzable tannins, condensed tannins and related polyphenols on the activity of xanthine oxidase (XOD), catalyzing uric acid formation from xanthine, were investigated. Marked differences in the strength of the inhibition were observed. Some of the differences among the monomeric hydrolyzable tannins were due to their molecular weights, reflecting the number of phenolic hydroxyl groups in the molecule. However, the inhibitory activity of several oligomaric hydrolyzable tannins seemed particularly low in spite of their large molecular size. It was also observed that differences in location of acyl groups on the carbohydrate cores caused differences in the inhibitory activity among monomeric and oligomeric hydrolyzable tannins. A caffeic acid derivative (caffeetannin), 3, 5-di-O-caffeoylquinic acid (24), also inhibited this enzyme. Galloylation and the degree of polymerization in proanthocyanidins were also shown to affect remarkably the strength of the inhibition. Among the compounds tested in the present study, valoneic acid dilactone (29), isolated from Mallotus japonicus, inhibited the enzyme most effectively. A kinetic study showed that this dilactone inhibited XOD non-competitively. Comparison of the inhibitory effect on XOD, with the binding activity to hemoglobin, for each tannin, suggests that their inhibition of XOD is not based on non-specific binding to the protein. Similar comparison of the inhibitory effect on XOD with the inhibitory effect on the generation of superoxide anion radical (O
2-) from the hypoxanthine-XOD system revealed that the inhibition of O
2- generation by tannins is due to their radical-scavenging activity, and not due to their inhibitory activity upon the enzyme.
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Chihiro ITO, Miyuki MATSUOKA, Takahiro OKA, Motoharu JU-ICHI, Masatake ...
1990 Volume 38 Issue 5 Pages
1230-1232
Published: May 25, 1990
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Two new binary coumarins, khelmarin-A (1) and -B (2), were isolated from root bark of Poncirus trifoliata which had been used as a rootstock of Citrus Hassaku (hassaku), and roots of original seedlings of Citrus canariculata (kiku-daidai), respectively. The structurs of the new binary coumarins 1 and 2 contain cis-khellactone (3) as a common structural component, which is linked with a nordentatin (5) or a xanthoxyletin (6) unit, respectively.
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Hiroshi NAKATANI, Taru Su SO, Hiroyuki ISHIBASHI, Masazumi IKEDA
1990 Volume 38 Issue 5 Pages
1233-1237
Published: May 25, 1990
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(±)-Cuparene, (±)-α-cuparenone, and (±)-tochuinyl acetate were synthesized from m-tolylthiomethyl chloride by using a Lewis acid-mediated [4
++2] polar cycloaddition with substituted cyclopentenes as a key step.
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Hiroyuki TAWADA, Yasuo SUGIYAMA, Hitoshi IKEDA, Yujiro YAMAMOTO, Kanji ...
1990 Volume 38 Issue 5 Pages
1238-1245
Published: May 25, 1990
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N-Acetic acid derivatives (I) of 2-substituted 1, 4-benzoxazines and benzothiazines were designed and synthesized for evaluation as new aldose reductase inhibitors. In general, 3-thioxo derivatives were more potent inhibitors of aldose reductase from human placenta in vitro than the corresponding 3-oxo derivatives. While many compounds (I) were not very effective in inhibiting sorbitol accumulation in the rat sciatic nerve in vivo, the 3-thioxo compounds bearing an isopropyl group at the 2-position showed highly potent activity in the in vivo assay. Compound 46 (AD-5467) was selected from this series as a candidate for further development.
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Tadashi EGUCHI, Nobuo IKEKAWA, Koji SUMITANI, Masayoshi KUMEGAWA, Shoh ...
