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金 叡淑, 松本 美弥子, 町田 勝之輔
1985 年 33 巻 10 号 p.
4125-4131
発行日: 1985/10/25
公開日: 2008/03/31
ジャーナル
フリー
The displacement velocity of each crystalline face of aspirin on dissolution in distilled water was determined by using large single crystals grown from ethanolic solution. It was found that each crystalline face of aspirin has its own displacement velocity. The specific surface energies for those crystalline surfaces in water and in vacuo were calculated from a set of atom-atom pairwise potential functions. The relative rate of diminution of surface area on dissolution of the crystal can be correlated to the sensitivity of the surface energy to the polarity of the solvent.
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古川 宏, 呉 天賞, 太田 智子, 郭 長生
1985 年 33 巻 10 号 p.
4132-4138
発行日: 1985/10/25
公開日: 2008/03/31
ジャーナル
フリー
Thirteen carbazole alkaloids were isolated from Murraya euchrestifolia HAYATA (Rutaceae) collected in Taiwan. Four of them are novel carbazolequinones [murrayaquinone-A (7), -B (8), -C (9), and -D (10)], isolated for the first time from natural sources. Three of others are new alkaloids having the normal carbazole nucleus [murrayafoline-A (1), -B (2), and (+)-murrayazoline (11)]. These structures were elucidated from spectral data and chemical transformations.
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石井 永, 市川 裕一郎, 川鍋 恵理, 石川 宗一, 石川 勉, 榑谷 和男, 猪俣 素子, 星 昭夫
1985 年 33 巻 10 号 p.
4139-4151
発行日: 1985/10/25
公開日: 2008/03/31
ジャーナル
フリー
Several nonphenolic benzo [c] phenanthridine alkaloids including naturally occurring nitidine (1a) and avicine (1e) were synthesized in excellent yields through an efficient synthetic method developed by us. Antitumor activities of twelve alkaloids including four naturally occurring O
5-alkaloids [chelilutine (1g), chelirubine (1h), sanguilutine (1k), and sanguirubine (11)] against Sarcoma 180 were tested. The structure-activity relationship of these alkaloids is discussed.
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大塚 栄子, 松儀 実宏, 山根 明男, 森岡 弘志, 池原 森男
1985 年 33 巻 10 号 p.
4152-4159
発行日: 1985/10/25
公開日: 2008/03/31
ジャーナル
フリー
Ribooligonucleotides (nonamer, decamer and nonadecamer) were synthesized by the solid phase phosphotriester method using 2'-O-tetrahydrofuranyl nucleosides. These oligomers were designed in order to obtain E. coli tRNA
Metf deficient in D-loop and D-stem and its analogs. Condensation was performed by using dimer blocks and the dimethoxytrityl group on the 5'-hydroxyl group was removed selectively by 1M ZnBr
2 without affecting the 2'-protection.
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金子 主税, 片桐 信弥, 内山 景志, 山田 徹
1985 年 33 巻 10 号 p.
4160-4166
発行日: 1985/10/25
公開日: 2008/03/31
ジャーナル
フリー
Irradiation (350nm) of 2-(3-butenyl)-and 2-(4-pentenyl) isoquinolin-1 (2H)-ones (1a and 1b) afforded the intramolecular [2+2] adducts (2a and 2b). The additions proceeded regioselectively to give only the parallel adducts. Though stable to irradiation at 350nm, these adducts (2a and 2b) gave o-vinylbenzamide derivatives (3a and 3b) on irradiation at 300nm. The intermolecular [2+2] adducts (7d and 7e) obtained by irradiation (≥300nm) of isoquinolin-1 (2H)-one (6) in the presence of a large excess of alkenes were also found to be unstable and reverted to the original components [isoquinolin-1 (2H)-one (6) and alkenes] on irradiation at 300nm in the absence of the alkenes.
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森 鉱次, 後藤 正文, 酒井 朝也
1985 年 33 巻 10 号 p.
4167-4174
発行日: 1985/10/25
公開日: 2008/03/31
ジャーナル
フリー
The oxygenated dimer (2a) of 3-methylindole, which was isolated from the reaction mixture obtained by oxygenation of 3-methylindole in the presence of N, N'-(cis-1, 2-cyclohexylene) bis (3-tert-butylsalicylideneaminato) cobalt (II) in chloroform, was shown to be the stereoisomer of 5aβ (H), 11aα (H)-12β-hydroxy-10bβ, 12α-dimethyl-5a, 10b, 11a, 12-tetrahydro-6H-oxazolo [3, 2a : 4, 5-b'] diindole (1a) with inverted configuration at the C
12 atom, on the basis of
1H and
13C-nuclear magnetic resonance (NMR) spectroscopic and chemical evidence. Kinetic parameters of restricted rotation about the amide bond in N-acetylated derivatives of 1a and 2a calculated from their dynamic NMR spectra were ΔH
≐̸
298=20.2±0.2 and ΔS
≐̸
298=+7.8±0.5 for the former, and ΔH
≐̸
298=19.7±0.2kcal mol
-1 and ΔS
≐̸
298=+5.9±0.6cal K
-1mol
-1 for the latter. Acid decomposition of both dimers, 1a and 2a, afforded 3, 3'-dimethyl-1-(2'-indolyl)-oxindole, resulting from ring cleavage at the ether bond followed by dehydration.
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佐武 紀子, 村上 孝夫, 横手 信昭, 斎木 保久, 陳 秋明
1985 年 33 巻 10 号 p.
