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高村 喜代子, 坂本 みずほ
1978 年 26 巻 8 号 p.
2291-2297
発行日: 1978/08/25
公開日: 2008/03/31
ジャーナル
フリー
Complex formation of flavonoids (rutin, quercetin, flavocummelin and flavonol) with copper (II) was studied by spectrophotometry. These flavonoids have some possible chelating sites (such as 3-hydroxy-4-keto, 5-hydroxy-4-keto and 3, 4-o-dihydroxy groups denoted as site a, b, and c, respectively) depending on the number and position of hydroxyl substituents in their molecules. Absorption spectra of the flavonoid-copper (II) systems with the changes of Cu
2+ concentrations were observed, and the molar ratio and continuous variation plots indicated the existence of only 1 : 1 complex in the flavonol-, flavocummelin-, and rutin-copper (II) systems, and both 1 : 1 and 1 : 2 types in the quercetin-copper (II) system. A comparison of the magnitudes of bathochromic shift was compared to consider the sites used for the complex formation. The 1 : 1 complex formation in the flavonol-copper (II) system appears to take place at site a whereas that of the flavocummelin-and the rutin-copper (II) systems at site b. In the case of quercetin, the initial complex formation seems to occur at site a and the subsequent complex formation at site c. In order to compare the relative stability of the flavonoid-copper (II) complexes, the free Cu
2+ concentrations equilibrated in the mixed solutions of each flavonoid and copper (II) were determined by polarography. The relative stability decreased in the order of quercetin, flavonol, rutin, and flavocummelin.
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後藤 茂, 小田原 よき子, 中野 節, 荒木 泰典
1978 年 26 巻 8 号 p.
2298-2304
発行日: 1978/08/25
公開日: 2008/03/31
ジャーナル
フリー
The binding of seven commercial diuretics with bovine serum albumin (BSA) was investigated at three different temperatures, 5°, 30° and 37°, by the equilibrium dialysis method and at 37° by the dynamic dialysis method. The binding data of diuretics were described on the basis that the sites per BSA molecule can be divided into two classes, except that of hydrochlorothiazide, and each class characterized by the binding constants, K
1, n
1, and K
2, n
2. The thermodynamic values, ⊿G°, ⊿H°, and ⊿S°for the primary site of binding were determined, and were discussed on the basis of the fact that a hydrophobic interaction is formed between diuretics and BSA. It was also shown that there are sizable negative entropy and enthalpy changes in the binding of ethacrynic acid and BSA, and that hydrochlorothiazide is bound very weakly with BSA and has a remarkable diffusion pattern through cellulose membrane in the dynamic dialysis.
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岡村 久也, 山田 俊一
1978 年 26 巻 8 号 p.
2305-2311
発行日: 1978/08/25
公開日: 2008/03/31
ジャーナル
フリー
The asymmetric synthesis of (3S 15S 20R)-(-)-yohimbone (III) was accomplished. The key reactions in the process are : (i) the asymmetric Pictet-Spengler reaction of L-tryptophan (IV) with sodium 3-(m-methoxyphenyl) glycidate (V) (1, 3-asymmetric induction), and (ii) the elimination of the chiral center derived from IV (1, 3-transfer of asymmetry). The latter was conveniently achieved by converting the cyclic α-amino acid amide (XIIIa) to the pentacyclic α-amino nitrile (XIV), followed by reductive decyanization with sodium borohydride. Thus, the indole alkaloids, natural yohimbol (XX) and natural corynantheine (XXI), may be synthesized from L-tryptophan.
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富沢 宏, 本郷 弘司, 加藤 秀樹, 藤田 礼子, 佐藤 昭
1978 年 26 巻 8 号 p.
2312-2315
発行日: 1978/08/25
公開日: 2008/03/31
ジャーナル
フリー
Studies on the Diels-Alder reaction of 1-methyl-2 (1H)-pyridone (I) with fumaric acid and its ester were carried out. Reaction of I with dimethyl fumarate in toluene gave dimethyl 2-methyl-3-oxo-2-azabicyclo [2. 2. 2] oct-7-ene-5-endo-6-exo-dicarboxylate (IV) in about 4% yield. Boiling of I and fumaric acid in water afforded 6-methyl-7-oxo-6-azabicyclo [3. 2. 1] oct-2-ene-2, 8-endo-dicarboxylic acid (VII) in about 20% yield.
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赤堀 昭, 升井 正生, 安東 正則
1978 年 26 巻 8 号 p.
2316-2320
発行日: 1978/08/25
公開日: 2008/03/31
ジャーナル
フリー
Carbon tetrachloride (CCl
4) was orally administered to female C57BL mice (0.02, 0.1, 0.5, 1.0 or 1.5 ml/kg). Activities of serum glutamic oxaloacetic transaminase (SGOT) were recorded at 15, 24, 39, 48, 63, 72 and 87 hr after administration. SGOT levels rose more slowly but reached higher maximum levels later in mice given higher doses of CCl
4. Therefore, an inverse dose response was observed at earlier times after drug administration. This phenomenon was observed also in female C3H mice and male and adrenalectomized female C57BL mice.