1990 Volume 38 Issue 5 Pages
1246-1249
Published: May 25, 1990
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A series of analogs of 1α, 25-dihydroxyvitamin D
3 [1, 25-(OH)
2D
3 (1)] with alkyl substitutions in 26- and 27- positions have been tested for their activity 1) in competing with 1, 25-(OH)
2D
3 for binding to chick intestinal cytosol receptor, 2) in ability for formation of multinucleated cells (MNC) with various osteoclastic cell characteristics from blast cells, and 3) in stimulating bone calcium mobilization in vitamin D-deficient rats. The relative potencies of 1, 25-(OH)
2D
3, 1α, 25-dihydroxy-26, 27-dimethylvitamin D
3 (2), 1α, 25-dihydroxy-26, 27-diethylvitamin D
3 (3), and 1α, 25-dihydroxy-26, 27-dipropylvitamin D
3 (4) in competing for intestinal cytosolic binding were 1 : 1.1 : 0.25 : 0.05. The similar order of the abilities on formation of the multinucleated cells in the same series was observed. In a bone calcium mobilization test with vitamin D-deficient rats, 1α, 25-dihydroxy-26, 27-dimethylvitamin D
3 showed slightly less activity than 1, 25-(OH)
2D
3 at 12h after administration, but long lasting activity was observed during time course experiments. 1α, 25-Dihydroxy-26, 27-diethylvitamin D
3, and 1α, 25-dihydroxy-26, 27-dipropylvitamin D
3 were found to be much less active than 1, 25(OH)
2D
3 in a bone calcium mobilization test.
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Eiichi MAKINO, Kazuya MITANI, Nobuhiko IWASAKI, Hideo KATO, Yasuo ITO, ...
1990 Volume 38 Issue 5 Pages
1250-1257
Published: May 25, 1990
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The effects of structural modifications of 6-substituted N-(1H-tetrazol-5-yl)-2-pyrazinecarboxamides on their anti-allergic activity was analyzed quantitatively by means of the Hansch-Fujita method. The activity of these compounds was correlated with hydrophobic (π) and steric (molecular refractivity and STERIMOL B
1) effects of the 6-substituent on the pyrazine ring. The 6-substituents with a length greater than n-propylamino possess an extra effect enhancing the activity. Moreover, the activity increased progressively from 6-non-amino via alkylamino- to dialkylamino-substituted compounds, other factors being equal. This could be attributable to an electronic effect of substituents. Electron-donating small and yet symmetric substituents with high hydrophobicity longer than n-propylamino seemed to be favorable to the activity. By compromising these contradictory requirements, small dialkylamino (including cyclic amino) groups were decided to be the most favorable substituents. This analysis was in agreement with the observation that the most effective compounds were the 6-dimethylamino (I-27) and 6-(1-pyrrolidinyl) (I-34) derivatives.
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Toshiyuki KONOSU, Noriko TAKEDA, Yawara TAJIMA, Hiroshi YASUDA, Sadao ...
1990 Volume 38 Issue 5 Pages
1258-1265
Published: May 25, 1990
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As part of our search for active agents against systemic fungal infections, a new series of triazole compounds with a thiolane ring was synthesized. Their antifungal activities were investigated in vitro and in vivo. Some of these thiolane-triazoles showed promising activity, comparable to that of ketoconazole, against a mouse systemic Candida albicans infection, after oral or parenteral dosing.
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Haruhiko SATO, Takashi DAN, Etsuro ONUMA, Haruko TANAKA, Hiroshi KOGA
1990 Volume 38 Issue 5 Pages
1266-1277
Published: May 25, 1990
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A series of substituted xanthonyloxyacetic acids (5 and 6), 1, 2-dihydrofuro[2, 3-c]xanthone-2-carboxylic acids (7) and 2, 3-dihydrofuro[3, 2-b]xanthone-2-carboxylic acids (8) were synthesized and tested for diuretic and uricosuric activities in rats. Most of the xanthon-3-yloxyacetic acids (5) and 7 showed potent diuretic activities, while 8 had lower activities. Uricosuric activities were found in 5c, 5f, 5k, 5m, 5o, 5p, 5r, 7m, 7p and 8q.
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Hiromitsu SAITO, Shigeru KOBAYASHI, Youichi UOSAKI, Akira SATO, Kazuhi ...
1990 Volume 38 Issue 5 Pages
1278-1285
Published: May 25, 1990
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Cyanation of quinocarcin readily opened the oxazolidine ring to provide DX-52-1 (2), which was a key compound in the synthesis of quinocarcin derivatives. Various electrophilic reactions toward aromatic ring of DX-52-1 were examined, and 10-substituted (e.g., halogen, nitro, formyl, cyano, hydroxy, etc.) analogs were prepared. Dehydrocyanation of the derivatives could be achieved to reproduce the oxazolidine ring upon treatment with HCl or AgNO
3. 10-Chloride 10 and 10-bromide 11 were the most promising among the derivatives prepared. Antitumor activity of 10 was extended to B-16 melanoma.