4175-4181
発行日: 1985/10/25
公開日: 2008/03/31
ジャーナル
フリー
A novel pterosin-type dinorsesquiterpene, mukagolactone (I), was isolated from the fronds of Monachosorum arakii TAGAWA (Pteridaceae), along with three new dinorsesquiterpene dimers, monachosorins A (II), B (III) and C (IV). Their structures were elucidated on the basis of spectroscopic and chemical data. Compound II may have been formed by an aldol-type condensation of 6-(2-hydroxyethyl)-5, 7-dimethylindan-1-one and the corresponding 5-formyl compound. The reduction of II afforded III, and the acid isomerization of II gave IV.
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和田 浩志, 佐武 紀子, 村上 孝夫, 児島 利典, 斎木 保久, 陳 秋明
1985 年 33 巻 10 号 p.
4182-4187
発行日: 1985/10/25
公開日: 2008/03/31
ジャーナル
フリー
From the fronds of Alsophila spinulosa TRYON biflavonoids Hegoflavone A (I) and B (II) were isolated and their structures were elucidated by spectroscopic analysis and chemical degradation to be 2, 3-dihydro-3'''-hydroxy-6, 6'''-biapigenin (I) and 2, 3-dihydro-6, 6'''-biluteolin (II) respectively. These are the first reports of a C-6/C-6'''-linked biflavonoid in nature.
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山口 正義, 周 俊, 林 紘司, 三橋 博
1985 年 33 巻 10 号 p.
4188-4192
発行日: 1985/10/25
公開日: 2008/03/31
ジャーナル
フリー
The chemical components of the Chinese crude drug "Pai-Wei, " dried root of Cynanchum atratum BUNGE, have been further investigated. Glaucogenin-A (1), glaucoside-C (2), glaucoside-H (3) and a new glycoside named cynatratoside-F (4) were isolated. The structure of 4 was determined on the bases of spectroscopic evidence and analyses of its hydrolysate.
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東野 武郎, 竹元 万寿美, 丹治 健一, 飯島 千穂子, 林 英作
1985 年 33 巻 10 号 p.
4193-4201
発行日: 1985/10/25
公開日: 2008/03/31
ジャーナル
フリー
The reaction of 2-aroylquinoxalines (1) with sodium hydroxide in dimethyl sulfoxide (DMSO) was found to result in aryl migration, fission of the C
2-C=O bond, and addition of DMSO to the C=O group, giving 2-arylquinoxalines (2), quinoxaline (4), aroic acids (5), and α-aryl-α-(methylsulfinylmethyl)-2-quinoxalinemethanols (6). Compounds 6 could be separated into two racemates, (αR
*, SR
*)-6 and (αR
*, SS
*)-6. In order to establish the generality of the aryl migration, other aroylated aromatic heterocycles were examined. 3-Aroylpyrido [2, 3-b] pyrazines (7) and 1-benzoyl-4-isoquinolinecarbonitrile (10) both underwent similar aryl migration to give 3-arylpyridopyrazines (14) and 1-phenyl-4-isoquinolinecarbonitrile (18), respectively. On the other hand, the reaction of 1-benzoylisoquinoline (9) and 2-benzoylquinoline (11) resulted not in migration, but in the addition of DMSO to give 1-isoquinolinemethanol (16) and 2-quinolinemethanol derivatives (20), respectively. In the case of 1-benzoylphthalazine (8), migration did not occur, but instead 4-benzoyl-1 (2H)-phthalazinone (15) was formed.
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今西 武, 八木 典幸, 花岡 美代次
1985 年 33 巻 10 号 p.
4202-4211
発行日: 1985/10/25
公開日: 2008/03/31
ジャーナル
フリー
A new elaboration method for the 2-azabicyclo [2.2.2] octane ring via an intramolecular Michael reaction has been developed and applied to the total synthesis of (±)-ibogamine (1) and (±)-epiibogamine (2). The unsaturated ester (9) derived from ethyl 1, 6-dihydro-3 (2H)-pyridinone-1-carboxylate (3a) was reacted with potassium carbonate or sodium hydride to provide two 2-azabicyclo [2.2.2] octanone derivatives (19 and 20), the stereochemistry of which was confirmed by chemical evidence. By a three-step sequence, the esters (19 and 20) were converted into 27 and 36, which were then transformed into the corresponding amides (31 and 40). Cyclization of 31 and 40 followed by reduction with a complex of lithium aluminum hydride-aluminum chloride furnished (±)-epiibogamine (2) and (±)-ibogamine (1), respectively, in good yields.
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広田 耕作, 北出 幸夫, 冨士 哲男, 牧 敬文
1985 年 33 巻 10 号 p.
4212-4215
発行日: 1985/10/25
公開日: 2008/03/31
ジャーナル
フリー
Reaction of 5-substituted 2', 5'-dichloro-2', 5'-dideoxyuridines (1a-d) with methanolic sodium hydroxide under reflux afforded the corresponding 5-substituted 2', 5'-anhydro-1-β-D-arabino-furanosyluracils (3a-d) in high yield. On the other hand, reaction of 5-substituted uridines (5a-d) with the Vilsmeier-Haack reagent (POCl
3/DMF) followed by treatment with methanolic sodium hydroxide under reflux led directly to the formation of the corresponding anhydrouridines (3a-d) in good yield.
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河田 恒佐, 北川 理, 田口 武夫, 榛沢 雄二, 小林 義郎, 飯高 洋一
1985 年 33 巻 10 号 p.
4216-4222
発行日: 1985/10/25
公開日: 2008/03/31
ジャーナル
フリー
Lewis acid-catalyzed aldol condensation of 2-trimethylsilyloxy-4-trifluoromethylfuran (2a) with aldehydes was found to proceed in a regio- and diastereoselective manner to give the 5-substituted 4-trifluoromethyl-2 (5H)-furanone (4) in good yield. The aldol product (4a) derived from benzyloxyacetaldehyde was successfully converted to the branched sugar (12), the first reported example of a trifluoromethylated branched sugar, and its crystal structure was determined by X-ray analysis.
