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2-メルカプトベンツイミダゾール水銀誘導体の合成並びにその抗白癬菌作用
中島 正太郎, 田中 一郎, 赤 輝也, 安茂 寿夫, 小松 信
1959 年 79 巻 9 号 p.
1113-1116
発行日: 1959/09/25
公開日: 2010/02/19
ジャーナル
フリー
In continuation of the previous work, 13 kinds of mercury derivatives of 2-mercaptobenzimidazole were prepared and their antifungal activity against Trichophyton was examined. These mercury derivatives were generally prepared by condensation of substituted 2-mercaptobenzimidazole and alkylmercury hydroxide. The compounds which showed powerful action against the Trichophyton among these mercury derivatives were 1-ethylmercuri-, 5- or 6-chloro-1-ethylmercuri-, and 1-phenyl-2-ethylmercuri-thiobenzimidazoles. These completely inhibited growth of
Trichophyton interdigitale and
T. asteroides in 2, 200, 000 dilution, and
T. rubrum in 3, 300, 000 to 5, 000, 000 dilution.
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黄色食用色素およびオーラミン, バターイエローの分析
鈴木 美智雄, 中村 栄三, 長瀬 雄三
1959 年 79 巻 9 号 p.
1116-1119
発行日: 1959/09/25
公開日: 2010/02/19
ジャーナル
フリー
Infrared spectral analysis of yellow dyes (Naphthol Yellow S, Yellow AB, Yellow OB, Tartrazine, Sunset Yellow FCF, Auramine, and Butter Yellow) with the use of KBr pellet method was examined and it was found that detection up to ca. 40 γ would be possible by the use of their characteristic absorption bands. As an example of this method of quantitative analysis, determination of Auramine and of Auramine present in Tartrazine was carried out, utilizing the absorption at 1008cm
-1 as a key band for Tartrazine and that at 945cm
-1 for Auramine. Standard deviation of analytical results of each component in the mixture was calculated from the method of Youden and the values were 1.39 for Tartrazine and 1.55 for Auramine.
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Cycleanineの液体アンモニア中金属リチウムによる分解反応
富田 真雄, 酒井 健, 松村 寿賀子
1959 年 79 巻 9 号 p.
1120-1123
発行日: 1959/09/25
公開日: 2010/02/19
ジャーナル
フリー
Cleavage of cycleanine (I), a biscoclaurine-type base, with metallic sodium in liquid ammonia was found to form two moles of
l-armepavine (II). In the present series of work, decomposition of (I) with metallic lithium in liquid ammonia, with dioxane as a solvent, at a comparatively high temperature was carried out and two kinds of phenolic base (Base A and Base B) were isolated. The structure of these two cleaved bases was determined and it was found that the ether linkages binding the two diphenyl ethers in (I) were first cleaved to form
l-armepavine (II) (Base B) and one of them underwent secondary demethylation of the methoxyl group in 6-position of the tetrahydroisoquinoline ring to form a phenolic hydroxyl, thereby producing
l-N-methylisococlaurine (III) (Base A).
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オキサゾロピリジン類およびその関連化合物について その3
高橋 酉蔵, 神代 昭
1959 年 79 巻 9 号 p.
1123-1129
発行日: 1959/09/25
公開日: 2010/02/19
ジャーナル
フリー
In order to synthesize oxazolo [4, 5-
c] pyridin-2-one, reaction of 3-amino-4-hydroxy-pyridine (I) and carbonic acid derivatives was attempted, and the objective was attained by distillation of ethyl N-(4-hydroxy-3-pyridyl) carbamate. In the presence of sodium hydrogen carbonate, (I) reacts with ethyl chlorocarbonate to form the diethoxycarbonyl compound and this compound was found to be identical with 1-ethoxycarbonyl-3-ethoxycarbamido-4-pyridone (IV) derived from 1-ethoxycarbonyl-3-nitropyridine (VII). Further, infrared absorption spectra of (VII) and (IV) were con-sidered. Reaction route whereby 3-ethyloxazolo [4, 5-
c] pyridin-2-one is obtained by distillation of (IV) was presumed.
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オキサゾロピリジン類およびその関連化合物について その4
神代 昭
1959 年 79 巻 9 号 p.