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Manabu HORI, Ryuichi IEMURA, Hideaki HARA, Akio OZAKI, Takayuki SUKAMO ...
1990 Volume 38 Issue 5 Pages
1286-1291
Published: May 25, 1990
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Several types of quinazoline derivatives were prepared and examined for anticonvulsive and antihypoxic activities. Many compounds showed potent anticonvulsive activity, and their anticonvulsive profile is similar to that of phenytoin. The analysis of quantitative structure-activity relationships indicated that the anticonvulsive activity was parabolically related to the lipophilicity of the compounds. Most of the 4-alkoxyquinazolines showed potent anticonvulsive and antihypoxic activities. It is confirmed that there is a good correlation between the potencies of these activites.
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Susumu KITANAKA, Michio TAKIDO
1990 Volume 38 Issue 5 Pages
1292-1294
Published: May 25, 1990
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Two new dimeric tetrahydroanthracene derivatives, torosaols I (1) and II (2), were isolated from the fresh roots of Cassia torosa Cav. along with pinselin, questin, 7-methyltorosachrysone, singueanol-I, germichrysone, germitorosone, methylgermitorosone, and phlegmacins A
2 and B
2. The structures of compounds 1 and 2 were established as 3, 3', 4, 4'-tetrahydro-2, 3, 3', 8, 8', 9, 9'-heptahydroxy-6, 6'-dimethoxy-3, 3', 7, 7'-tetramethyl-10, 10'-bi-1(2H)-anthracenone and 5-[3', 4'-dihydro-3', 8', 9'-trihydroxy-6'-methoxy-3', 7'-dimethyl-1' (2'H)-anthracenon-10'-yl]-3, 4-dihydro-9, 10-dihydroxy-3-hydroxymethyl-7-methoxy-3, 8-dimethyl-1H-naphtho[2, 3-c]pyran-1-one, respectively, on the basis of spectral evidence.
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Bao-Chang CAI, Masao HATTORI, Tsuneo NAMBA
1990 Volume 38 Issue 5 Pages
1295-1298
Published: May 25, 1990
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In the course of our study on the drug-processing of the seeds of Strychnos nux-vomica L. (Loganiaceae), the alkaloid composition of the heat-treated seeds of S. nux-vomica was compared to that of the untreated seeds. On heat treatment, the contents of the major alkaloids such as strychnine and brucine declined significantly with increases in the amounts of isostrychnine, isobrucine, strychnine N-oxide and brucine N-oxide. The cleavage of an ether linkage and the occurrence of N-oxidation were demonstrated by heat treatment of authentic strychnine and brucine.
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Yukio IZUMITANI, Shoji YAHARA, Toshihiro NOHARA
1990 Volume 38 Issue 5 Pages
1299-1307
Published: May 25, 1990
Released on J-STAGE: March 31, 2008
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Capsicum species are very important plants used as vegetable foods, spices and external medicines. We obtained novel acyclic diterpene glycosides, named capsianosides A-F (1-6) and I-V (7, 1b, 10, 9, 8) from various fruits of the Capsicum annuum species and their structures were elucidated by spectroscopic and chemical means. Capsianosides are classified into two groups, monomeric diterpene glycosides (capsianosides I-V) and their dimeric esters (capsianosides A-F).
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Shigeru SHIMIZU, Toshio MIYASE, Kaoru UMEHARA, Akira UENO
1990 Volume 38 Issue 5 Pages
1308-1312
Published: May 25, 1990
Released on J-STAGE: March 31, 2008
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Ten 11-oxygenated kauran-19-oic acids, ent-11α, 15α-dihydroxykaur-16-en-19-oic acid, ent-11α-hydroxy-15α-acetoxykaur-16-en-19-oic acid, ent-11α-hydroxy-15-oxo-kaur-16-en-19-oic acid and adenostemmoic acids A-G and their nine glycosides, paniculosides II and III and adenostemmosides A-G were characterized from Adenostemma lavenia O. KUNTZE. ent-11α-Hydroxy-15-oxo-kaur-16-en-19-oic acid and adenostemmoic acid B showed cytotoxic activity against L-5178Y cultured cell and prolonged the survival of mice.