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横井 利夫, 新宮 徹朗, 門田 重利, 菊池 徹
1985 年 33 巻 10 号 p.
4223-4227
発行日: 1985/10/25
公開日: 2008/03/31
ジャーナル
フリー
Pachysana-16, 21-diene-3β, 28-diol and pachysan-16-ene-3β, 28-diol, new triterpene-diols having a 28-nor-16-methylfriedelane skeleton, were isolated from Pachysandra terminalis SIEB. et ZUCC. and their structures were elucidated. The name "pachysanane" is proposed for this new skeleton.
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小林 孝次, 上里 新一, 上田 伸一, 井上 博之
1985 年 33 巻 10 号 p.
4228-4234
発行日: 1985/10/25
公開日: 2008/03/31
ジャーナル
フリー
Administration of
3H- or
13C-labeled acyclic monoterpenes to Gardenia jasminoides f. grandiflora cell suspension cultures showed that tarennoside (20) and gardenoside (21) were biosynthesized in the cell cultures via the cyclization of 10-oxogeranial (5a)/10-oxoneral (5b) to iridodial cation (14). followed by extensive randomization of the carbon atoms 3 and 11. Furthermore, the intermediacy of (R)-(+)-and (S)-(-)-10-hydroxycitronellol (24a, 24b) and (R)-(+)-and (S)-(-)-9, 10-dihydroxycitronellol (28a, 28b) was disproved.
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北 泰行, 田村 修, 安田 均, 伊藤 文雄, 田村 恭光
1985 年 33 巻 10 号 p.
4235-4241
発行日: 1985/10/25
公開日: 2008/03/31
ジャーナル
フリー
Treatment of alkyl phenyl sulfoxides (2a-h) with O-methyl-O-tert-butyldimethylsily ketene acetal (1a) in dry acetonitrile in the presence of a catalytic amount of zinc iodide caused a Pummerer-type rearrangement to give α-siloxy phenyl sulfides (3a-h) under mild conditions. On the other hand, treatment of the sulfoxide (2d) with O-methyl-O-trimethylsilyl ketene acetals (1b, c) under similar conditions gave carbon-carbon bond-formed products, methyl 3-(phenylthio)-butyrates (8 and 9).
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JEANCHARLES LANCELOT, DANIEL LADUREE, MAX ROBBA
1985 年 33 巻 10 号 p.
4242-4246
発行日: 1985/10/25
公開日: 2008/03/31
ジャーナル
フリー
The synthesis of 2-methyl-pyrido [3, 2-e] pyrrolo [1, 2-a] pyrazine is described. The starting materials, 2-amino-6-methyl-3-nitropyridine and 2-amino-6-methyl-3-hydroxypyridine, were converted into pyrrolyl derivatives by using 2, 5-dimethoxytetrahydrofuran in glacial acetic acid. Subsequent elaboration of the latter afforded the title compounds. The proton nuclear magnetic resonance (
1H-NMR) spectra of the products were also studied.
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佐々木 茂貴, 川崎 元士, 古賀 憲司
1985 年 33 巻 10 号 p.
4247-4266
発行日: 1985/10/25
公開日: 2008/03/31
ジャーナル
フリー
The rates of transacylation were studied between thiol-bearing chiral crown ethers (1-10) and α-amino acid p-nitrophenyl ester salts. Enantioselectivities, k
D/k
L ratios, of 6.5 for valine ester salt, 8.7 for phenylalanine ester salt, and 7.7 for valine ester salt were achieved by 1, 5, and 8, respectively. Saturation phenomena of rate acceleration depending on crown concentration were observed and analysis of these data revealed that the chiral recognition occurs in the step of liberation of p-nitrophenol by intra-complex thiolysis, not in the complex-forming step. A possible mechanism for the enantioselectivity is proposed on the basis of the kinetic data.
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吉川 雅之, 王 恵康, 茅切 浩, 谷山 登志男, 北川 勲
1985 年 33 巻 10 号 p.
4267-4274
発行日: 1985/10/25
公開日: 2008/03/31
ジャーナル
フリー
A new bisdesmoside of soyasapogenol B (3), named sophoraflavoside I (2), was isolated together with soyasaponin I (1) from Sophorae Radix (Sophora flavescens AITON, root). By employing a photochemical cleavage method for the glucuronide linkage in 2 and on the bases of chemical reactions and spectral analyses, the structure of sophoraflavoside I has been determined to be 3-O-[α-L-rhamnopyranosyl (1→2)-β-D-galactopyranosyl (1→2)-β-D-glucuronopyranosyl]-22-O-[β-D-glucopyranosyl (1→2)-α-L-arabinopyranosyl] soyasapogenol B (2).
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田中 崇嗣, 田中 治, 林 中文, 周 俊
1985 年 33 巻 10 号 p.
4275-4280
発行日: 1985/10/25
公開日: 2008/03/31
ジャーナル
フリー
The assignment of the source plant of the Chinese plant drug "Bai-Yun-Shen" as Salvia digitaloides DIELS (Labiatae), was revised to Phlomis betonicoides DIELS of the same family. From roots of this plant, a sweet glycoside named phlomisoside-I (5) and a bitter glycoside named phlomisoside-II (6) were isolated. The aglycone of both compounds was proved to be baiyunol (7, furano-labdane-type diterpene), the aglycone of baiyunoside (1), which has already been isolated as the sweet principle from this plant drug. The structures of 5 and 6 were elucidated as the 3-O-α-rhamnopyranosyl-(1→2)-β-glucopyranoside and the 3-O-sophoroside of 7, respectively.