1129-1132
発行日: 1959/09/25
公開日: 2010/02/19
ジャーナル
フリー
Nitration of 2-amino-5-bromopyridine (I) with sulfuric and nitric acid mixture afforded the 3-nitro compound in a better yield than that reported in past literature. Nitration of (I) with 3.2 moles of nitric acid at 55-65° was found to give 2-hydroxy-3-nitro-5-bromopyridine in one step. Consideration of this reaction course revealed that the reaction proceeded via formation of 2-nitramino-3-nitro-5-bromopyridine.
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パラジウム炭によるニトリル類の接触還元について
海尾 澄則
1959 年 79 巻 9 号 p.
1133-1138
発行日: 1959/09/25
公開日: 2010/02/19
ジャーナル
フリー
Catalytic reduction of a nitrile over palladium-carbon, in the presence of hydro-chloric acid, was found to reduce the nitrile to a primary alcohol, and examinations were made to find what kind of compounds underwent this reaction. As far as the present series of experiments are concerned, the nitrile group is reduced to the primary alcohol group when basic nitrogen atom is present in the position alpha to the nitrile group. It was also revealed that the condensate of ketones and ethyl cyanoacetate, i. e. nitriles having the structure of the type =C (CN)-COOC
2H
5, are also reduced to the primary alcohol when this double bond is difficult to be saturated.
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石黒 武雄, 柳生 正見, 高木 要
1959 年 79 巻 9 号 p.
1138-1140
発行日: 1959/09/25
公開日: 2010/02/19
ジャーナル
フリー
Vapor-liquid equilibrium of the diethylamine-water system was examined. Aqueous solution of diethylamine of various concentrations was submitted to flash distillation at atmospheric pressure, and the temperature-composition curve and
x-y equilibrium diagram of this system at constant pressure were calculated. These results indicated that there is no azeotropic mixture in the diethylamine-water system, contrary to the triethylamine-water system. As will be clear from the equilibrium diagram, it seems difficult to prepare completely anhydrous diethylamine merely by distillation from a very concentrated solution of diethylamine. Actually, the data of fundamental studies made on diethylamine-water-sodium hydroxide system reported earlier would be an important material when preparing completely anhydrous diethylamine by dehydration from its aqueous solution.
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Acetyl-1-naphthol類のMannich反応
奥田 高千代, 松本 潮
1959 年 79 巻 9 号 p.
1140-1145
発行日: 1959/09/25
公開日: 2010/02/19
ジャーナル
フリー
The Mannich reaction of α-naphthol will effect facile introduction of alkylamino-methyl group into the naphthol ring, but such introduction cannot be effected by condensation of acetyl-α-naphthols (4- and 2-acetyl-1-naphthols, and 2, 4-diacetyl-1-naphthol) and formaldehyde or with various secondary amines (dimethylamine, dieth-ylamine, morpholine, and piperidine). In all cases, it was found that an acetyl group was introduced into the side chain.
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ナフトールの分析
長瀬 雄三, 馬場 茂雄, 鈴木 美智雄
1959 年 79 巻 9 号 p.
1145-1148
発行日: 1959/09/25
公開日: 2010/02/19
ジャーナル
フリー
Determination of stereoisomers of α- and β-naphthols was attempted through infrared absorption spectra. Determination of β-naphthol present in α-naphthol was effected by the solution method using carbon disulfide as the solvent and by the KBr pellet method, but determination of α-naphthol present in β-naphthol could not be made by the solution method due to the sparing solubility of β-naphthol in carbon disulfide. Standard deviation of the determination calculated by Youden's assay method was the maximum at 1.18% and there was no significant difference in accuracy between the solution and KBr-pellet method. The absorbancy coefficient of the absorption band at 837cm
-1 (CS
2) of β-naphthol in a mixture is different from that of β-naphthol alone and cannot be used as the key band. This absorption band was assumed to have a bearing on intermolecular action.
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20-オキソステロイドの16β-水酸基および16β-アシルオキシ基の還元的脱離
西川 正元, 森田 桂, 野口 俊作
1959 年 79 巻 9 号 p.
1149-1151
発行日: 1959/09/25
公開日: 2010/02/19
ジャーナル
フリー
Reduction of diosone diacetate (Ia), 20-oxo-5-pregnene-3β, 16β-diol 3-acetate (Ib), and 20-oxo-5-pregnene-3β, 16β-diol diacetate (Ic) with zinc dust and acetic acid was found to result in reductive cleavage of the hydroxyl or acyloxy group in 16β-position to form 20-oxo-5-pregnen-3β-ol acetate (III). Catalytic reduction of these compound over Raney nickel left (Ic) intact but 20-ketone in (Ib) was reduced to 20β-ol to form 5-pregnene-3β, 16β, 20β-triol 3-acetate (IVa). Reduction of 20-oxo-5, 6, 17-tribromopregnane-3β, 16β-diol 3-acetate (V) over Raney nickel in pyridine afforded 20-oxo-5, 16-pregnadien-3β-ol acetate (II).