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大和 正利, 橋垣 国子, 三戸 久美子, 小山 鷹二
1978 年 26 巻 8 号 p.
2321-2327
発行日: 1978/08/25
公開日: 2008/03/31
ジャーナル
フリー
On the basis of the information from our previous studies on structure-sweetness relationships of phyllodulcin and related 3, 4-dihydroisocoumarins, syntheses of sweet flavanones and dihydrochalcones are designed. 5-Hydroxyflavanones, VII, IX, and X, and dihydrochlacone XIII has a sweet taste and the others are tasteless. The structuresweetness relationships of these compounds are discussed. It is considered that the mode of interaction of 5-hydroxyflavanones and Dihydrochalcone (DHC) lacking glycoside group with a sweet receptor seems to be similar to that of 3, 4-dihydroisocoumarins.
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宮野 耕一, 逆井 武次, 濱野 弘明
1978 年 26 巻 8 号 p.
2328-2333
発行日: 1978/08/25
公開日: 2008/03/31
ジャーナル
フリー
The improved synthesis of 5-(4-chlorobutyl) picolinic acid (II), the potent dopamine β-hydroxylase inhibitor, was reported. The key intermediate, 2-cyclopropyl-5-cyclopropylcarbonylpyridine (IV) was converted to 5-(4-chlorobutyl)-2-cyclopropylpyridine (VII), which was directly oxidized with nitric acid to give II. Similarly, fusaric acid (I) was synthesized from 2-cyclopropyl-5-(cyclopropylhydroxy) methylpyridine (V).
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宮寺 哲男, 桑野 晴光, 川野 洋一, 高岸 靖
1978 年 26 巻 8 号 p.
2334-2339
発行日: 1978/08/25
公開日: 2008/03/31
ジャーナル
フリー
Benzo [c]-and benzo [α] quinolizinium bromides (X and XIII) were reacted with phenylmagnesium bromide in order to examine their chemical reactivities. Ring opening reactions occurred with preferential attack of the nucleophile at C-1 for X and C-4 for XIII to give phenylbutadienylquinoline (XII) and isoquinoline (XV), respectively. In connection with the structural determination of XII and XV, the nuclear magnetic resonance spectra of phenylbutadienylpyridine derivatives (VII and its derivatives) were compared with calculated spectra. The calculated band positions and intensities of the olefinic protons are in accord with the observed values.
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松田 彰, 井上 英夫, 上田 亨
1978 年 26 巻 8 号 p.
2340-2345
発行日: 1978/08/25
公開日: 2008/03/31
ジャーナル
フリー
Treatment of 5-bromocytidine or its 2', 3', 5'-tri-O-acetate, and 2', 3'-O-isopropylidene derivative with sodium cyanide gave the respective 6-cyanocytidine. Methoxide treatment of the 6-cyano compound gave methyl cytidine-6-carboximidate which was converted to cytidine-6-carboxylic acid. Treatment of 2', 3'-O-isopropylidene-N
4-acetyl-5-bromocytidine with sodium cyanide afforded the O
6, 5'-cyclo-N
4-acetylcytidine through the 6-cyanocytidine as the intermediate.
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義平 邦利, 福岡 正道, 黒柳 正典, 名取 信策, 梅田 誠, 諸星 利男, 榎本 眞, 斎藤 守
1978 年 26 巻 8 号 p.
2346-2364
発行日: 1978/08/25
公開日: 2008/03/31
ジャーナル
フリー
Toxicity tests to experimental animals and cultured HeLa cells were performed on the extracts of young fronds of bracken, Pteridium aquilinum var. latiusculum, aiming the isolation and characterization of the carcinogen (s) and the cattle poison (s). The separation of the extracts monitored by cytotoxicity tests resulted in the isolation of more than twenty kinds of sesquiterpenes having 1-indanone nucleus, named pterosins, and their glucosides, pterosides, and several known phenolics and steroids. Although the dried fronds and rhizomes of the fern exhibited carcinogenicity by feeding to rats, none of the extracts and the fractions along with pterosin B and pteroside B, major indanones, induced tumors under the employed conditions.
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福岡 正道, 黒柳 正典, 義平 邦利, 名取 信策
1978 年 26 巻 8 号 p.
2365-2385
発行日: 1978/08/25
公開日: 2008/03/31
ジャーナル
フリー
The structures of twenty-four sesquiterpenes isolated from the young fronds were disclosed by chemical and physical methods. The stereostructures were established as 1-22 by degradation and correlation reactions and physical data.
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越智 清成, 松永 功, 新藤 実, 金子 主税
1978 年 26 巻 8 号 p.