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細田 宏, 高崎 渉, 三浦 裕也, 頭金 正博, 圓山 優子, 南原 利夫
1985 年 33 巻 10 号 p.
4281-4287
発行日: 1985/10/25
公開日: 2008/03/31
ジャーナル
フリー
A method for the conversion of 11-deoxycortisol into 3α-hydroxy-5α-compounds is described. The allotetrahydro-11-deoxycortisol monoacetates (8, 14), which are key intermediates in the preparation of the 3- or 21-glucuronide of allotetrahydro-11-deoxycortisol, were the target compounds. The preparation of 5α-dihydro-11-deoxycortisol 21-acetate (4) was carried out by hydrogenation of the 3-ethoxy-3, 5-diene (2), followed by acid hydrolysis. When the 21-tetrahydropyranyl ether (6) and 21-tert-butyldimethylsilyl ether (7) were treated with potassium tri-secbutylborohydride in tetrahydrofuran under mild conditions, selective reduction of the carbonyl group at C-3 took place, yielding the 3α-alcohols (9 and 10, respectively). Allotetrahydro-11-deoxycortisol 3-glucuronide (21) and allotetrahydro-11-deoxycortisol 21-glucuronide (23) were then prepared.
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深井 俊夫, 羽野 芳生, 平倉 一弘, 野村 太郎, 鵜沢 洵
1985 年 33 巻 10 号 p.
4288-4295
発行日: 1985/10/25
公開日: 2008/03/31
ジャーナル
フリー
A new 2-arylbenzofuran derivative, mulberrofuran H and two isoprenylated flavones, kuwanons S and T, were isolated from the ethyl acetate extract of the root bark of cultivated mulberry tree (Japanese name "Roso, "a cultivated variety of Morus lhou KOIDZ.). The structures of mulberrofuran H and kuwanons S and T were shown to be 1, 2, and 3, respectively, on the basis of spectral evidence. Mulberrofuran H can be regarded biogenetically as a variation of a Diels-Alder type adduct of a chalcone derivative and a dehydroprenyl-2-arylbenzofuran derivative.
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前林 行雄, 山崎 幹夫
1985 年 33 巻 10 号 p.
4296-4298
発行日: 1985/10/25
公開日: 2008/03/31
ジャーナル
フリー
Biosynthetic incorporation of [1-
13C]- and [1, 2-
13C
2] acetates into silvaticamide (1) was investigated in Aspergillus silvaticus. The incorporation experiments unambiguously demonstrate that silvaticamide is biosynthesized through the acetate-malonate pathway.
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高畑 広紀, 中島 智子, 中野 正晴, 冨口 明, 山崎 高應
1985 年 33 巻 10 号 p.
4299-4308
発行日: 1985/10/25
公開日: 2008/03/31
ジャーナル
フリー
Reaction of ketene-S, N-acetals (1-6), which are useful synthetic intermediates for heterocycles, with aryl isocyanates (7) is described. Annulation of 1-3 and 4-6 with 7 in boiling toluene gave bicyclic (8-10) and monocyclic (11-13) uracil derivatives, respectively. Addition of 2, 3, and 4 to 7 under mild conditions afforded the 1 : 1 adducts (18, 19, and 21), respectively. Compounds 18 and 19 also reacted with 7 to give bicyclic uracil derivatives.
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山中 宏, 安中 正幸, 根東 義則, 坂本 尚夫
1985 年 33 巻 10 号 p.
4309-4313
発行日: 1985/10/25
公開日: 2008/03/31
ジャーナル
フリー
In the presence of tetrakis (triphenylphosphine) palladium, 2-iodo-4, 6-dimethylpyrimidine and 4-iodo-2, 6-dimethylpyrimidine reacted with ethoxycarbonylmethylzinc bromide (Reformatsky reagent) to give ethyl 4, 6-dimethyl-2-pyrimidineacetate and ethyl 2, 6-dimethyl-4-pyrimidineacetate, respectively. In contrast, the reaction of 5-iodo-2, 4-dimethylpyrimidine with the same reagent resulted in recovery of the starting iodide. Similar results were observed in the reactions of various N-heteroaryl iodides.
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藤井 澄三, 大場 正志
1985 年 33 巻 10 号 p.
4314-4319
発行日: 1985/10/25
公開日: 2008/03/31
ジャーナル
フリー
The racemic synthesis of the Alangium lamarckii alkaloid 10-demethyltubulosine (2) has been accomplished for the first time via a "lactim ether route, "which included the intermediates (±)-7, (±)-8, (±)-10, and (±)-9. The 1'α-H isomers (±)-12 and (±)-11 were also obtained through this synthetic route. The assignments of the configuration at C-1'of (±)-2, (±)-9, (±)-11, and (±)-12 were based on four criteria, namely, the ratio of products from the catalytic reduction of (±)-10, thin-layer chromatographic mobility, and
1H and
13C nuclear magnetic resonance spectral features. The identity of synthetic (±)-2 with (-)-demethyltubulosine from A. lamarckii unequivocally established the structure of this alkaloid.
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友田 正司, 権田 良子, 清水 訓子, 秋山 幸子, 荒井 仁美
1985 年 33 巻 10 号 p.
4320-4325
発行日: 1985/10/25
公開日: 2008/03/31
ジャーナル
フリー
A representative mucilage, named Althaea-mucilage RL, was isolated from the leaves of Althaea rosea CAVAILLES. The final preparation was homogeneous as determined by ultracentrifugal analysis, electrophoresis, and gel chromatography. Its water solution gave an intrinsic viscosity value of 32. 5. It was mainly composed of partially acetylated acidic polysaccharide, and its molecular weight was estimated to be about 1800000. The polysaccharide was composed of L-rhamnose : D-galactose : D-galacturonic acid : D-glucuronic acid : O-acetyl groups in the approximately molar ratio of 20 : 1 : 16 : 16 : 10. Methylation and partial hydrolysis studies made it possible to deduce the structural features of the polysaccharide moiety in the mucilage.