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Fumihide TAKANO, Fumihiko YOSHIZAKI, Kazuo SUZUKI, Naoko SUYA, Toshio ...
1990 Volume 38 Issue 5 Pages
1313-1316
Published: May 25, 1990
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Anti-ulcer activities of fruits of Trichosanthes kirilowii MAXIMOQWICZ var. japonica KITAMURA (50% ethanolic extract, TKE) were investigated in rats.TKE, at doses of 100-1000mg/kg, showed potent protection against experimental gastric lesions, namely, those induced by water-immersion, histamine, serotonin, HCl·ethanol, 0.6N HCl, 0.2N NaOH, 35% NaCl, and Shay' ulcer and acetic acid-induced gastric ulcer.At doses of 500-1000mg/kg, TKE decreased the gastric secretion and acid output in pylorus-ligation (for 7h), but 100mg/kg of TKE had no influence on the gastric secretion. On the other hand, TKE exerted inhibition on the contractile responses of the isolated ileum of mouse to acetylcholine.These results suggested that TKE has an anti-ulcer effect.
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Atushi NISHIZAWA, Gisho HONDA, Mamoru TABATA
1990 Volume 38 Issue 5 Pages
1317-1319
Published: May 25, 1990
Released on J-STAGE: March 31, 2008
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Incorporation of
14C-labeled sucrose, acetate, butyrate, and mevalonate into the terpenoid components of essential oils was examined using the detached cotyledons and foliage leaf discs of Perilla frutescens. Althought the radioactivity of sucrose administered was incorporated into the mono- and sesquiterpenoids of both tissues, that of acetate or butyrate was hardly detectable in the lower terpenoids of any foliage leaves except cotyledons. These results suggest that the conversion of acetyl CoA derived from fatty acids into lower terpenoids in the cotyledons does not occur in the foliage leaves.
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Ryoji KASAI, Takahiro TANAKA, Rui-Lin NIE, Masazumi MIYAKOSHI, Jun ZHO ...
1990 Volume 38 Issue 5 Pages
1320-1322
Published: May 25, 1990
Released on J-STAGE: March 31, 2008
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From rhizomes of a Chinese cucurbitaceous medicinal plant, Hemsleya graciliflora, eight oleanolic glucuronide saponins were isolated together with three known cucurbitane-type triterpenes, dihydrocucurbitacin F, 25-O-acetyl-dihydrocucurbitacin F and its 2-O-β-glucosides. Of these saponins, six were known and identified as β-D-glucosyl ester of oleanolic acid, chikusetsusaponins IV a and V and hemslosides Ma1, Ma3 and H1. Structures of two new saponins called hemslosides G1 and G2 were elucidated as β-gentiobiosyl esters of oleanolic acid 3-O-α-L-arabinopyranosyl-(1→3)-β-D-glucuronide and oleanolic acid 3-O-β-D-glucopyranosyl-(1→2)-β-D-glucuronide, respectively.
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Kazumi SASAMOTO, Yosuke OHKURA
1990 Volume 38 Issue 5 Pages
1323-1325
Published: May 25, 1990
Released on J-STAGE: March 31, 2008
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A new type of chemiluminogenic substrate for N-acetyl-β-D-glucosaminidase, o-aminophthalylhydrazido-N-acetyl-β-D-glucosaminide, was prepared by incorporating an enzyme-removable substituent, N-acetyl-D-glucosaminide group, into the hydrazide moiety of luminol. This substrate releases luminol upon enzymatic hydrolysis. The enzyme was detected chemiluminescently using this substrate.
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Kyoichi KOBASHI, Sachiko TAKEBE, Tatsuo SAKAI
1990 Volume 38 Issue 5 Pages
1326-1328
Published: May 25, 1990
Released on J-STAGE: March 31, 2008
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Urethane, a cancer-causing chemical, was reported to contaminate alcoholic beverages such as whisky, liquor, wine and sake. Enzymatic removal of urethane would be a possible approach to remove this potentially hazardous chemical form alcoholic beverages. We found that Citrobacter sp. isolated from mouse feces stoichiometrically decomposed urethane to ethanol and ammonia. We named this enzyme "urethanase." Partially purified urethanase could hydrolyze several carbamates and some amides. However, urea, N-alkyl ureas and ethyl esters of organic acids were not hydrolyzed at all. These results suggest that urethanase belongs to the category of amidase. The enzyme was inactive in high concentrations of alcohol and at acidic pH and was practically ineffective for the elimination of urethane from alcoholic beverages.