2386-2390
発行日: 1978/08/25
公開日: 2008/03/31
ジャーナル
フリー
From 5α-cholestane-3α, 24 (R)- or -3α, 24 (S)-diol (2a and 2b) obtained from lithocholic acid in the previous work, both 24-epimers of 1α, 24-dihydroxycholesterol (6a and 6b) were synthesized. Thus, syntheses of these compounds were accomplished by dehydrogenation of the diols with dichlorodicyanobenzoquinone followed by the 1α-hydroxylation of the resulted 1, 4-dien-3-ones (3a and 3b) by the three-step procedure originally uncovered by one of the present authors (C. K.). The last step in the above transformation, the modified procedure reported recently by Ikekawa's group : oxymercuration-demercuration, was used. An alternative preparation of 1α, 24ξ-dihydroxycholesterol (6) either from lithocholic acid or from hyodeoxycholic acid was also described.
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山次 信幸, 田原 恭子, 加藤 元彦
1978 年 26 巻 8 号 p.
2391-2395
発行日: 1978/08/25
公開日: 2008/03/31
ジャーナル
フリー
Because of the presence of etheno group, the reactivity of mercapto residue at 2 position in purine skeleton is so high that 2-chloro-1, N
6-etheno adenosine 3', 5'-cyclic phosphate (2-chloro-1, N
6-etheno c-AMP) and 2-iodo-1, N
6-etheno c-AMP were easily synthesized from 2-mercapto-1, N
6-etheno c-AMP. The deblocking reaction of the etheno group from these two halogenated products with N-bromosuccinimide (NBS) gave 2-chloro-c-AMP and 2-iodo-c-AMP. When 2-amino-c-AMP, which was synthesized from 2-amino-1, N
6-etheno c-AMP by the same deblocking reaction, was diazotized with sodium nitrite in 42% fluoroboric acid (HBF
4) at -10--20°, 2-fluoro-c-AMP was obtained in a yield of 17.8%. Since 2-bromo-c-AMP has been similarly obtained in previous work, the deblocking reaction of etheno group offers an excellent new route to synthesis of 2-halogeno-c-AMPs from c-AMP.
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上杉 晴一, 田中 正治, 大塚 栄子, 池原 森男
1978 年 26 巻 8 号 p.
2396-2406
発行日: 1978/08/25
公開日: 2008/03/31
ジャーナル
フリー
Polymerization of tri (adenylic acid) bearing a 2'-O-(o-nitrobenzyl) group and a 3'-phosphate group at the 3'-end (A-A-A
-NBD) was attempted in the presence of poly (uridylic acid), poly (U), using water-soluble carbodiimide. The nitrobenzyl group can be removed photochemically under mild conditions. A reaction containing the trimer and poly (U) in 1 : 2 ration at 0°for 15 days gave polymerized products (up to the 9-mer) in 14% yield and was proved to be dependent on the template. Raising the reaction temperature to 15°accelerated the polymerization rate. Reaction with a doubled trimer concentration at 0°did not improve the polymerization yield. Although the newly formed phosphodiester linkage was exclusively 3'-5', some isomerization (7%) to 2'-5' linkages seems to occur at bonds adjacent to free 2'-hydroxyl groups. As a side product, cyclic tri-(adenylic acid), which was formed by intramolecular condensation, was obtained in these reactions and in control reactions without template.
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上野 明, 平川 清, 福島 清吾, 野呂 忠敬, 森永 邦夫
1978 年 26 巻 8 号 p.
2407-2410
発行日: 1978/08/25
公開日: 2008/03/31
ジャーナル
フリー
New 2-alkylchromone derivatives were isolated from the epigeal part of Sophora flavescens AITON. These compounds were obtained as a mixture of 2-n-heneicosyl-5, 7-dihydroxy-6, 8-dimethylchromone, 2-n-tricosyl-5, 7-dihydroxy-6, 8-dimethoxychromone and the homologous compounds, in which 2-alkyl groups are n-undecyl, n-tridecyl, n-pentadecyl, n-heptadecyl and n-tricosyl. Their structures were clarified by the spectral and chemical data, and the synthesis of 2-n-heptadecyl-5, 7-dihydroxy-6, 8-dimethylchromone.
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上野 明, 池谷 幸信, 福島 清吾, 野呂 忠敬, 森永 邦夫, 桑野 晴光
1978 年 26 巻 8 号 p.
2411-2416
発行日: 1978/08/25
公開日: 2008/03/31
ジャーナル
フリー
A new flavone derivative named desmodol was isolated together with N, N-dimethyltryptamine, bufotenine and bufotenine N-oxide from the roots and stems of Desmodium caudatum DC. The structure of desmodol was presented to be 5-hydroxy-6-methyl-8, 8-dimethyl-2-(3, 4-dihydroxyphenyl)-4H, 8H-benzo [1, 2-b : 3, 4-b'] dipyran-4-one (5, 3', 4'-trihydroxy-6-methyl-8, 8-dimethylpyrano (2, 3-h)-flavone) by the spectral and chemical data.
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水柿 道直, 福山 はる, 坂本 尚夫, 山中 宏
1978 年 26 巻 8 号 p.