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藤井 信孝, 桜井 満也, 久野 鈴光, 矢島 治明, 佐藤 公道, 松下 真理子, 山本 紀子, 高木 博司, 王 宗睦, 李 惟, 王 ...
1985 年 33 巻 10 号 p.
4326-4332
発行日: 1985/10/25
公開日: 2008/03/31
ジャーナル
フリー
Adrenorphin, H-Tyr-Gly-Gly-Phe-Met-Arg-Arg-Val-NH
2, and its D-Met (O)
2-analog were synthesized. In addition, analogs of [Arg
6, Phe
7] enkephalin substituted at the 2nd position by D-Ala and D-Met (O) were also synthesized, together with four other enkephalin analogs. Among these compounds, [D-Met (O)
2] adrenorphin exhibited high analgesic activity (29.1 times that of morphine) antagonized by naloxone, when administered intracisternally to mice.
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富岡 清, 石黒 恒男, 古賀 憲司
1985 年 33 巻 10 号 p.
4333-4337
発行日: 1985/10/25
公開日: 2008/03/31
ジャーナル
フリー
Optically pure trans- and cis-burseran (4, 10) were stereoselectively synthesized in an unequivocal manner. Comparison of their behaviors on gas chromatography indicated that naturally occurring antitumor lignan, burseran, is the trans-isomer.
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森元 聡, 野中 源一郎, 西岡 五夫
1985 年 33 巻 10 号 p.
4338-4345
発行日: 1985/10/25
公開日: 2008/03/31
ジャーナル
フリー
A proanthocyanidin trimer (1), two tetramers (2 and 3) and a pentamer (4) have been isolated from the root bark of Cinnamomum sieboldii MEISNER (Lauraceae). The structures of these compounds were established by acid-catalyzed thiolytic degradation, in conjunction with proton and carbon-13 nuclear magnetic resonance analyses. In addition, the presence of (-)-epicatechin (13), (+)-catechin (14) and known proanthocyanidins B-1 (5), B-2 (6) and B-5 (7), trimers (8 and 9), tetramers (10 and 11) and a pentamer (12) in this plant was demonstrated.
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小名 寿男, 上尾 庄一郎, 元川 清司, 吉田 正
1985 年 33 巻 10 号 p.
4346-4360
発行日: 1985/10/25
公開日: 2008/03/31
ジャーナル
フリー
Racemic carbapenem antibiotics having a 1-(hydroxymethyl) ethylidene side-chain at C-6 [dl-asparenomycins A (54), B (37), C (53) and related compounds, 55, 56, 38, 59 and 45] were synthesized starting from the common intermediates 9a and 9b, and their antibacterial activities were examined. The synthesis involves transformation of a cyclic carbonate group into the 1-(hydroxymethyl) ethylidene moiety with a catalytic amount of 1, 8-diazabicyclo [5. 4. 0] undec-7-ene (DBU) in an appropriate solvent, and deblocking of the p-methoxybenzyl ester group by the AlCl
3-anisole method.
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伊牟田 充, 小名 寿男, 上尾 庄一郎, 元川 清司, 吉田 正
1985 年 33 巻 10 号 p.
4361-4370
発行日: 1985/10/25
公開日: 2008/03/31
ジャーナル
フリー
Racemic 2-acetoxymethyl and 2-(heteroaromatic) thiomethyl carbapenems having a 1-(hydroxymethyl) ethylidene or cyclic carbonate side-chain at C-6 (5, 25, 38, 40, 42, and 36b, 23b, 28b, 30b, 32b, 34b) were synthesized from the common intermediates 3a and 3b, and their antibacterial activities were determined.
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伊牟田 充, 上尾 庄一郎, 中野 雅夫, 吉田 正
1985 年 33 巻 10 号 p.
4371-4381
発行日: 1985/10/25
公開日: 2008/03/31
ジャーナル
フリー
Racemic and optically active 2-(heteroaromatic) thiomethyl penems having a 1-(hydroxymethyl) ethylidene or cyclic carbonate side-chain at C-6 (24, 51, 63, 65, 37, 40, 69 and 21b, 61b, 26b, 30b, 64b, 35b, 66b, 39b, 68b) were synthesized, and their antibacterial activities are determined.
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小名 寿男, 上尾 庄一郎, 深尾 孝, 土肥 正善, 吉田 正
1985 年 33 巻 10 号 p.
4382-4394
発行日: 1985/10/25
公開日: 2008/03/31
ジャーナル
フリー
Racemic 2-acetoxymethyl and 2-(heteroaromatic) thiomethyl carbapenem and penem antibiotics having a 1-(R
*)-hydroxyethyl side-chain at C-6 (6, 7, 8, and 45, 59, 47, 49, 51) were synthesized, and their antibacterial activities were determined.
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GIULIANO BANDOLI, ANTONIO GRASSI, MARINO NICOLINI, GIUSEPPE C. PAPPALA ...
1985 年 33 巻 10 号 p.
