-
菊池 徹, 上尾 庄一郎
1967 年 15 巻 5 号 p.
549-570
発行日: 1967/05/25
公開日: 2008/03/31
ジャーナル
フリー
Pachystermine-A (I) and -B (II), weakly basic alkaloids isolated from Pachysandra terminalis SIEB. et ZUCC.(Buxaceae), were investigated. The structures and stereochemistry of these alkaloids are now assigned to the formula I and II, respectively. They represent a novel type of 3, 20-diamino-5α-pregnane alkaloid carrying a four-membered β-lactam ring system.
抄録全体を表示
-
菊池 徹, 上尾 庄一郎
1967 年 15 巻 5 号 p.
571-576
発行日: 1967/05/25
公開日: 2008/03/31
ジャーナル
フリー
Pachysantermine-A is one of the minor alkaloids of Pachysandra terminalis SIEB. et ZUCC., a Buxaceous plant, and the structure including absolute configuration of pachysantermine-A is now assigned to the formula Ia. It is unique in that it has a seven-membered ring ester grouping containing a nitrogen atom. Also a biogenetic pathway of pachysantermine-A (Ia) in the living plant and of pachystermine-A (VIIa) and -B (VIIb), which are the closely related alkaloids, was presumed.
抄録全体を表示
-
菊池 徹, 上尾 庄一郎, 西永 俊也
1967 年 15 巻 5 号 p.
577-581
発行日: 1967/05/25
公開日: 2008/03/31
ジャーナル
フリー
In succession to the structure determination of a number of 3, 20-diamino-5α-pregnane type alkaloids of Pachysandra terminalis SIEB. et ZUCC., another new alkaloid, epipachysandrine-A, which was obtained from the weakly basic alkaloid fraction was investigated. The structure and stereochemistry of the alkaloid was proved to be represented by the formula Ia.
抄録全体を表示
-
上尾 庄次郎, 神代 昭, 入江 寛, 山本 健次
1967 年 15 巻 5 号 p.
582-584
発行日: 1967/05/25
公開日: 2008/03/31
ジャーナル
フリー
The chemical evidence for structure II assigned previously to the product obtained by treatment of 14-hydroxydeoxydihydrocodeine methine with silver acetate and iodine followed by potassium hydroxide under the Prevost-Woodward reaction conditions is presented.
抄録全体を表示
-
中村 優, 小松 京子, 権藤 宜子, 太田 紀代子, 上田 陽
1967 年 15 巻 5 号 p.
585-592
発行日: 1967/05/25
公開日: 2008/03/31
ジャーナル
フリー
A series of 131 N-benzylideneaniline derivatives was prepared, and their infrared spectra were measured in the same conditions. Statistical tests showed that differences of substitution in benzene ring of benzylidene group affected acceptably on the region of C=N stretching absorption peak, but those in benzene ring of aniline group had smaller effect on it.
抄録全体を表示
-
金岡 祐一, 谷沢 和隆, 佐藤 英助, 米光 宰, 伴 義雄
1967 年 15 巻 5 号 p.
593-595
発行日: 1967/05/25
公開日: 2008/03/31
ジャーナル
フリー
Aryl esters are formed from various free carboxylic acids and phenols by means of polyphosphate ester (PPE) under mild conditions.
抄録全体を表示
-
Masao Okamoto
1967 年 15 巻 5 号 p.
596-598
発行日: 1967/05/25
公開日: 2008/03/31
ジャーナル
フリー
-
佐々木 喜男, 鈴木 美代子, 日比野 俊彦, 唐井 和子
1967 年 15 巻 5 号 p.
599-607
発行日: 1967/05/25
公開日: 2008/03/31
ジャーナル
フリー
Proton magnetic resonance spectra of para-disubstituted benzene, 1-substituted-3, 4-dimethoxy- and 1-substituted-3, 4-methylenedioxy benzene series are investigated in the following items : 1. Ring proton chemical shift and Shielding parameter. 2. Ring proton coupling constant and electronegativity of the substituent. 3. Inspection on the analysis of the spectra. 4. Side chain proton shift and Hammett's constant.
抄録全体を表示
-
亀谷 哲治, 大久保 一三
1967 年 15 巻 5 号 p.
608-612
発行日: 1967/05/25
公開日: 2008/03/31
ジャーナル
フリー
Re-examination of the experimental data for corpaverine by chemical methods previously reported and the structural elucidation of sendaverine by physical methods led to propose the structure of I. A total synthesis of sendaverine is finally described, confirming the structure for the alkaloid.
抄録全体を表示
-
亀谷 哲治, 気賀沢 和雄, 菅原 宏, 柊木 峯治, 早坂 鉄太郎, 岩田 武彦, 石丸 春秀
1967 年 15 巻 5 号 p.