2417-2421
発行日: 1978/08/25
公開日: 2008/03/31
ジャーナル
フリー
6-Hydroxydodec-cis-3-enoic acid was synthesized to identify a metabolite of ricinoleic acid by Escherichia coli and to use it as substrate in the investigation on unsaturated fatty acid metabolism. In a total synthesis of the 6-hydroxy acid, the key step involved the reaction of the trialkynylborane with ethyl diazoacetate. Dec-1-yn-4-ol was lithiated after protection of the hydroxyl group with dihydropyran, and was transformed into the trialkynylborane by treating with boron trifluoride etherate. The subsequent reaction with ethyl diazoacetate afforded the 6-hydroxy-3-ynoate, which was hydrogenated over Lindlar catalyst to yield 6-hydroxydodec-3-cis-enoic acid. The results obtained by gas chromatography-mass spectrometry (GC-MS) showed that the final metabolite of ricinoleic acid by E. coli was identical with the synthetic 6-hydroxy acid.
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高山 浩明, 岡本 敏彦
1978 年 26 巻 8 号 p.
2422-2427
発行日: 1978/08/25
公開日: 2008/03/31
ジャーナル
フリー
The reactions of N-methoxypyridinium iodide with nitromethane, nitroethane, and 1-nitropropane in the presence of sodium ethoxide in anhydrous ethanol afforded 1-methoxyimino-6-nitrohexa-2, 4-diene, 1-methoxyimino-6-aci-nitrohepta-2, 4-diene, and 1-methoxyimini-6-aci-nitroocta-2, 4-diene, respectively. The spectral behaviors of these products were discussed in relation to the nitro-acinitro prototropy and the assumed reaction mechanism was also offered.
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大沢 昭緒, 上江洲 富夫, 井下田 浩
1978 年 26 巻 8 号 p.
2428-2434
発行日: 1978/08/25
公開日: 2008/03/31
ジャーナル
フリー
Side-chain lithiation with lithium diisopropylamide and subsequent alkylation of various alkylpyridazines have been investigated. The lithiated side chains of alkylpyridazines were alkylated efficiently with alkyl halides.
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高山 浩明, 岡本 敏彦
1978 年 26 巻 8 号 p.
2435-2441
発行日: 1978/08/25
公開日: 2008/03/31
ジャーナル
フリー
The reaction of N-methoxy quinolinium methosulfate with malononitrile in dimethylsulfoxide afforded 2-and 4-dicyanomethylene-quinoline (II and III), N-methoxy-2- and 4-dicyanomethylene-quinoline (IV and V) in addition to quinoline and quinoline-1-oxide. The reaction at the higher temperature (100-110°) gave anomalous products (VI and VII). The assumed reaction mechanism was offered.
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井深 俊郎, 森 裕二, 犬伏 康夫
1978 年 26 巻 8 号 p.
2442-2448
発行日: 1978/08/25
公開日: 2008/03/31
ジャーナル
フリー
dl-Pumiliotoxin C (1) was stereoselectively synthesized via 5β-methyl-cis-decahydroquinoline-2, 7-dione (5) which was prepared in two routes. The Diels-Alder reaction of 1, 3-bis (trimethylsiloxy)-5-methylcyclohexa-1, 3-diene (6) with acrylonitrile gave the cycloadducts (7) from which anti-8-methyl-exo-2-cyanobicyclo [2. 2. 2] oct-5-en-1-ol (2) was obtained in four steps. Treatment of the compound (2) with acid gave the keto-lactam (5). The Diels-Alder reaction of 1, 3-bis (trimethylsiloxy)-1, 3-butadiene (11) with ethyl crotonate furnished the adduct (12) from which the keto-lactam (5) was obtained via the compound (19) in seven steps. Reduction of the carbonyl group at the C
7 position and introduction of the n-propyl group at the C
2 position of the keto-lactam (5) gave dl-pumiliotoxin C.
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池原 森男, 三木 弘子
1978 年 26 巻 8 号 p.
2449-2453
発行日: 1978/08/25
公開日: 2008/03/31
ジャーナル
フリー
9-(2'-O-Methanesulfonyl- or trifluoromethanesulfonyl-3', 5'-di-O-tetrahydropyranyl-β-D-arabinofuranosyl) adenine (Ia, b) were reacted with lithium chloride or tetrabutylammonium halide to yield 2'-halogeno-2'-deoxy compounds (IIa-d). These halogeno compounds were deprotected with 80% acetic acid to give 2'-chloro-, 2'-bromo-, 2'-fluoro and 2'-iodo-2'-deoxyadenosine (IVa-d) in overall yields of 12-25% from the compound I. Ultraviolet absorption properties,
1H and
13C-nuclear magnetic resonance spectral properties were recorded on the compounds IVa-d.
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高島 紘毅, 森 哲治, 大山 一明, 仁田 修治, 竹山 茂之
1978 年 26 巻 8 号 p.
