-
不齊転位による光学的活性α-Aminopropiophenone類の生成
高松 秀二
1956 年 76 巻 11 号 p.
1219-1222
発行日: 1956/11/25
公開日: 2010/02/19
ジャーナル
フリー
α-Aminopropiophenones easily undergo racemization by enolization due to their tautomerism. This property was utilized in their optical resolution with
d-tartaric acid derivatives and optically active compounds were obtained in a good yield by asymmetric transformation. Such transformation did not occur when
d-camphor-β-sulfonic acid was used. By this means, optically active compounds of α-amino-, α-methylamino-, α-dimethylamino-, α-piperidino-, and α-benzylmethylamino-propio-phenones were prepared.
抄録全体を表示
-
光学的活性α-Aminopropiophenone類のラセミ化について
高松 秀二
1956 年 76 巻 11 号 p.
1223-1226
発行日: 1956/11/25
公開日: 2010/02/19
ジャーナル
フリー
Racemization velocity of optically active α-aminopropiophenones was measured from the changes in the angle of rotation. It was thereby found that in the state of a base, racemization is more rapid the greater the basicity and, in the presence of an alkali, racemization is markedly accelerated. Racemization is facilitated by the presence of a weak acid, such as acetic acid, in organic solvents but the compounds are stabilized to a certain extent in an aqueous solution. It was found that the compounds become extremely stable in the presence of a strong acid, such as hydrochloric acid.
抄録全体を表示
-
l-Ephedrine及びその類似体の合成
高松 秀二
1956 年 76 巻 11 号 p.
1227-1229
発行日: 1956/11/25
公開日: 2010/02/19
ジャーナル
フリー
The reduction of the optically active α-aminopropiophenones, either catalytically or with lithium aluminum hydride or sodium borohydride, afforded
l-ephedrine and other optically active phenylpropanolamines. Catalytic reduction of α-benzylmethyl-aminopropiophenone with palladium-carbon in glacial acetic acid, in the presence of perchloric acid, results first in the reduction of the carbonyl group, followed by debenzylation, whereas debenzylation occurs first under other conditions, and pseudoephedrine was chiefly formed, perhaps due to the steric effect. Formation of such pseudo compound was also observed in the reduction of α-benzylmethylamino- or α-piperidino-propiophenone with lithium aluminum hydride. Optically active 2-phenylisopropylamines were prepared by the catalytic reduction of α-aminopropiophenones by warming them in glacial acetic acid, in the presence of perchloric or conc. sulfuric acid.
抄録全体を表示
-
光学的活性1-Aryl-2-amino-1-propanol類及び1-Phenyl-2-methyl-3-amino-1-propanol類の合成
高松 秀二, 三奈木 康夫
1956 年 76 巻 11 号 p.
1230-1233
発行日: 1956/11/25
公開日: 2010/02/19
ジャーナル
フリー
Asymmetric transformation of α-aminopropiophenones and α-methyl-β-aminopropiophenones, possessing a hydroxyl or methoxyl group in the phenyl ring, by the use of
d-tartaric acid and its derivatives afforded their optically active compounds in a good yield. The racemization velocity of the optical active compounds was measured under various conditions and the values obtained were compared with experimental results obtained with α-aminopropiophenones. It was thereby found that a similar tendency also existed in this case, racemization in organic solvent being rapid in the presence of a weak acid and the compounds being stabilized with a strong acid. There was no marked effect of the hydroxyl group in the phenyl ring on racemization rate. The racemization velocity of α-methyl-β-aminopropiophenones was somewhat smaller than that of the similarly structured α-aminopropiophenones. Catalytic reduction of these optically active compounds afforded
d- or
l-1-(
p-hydroxyphenyl)-2-methylaminopropan-1-ol,
l-1-phenyl-2-methyl-3-dimethylaminopropan-1-ol, and several other kinds of optically active alkanolamines.
抄録全体を表示
-
光学的活性α-Amino-及びα-Aminomethyl-propiophenone類に対するグリニヤ反応
高松 秀二, 三奈木 康夫
1956 年 76 巻 11 号 p.
1234-1235
発行日: 1956/11/25
公開日: 2010/02/19
ジャーナル
フリー
Grignard reaction of the optically active α-amino- and α-aminomethyl-propiophenones afforded optically active 1-phenyl-1-alkyl(or aryl)-2-aminopropan-1-ols and 1-phenyl-1-alkyl(or aryl)-2-methyl-3-aminopropan-1-ols. In all these cases, the reaction was asymmetric and only one kind of optically active compounds was obtained. Further catalytic reduction of the benzylmethylamino derivatives effected debenzylation to the methylamino derivatives.