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Bis (2-thiazolyl) Sulfide体の研究 その4 Bis (2-thiazolyl) Sulfide体塩酸塩の熔融分解反応
前田 量三
1959 年 79 巻 9 号 p.
1151-1154
発行日: 1959/09/25
公開日: 2010/02/19
ジャーナル
フリー
Both bis [4-methyl-5-(2-hydroxyethyl)-2-thiazolyl] sulfide (V) and bis (4, 5-dimethyl-2-thiazolyl) sulfide (XVI) form dihydrochlorides (Va and XVIa), while 4-methyl-5-(2-hydroxyethyl)-2-thiazolyl 4-methyl-5-ethoxycarbonyl-2 thiazolyl sulfide (XII) and 4, 5-dimethyl-2-thiazolyl 4-methyl-5-ethoxycarbonyl-2-thiazolyl sulfide (XX) form monohydrochlorides (XIIa and XXa). These hydrochlorides regenerate the bases by treatment with water. Bis (4-methyl-5-ethoxycarbonyl-2-thiazolyl) sulfide (X) does not form a hydrochloride. Decomposition of (Va) and (XVIa) by fusion produces a small amount of the corresponding 2-mercaptothiazole derivative and 2-chlorothiazole derivative. The same decomposition of (XIIa) and (XXa) affords two kinds of symmetric bis (2-thiazolyl) sulfide derivatives, (V) and (X) from (XIIa), and (XVI) and (X) from (XXa). These facts seem to indicate that 2-mercaptothiazole and 2-chlorothiazole derivatives formed by primary decomposition undergo secondary reaction toward formation of (X), which does not form a hydrochloride.
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Bis (2-thiazolyl) Sulfide体の研究 その5 Bis (2-thiazolyl) Sulfide体塩酸塩と2-Mercaptothiazole誘導体の反応
前田 量三
1959 年 79 巻 9 号 p.
1155-1158
発行日: 1959/09/25
公開日: 2010/02/19
ジャーナル
フリー
The hydrochloride of bis (2-thiazolyl) sulfide undergoes decomposition by heating in carbon disulfide to form the corresponding 2-mercaptothiazole and 2-chlorothiazole compounds, and this decomposotion is affected by the substituent present in the 5-position of the thiazole moiety. The decomposition of 4, 5-dimethyl-2-thiazolyl 4-methyl-5-ethoxycarbonyl-2-thiazolyl sulfide hydrochloride (XXa) selectively into 2-mercapto-4, 5-dimethylthiazole (XVI) and ethyl 2-chloro-4-methyl-5-ethoxycarbonyl-2-thiazolyl sulfide hydrochloride (XIIa) into 2-(2-mercapto-4-methyl-5-thiazolyl) ethanol (I) and (IX) was proved from the reaction of bis (2-thiazolyl) sulfide hydrochloride and 2-mercapto-thiazole derivatives.
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Bis (2-thiazolyl) Sulfide体の研究 その6 Bis (2-thiazolyl) Sulfide体塩酸塩 (或いは臭化水素酸塩) と2-Chlorothiazole誘導体の反応
前田 量三
1959 年 79 巻 9 号 p.
1158-1162
発行日: 1959/09/25
公開日: 2010/02/19
ジャーナル
フリー
Decomposition of the hydrochloride of bis (2-thiazolyl) sulfide compounds by heating in carbon disulfide is affected by the substituent in 5-position of the thiazole ring. While CH
3 and CH
2CH
2OH have no effect on the 2-position, COOC
2H
5 group in 5-position results in selective formation of ethyl 2-chloro-4-methyl-5-thiazolecarboxylate (IX), and this was proved by reaction between bis (2-thiazolyl) sulfide hydrochloride (or hydrobromide) and 2-chlorothiazole derivatives. The reason for formation of two kinds of symmetric bis (2-thiazolyl) sulfides by reaction of ethyl 2-mercapto-4-methyl-5-thiazolecarboxylate (VIII) and 2-chlorothiazole derivatives, 2-mercapto-4, 5-dimethylthiazole (XIV) and 2-(2-chloro-4-methyl-5-thiazolyl) ethanol (IV), or 2-(2-mercapto-4-methyl-5-thiazolyl) ethanol (I) and 2-chloro-4, 5-dimethylthiazole (XV), during syntheses of non-symmetric bis (2-thiazolyl) sulfide compounds, was assumed to be due to the similar decomposition reaction of an intermediary produced hydrochloride and subsequent reaction of the decomposition products or starting materials with each other to fix hydrochloric acid or to form bis (4-methyl-5-ethoxycarbonyl-2-thiazolyl) sulfide (X) which does not form a hydrochloride.