2454-2457
発行日: 1978/08/25
公開日: 2008/03/31
ジャーナル
フリー
The hypocholesterolemic activities of LK-903 (α-methyl-p-myristyloxycinnamic acid-1-monoglyceride) and clofibrate were examined in miniature pigs (OHMINI-875) and beagle dogs. When administered in the diet for one week, LK-903 and clofibrate were active in the miniature pig at doses of 5 and 10 mg/kg/day, respectively, whereas the two drugs showed no hypocholesterolemic activity in the beagle dog. In cynomolgus monkeys, LK-903 showed a hypocholesterolemic effect, but serum cholesterol depression was less marked than in the miniature pig.
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大塩 春治, 成瀬 義知, 津久井 誠
1978 年 26 巻 8 号 p.
2458-2464
発行日: 1978/08/25
公開日: 2008/03/31
ジャーナル
フリー
A study on the estimation of sennosides and derivatives of oxyanthraquinones in rhubarb and senna is described. After extracing a ground crude drug with the mixture of calcium acetate buffer and tetrahydrofuran (THF), the extract was fractionated to aqueous and THF phases. Both fractions were heated with sulfuric acid to hydrolyze the glycosides contained, and the resulting aglycones were extracted with ether. The aqueous fraction containing sennidins and rhein was analyzed by spectrophotometry. The THF fraction containing only oxyanthraquinones was analyzed by densitometry on a thin-layer plate. It was suggested that sennosides were the main purgative principles of rhubarb or senna, and that oxyanthraquinones had little contribution to the activities of crude drugs. The qualities of rhubarbs varied more markedly than those of sennas. It was clarified that the activities of crude drugs in mice correlated closely to the contents of sennosides. One can, therefore, estimate the purgative activity roughly from the contents of sennosides.
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坂口 洋, 安斎 博, 古畑 公夫, 小倉 治夫, 飯高 洋一, 藤田 忠男, 坂口 武一
1978 年 26 巻 8 号 p.
2465-2474
発行日: 1978/08/25
公開日: 2008/03/31
ジャーナル
フリー
The crystal structure of fac-[bis-(adeninato)(dien) copper (II)] monohydrate has been determined from three-dimensional X-ray diffractometer data by heavy atom Fourier methods. Crystals of fac-[Cu (Ade)
2 (dien)]·H
2O are monoclinic with unit cell dimensions a=16.015 (2), b=14.577 (2), c=7.959 (1) A, β=90.11 (1)°, space group P2
1/n, and Z=4. Block-diagonal least-squares refinement using 2695 independent reflexions yielded the R value of 0.068. The copper ion assumes a distorted square pyramidal coordination with five coordination sites of which four square planar sites are occupied by the nitrogen N (9) atoms of two unidentate adenine monoanions and the two (terminal and central) nitrogen atoms of tridentate dien, and the axial site (apical position) is occupied by another terminal nitrogen atom of dien. Therefore, the present dien-copper (II) complex takes a bent form (facial coordination). The propensity of adenine to occupy the cis position in equatorial plane of the copper (II) coordination is much stronger than that of dien to take a planar coordination form.
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青野 哲也, 今西 正之, 川野 泰彦, 岸本 彰二, 野口 俊作
1978 年 26 巻 8 号 p.
2475-2482
発行日: 1978/08/25
公開日: 2008/03/31
ジャーナル
フリー
Phenoxy-1-indancarboxylic acids (II and III) and (2-thienylcarbonyl)-1-indancarboxylic acids (V, VI and VII) were synthesized via the corresponding phenoxy- and (2-thienylcarbonyl)-1-indancarbonitriles (XII, XVII and XXIII). The relationship between the antiinflammatory activity and the stereochemical features of the substituents of the compounds synthesized was also discussed.
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森永 邦夫, 上野 明, 福島 清吾, 浪越 通夫, 飯高 洋一, 奥田 重信
1978 年 26 巻 8 号 p.
2483-2488
発行日: 1978/08/25
公開日: 2008/03/31
ジャーナル
フリー
A new stereoisomer (I) of (-)-sophocarpine (II) was isolated from epigeal part of Sophora flavescens. The relative configuration and stereochemistry were determined by X-ray diffraction studies with monohydrate of free base. The absolute configuration was elucidated by chemical interrelation of I with (+)-matrine (III) and (+)-allomatrine (IV) of known absolute configuration.
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関川 彬, 堀 了平, 有田 隆一, 伊藤 圭二, 中野 眞汎
1978 年 26 巻 8 号 p.
2489-2496
発行日: 1978/08/25
公開日: 2008/03/31
ジャーナル
フリー
Polyvinylpyrrolidone (PVP) aqueous solution exhibited coacervation by addition of some inorganic salts and organic compounds. The cloud point of PVP K-90 solution appeared by addition of the least amount of ammonium sulfate, among PVP K-15, K-30 and K-90. Effect of some aromatic compounds on the cloud point of PVP aqueous solution containing ammonium sulfate was investigated. The extent of the aromatic compounds to lower the cloud point of PVP solution differed depending upon their functional groups, number of their substituents, and mutual position of the substituents. Urea derivatives elevated the cloud point, its extent being increased with the number of substituted methyl groups. Thiourea derivatives, on the other hand, lowered the cloud point. The order of the compounds to lower the cloud point was in parallel with the order of extent of interaction studied by the equilibrium dialysis method.