613-618
発行日: 1967/05/25
公開日: 2008/03/31
ジャーナル
フリー
The choline salicylate (I) was obtained by the reaction of 2-dimethylaminoethanol with methyl salicylate. Furthermore, a novel methylation of tertiary amines with alkyl salicylate was also established.
抄録全体を表示
-
相馬 信夫, 中沢 準一, 渡辺 泰一郎, 佐藤 良雄, 砂川 玄俊
1967 年 15 巻 5 号 p.
619-626
発行日: 1967/05/25
公開日: 2008/03/31
ジャーナル
フリー
The preparation of tropylium ions having a fused oxazole, imidazole or thiazole nucleus is described. The heating of 2-benzoylaminotropone (I) and dimethyl sulfate produced 2-phenyloxazolotropylium ion (IIIa). The disproportionation reaction of IIIa with aqueous alkali gave 2-phenyl-6H-cycloheptoxazole (V) and 2-phenyl-6H-cycloheptoxazol-6-one (IV), The structures of which were proved by the reactions shown in Chart 1 and by examination of the spectra. 2-Phenylthiazolotropylium ion (XVIIb) and 1-p-tolyl-2-phenylimidazolotropylium ion (XXI) were prepared, respectively, by the simple dissolution of 2-benzoylaminotroponthion (XVI) and 2-benzoylamino-N-p-tolyltroponeimine (XX) in dilute hydrochloric acid. Treatment of both ions XVIIb and XXI with aqueous alkali resulted in the disproportionation reaction in which the former gave XVIII and XIX and the latter XXII and XXIII. The NMR spectra of the ions, XVII and XXI, showed the significant contribution of the tropylium ion structure of these compounds.
抄録全体を表示
-
相馬 信夫, 中沢 準一, 渡辺 泰一郎, 佐藤 良雄, 砂川 玄俊
1967 年 15 巻 5 号 p.
627-633
発行日: 1967/05/25
公開日: 2008/03/31
ジャーナル
フリー
Reactions of tropylium ions having a fused heterocyclic system with various amines were examined. Reaction of 2-phenyloxazolotropylium monomethylsulfate (I) and 2-phenylthiazotropylium chloride (XXIV) with dimethylamine produced 2-phenyl-6-dimethylamino-6H-cycloheptoxazole (II) and 6-dimethylamino-2-phenyl-6H-cycloheptathiazole (XXV), respectively. Regarding the reaction with p-toluidine, both I and 1-p-tolyl-2-phenylimidazolotropylium chloride (XXVI) gave 1-p-tolyl-2-phenyl-1, 6-dihydrocycloheptimidazole (VI) and 1-p-tolyl-2-phenyl-6-p-tolylimino-1, 6-dihydrocycloheptimidazole (VII). Reaction of I with N-methylaniline produced 2-phenyl-6-p-methylaminophenyl-6H-cycloheptoxazole (XIX) and 2-phenyl-4-p-methylaminophenyl-4H-cycloheptoxazole (XX). From these results, it is concluded that the tropylium ions condensing a heterocycle has a priority for amination at C-6.
抄録全体を表示
-
佐藤 裕信, 砂川 玄俊
1967 年 15 巻 5 号 p.
634-643
発行日: 1967/05/25
公開日: 2008/03/31
ジャーナル
フリー
8-Methylimino-1, 8-dihydrocyclohepta [b] pyrrole derivatives (XIa∼d) were synthesized by cyclization of azines obtained from 2-methylaminotropone hydrazone and various carbonyl compounds. Direct methylation of cyclohepta [b] pyrrol-8(1H)-one derivatives with dimethyl sulfate resulted in O-methylation affording 8-methoxycyclohepta [b] pyrroles (XVa∼c) which on condensation with methylmine also gave XIa∼c. Cyclohepta [b] pyrrole-8(1H)-thione derivatives were synthesized by reaction of XVa∼c and sodium sulfide. In addition, tropone analogues of tryptamine, 3-(2-aminoethyl) cyclohepta [b] pyrrole derivatives were prepared.
抄録全体を表示
-
太田 元吉, 長瀬 脩, 細川 恭宏, 田川 博昭, 清水 正夫
1967 年 15 巻 5 号 p.
644-647
発行日: 1967/05/25
公開日: 2008/03/31
ジャーナル
フリー
Synthesis of L-N, N'-diacylcystine (VI) from L-cysteine and nitrile (II) by using thiazoline (III) as an intermediate is described.
抄録全体を表示
-
長瀬 脩
1967 年 15 巻 5 号 p.