4395-4401
発行日: 1985/10/25
公開日: 2008/03/31
ジャーナル
フリー
The crystal and molecular structure of 4-hydroxy-2-oxo-1-pyrrolidineacetamide was determined by X-ray analysis. The molecular conformation found in the solid was compared with results of theoretical quantum mechanical calculations carried out by using an ab-initio method at the STO-3G level. Crystals (orthorhombic) of the studied nootropic agent were as follows : a=7.162 (6), b=8.852 (3), c=11.340 (8) Å ; Pbc2
1. The five-membered ring deviates from planarity, while the planes of the amide group and of the four atoms N (1)-C (1)-C (2)-C (4) are almost perpendicular in cis arrangement, with the 4-hydroxy group in the axial position. In the crystals, molecules are linked by two intermolecular hydrogen-bonds, namely O (3)…O (2) and N (2)…O (1), which are 2.77 and 2.92 Å long, respectively. Results of theoretical calculations indicate for the free molecule a twisted cis conformation, with the 4-hydroxy goup in the axial position, as the most preferred one. This appears to be determined by the intramolecular hydrogen-bond between the O (1) atom and amide group hydrogen atoms. The relative conformational energies indicate that several conformations about the minimum can be populated in the solution state. The geometry and conformational profile of the pharmacologically active investigated molecule were found to reproduce, with the exception of the puckered conformation of the fivemembered ring, those previously determined for the related analogous nootropic agent 2-oxo-1-pyrrolidineacetamide (piracetam), whose chemical structure differs only in the lack of the 4-hydroxy group in the β-position to the carbonyl group.
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三塩 晋作, 廣瀬 徹, 南田 明, 松本 純一, 南 新作
1985 年 33 巻 10 号 p.
4402-4408
発行日: 1985/10/25
公開日: 2008/03/31
ジャーナル
フリー
A series of 7-substituted 1, 4-dihydro-4-oxo-1-vinyl-1, 8- and 1, 6-naphthyridine-3-carboxylic acids (5a-e and 13a-c) was prepared. During the preparation of 5a, unexpected compounds (4, 7 and 8) were also obtained. Structural elucidation of these compounds was achieved on the basis of chemical and spectral (ultraviolet, mass and proton nuclear magnetic resonance) data. The structure-antibacterial activity relationships are discussed.
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松尾 昌昭, 谷口 清, 桂 洋介, 上谷 利治, 植田 育男
1985 年 33 巻 10 号 p.
4409-4421
発行日: 1985/10/25
公開日: 2008/03/31
ジャーナル
フリー
2-(2-Phenoxyphenylimino) imidazolidine and related compounds (IV and XII) were synthesized and evaluated for hypotensive activity in rats. Most of the 2-aryliminoimidazolidines (IV) were synthesized via the aniline derivatives (VI) by two different methods. Some imidazolidines (IV) were found to be significantly active, with 2-(5-chloro-2-phenoxyphenylimino) imidazolidine (IV-19) being more active than prazosin, the reference compound. The mechanism of action of IV-9 may involve the blockade of peripheral α-adrenergic receptors. This paper describes the synthesis, pharmacology, and structure-activity relationships of the 2-(2-phenoxyphenylimino) imidazolidines.
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後藤 義一, 岡本 加世子, 奥谷 哲也, 今田 伊助
1985 年 33 巻 10 号 p.
4422-4431
発行日: 1985/10/25
公開日: 2008/03/31
ジャーナル
フリー
6-(ω-Hydroxyalkyl)-2, 3-dimethoxy-5-methyl-1, 4-benzoquinones (3) and 6-(ω-acetoxyalkyl)-2, 3-dimethoxy-5-methyl-1, 4-benzoquinones (26) having various carbon numbers (n) of the side chain were synthesized by the Friedel-Crafts coupling of 3, 4, 5-trimethoxytoluene (4) and ω-acetoxyalkanoyl chlorides (5) as a key step. The Fremy's salt oxidation or the salcomine-catalyzed oxidation of 6-(ω-hydroxyalkyl)-2, 3-dimethoxy-5-methylphenols (25) and their acetates (24), the key intermediates of the process, gave rise to 3 and 26, respectively, in good yields. The described method provides a good yield of the 1, 4-benzoquinones and is suitable for the synthesis of other quinonyl analogs. The effect on lipid peroxidation in canine brain homogenate of the 1, 4-benzoquinones (3) having various carbon numbers (n) of the side chain was studied. Among the compounds tested, 3 having a carbon number in the range of n=9-13 showed rather strong antioxidant activity.
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鵜川 清, 石黒 敏弘, 栗木 久, 野原 昭
1985 年 33 巻 10 号 p.
4432-4437
発行日: 1985/10/25
公開日: 2008/03/31
ジャーナル
フリー
The metabolites and degradation products of 2-amino-7-isopropyl-5-oxo-5H-[1] benzopyrano-[2, 3-b] pyridine-3-carboxylic acid (Amoxanox, AA-673, 1), a promising drug for the treatment of bronchial asthma, were synthesized to confirm the proposed structures and to determine their activity in the rat passive cutaneous anaphylaxis test.
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福田 直通, 米光 美知子, 木村 孟淳, 八山 しづ子, 宮原 一元, 川崎 敏男
1985 年 33 巻 10 号 p.
4438-4444
発行日: 1985/10/25
公開日: 2008/03/31
ジャーナル
フリー
A new diterpene glucoside, borapetoside A (1), and its aglycone, borapetol A (2), were isolated from the stems of Tinospora tuberculata BEUMEE as the bitter principles, and their structures were elucidated.
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宮瀬 敏男, 黒柳 正典, 野呂 忠敬, 上野 明, 福島 清吾
1985 年 33 巻 10 号 p.
4445-4450
発行日: 1985/10/25
公開日: 2008/03/31
ジャーナル
フリー
Four new guaiane-type sesquiterpene glycosides, macroclinisides F (II), G (III), H (IV) and I (V), and a new phenyl propanoid glycoside, 4-allyl-2, 6-dimethoxyphenol glucoside (VI), have been isolated from Macroclinidium trilobum MAKINO together with isolipidiol (I). The structures were determined on the basis of chemical and spectral data.