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Takayuki NAGAI, Yukinori MIYAICHI, Tsuyoshi TOMIMORI, Yujiro SUZUKI, H ...
1990 Volume 38 Issue 5 Pages
1329-1332
Published: May 25, 1990
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Flavonoids (103 species) were tested for inhibitory activity against influenza virus sialidase using sodium p-nitrophenyl-N-acetyl-α-D-neuraminate as substrate. 5, 7, 4'-Trihydroxy-8-methoxyflavone from the root of Scutellaria baicalensis showed the most potent activity (IC
50, 55μM), and this flavone appeared to be a non-competitive inhibitor of the enzyme, Whereas, negligible or weak inhibitory activities were observed for mouse liver sialidase, β-galactosidase and α-mannosidase as tested. This flavone also inhibited the infection by influenza virus A/PR/8/34 of Madin-Darby canine kidney cells, and replication of the virus in the allantoic sack of embryonated egg. These results suggest that flavone, which has potent influenza virus sialidase inhibitory activity, may have anti-influenza virus activity.
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Ken-ichi GOTOH, Mineo TAKEI, Takafumi WATANABE, Tetsuya SUGA
1990 Volume 38 Issue 5 Pages
1333-1337
Published: May 25, 1990
Released on J-STAGE: March 31, 2008
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The effects of inhibitors on peroxisomal enzymes were examined in order to clarify the role of peroxisomes in the grouwth of Tetrahymena pyriformis. With the supplementation of chlorpromazine, known as an inhibitor of the peroxisomal β-oxidation system, to the culture medium, the growth of T. pyriformis was suppressed and the activity of the glyoxylate cycle which is linked to β-oxidation, was reduced. Supplementation of itaconic acid to the medium, a competitive inhibitor of isocitrate lyase of the glyoxylic acid cycle, also inhibited the growth. In these cases, no change in the activity of mitochondrial β-oxidation was observed. On the other hand, in an experiment concerning the fatty acid metabolism using [U-
14C]palmitic acid conversions to glycogen and proteins were significantly inhibited by these inhibitors. Thus, a decrease in the supply of carbon atoms, which are necessary for energy production and the biosynthesis of materials used in cell construction, was suggested. The acyl-coenzyme A not subjected to β-oxidation might be used for lipid synthesis, resulting in an accumulation of triglyceride and phospholipids.From these results, it was concluded that in Tetrahymena peroxisome is not merely an assistant in the mitochondrial metabolic system, but has an important role in the production of energy essential for cell movement and cell growth, and in the conversion of fatty acids to carbohydrates and proteins.
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Nobuo AOYAGI, Nahoko KANIWA, Hiroyasu OGATA
1990 Volume 38 Issue 5 Pages
1338-1340
Published: May 25, 1990
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Two different indomethacin capsules, a commercial one containing fine drug particles and an experimental capsule containing 125-177μm particles, were employed in this study. The commercial preparation showed faster in vitro dissolution than the experimental one. When administered to humans having normal acidity of the gastric juices, the commercial capsule exhibited higher C
max and smaller T
max and mean residence time (MRT) than the experimental one both in fasting and nonfasting states, although the two capsules were equivalent in area under the serum concentration-time curve (AUC). The ingestion of a breakfast delayed the gastrointestinal absorption from both preparations, which resulted in larger T
max's and MRT's and smaller C
max's in the nonfasting state. Food, however, did not have any significant effect on the AUC's of the preparations.