抄録全体を表示
-
α-Aminopropiophenone類の分解反応について その1
高松 秀二
1956 年 76 巻 11 号 p.
1236-1238
発行日: 1956/11/25
公開日: 2010/02/19
ジャーナル
フリー
It had been observed during optical resolution of α-aminopropiophenones that amine salts assumed to have been formed by the severance of the C-N bond are produced. Examination of this cause revealed that when α-aminopropiophenones are heated in the presence of a weak acid, such as acetic acid, or allowed to stand with it for a long time, the propiophenones underwent decomposition into amines and phenylacetylcarbinol (I). In the presence of a strong acid, however, such decomposition hardly took place and that the decomposition also did not occur even in the presence of a weak acid if derived to quaternary ammonium salts. Since benzoyl-methylcarbinol hardly undergoes rearrangement to (I) under these decomposition conditions, it seems certain that (I) was not produced secondarily. The mechanism of this decomposition reaction is proposed.
抄録全体を表示
-
α-Aminopropiophenone類の分解反応について その2
高松 秀二
1956 年 76 巻 11 号 p.
1239-1241
発行日: 1956/11/25
公開日: 2010/02/19
ジャーナル
フリー
Decomposition of α-aminopropiophenones, possessing a hydroxyl or methoxyl group in the
para position of phenyl ring, with acetic acid afforded a mixture of arylacetylcarbinols (I) and aroylmethylcarbinols (II). This is due to the rearrangement of (I) during the reaction to a more stable (II). In a similar manner, benzoin and benzylmethylamine were obtained from α-benzylmethylaminodesoxybenzoin.
抄録全体を表示
-
Phenylpropanolamine類よりDimeric Etherの生成
高松 秀二
1956 年 76 巻 11 号 p.
1241-1243
発行日: 1956/11/25
公開日: 2010/02/19
ジャーナル
フリー
The reaction product obtained by
l-ephedrine with perchloric acid or a small amount of conc. sulfuric acid was found to be
d-bis (1-phenyl-2-methylaminopropyl) ether. Various kinds of dimeric ethers were prepared similarly from racemic and optically active ephedrine analogs. A small amount of phenylacetone was obtained as a by-product in this reaction.
抄録全体を表示
-
ヒドラミン分解について
高松 秀二
1956 年 76 巻 11 号 p.
1244-1246
発行日: 1956/11/25
公開日: 2010/02/19
ジャーナル
フリー
Treatment of ephedrine and its analogs by warming with 80-85% sulfuric acid on a water bath results in their decomposition to phenylacetone and the corresponding amines but this decomposition was found not to take place with 90% phosphoric acid or dilute sulfuric acid. The same treatment of 1, 2-diphenyl-2-methylamino-1-ethanol afforded desoxybenzoin and methylamine. Such reactions are new decomposition of ephedrines different from the known hydramine fission and is assumed to proceed by dehydration to vinylamine compound. Examinations were made on the so-called apoephedrine, obtained by the treatment of
l-(or
d-pseudo) ephedrine with cold conc. sulfuric acid, revealed that it is a kind of a polymerized product and not the structure assumed by Schmidt.
抄録全体を表示
-
芳香族アルデヒドシアンヒドリンに対するアルキルGrignard試薬の反応
鍛冶 健司, 長島 弘
1956 年 76 巻 11 号 p.
1247-1250
発行日: 1956/11/25
公開日: 2010/02/19
ジャーナル
フリー
Several kinds of mixed acyloins, arylacylcarbinols, were prepared, though in a low yield, by the reaction of alkyl Grignard reagents on aromatic aldehyde cyanohydrins (mandelonitrile). At the same time, it was found that a fair amount of arylalkylcarbinols are formed as by-products. It was therefore assumed that the action of the Grignard reagents on mandelonitrile was accompanied, besides the normal addition, with a kind of nucleophilic replacement.
抄録全体を表示
-
芳香族アルデヒドシアンヒドリンイミノエステルに対するGrignard試薬の新反応
鍛冶 健司, 長島 弘
1956 年 76 巻 11 号 p.
1250-1253
発行日: 1956/11/25
公開日: 2010/02/19
ジャーナル
フリー
Several kinds of mixed acyloin, including phenylacetylcarbinol (b. p
7 105-108° in 35.7% yield), were obtained by the application of alkyl Grignard reagent on aromatic aldehyde cyanohydrin imino ester. The yield of the mixed acyloin in this reaction is better than that in the reaction of mandelic nitrile and alkyl Grignard reagent but the formation of arylalkylcarbinols, such as phenylmethylcarbinol (b. p
7 78-82° in 28.9% yield), cannot be avoided. However, the reaction of mandelic nitrile imino ester and phenylmagnesium bromide afforded on benzoin (m. p. 131° in 51.5% yield) and benzhydrol was not formed.