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宮瀬 敏男, 上野 明, 野呂 忠敬, 黒柳 正典, 福島 清吾
1985 年 33 巻 10 号 p.
4451-4456
発行日: 1985/10/25
公開日: 2008/03/31
ジャーナル
フリー
Nine new guainolide-type glycosides, crepisides A (II), B (III), C (IV), D (V), E (VI), F (VII), G (VIII), H (IX), and I (X), have been isolated from Crepis japonica BENTH., together with a known glycoside, glucozaluzanin C (I). The structures of II-X were established on the basis of chemical and spectral data.
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富森 毅, 宮一 諭起範, 井本 吉隆, 木津 治久, 難波 恒雄
1985 年 33 巻 10 号 p.
4457-4463
発行日: 1985/10/25
公開日: 2008/03/31
ジャーナル
フリー
Four new flavanones (I-IV) and a new chalcone (V) were isolated from the root of Scutellaria discolor COLEBR., together with wogonin, norwogonin, 5, 7, 2'-trihydroxy-8-methoxyflavone, 5, 7-dihydroxy-8, 2'-dimethoxyflavone and wogonin 7-O-glucuronide. The structures of I-V were shown to be 2 (S)-5, 7-dihydroxy-8, 2'-dimethoxyflavanone, 2 (S)-7-hydroxy-5, 8, 2'-trimethoxyflavanone, (±)-5, 2'-dihydroxy-7, 8, 6'-trimethoxyflavanone, (±)-5, 2'-dihydroxy-6, 7, 6'-trimethoxyflavanone and 2', 4'-dihydroxy-2, 3', 6'-trimethoxychalcone, respectively, based on spectral data and simple chemical modifications.
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岡田 惇也, 近藤 貞雄
1985 年 33 巻 10 号 p.
4464-4470
発行日: 1985/10/25
公開日: 2008/03/31
ジャーナル
フリー
A double-antibody solid-phase enzyme immunoassay for determining des-Gly
10-NH
2-LH-RH-ethylamide (fertirelin) in bovine plasma was developed. Antiserum was raised against fertirelin-BSA conjugate, and enzyme-labeled antigens were prepared by coupling fertirelin analogues bearing an N-terminal amino group with β-D-galactosidase using N-(m-maleimidobenzoyloxy)-succinimide (MBS). The antiserum cross-reacted hardly at all with LH-RH and only slightly with peptides bearing a different C-terminal alkyl substituent, but it was less specific for the N-terminus. Plasma specimens were extracted with antibody-immobilized cellulose in order to minimize substances interfering with the assay. This assay system could detect as little as 0.2 ng/ml of fertirelin in the absence of plasma extract and 1.0 ng/ml in the presence of the extract. The mean recovery of fertirelin added to plasma was 80.9% and the coefficients of variation were 14.4% (within assay) and 17.5% (between assay).
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佐用 博照, 細川 幹夫
1985 年 33 巻 10 号 p.
4471-4477
発行日: 1985/10/25
公開日: 2008/03/31
ジャーナル
フリー
The stoichiometry and kinetic mechanism of the cumene hydroperoxide (CHP)-supported N-demethylation of N, N-dimethylaniline (DMA) catalyzed by catalase were studied. The formations of formaldehyde, 2-phenyl-2-propanol and N-methylamiline, and the consumption of DMA exhibited a 1 : 1 : 1 : 1 stoichiometry up to 5 min after initiation of the reaction. Plots of reciprocal initial velocity versus the reciprocal concentration of either substrate at several different fixed concentrations of the other substrate resulted in a family of straight lines which converged to a common intersection point on the left side of the ordinate and above the abscissa, suggesting a sequential mechanism involving the formation of a ternary complex of catalase, DMA and CHP followed by one or more reactions and the subsequent release of the products. N, N, N', N'-Tetramethylbenzidine radical cation was detected by electron spin resonance spectroscopy during the CHP-supported oxidation of DMA, whereas the corresponding amine radical cations were detected during the oxidations of N, N-dimethyl-p-toluidine and N, N-dimethyl-p-anisidine. These results suggest that the mechanism of the CHP-supported oxidation of DMA catalyzed by catalase is the same as that of aminopyrine.
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稲森 善彦, 久保 真百合, 小川 雅史, 森脇 将光, 辻坊 裕, 馬場 きみ江, 小澤 貢
1985 年 33 巻 10 号 p.
4478-4483
発行日: 1985/10/25
公開日: 2008/03/31
ジャーナル
フリー
Diethylstilbestol (I), a nonsteroidal estrogen, showed strong coronary vasodilator action on isolated guinea-pig heart, as well as ichthyotoxicity and antimicrobial activity. First, the coronary vasodilator action of I (ED
50 : 0.26μg/heart) on isolated guinea-pig heart was much stronger than that of papaverine (ED
50 : 7.0μg/heart) used as a standard. On the other hand, the activities of derivatives of I, i. e., I-diphosphate (II), I-dimethyl ether (III), I-diacetate (IV), I-dipropionate (V) and hexestrol (VI) were weaker than that of I. Second, I showed strong ichthyotoxicity (median tolerance limit at 48h : 3.30 ppm in Oryzias latipes and 4.50 ppm in Carassius auratus). On the other hand, the ichthyotoxic activities of II-V were weaker than that of I. However, VI showed the same toxicity as I on both fishes. Third, the antimicrobial activities of II-V were weaker than that of I, whereas that of VI was stronger. In particular, I and VI showed strong antifungal activity against Trichophyton spp. It was concluded that both the hydroxyl groups attached to the benzene rings and the transolefin structure are necessary for coronary vasodilator action, while only the hydroxyl groups attached to the benzene ring are necessary for the ichthyotoxic and antimicrobial activities.