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アンチピリン誘導体について その9
高橋 酉蔵, 兼松 顕, 水谷 民雄
1959 年 79 巻 9 号 p.
1163-1166
発行日: 1959/09/25
公開日: 2010/02/19
ジャーナル
フリー
4-Dialkylamino (piperidino, morpholino) methylantipyrine methiodides (VI to IX) were reacted with the sodium salt of ethyl acetoacetate, diethyl malonate, diethyl form-amidomalonate, or diethyl acetamidomalonate to form ethyl 2-(4-antipyrinylmethyl)-acetoacetate (X), ethyl 4-antipyrinylmethylmalonate (XI), ethyl 2-(4-antipyrinylmethyl)-formamidomalonate (XII), and ethyl 2-(4-antipyrinylmethyl) acetamidomalonate (XIII). Hydrolysis of (XI) with 30% hydrochloric acid afforded 4-antipyrinepropionic acid (XIV) which was derived to 4-(2-aminoethyl) antipyrine (XV) by the Curtius reaction. Crystallization of (XIII) was not effected and it was led to 4-antipyrinylalanine (XIX) by hydrolysis with 30% hydrochloric acid and (XIX) was benzoylated to form N-benzoyl-(4-antipyrinyl)-alanine (XX) which was isolated and characterized.
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1-Phenethyl-4 (or 5)-amino-2-pyridoneのSandmeyer反応
富沢 宏
1959 年 79 巻 9 号 p.
1167-1169
発行日: 1959/09/25
公開日: 2010/02/19
ジャーナル
フリー
The present series of experiments was carried out because of the interest in the behavior of 1-alkylaminopyridone to the Sandmeyer reaction and because 1-alkyl-2-pyridones with reliable substituted position were required. The starting material, 1-phenyl-4 (or 5)-amino-2-pyridone (VII) was prepared by the method similar to that adopted by Sugasawa and others by oxidation of the quaternary salt of pyridine-carboxylic acid ester with potassium ferricyanide, followed by the Curtius reaction, through the route of (I) to (VI).
The diazonium salt of 5-amino-2-pyridone (VIIa) is comparatively stable in conc. mineral acids and afforded the chloro derivative (VIIIa) in 53% yield, bromo compound (VIIIb) in 52% yield, iodo compound (VIIIc) in 45% yield, nitro compound (VIIId) in 44% yield, and cyano compound (VIIIe) in 30% yield, but the hydroxyl derivative was not obtained.
The diazonium salt of 4-amino-2-pyridone (VIIb) is unstable and undergoes decomposition prior to reaction with copper (I) salt. Consequently, only the chloro compound (VIIIf) was obtained in 26% yield but not bromine, iodine, cyano, or nitro derivative. Diazotization of (VIIb) in a large quantity of 60% sulfuric acid afforded a substance in 80% yield which corresponded to the hydroxyl compound (VIIIg).
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1-Phenethyl-2-pyridoneの双極子能率
富沢 宏
1959 年 79 巻 9 号 p.
1170-1173
発行日: 1959/09/25
公開日: 2010/02/19
ジャーナル
フリー
The process elaborated by Sugasawa and others of oxidation of 1-alkylpyridinium salt with potassium ferricyanide, followed by cyclization, is an important measures in the synthesis of benzoquinolizine ring. The ferricyanide oxidation differs according to the presence of a substituent in 3-position of the pyridinium salt, forming either the 2-pyridone (A) or 6-pyridone (B), and the structure of this product must be determined. In the present series of work, the dipole moment method, which is simple in procedure, was adopted for this purpose. Tatsuno proposed the limit formulae (C) and (D) for the resonance of 1-alkyl-2-pyridone and the direction of its moment as (C′) or (D′). Based on this hypothesis, he assumed that the dipole moment will become greater if the alkyl group enters the 5-position, while the moment will be smaller if the alkyl enters the 3-position. In the present series of experiments, several 1-phenethyl-2-pyridones, whose syntheses were reported in Part I of this series and whose structure is reliable, were submitted to dipole moment measurements. Examination of the results showed that the dipole moment of 1-phenethyl-2-pyridone is 4.2D and direction of the moment is as shown in (E). Vector calculations using the value of Smyth as the moment factor of a substituent gave values of dipole moment corresponding to 4- and 5-substituted 1-phenethyl-2-pyridone. This has proved the assumption of Tatsuno to be correct. Moreover, this method was found to offer a facile and reliable means for determining the direction of ferricyanide oxidation of 1-phenethylpyridinium salts.