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Mariko NAGATA, Toshihisa YOTSUYANAGI, Ken IKEDA
1990 Volume 38 Issue 5 Pages
1341-1344
Published: May 25, 1990
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The disintegration kinetics of egg phosphatidylcholine small unilamellar liposomes in various bile salts (nine species) were investigated by monitoring turbidity changes with a stopped-flow apparatus. The pseudo-first-order rate constants obtained as a function of bile salt concentration (up to 25mM) were analyzed based on a two-step model in which a penetration-saturation step of bile salt into the bilayer and a lamellar-micellar transition step were assumed for the disintegration mechanism of the bilayer. The order of the rate of the penetration-saturation step, which is assumed to be a measure of the disintegration ability, was as follows : SCDOC>SDOC>STCDOC>STDOC>STC>SC>SGCDOC>SGDOC>SGC. The results indicated that (1) the dihydroxy bile salts have a greater disintegration ability than the corresponding trihydroxy bile salts, (2) the chenodeoxy bile salts have a greater ability than the corresponding deoxy-bile salts regardless of non-conjugated or conjugated form, (3) the taurine conjugates always have a greater ability than the glycine conjugates. The penetration-saturation rate of the bile salts against the lipid bilayer depends considerably on the chemical nature of each bile salt, varying by a factor of about 10
5. In the conjugated bile salts alone, they were in a narrower range of a factor of 10
3. The physical integrity of liposomes can hardly be maintained in the bile salt-rich intestinal tract but the resulting mixed micelles may contribute substantially to solubilization and enhanced delivery of drugs.
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Yoshinobu NAKAI, Keiji YAMAMOTO, Toshio OGUCHI, Etsuo YONEMOCHI, Takeh ...
1990 Volume 38 Issue 5 Pages
1345-1348
Published: May 25, 1990
Released on J-STAGE: March 31, 2008
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The inclusion compound of heptakis-(2, 6-di-O-methyl)-β-cyclodextrin (DM β CD) and benzoic acid was prepared by heating in a sealed container. Inclusion formation was studied as a function of heating temperature, heating time, mixing molar ratio, and crystallinity of DMβ CD measured by X-ray diffractometry and infrared spectrometry. The combining molar ratio of benzoic acid to DMβ CD increased with an increase in heating temperature and time. When amorphous DMβ CD was used for the inclusion formation, the combining molar ratio of benzoic acid to DMβ CD increased to about double the amount of crystalline DMβ CD used. It was found that the heating temperature, heating time, mixing molar ratio, and crystallinity of DMβ CD affected the formation of inclusion compound.
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Takanori SAKAI, Norio AWATA, Jun WATANABE
1990 Volume 38 Issue 5 Pages
1349-1352
Published: May 25, 1990
Released on J-STAGE: March 31, 2008
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Interspecies differences in the hepatic transport of an antiallergic agent, emedastine difumarate (KG-2413), were investigated in rats and guinea pigs, taking notice of the influx, efflux and metabolic processes. When the concentration of emedastine in the injection was varied from 2μM to 10mM, the extraction ratio of total radioactive compound to the liver at 18s in rats and 25s in guinea pigs after the rapid portal injection was more than 90% of the dose. This suggested that the influx velocity of emedastine into the liver was extremely fast, and that there was no interspecies difference in the influx process. The disappearance of unchanged emedastine from the liver was described by biexponential curve in rats and monoexponential curve in guinea pigs after rapid portal injection of 100μM solution. This difference might be related to the interspecies difference in the binding of emedastine to the liver tissue. The time courses of disappearance of total radioactive compound and unchanged emedastine from the liver were analyzed using a compartment model for the examination of the efflux and metabolic processes. Emedastine was observed to have a pronounced interspecies difference in metabolic rate constant, but there was no pronounced interspecies difference in its efflux rate constant.
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Kiyoshi SHIMIZU, Motoharu IWATSURU
1990 Volume 38 Issue 5 Pages
1353-1358
Published: May 25, 1990
Released on J-STAGE: March 31, 2008
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In nonionic-nonionic mixed surfactant systems, when two surfactants below their individual critical micelle concentrations (cmc) were mixed, the formation of mixed micelles was confirmed and the cmc values were measured by the first derivative absorption spectrum (FDAS) method, the solubilization method (with Sudan Red dye) and the surface tension method (Wilhelmy plate method). The region corresponding to mixed micelle formation was obtained from plots of the sum of the concentrations corresponding to the cmc (=[OED]
*PED/cmc
OED+[PED]
*OED/cmc
PED : [OED]
*PED (or [PED]
*OED) is the concentration of OED (or PED) in the cmc for mixed micelle formation of OED-PED binary systems, and cmc
OED (or cmc
PED) is the cmc of OED (or PED)) on the ordinate against the mole fraction normalized with respect to cmc (=[[OED]/cmc
OED/[[OED]/cmc
OED+[PED]/cmc
PED] : [OED] (or [PED]) is the concentration of OED (or PED)) on the abscissa by the FDAS method.In the region of cooperative micelles which was a part of the region forming mixed micelles, it was found that the longer the ethylene glycol chain length of the nonionic-nonionic mixed surfactants, the wider was the region of cooperative micelles. The order of the width was 0.78mM OED-0.43mM PED>0.43mM OED-0.43mM PED>0.78mM OED-0.43mM TED=0.43mM PED-0.43mM TED>0.43mM OED-0.43mM TED mixed surfactant systems. In ionic-nonionic mixed surfactant systems, the cmc values of the mixed micelles were under the influence of the nonionic surfactant. But in nonionic-nonionic mixed surfactant systems, the cmc values of the mixed surfactant systems were under the influence of both nonionic surfactans. (Abbreviations used are : OED, PED and TED=octa-, penta- and triethylene glycol dodecyl ether.)