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柴山 敏子, 中谷 一泰, 中村 泰治
1985 年 33 巻 10 号 p.
4484-4488
発行日: 1985/10/25
公開日: 2008/03/31
ジャーナル
フリー
Two nonhistone proteins with molecular weights of 63000, and 53000 were isolated from bovine cerebral cortex by polyacrylamide gel electrophoresis with a urea-acetic acid system, followed by extraction from the gel. These proteins have a particularly large proportions of Ser, Gly and Glu, which represent 40% of total amino acids. Such amino acid compositions are unusual among nonhistone proteins. These proteins also contained 1.00 and 0.27% (w/w) phosphate/mg protein.
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山口 正義, 吉田 博之
1985 年 33 巻 10 号 p.
4489-4493
発行日: 1985/10/25
公開日: 2008/03/31
ジャーナル
フリー
The role of a calcium-binding protein (CaBP) isolated from rat liver cytosol was investigated in relation to the activation of hepatic fructose 1, 6-diphosphatase by Ca
2+-calmodulin. Fructose 1, 6-diphosphatase activity in rat liver cytosol was markedly increased by addition of Ca
2+ (1.0-5.0 μM) to the incubation mixture. This increase was completely inhibited in the presence of N-(6-aminohexyl)-5-chloro-1-napthalenesulfonamide (W-7 15 μM), an inhibitor of calmodulin. Added Ca
2+ (5.0 μM)-increased cytosolic fructose 1, 6-diphosphatase activity was markedly enhanced by the coexistence of calmodulin (2.5 μg/ml). Further, fructose 1, 6-diphosphatase isolated from rabbit liver cytosol was activated by Ca
2+-calmodulin. This activation was completely inhibited by CaBP (20 μg/ml) isolated from rat liver cytosol, though CaBP in the absence of calmodulin had no effect on liver fructose 1, 6-diphosphatase activity. The present data suggest that CaBP can modify the action of Ca
2+-calmodulin in liver cells. It is proposed that CaBP, which may regulate Ca
2+ effects on liver function, should be named calregulin.
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長沢 哲郎, 大浦 彦吉, 野中 源一郎, 西岡 五夫
1985 年 33 巻 10 号 p.
4494-4499
発行日: 1985/10/25
公開日: 2008/03/31
ジャーナル
フリー
The mechanism by which rhatannin (condensed tannin purified from Rhei Rhizoma) produces a prolonged decrease in plasma amino acids in the postabsorptive state was investigated in vivo by measuring the incorporation of [
14C] phenylalanine (Phe) into proteins in serum, liver, kidney and muscle. Enhanced incorporation into serum proteins was observed 4 to 8 h after the intraperitoneal administration (12.5 mg/kg body weight), and the maximal enhancement was observed 6 h after the treatment. Incorporations into other proteins did not change. Further, a fluorogram of the polyacrylamide gel electrophoretic pattern of serum obtained from rats after rhatannin treatment revealed incorporation of the labeled amino acid into protein (s) which corresponded to albumin in terms of electrophoretic mobility. Incorporation of [
3H] phenylalanine after a 20 min in vivo labeling 6 h after rhatannin treatment was enhanced in hepatic microsomal and mitochondrial fractions. In addition, stimulated incorporation of [
3H] orotic acid into rat hepatic nuclear and cytoplasmic ribonucleic acids (RNA) was observed after rhatannin treatment and the maximal enhancements were achieved at 6 h. Thus, the decrease of plasma amino acid level 4 to 8 h after rhatannin treatment may be due in part to the increased removal of amino acids by the liver, although the underlying mechanisms of enhancement of the syntheses of hepatic protein and RNA in rhatannintreated rats remain obscure.
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渡辺 英昭, 杉山 さかえ, 中本 佳美, 松野 京子, 扇 和子, 入江 昌親
1985 年 33 巻 10 号 p.
4500-4507
発行日: 1985/10/25
公開日: 2008/03/31
ジャーナル
フリー
The role of tyrosyl residues in the enzymatic activity and the state of tyrosyl residues of guanine preferential ribonuclease (RNase Ms) from Aspergillus saitoi were studied. 1) The solvent perturbation difference spectra of RNase Ms measured with ethylene glycol and polyethylene glycol as perturbants indicated that ca. 5 tyrosyl residues and one tryptophan residue were exposed to solvents. 2) The spectrophotometric titration of RNase Ms indicated that ca. 5 tyrosyl residues were titrated first, giving an apparent pK
a value of 10.5, and the rest of the tyrosine residues gave higher pK
a values. 3) About 8 tyrosine residues in RNase Ms were acetylated by excess N-acetylimidazole and about 6 of them were reactive towards a relatively low concentration of the reagent. Extrapolation of the curve showing the relation between the tyrosyl residues modified and the remaining activity indicated that the enzyme was inactivated when 4-5 tyrosyl residues were modified. 4) The chemical modification of RNase Ms with diazonium 1 (H)-tetrazole was also studied. The plot of the relationship between the residual activity and the tyrosyl residues modified showed that 1-1.5 tyrosyl residue (s) was responsible for the loss in enzymatic activity. 5) The enzymatic activities of RNase Ms modified by the two kinds of tyrosine-modifying reagents were measured with ribonucleic acid (RNA) and guanyl (3'→5') cytidine (GpC) as substrates at pH 5.0. The loss in enzymatic activity was more marked when RNA was used as a substrate than with GpC as a substrate. 6) Based on the reported (Heinemann and Saenger, Nature, 299, 27 (1982)) three-dimensional structure of RNase T
1, which is about 60% sequence-homologous with RNase Ms, the possible site of the diazotization is discussed.
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