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西垣 貞男, 金森 由香子, 千賀 慶太郎
1978 年 26 巻 8 号 p.
2497-2501
発行日: 1978/08/25
公開日: 2008/03/31
ジャーナル
フリー
The reaction of 6-hydroxyamino-1, 3-dimethyluracil (1) with Vilsmeier reagent (phosphorus oxychloride and dimethylformamide) or arylaldehydes afforded 5, 7-dimethyl-isoxazolo [3, 4-d] pyrimidine-4, 6 (5H, 7H)-dione (2) and its 3-aryl derivatives (10-17), respectively. The 3-arylisoxazolo [3, 4-d] pyrimidines (9, 10) underwent photorearrangement to yield the corresponding 2-aryloxazolo [4, 5-d] pyrimidines (19-20). Some reactions on 2 are also reported.
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笹島 紀久雄, 小野 圭一, 勝部 純基, 山本 久夫
1978 年 26 巻 8 号 p.
2502-2507
発行日: 1978/08/25
公開日: 2008/03/31
ジャーナル
フリー
A new synthesis of 2'-amino-4'-fluoro-4-[4-hydroxy-4-(α, α, α-trifluoro-m-tolyl) piperidino] butyrophenone using a selective ortho-amination as a key step was described. The solvents and temperature effects on the selectivity for this ortho-amination of 2', 4'-difluoro-4-[4-hydroxy-4-(α, α, α-trifluoro-m-tolyl) piperidino] butyrophenone were investigated.
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金子 主税, 林 令子, 山森 雅美, 徳村 邦弘, 伊藤 道也
1978 年 26 巻 8 号 p.
2508-2514
発行日: 1978/08/25
公開日: 2008/03/31
ジャーナル
フリー
The photolysis of 6-cyanophenanthridine 5-oxide (1) in various solvents was reported. In addition to the expected 6-cyanodibenz [d, f] [1, 3] oxazepine (2), two new types of rearrangement products : 5-alkoxyphenanthridin-6 (5H)-one (3), as a byproduct in the photolyses using an aprotic solvent, were obtained in the present experiments. In order to account for the formation of these products (3 and 9), reasonable assumptions that the oxygen walk process from the oxaziridine species (11) leading to the oxazepine (2) is relatively inhibited to occur and thus 11 has a longer life time as compared to the related oxaziridines derived from α-cyanated bicyclic amine N-oxides were proposed. A mechanistic rationalization and characteristic features in the photochemical rearrangement reactions of 1 are discussed in detail, together with the structure determinations of the photoproducts.
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冨士 薫, 山田 敏英, 藤田 栄一, 村田 弘之
1978 年 26 巻 8 号 p.
2515-2521
発行日: 1978/08/25
公開日: 2008/03/31
ジャーナル
フリー
The basic components of Lagerstroemia subcostata collected on Amami-ohshima Island and two slightly different types of Lagerstroemia fauriei collected on Tanegashima Island were investigated. We distinguished the two types by calling them L. fauriei and L. fauriei (Tanegashima-type). Four new alkaloids, lasubine-I (12), -II (14), subcosine-I (15), and -II (16), all of which belong to type E, were isolated from the former. From the latter two, however, lythrine (3), cryogenine (17), and lythridine (18), all of which belong to type C, were isolated. L. fauriei has been classified as L. subcostata var. fauriei by S. Hatusima, but from the chemotaxonomical aspect, it shows prominent differences from L. subcostata. Thus their classification under species would be more appropriate.
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染井 正徳, 松原 真理, 神田 好宏, 夏目 充隆
1978 年 26 巻 8 号 p.
2522-2534
発行日: 1978/08/25
公開日: 2008/03/31
ジャーナル
フリー
A novel N-amination method was investigated under various conditions and optimum reaction condition was established. The method was successfully applied for the synthesis of 1-aminoindoles, 1-aminobenzimidazole, and 9-aminopurines. Some chemical reactivity of 9-aminopurines was investigated.
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吉田 隆志, 延原 順子, 内田 満子, 奥田 拓男
1978 年 26 巻 8 号 p.
2535-2542
発行日: 1978/08/25
公開日: 2008/03/31
ジャーナル
フリー
Two new piscicidal sesquiterpenes, buddledin A (1) and B (2), have been isolated from the root bark of Buddleja davidii FRANCH. These structures have been deduced on the basis of spectroscopic and chemical evidences, and confirmed by X-ray analysis of the bromohydrin (8). The absolute configuration was determined by the applications of benzoate rule and dibenzoate chirality rule. Buddledin A and B are the first examples of toxic compounds possessing the caryophyllene skeleton.
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吉田 隆志, 延原 順子, 藤井 夏子, 奥田 拓男
1978 年 26 巻 8 号 p.