648-654
発行日: 1967/05/25
公開日: 2008/03/31
ジャーナル
フリー
D-Pantetheine 4'-phosphate (VIa) and D-pantothenoyl-L-cysteine 4'-phosphate (VIb) was prepared by two different routes. The first involved reaction of D-pantothenonitrile 4'-dibenzyl phosphate (II) with cysteamine or L-cysteine followed by acid hydrolysis and then reduction with sodium in liquid ammonia. In the second route, D-pantothenonitrile 4'-phosphate (VII) was treated with cysteamine or L-cysteine to form thiazoline (VIII), which was then hydrolyzed.
抄録全体を表示
-
清水 正夫, 長瀬 修, 岡田 清三郎, 細川 恭宏, 田川 博昭, 安孫子 雍史, 鈴木 忠生
1967 年 15 巻 5 号 p.
655-662
発行日: 1967/05/25
公開日: 2008/03/31
ジャーナル
フリー
Synthesis of coenzyme A using thiazoline (Vb) as intermediate is described. D-Pantothenonitrile (I) was treated with adenosine 2', 3'-cyclic phosphate 5'-phosphoromorpholidate (IIb) in pyridine followed by ribonuclease T
2 to yield P
1-adenosine 3'-phosphate 5'-P
2-D-pantothenonitrile 4'-pyrophosphate (IVb). Condensation of IV b with cysteamine gave thiazoline (Vb), which was then hydrolyzed to afford coenzyme A.
抄録全体を表示
-
金子 主税, 山田 幸子
1967 年 15 巻 5 号 p.
663-669
発行日: 1967/05/25
公開日: 2008/03/31
ジャーナル
フリー
The oxaziranes (Ia∼d) prepared by the irradiation of the corresponding 2-cyanoquinoline 1-oxides in an aprotic solvent all rearranged to the corresponding 3-quinolinols under a variety of conditions described. The mechanism of this novel isomerization has been postulated.
抄録全体を表示
-
三木 卓一, 平賀 謙太郎, 朝子 典彦, 桝屋 浩大
1967 年 15 巻 5 号 p.
670-673
発行日: 1967/05/25
公開日: 2008/03/31
ジャーナル
フリー
2-Methyl, 2-propyl and 2-phenethylcyclopentane-1, 3-dione (III) were prepared by the catalytic hydrogenation of the corresponding 2-(α-ethoxyalkylidene) cyclopent-4-ene-1, 3-diones, (II), which were obtained by the condensation of cyclopent-4-ene-1, 3-dione (I) and ethyl ester of ortho acids.
抄録全体を表示
-
鈴木 徳治, 谷村 勇一
1967 年 15 巻 5 号 p.
674-681
発行日: 1967/05/25
公開日: 2008/03/31
ジャーナル
フリー
General base-catalyzed hydrolysis for several choline salt esters of carboxylic acids as well as succinylcholine chloride was investigated. Acetylcholine chloride, a part of succinylcholine chloride molecule, also was subject to general base-catalyzed hydrolysis. The ratio, k
AC- to k
OH-, of acetylcholine chloride was almost equal in magnitude to that of succinylcholine chloride. Degree of the influence of catalytic effect of general bases on the overall rate constant of ester hydrolysis was discussed. Imidazole was a less effective catalyst than phosphate dianion for the hydrolysis of the choline salt esters of carboxylic acids. The general base-catalyzed hydrolysis for these esters appears to represent classical general base catalysis rather than nucleophilic catalysis, as shown in the catalytic hydrolysis for the esters activated in acyl portion, enthyl haloacetates.
5) An attempt was made to compare the effect of acetate ions on the hydrolytic rate constants of the Choline salt esters with that of the corresponding tertiary aminoesters. The catalytic contribution of acetate ions for the latter esters became less pronounced. The logarithms of rate constants of alkaline hydrolysis and acetate ion catalysis were not linearly related.
抄録全体を表示
-
小倉 治夫, 太田越 朗子, 佐野 敬元, 秦 藤樹
1967 年 15 巻 5 号 p.
682-684
発行日: 1967/05/25
公開日: 2008/03/31
ジャーナル
フリー
Amaromycin is the same compound as pikromycin, which fact was proved hydrolytic studies of amaromycin and their direct comparison. Stereochemistry of amaromycin was studied by nuclear magnetic resonance spectra and it was concluded that desosamine linkage has a β-configuration, and there is trans-olefinic structure in the lactone.
抄録全体を表示
-
野上 寿, 長谷川 淳, 五十里 紀子
1967 年 15 巻 5 号 p.