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Seung Y. LEE, Hee M. RHEE
1990 Volume 38 Issue 5 Pages
1359-1364
Published: May 25, 1990
Released on J-STAGE: March 31, 2008
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In an effort to understand the mechanism of cardiovascular actions of Ganoderma lucidum which was cultivated in Korea, the mycelium was isolated for a large-scale culture. Water extract of the mycelia was evaluated for its cardiovascular activity in anesthetized rabbits and rats. The left femoral artery and vein were cannulated for the measurement of arterial pressure and subsequent delivery of drugs. The left kidney was exposed retroperitoneally and a branch of the renal nerve was used to integrate renal efferent of afferent nerve activities. The extract decreased systolic and diastolic blood pressure, which was accompanied by an inhibition of renal efferent sympathetic nerve activity. The extract did not decrease heart rate in these animals, although there was clear hypotension in the extract dose dependent manner. This suggests that the hypotension induced by the treatment of the extract was secondary to the primary effect of the extract in the central nerve system. which suppressed the sympathetic outflow. Therefore we concluded that the mechanism of hypotensive action of Ganoderma lucidum was due to its central inhibition of sympathetic nerve activity.
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Shizuo NARIMATSU, Kazuhito WATANABE, Tamihide MATSUNAGA, Ikuo YAMAMOTO ...
1990 Volume 38 Issue 5 Pages
1365-1368
Published: May 25, 1990
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The mechanism of inhibitory effect of cannabidiol (CBD) on the hepatic drug-metabolizing enzyme system was studied in adult male rats in vivo. Time course studies revealed that microsomal d-benzphetamine N-demethylation and testosterone 2α-, 16α- and 17-oxidation were markedly suppressed 6 to 48h after the single administration of CBD (10mg/kg, intraperitoneally). Decreases in activities of aniline hydroxylation and p-nitroanisole O-demethylation and in content of total cytochrome P450 were intermittent and moderate. On the other hand, no change was observed in reduced nicotinamide adenine dinucleotide phosphate (NADPH)-cytochrome c reductase activity or cytochrome b
5 content in the hepatic microsomes of the CBD-treated rats. Western blotting analysis showed a marked decrease in the male-specific cytochrome P450 UT-2 in the hepatic microsomes, especially 24 to 48h after pretreatment with CBD. It is possible that CBD given 6 to 12h before the sacrifice might interact with cytochrome P450 as a substrate, resulting in inhibition of the drug-metabolizing enzyme activities in the earlier stages. In the later stages from 24 to 48h after CBD treatment, the reduction in content of the male-specific cytochrome P450 UT-2 may play a major role in the inhibitory effect of CBD on the hepatic drug-metabolizing enzyme system in the adult male rat in vivo.
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Masaki HAGIWARA, Eiko OHUCHI, Kazuya HONGO, Miyuki OKI, Masaharu NAKAN ...