2543-2549
発行日: 1978/08/25
公開日: 2008/03/31
ジャーナル
フリー
Further toxic principle, buddledin C, and two additional sesquiterpenes, buddledin D and E, have been isolated from the root bark of Buddleja davidii FRANCH. The structures of buddledin C and D have been determined to be 3 and 4 by chemical transformation of buddledin A into buddledin D and dihydrobuddledin C (6), and by comparisons of their spectral data with those of buddledin A and its cis-isomer (8), which was obtained by the photoisomerization of 1. Structure 5 has been assigned for buddledin E by its spectral data and deuteration experiment.
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大沢 昭緒, 阿部 義人, 井下田 浩
1978 年 26 巻 8 号 p.
2550-2554
発行日: 1978/08/25
公開日: 2008/03/31
ジャーナル
フリー
Alkyl- and arylpyridazines have been prepared by cross-coupling reaction between chloropyridazines and Grignard reagents in the presence of nickel-phosphine complexes (as catalysts). Hitherto unaccessible naphthyl- and thienylpyridazines have been obtained.
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杉浦 真喜子, 高尾 楢雄, 藤原 英明, 佐々木 喜男
1978 年 26 巻 8 号 p.
2555-2561
発行日: 1978/08/25
公開日: 2008/03/31
ジャーナル
フリー
The nitrogen inversion rate of 1, 2, 3, 4, 6, 7-hexahydro-11bH-benzo [α] quinolizine (I) is determined by means of line broadening of
13C FT nuclear magnetic resonance under the successive alteration of pD. The k
trans thus obtained was confirmed to be reasonable but k
cis was presumed to be smaller than the actual one, which is responsible to the difference of pK
a between trans- and cis "a"-conformer. Actually, it was realized for benzo [α]-quinolizidines that trans-conformer takes lower pK
a than that of cis "a"-conformer because of the steric effect.
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木曽 良明, 井沢 博子, 北川 幸己, 秋田 正
1978 年 26 巻 8 号 p.
2562-2564
発行日: 1978/08/25
公開日: 2008/03/31
ジャーナル
フリー
The use of thioanisole as a scavenger was found to suppress a side reaction when the O-protecting groups of tyrosine were deblocked under the acidic conditions. This good result gives a promising outlook for the synthesis of tyrosine-containing peptides by solid-phase method.
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黒田 耕司, 横山 照由, 梅田 常雄, 高岸 靖
1978 年 26 巻 8 号 p.
2565-2568
発行日: 1978/08/25
公開日: 2008/03/31
ジャーナル
フリー
Form I, form II, and CHCl
3-II type of acetohexamide are obtained by recrystallization from different solvents. X-ray diffraction patterns, infrared spectra, and differential scanning calorimeter curves of the CHCl
3-II type are identical with those of form II, but CHCl
3-II type contains a chloroform molecule, which cannot be removed by normal drying condition, and CHCl
3-II type seems unsuitable for medical use. The solubility of form II is 1.2 times that of form I.
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山口 正義, 山本 丈夫
1978 年 26 巻 8 号 p.
2568-2571
発行日: 1978/08/25
公開日: 2008/03/31
ジャーナル
フリー
The change of calcium concentrations in the serum, liver, and bile of rats was investigated after a single oral administration of calcium chloride. The administration of calcium produced a corresponding increase of calcium concentration in the serum and liver, and this increase was dose dependent. A remarkable elevation of calcium content in the bile was caused by the administration of calcium. By the ligation of bile duct, the calcium concentration in the serum was markedly enhanced after the administration of calcium (10 and 50 mg/100g) when compared with that of the sham-operated rats. These results suggest that the excretion of calcium into the bile prevents the elevation of calcium concentration in the serum after the absorption of calcium from the intestine.
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小沢 俊彦, 花木 昭
1978 年 26 巻 8 号 p.
2572-2575
発行日: 1978/08/25
公開日: 2008/03/31
ジャーナル
フリー
The spin trap, 5, 5-dimethyl-1-pyrroline-1-oxide has been used to detect the OH radical produced by the Haber-Weiss reaction between superoxide ion and hydrogen peroxide. In the presence of a small amount of H
2O
2, the OH radical adduct can be detected by electron spin resonance spectroscopy, while, H
2O
2 being added excessively, the HO
2 radical adduct can be detected.
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高山 浩明
1978 年 26 巻 8 号 p.
2575-2578
発行日: 1978/08/25
公開日: 2008/03/31
ジャーナル
フリー
Chemical transformations of 1-methoxyimino-6-nitrohexa-2, 4-diene (II), resulted from the reaction of N-methoxypyridinium iodide (I) with nitromethane, were examined in relation to the nitro-aci-nitro prototropy. II reacted with diazomethane to afford methyl 1-methoxyimino-hexa-2, 4-diene-6-acinitronate (III), with acetic anhydride and with benzoyl chloride to give O-acetate and O-benzoate of 1-methoxyimino-hexa-2, 4-diene-6-hydroxamic acid (VI) respectively. The ultraviolet spectra of them were correlated to their structures.
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織田 範一, 小林 和弘, 植田 泰誠, 伊藤 磯雄
1978 年 26 巻 8 号 p.