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1-Phenethyl-3-phenoxy (3-cyanoおよび3-bromo) pyridinium塩の赤血塩酸化
富沢 宏
1959 年 79 巻 9 号 p.
1173-1176
発行日: 1959/09/25
公開日: 2010/02/19
ジャーナル
フリー
Structure of products from ferricyanide oxidation of three kinds of 1-phenethyl-pyridinium salts, using the method reported in Part II of this series.
1) Ferricyanide oxidation of 1-phenethyl-3-phenoxypyridinium bromide afforded a pyridone in ca. 30% yield and it formed prismatic crystals of m.p. 121-123°. Its dipole moment is 5.03D. When the group moment of the phenoxyl is taken as 1.23, the measured value of 2.99D for 3-phenoxypyridine agrees well with the calculated value of 3.05D. Vector calculation using this value gives the dipole moment value of 5.03D for 5-phenoxy derivative and 2.97 Dfor 3-phenoxy derivative. Consequently, the pyridone obtained by this oxidation is a 5-substituted compound.
2) The oxidation product from 1-phenethyl-3-cyanopyridinium salt is obtained in 95% yield and forms prismatic crystals of m.p. 115-116°. Its dipole moment is 7.45D and 7.35D. The calculated values are 3.68D for the 5-cyano derivative and 8.2D for 3-cyano derivative. With the consideration of the 5-substituted compound described in Part I of this series, this oxidation product was determined as the 3-substituted compound. Bradlow reported that oxidation of 1-methyl compound had afforded a mixture of 3- and 5-cyano derivatives but the presence of 5-cyano derivative was not confirmed in the present work.
3) The oxidation product of 1-phenethyl-3-bromopyridinium salt is obtained in 72% yield and forms rhomboprismatic crystals of m.p. 139.5-140°. Its dipole moment is 5.23D, while the calculated values are 3.49D for 5-substituted compound and 5.72D for 3-substituted compound. Comparison with the 5-bromo compound described in Part I of this series, this oxidation product was determined as the 3-bromo compound. This result agrees with the data reported by Bradlow.
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涌井 袈裟参, 河内 佐十
1959 年 79 巻 9 号 p.
1177-1181
発行日: 1959/09/25
公開日: 2010/02/19
ジャーナル
フリー
Lecithinase-A activity was compared in 10 kinds of serpent venom from Japan and Formosa. In general, venoms of the cobra family (Crotalidae) had stronger lecithinase activity than that from Elapidae family, but the activity of the venom from Japanese Mamushi (
Agkistrodon blomhoffi BOIE) and Habu (
Trimeresurus flavoviridis HOLL.) was comparable to that of the cobra family. None of these 10 kinds of venom appeared to contain lecithinase-B and a component that causes direct hemolysis of washed blood cells.
Paper electrophoresis of venom proteins from Japanese Habu, blue Habu (
Tr. gramineus stjnegeri), Formosan Habu (
Tr. macrosquamatus), and Mamushi indicated the presence of lecithinase-A active portion in two places and the migration of lecithinase-A protein differs with individual venom. The Mamushi venom was separated by the Slotta method into crotoxin portion and a supernatant, and both these fractions had lecithinase-A activity. Paper electrophoresis of the two fractions at pH 8.5 showed that the crotoxin fraction migrated toward the anode and the supernatant to the cathode side.
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コウヤマキ葉のフラボノイドSciadopitysinの構造研究 (6). メタノール性水酸化バリウムによるSciadopitysin Trimethyl Etherの分解
刈米 達夫, 河野 信助, 三浦 博史
1959 年 79 巻 9 号 p.