685-692
発行日: 1967/05/25
公開日: 2008/03/31
ジャーナル
フリー
Experimental conditions for the kinetic study of exchange reaction between thiamine propyl disulfide (TPD) and L-cysteine were examined where the possible side reactions shown in Chart 1 proved by thin-layer chromatography could be safely ignored. The following conclusions were drawn from the results obtained. 1) It was proved that the formation of thiamine was the main product and the formation of propylmercaptan was negligible when the reactants were mixed in a molar ratio of 1 : 1 and an initial concentration of 1×10
-3∼5×10
-5 molar. 2) The exchange reaction followed second order kinetics examined from half-life, the plot of integrated equation, and the result of pseudo first order reaction converted by experimental conditions. The rate constants observed were 1.723 and 444.4 L. mole
-1 min.
-1at 15°and pH 4.6 and 8.0, respectively. 3) The rate constant of the thiamine formed from TPD and propylmercaptan which was the largest side reaction among the various possibilities, was 0.607 L. mole
-1 min.
-1 at pH 4.6 and 15°as a second order reaction.
抄録全体を表示
-
野上 寿, 長谷川 淳, 五十里 紀子
1967 年 15 巻 5 号 p.
693-700
発行日: 1967/05/25
公開日: 2008/03/31
ジャーナル
フリー
The Kinetics between thiamine propyl disulfide or its homologes and L-cysteine were studied under the experimental conditions determined in the preceding paper. The effects of alkyl substitution of TPD on kinetic parameter were also studied, using thiamine benzyl disulfide, thiamine allyl disulfide, and thiamine hydroxyethyl disulfide. The following conclusions were drawn from the results presented. 1) From an analysis of the pH-rate profile of the reaction which followed a second order kinetics throughout the pH range of 3.5 to 13.2, the reaction was revealed as the combination of the following elementary reactions. [numerical formula] where HG
1-SS-Pr is the protonated form of TPD, NH
3+-Cy-S
- is protonated cysteine anion, and k
1, k
2 and k
3 are specific rate constants of individual elementary reactions. The values determined were 1.82, 0.261 and 1.10 in 10
4L. mole
-1 min.
-1for k
1, k
2 and k
3, respectively. 2) No detectable effect of ionic strength and buffer concentration on the rate constant was observed at pH 4.0 on Reaction (I). 3) The activation energy obtained from an Arrhenius type plot was 12.3 and 10.9 kcal./mole for Reaction (I) and (II) after correction for ionic dissociation of thiol and amino groups in cysteine. 4) From the kinetic data tabulated on TPD derivatives, the order of the reactivity was TBD>TAD-TOED>TPD. The activation energies of Reaction (I) were about 10 to 12 kcal./mole.
抄録全体を表示
-
片岡 美紀子, 宮田 健, 与儀 啓子, 加瀬 佳年
1967 年 15 巻 5 号 p.
701-703
発行日: 1967/05/25
公開日: 2008/03/31
ジャーナル
フリー
-
亀谷 哲治, 気賀沢 和雄, 柊木 峯治
1967 年 15 巻 5 号 p.
704-707
発行日: 1967/05/25
公開日: 2008/03/31
ジャーナル
フリー
-
緒方 一美, 石井 覚
1967 年 15 巻 5 号 p.
707-710
発行日: 1967/05/25
公開日: 2008/03/31
ジャーナル
フリー
-
河野 信助, 三浦 博史, 松石 英子
1967 年 15 巻 5 号 p.
711-712
発行日: 1967/05/25
公開日: 2008/03/31
ジャーナル
フリー
-
岡田 清三郎, 長瀬 脩, 清水 正夫
1967 年 15 巻 5 号 p.
713-715
発行日: 1967/05/25
公開日: 2008/03/31
ジャーナル
フリー
-
橋本 真志, 服部 清
1967 年 15 巻 5 号 p.
718-720
発行日: 1967/05/25
公開日: 2008/03/31
ジャーナル
フリー
-
庄司 順三, 川西 幸子, 佐久間 聖一, 柴田 承二
1967 年 15 巻 5 号 p.
720-723
発行日: 1967/05/25
公開日: 2008/03/31
ジャーナル
フリー
-
村山 圭介, 吉岡 孝雄
1967 年 15 巻 5 号 p.
723-725
発行日: 1967/05/25
公開日: 2008/03/31
ジャーナル
フリー
-
二階堂 宏夫, 清水 譲, 三橋 博
1967 年 15 巻 5 号 p.
725-726
発行日: 1967/05/25
公開日: 2008/03/31
ジャーナル
フリー
-
由岐 英剛, 仮家 公夫, 橋本 嘉幸
1967 年 15 巻 5 号 p.
727-729
発行日: 1967/05/25
公開日: 2008/03/31
ジャーナル
フリー