2578-2581
発行日: 1978/08/25
公開日: 2008/03/31
ジャーナル
フリー
Diels-Alder reaction of 5-nitro-1, 4-naphthoquinone (1) and unsymmetrical butadienes was carried out. Reaction of 1 and 2-methyl-1, 3-butadiene gave 1, 4, 4a, 9a-tetrahydro-2-methyl-5-nitro-anthraquinone (2) and its 3-methyl analogue (3) at the ratio of 9.2 : 1. Reaction of 1 and 1, 3-pentadiene gave 1, 4, 4a, 9a-tetrahydro-1-methyl-8-nitroanthraquinone (8) and its 5-nitro analogue (9) at the ratio of 10 : 7. Their structures have been determined by aromatization to methyl-nitroanthraquinones.
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宮崎 元一, 福本 博己, 山田 須賀子, 大久保 登
1978 年 26 巻 8 号 p.
2582-2585
発行日: 1978/08/25
公開日: 2008/03/31
ジャーナル
フリー
Spectrophotometric studies on the complex formation between Fe
2+ ion and three kinds of aryl β-ketoimines derived from 2, 4-pentanedione and anilin were reported. Spectra of these Fe (III)-ketoimine complexes revealed similar features to that of tris (2, 4-pentanedionato) iron (III) in 80% EtOH. The composition, equilibrium constant and stability constant were also determined for the complexes.
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森本 雍憲, 泉 都貴子, 有田 隆一
1978 年 26 巻 8 号 p.
2585-2588
発行日: 1978/08/25
公開日: 2008/03/31
ジャーナル
フリー
Effect of pyrazolone derivatives on the critical micelle concentration (cmc) of surfactants was investigated by using ionic surfactants which were sodium dodecyl sulfate (SDS) and dodecyl N-dimethylethylammonium bromide (DDAB). It is shown that antipyrine and 4-aminoantipyrine which are very water soluble is in breaking up micelles of SDS and DDAB. However, addition of phenylbutazone which is very slightly soluble in water results in increase in stability of the micelles. It is presumed from these results that the affinity of these additive for water plays an important role in stability of the micelles.
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百瀬 雄章, 村岡 修
1978 年 26 巻 8 号 p.
2589-2593
発行日: 1978/08/25
公開日: 2008/03/31
ジャーナル
フリー
The Baeyer-Villiger oxidation of 3β-benzoylbicyclo [3. 3. 1] nonane (1), 8β-benzoylbicyclo [4. 3. 1] decane (2), and 3β-benzoylbicyclo [3. 2. 1] octane (3) is described. The ratio of the main product bicycloalkyl benzoate to its isomeric product phenyl bicycloalkanecarboxylate was determined to be ca. 10 : 1 by the
1H-NMR measurement of the crude mixture. The Baeyer-Villiger reaction of cyclohexyl phenyl ketone (11) was also carried out and was found to give a similar result in its isomer ratio of the products. The high selectivity in this oxidation enabled the practicable preparation of bicyclo [3. n. 1] alkan-3-ones via bicyclo [3. n. 1] alk-3β-yl phenyl ketones to be achieved.
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今成 登志男, 石田 祐子, 早川 和一, 宮崎 元一
1978 年 26 巻 8 号 p.
2594-2595
発行日: 1978/08/25
公開日: 2008/03/31
ジャーナル
フリー
Superoxide dismutase (SOD)-like activity was found in rabbit plasma and the active substance was separated. Its properties were similar to those of copper-zinc SOD in cyanide and azide sensitivity and heat-stability, but its molecular weight was presumed to be 140000 by Sephadex G-150 column.
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坂井 進一郎, 新間 信夫
1978 年 26 巻 8 号 p.
2596-2598
発行日: 1978/08/25
公開日: 2008/03/31
ジャーナル
フリー
Heteroyohimbine alkaloids, akuammigine and 3-isorauniticine, were synthesized using a modified Polonovski reaction followed by NaCNBH
3 reduction from desmethylhirsuteine N-oxide, which was derived from the indole alkaloid hirsuteine. Corynanthe alkaloid, corynantheidine was also synthesized using the same method from hirsuteine N-oxide.
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石井 永, 石川 勉
1978 年 26 巻 8 号 p.
2598-2600
発行日: 1978/08/25
公開日: 2008/03/31
ジャーナル
フリー
New coumarins, arnocoumarin (1) and arnottiacoumarin (2), were isolated from X. arnottianum MAXIM. The structures of these coumarins were established by chemical transformation from marmesin (7) and rutaretin methyl ether (10) respectively.
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佐武 紀子, 村上 孝夫, 斎木 保久, 陳 秋明
1978 年 26 巻 8 号 p.
2600-2602
発行日: 1978/08/25
公開日: 2008/03/31
ジャーナル
フリー
Die oberirdischen Teilen von Lindsaea ensifolia Sw. enthalten neben einem bereits bekannten Flavon-C-Glykosid, Vitexin ein neuartiges Chromen-Derivat, Lindsaeasaure (I), deren Struktur durch spektroskopische Methoden aufgeklart wird.
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