1182-1184
発行日: 1959/09/25
公開日: 2010/02/19
ジャーナル
フリー
Decomposition of sciadopitysin trimethyl ether by boiling in methanolic barium hydroxide solution afforded xanthoxylin, anisic acid, and a substance B, all of which were isolated in fair yield. This fact would be difficult to explain by the structure (I) assumed for sciadopitysin proposed earlier and a new formula (II) was proposed for its trimethyl ether. It was considered that the substance B is a biphenyl derivative (III).
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Benzocycloheptenone類のRobinson-Mannich反応 その3 3-Oxo-11b-methyl-1,2,3,6,7,11b-hexahydro-5H-dibenzo [a,c] cycloheptatrieneの合成
藤田 公司, 河津 光高, 綾田 渙
1959 年 79 巻 9 号 p.
1184-1187
発行日: 1959/09/25
公開日: 2010/02/19
ジャーナル
フリー
In order to synthesize compounds possessing a dibenzocycloheptene ring, the Robinson-Mannich reaction was found to be applicable to the synthesis of steroids and 3-methylbenzocyclohepten-4-one was synthesized. Robinson-Mannich reaction of this ketone compound afforded 3-oxo-11b-methyl-1, 2, 3, 6, 7, 11b-hexahydro-5
H-dibenzo-[
a, c] cycloheptatriene.
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Benzocycloheptenone類のRobinson-Mannich反応 その4 3-Oxo-11b-methyl-9,10-dimethoxy-および9,10,11-trimethoxy-1,2,3,6,7,11b-hexahydro-5H-dibenzo [a,c] cycloheptatrieneの合成
藤田 公司, 河津 光高, 綾田 渙
1959 年 79 巻 9 号 p.
1187-1192
発行日: 1959/09/25
公開日: 2010/02/19
ジャーナル
フリー
In order to synthesize the compounds with dibenzocycloheptene ring, 3-methyl-2′, 3′-dimethoxy- and 3-methyl-2′, 3′, 4′-trimethoxybenzocyclohepten-4-one were prepared. Each of these ketones was submitted to the Robinson-Mannich reaction, and 3-oxo-11b-methyl-9, 10-dimethoxy- and -9, 10, 11-trimethoxy-1, 2, 3, 6, 7, 11b-hexahydro-5
H-dibenzo [
a, c] cycloheptatriene were prepared. This reaction proceeds easily in 2′, 3′-dimethoxy compound but not in 2′, 3′, 4′-trimethoxy compound, majority of the starting material being recovered. This is considered to be due to steric interference of the methoxyl group in 4′-position.
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Benzocycloheptenone類のRobinson-Mannich反応 その5. 3-Oxo-1,2,3,6,7,11b-hexahydro-5H-dibenzo [a,c] cycloheptatrieneの合成
藤田 公司
1959 年 79 巻 9 号 p.
1192-1195
発行日: 1959/09/25
公開日: 2010/02/19
ジャーナル
フリー
In order to prepare compounds with a dibenzocycloheptene ring, benzocyclohepten-3-one was derived to benzocyclohepten-4-one and formylation of this ketone solely gave 3-formyl-benzocyclohepten-4-one. The Robinson-Mannich reaction of the formylated compound afforded 3-oxo-1, 2, 3, 6, 7, 11b-hexahydro-5
H-dibenzo [
a, c] cycloheptatriene.
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Benzocycloheptenone類のRobinson-Mannich反応 その6. 3-Oxo-9,10-dimethoxy-1,2,3,6,7,11b-hexahydro-5H-dibenzo [a,c] cycloheptatrieneおよび3-Oxo-7,8-dimethoxy-1,2,3,10,11,11a-hexahydro
藤田 公司
1959 年 79 巻 9 号 p.
1196-1201
発行日: 1959/09/25
公開日: 2010/02/19
ジャーナル
フリー
In order to synthesize the compounds with dibenzocycloheptene ring, 2′, 3′-dimethoxybenzocyclohepten-3-one was derived to 2′, 3′-dimethoxybenzocyclohepten-4-one and its formylation gave a mixture of 3-and 5-formylated compounds. The position of the formyl group was determined by reduction of the benzoyl derivative of the ketone obtained above to the methyl ketone compound.
Robinson-Mannich reaction of each of the formylated compounds afforded 3-oxo-9, 10-dimethoxy-1, 2, 3, 6, 7, 11b-hexahydro-5
H-dibenzo [
a, c] cycloheptatriene and 3-oxo-7, 8-dimethoxy-1, 2, 3, 10, 11, 11a-hexahydro-5
H-dibenzo [
a, e] cycloheptatriene.