1990 Volume 38 Issue 5 Pages
1369-1372
Published: May 25, 1990
Released on J-STAGE: March 31, 2008
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The pharmacological activities of synthetic human CCK-33, in which a tyrosine molecule was sulfated by arylsulfotransferase, were investigated in the rat and the guinea-pig. The activities were compared with those of non-sulfated CCK-33 (CCK-33NS), CCK-8 and CCK-4. CCK-33 was about 100 fold more potent than non-sulfated CCK-33(CCK-33NS)but was about 20 fold less potent than CCK-8 in the contraction of the isolated gallbladder of the guinea-pig. In rat pancreatic secretion, intravenous CCK-33 and CCK-8 showed almost the same activity. The potency of each was about 1000 fold more than the individual potency of CCK-33NS, non-sulfated CCK-8 (CCK-8NS) and CCK4. There were no significant differences in gastric acid stimulatory activities among CCK-33, CCK-8, CCK-4, but the activities of CCK-33NS and CCK-8NS were less than those of CCK-33 and CCK-8, respectively. CCK-33 and CCK-8 produced a reduction in the intake of powder chow in doses of 10
-8 and 3×10
-8mol/kg i.p., but CCK-33NS, CCK-8NS and CCK-4 did not. In conclusion, the activities of synthetic human CCK-33 are almost the same as those of CCK-8 on exocrine pancreatic secretion, gastric acid secretion and food intake, but less than CCK-8 on isolated gallbladder contraction.
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Machiko ONO, Ichiro ARAYA, Shinzo TAMURA
1990 Volume 38 Issue 5 Pages
1373-1378
Published: May 25, 1990
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N
1-Tosyl-N
1, N
2-diarylacetamidine (1) suffered nucleophilic attack of N-tosylamines and N-acylamines at the amidine central carbon to give N
1-tosyl and N
1-acyl derivatives of N-1, N
2-disubstituted acetamidine in the presence of a basic catalyst.Preparation of N
1-(p-nitrobenzenesulfonyl)-N
1, N
2-diarylacetamidines (8) was attempted to obtain better starting materials for the above amide exchange reaction. These compounds, however, proved to be unsuitable for the purpose because they readily underwent Smiles rearrangement to give N
1-(p-nitrophenyl-N
1, N
2-diarylacetamidines (9) with loss of sulfur dioxide.N
1-(p-Nitrophenyl)-N
1-(p-methylphenyl)-N
2-(p-chlorophenyl)acetamidine (9d) was formed when an ethanol solution of N
1-(p-nitrobenzenesulfonyl)-N
1-(p-chlorophenyl)-N
2-(p-methylphenyl)acetamidine (8d) was refluxed for 2.5h in the absence of any catalyst.
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Machiko ONO, Kazumi AOKI, Shinzo TAMURA
1990 Volume 38 Issue 5 Pages
1379-1388
Published: May 25, 1990
Released on J-STAGE: March 31, 2008
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N
1-Tosyl-N
1, N
2-diarylacetamidines (1) undergo uncleophilic attack of N-tosylamide anion at the amidine central carbon, and the less basic N-tosylamido group is expelled from the intermediate, resulting in an amide exchange reaction. Reaction of 1 and N-arylcarboxamide afforded N
1-acyl-N
1, N
2-diarylacetamidine (2). N
1-(p-Chlorobenzoyl)-N
1-(p-methoxyphenyl)-N
2-(p-chlorophenyl)acetamidine (2a) could not be obtained as such, but was obtained as an equilibrium mixture of 2a and N
1-(p-chlorobenzoyl)-N
1-(p-chlorophenyl)-N
2-(p-methoxyphenyl)acetamidine (2a') owing to rapid 1, 3-N, N-acylotropic rearrangement.N
1-Acyl derivatives of unsymmetrical N
1, N
2-disubstituted formamidines could be isolated as such, showing that 1, 3-N, N-acyl migration takes place more slowly in the acylated formamidine system. An acyl derivative of formamidine in which the acyl group is attached at the less basic nitrogen of amidine underwent 1, 3-N.N-acyl migration to give another acyl derivative at elevated temperature.Reaction of N
1-tosyl-N
1-(p-nitrophenyl)-N
2-(m-nitrophenyl)acetamidine (1h) and N-acylarylamines gave N
1-acyl-N
1-aryl-N
2-(m-nitrophenyl)acetamidines (2) which underwent alcoholysis to give carboxylic acid ester and N
1-aryl-N
2-(m-nitrophenyl)acetamidines (3) at room temperature, and the latter was hydrolyzed to give arylamines and N-acetyl-m-nitroaniline on heating in aqueous tetrahydrofuran solution in the presence of acetic acid. Thus, the alcoholysis of N-acylarylamines was achieved under mild conditions.
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