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Benzocycloheptenone類のRobinson-Mannich反応 その7. 3-Oxo-6,7,8-trimethoxy-1,2,3,10,11,11a-hexahydro-5H-dibenzo [a,e] cycloheptatrieneの合成
藤田 公司
1959 年 79 巻 9 号 p.
1202-1208
発行日: 1959/09/25
公開日: 2010/02/19
ジャーナル
フリー
In order to synthesize compounds possessing a dibenzocycloheptene ring, purpurogallin was derived to 2′, 3′, 4′-trimethoxybenzocyclohepten-4-one and formylation of this ketone afforded a mixture of the 3- and 5-formyl compounds, in which the 5-formyl compound is the main product. Robinson-Mannich reaction of 3-formylated compound was not effect in methanol, ethanol, or
tert-butanol, probably due to steric hindrance of the methoxyl in 4′-position. The same Robinson-Mannich reaction of the 5-formylated compound afforded 3-oxo-6, 7, 8-trimethoxy-1, 2, 3, 10, 11, 11a-hexahydro-5
H-dibenzo [
a, e] cycloheptatriene.
2′, 3′, 4′-Trimethoxy-5-aminobenzocyclohepten-4-one was derived to 2′, 3′, 4′-trimethoxy-5-phthalimido-benzocyclohepten-4-one but its formylation was not effected.
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緑色食用色素およびマラカイトグリンの分析
鈴木 美智雄, 中村 栄三, 長瀬 雄三
1959 年 79 巻 9 号 p.
1209-1211
発行日: 1959/09/25
公開日: 2010/02/19
ジャーナル
フリー
In continuation of the previous work, infrared spectral analysis by the KBr-pellet method was carried out for detection of green dyes permitted for food (Guinea Green B, Light Green SF Yellowish, and Fast Green FCF) and Malachite Green. Examination of their absorption curves showed that it would be possible to detect up to ca. 40 γ by the use of their characteristic bands. As an example of this method, determination of Malachite Green present in Light Green SF Yellowish was carried out. Use of the absorption at 945cm
-1 as a key band for Malachite Green and that at 1024cm
-1 for Light Green SF Yellowish made it possible to determine each component from their mixture with a standard deviation, calculated by the method of Youden, of 0.878 for Light Green SF Yellowish and 1.159 for Malachite Green.
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久保田 和彦, 加来 天民
1959 年 79 巻 9 号 p.
1212-1215
発行日: 1959/09/25
公開日: 2010/02/19
ジャーナル
フリー
The alkylamino group in pharmaceutics of Methadone series was substituted with piperidine group or carbonyl group with sulfonyl group to prepare 6-piperidino-4, 4-diphenylhexan-3-one, 6-piperidino-4, 4-diphenylheptan-3-one, ethyl 1, 1-diphenyl-3-piperidinopropyl sulfone, and ethyl 1, 1-diphenyl-3-piperidinobutyl sulfone. Comparative examination of these compounds was made on toxicity, antitussive and analgesic action, antihistamine and antiacetylcholine action, effect on respiration and blood pressure of a rabbit, and effect on isolated heart of a toad and rabbit. The activity of these compounds was similar to that of morphine, and the compounds had extremely strong antitussive, analgesic, and respiration sedative activity. On the contrary, antihistamine and antiacetylcholine activity of these compounds were weak. The compounds of heptanone series had stronger activity than those of hexanone series, their antitussive and analgesic activity being comparable to that of heroine and almost three times stronger than that of morphine. The compounds of hexanone series were comparable to morphine. The toxicity of sulfohexanone and sulfoheptanone was weaker than those of hexanone and heptanone, while their analgesic and antitussive effect was much stronger.
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Callicrein 水溶液の安定性
守屋 寛
1959 年 79 巻 9 号 p.
1216-1217
発行日: 1959/09/25
公開日: 2010/02/19
ジャーナル
フリー
Stability of the callicrein, described in past reports of this series, to acids, alkalis, oxidation agents, reducing agents, and biological activity to some proteases was examined. Aqueous solution of callicrein is extremely labile to strong acids and alkalis but comparatively stable at neutral regions of pH 5.0-7.8. Callicrein lost its activity by hydrogen peroxide and iodine but was stable to sodium hydrogen sulfite. It also did not lose activity by the action of trypsin and papain.
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非対称性芳香ジアゾアミノ化合物の分解と 2-ナフトールとの連結反応
萩庭 丈寿, 高山 浩明, 石井 靖夫
1959 年 79 巻 9 号 p.
1217-1219
発行日: 1959/09/25
公開日: 2010/02/19
ジャーナル
フリー
Reaction of unsymmetric aromatic diazoamino compounds and 2-naphthol in weak acidity results in cleavage of diazoamino compound and the diazo compound so formed undergoes coupling with 2-naphthol. Cleavage of diazoamino compound usually results in formation of an amine having a substituent with large negativity and diazo compound of less negative amine. Reaction of 4-nitro-diazoaminobenzene with 2-naphthol at pH 4-0.5 only resulted in invariable regeneration of
p-nitroaniline and formation of 1-(4-nitrophenylazo)-2-naphthol was not detected even at a strong acidity.
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山崎 高応, 永田 正典
1959 年 79 巻 9 号 p.
1219-1222
発行日: 1959/09/25
公開日: 2010/02/19
ジャーナル
フリー
Fusion of diethyl methylimino-diacetate or diethyl methylimino-dipropionate with 3, 4-dimethoxyphenethylamine affords, besides the corresponding diamide compounds, 1-(3, 4-dimethoxyphenethyl)-4-methyl-2, 6-dioxopiperazine and 1, 5-diazacycloöctane-2, 8-dione. Isoquinoline cyclization of the diamide with phosphoryl chloride effects cyclization of only one of the amides and the other remains
per se. The treatment of this isoquinoline derivative further with phosphorus pentachloride in chloroform did not effect further isoquinoline cyclization of the remaining amide and the starting compound was recovered intact.
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山崎 高応, 永田 正典
1959 年 79 巻 9 号 p.
1222-1224
発行日: 1959/09/25
公開日: 2010/02/19
ジャーナル
フリー
N-Aralkylglycine ester, obtained by the reaction of two moles of aralkylamine and ethyl chloroacetate, was heated in ethylene glycol at 180° and 1, 4-diaralkyl-2, 5-dioxopiperazine was obtained in good yield. The Tafel electrolytic reduction of this piperazine compound afforded 1, 4-diaralkylpiperazine.
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みぶよもぎ水耕栽培とCH314COONaの投与について
三橋 博, 金子 光, 江口 静子, 吉田 尚利
1959 年 79 巻 9 号 p.
1224-1225
発行日: 1959/09/25
公開日: 2010/02/19
ジャーナル
フリー
In order to elucidate the mechanism of santonin biosynthesis in
Artemisia maritima, experiments were carried out with sodium acetate (
carboxyl-
14C), supplying this labeled compound several times during flower-bud season in hydroponic cultivation and cutting process, and distribution of the administered
14C in the plant and in the component was examined. Studies extending over three years revealed that transition of labeled carbon from sodium acetate (
carboxyl-
14C) was not so marked.
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米一 一亨, 沢田 英夫
1959 年 79 巻 9 号 p.
1226-1228
発行日: 1959/09/25
公開日: 2010/02/19
ジャーナル
フリー
A glycoside (I) of m.p. 190-191°, C
17H
24O
9⋅H
2O, was obtained from the methanolic extract of the trunk bark of
Paulownia tomentosa STEUD. Hydrolysis of (I) with sulfuric acid afforded a glucose. Oxidation of (I) with alkaline permanganate gave syringaic acid (II) and that with neutral permanganate gave glucosyringaic acid (III). (III) afforded syringaic acid by hydrolysis with sulfuric acid. It was assumed from these results that (I) might be syringin and the fact was confirmed by mixed fusion with syringin.
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フユザンショウ Xanthoxylum planispium SIEB. et ZUCC. のアルカロイド その1
富田 真雄, 石井 永
1959 年 79 巻 9 号 p.
1228-1230
発行日: 1959/09/25
公開日: 2010/02/19
ジャーナル
フリー
Examinations were made on the alkaloids contained in
Xanthoxylum planispium SIEB. et ZUCC. (Japanese name ‘Fuyu-Zansho’) (Rutaceae) growing wild in the suburbs of Kyoto City. The known dictamnine (I) and skimmianine (II) were isolated from the root as the tertiary bases and their content was extremely minute. As a water-soluble quaternary base, magnoflorine (III) and a minute amount of XPQR-base-I was isolated as a picrate of m.p. 228°. The cortex did not contain any tertiary base but contained a water-soluble quaternary base, XPQE-base-I, isolated as a styphnate of m.p. 180-183° (decomp.).
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