抄録全体を表示
-
アシルーフロログルシノール, -メチルフロログルシノールの合成並びにこれらとフォルムアルデヒドの縮合
稻垣 勳, 久田 末雄, 小川 宗治, 野呂 征男
1956 年 76 巻 11 号 p.
1253-1255
発行日: 1956/11/25
公開日: 2010/02/19
ジャーナル
フリー
Acyl derivatives of phloroglucinol and methylphloroglucinol were prepared by the Hoesch method (Tables I and II) and their condensation with formaldehyde was carried out. The condensates with acylphloroglucinols were all amorphous powder while those with acylmethylphloroglucinols were obtained in crystalline state (Table III).
抄録全体を表示
-
DimedoneのC-Acyl誘導体の合成
稻垣 勳, 久田 末雄, 小川 宗治, 野呂 征男, 大須賀 敏明
1956 年 76 巻 11 号 p.
1256-1258
発行日: 1956/11/25
公開日: 2010/02/19
ジャーナル
フリー
C-Acyl derivatives of dimedone (
gem-dimethylhydroresorcinol) were prepared by one of the following processes (Table I). (1) Heating with acid anhydride and anhydrous sodium salt of its acid; (2) Friedel-Crafts method; (3) heating of the O-acyl derivatives with anhydrous sodium salt to effect rearrangement to the C-acyl compounds; and (4) Spassow method. The aliphatic C-acyl derivatives, except the C-acetyl compound, are all thick oil at room temperature and can be distilled under a reduced pressure. Differing from the O-acyl derivatives, they all give positive reaction with ferric chloride and form with copper acetate pale blue, crystalline copper salts insoluble in water and ether. The monoanilide obtained by dehydrative condensation with 1 mole of aniline is easily crystallizable, shows sharp melting point, and is suitable for the identification of C-acyldimedones.
抄録全体を表示
-
フィリチン酸のアシル誘導体フィリチン酸ブタノン, アルバスピジン等の合成
稻垣 勳, 久田 末雄, 小川 宗治, 野呂 征男, 石原 利克
1956 年 76 巻 11 号 p.
1258-1260
発行日: 1956/11/25
公開日: 2010/02/19
ジャーナル
フリー
Filicinic acid was prepared in a comparatively good yield by the modified Robertson method and the application of aluminum chloride, nitrobenzene, and carbon disufide with acid anhydride to filicinic acid afforded butyroyl-, isovaleroyl-, and hexanoyl-filicinic acids (Table I). The condensation of these acids with formaldehyde yielded albaspidin, i.e. methylene-bis (butyroylfilicinic acid), m.p. 149.5-150°. Methylene-bis (isovaleroyl- and hexanoylfilicinic acids), m.p. 121-122° and 131-132°, were prepared by the same procedure.
抄録全体を表示
-
in vivoの新検定法に就いて
稻垣 勳, 久田 末雄
1956 年 76 巻 11 号 p.
1261-1265
発行日: 1956/11/25
公開日: 2010/02/19
ジャーナル
フリー
A group of mice infected with
Hymenolepis nana was administered orally with drugs, the number of worm eggs in the feces was counted once a day for a few days, and fluctuation in the number was recorded. Finally, the small intestine was cut open and the presence or absence of mature worm and their size were examined. The animal in which the number of worm eggs had markedly decreased or disappeared and in which mature tapeworm (over 10mm. in length) no longer remained was taken as the effective case and the animal in which the mature worm remained was taken as the ineffective case. Since the eggs of
H. nana repeatedly hatches inside the intestines to become a mature worm, the remaining eggs will again hatch into small tapeworms during the counting of eggs even if mature worms were entirely eliminated, This is the reason why limitation is placed on the mature worm. The number of eggs in the feces fluctuates without any direct relation with the number of worms and the calculation of eggs may be omitted. In such a case, the animal is autopsied on the day after the end of drug administration and if worms are found in the intestines, even below 10mm, in length, the animal is taken as the ineffective case. The anthelmintic percentage (A. P.) is calculated from the following equation, where a is the number of animals in effective cases and b, the number in ineffec
A. P.=a/a+b×100
tive cases. The comparison of A. P. is made by the calculation of statistical probabilities. A few experimental examples are given in Tables I to IV.
抄録全体を表示
-
種々の薬物の条虫駆除力検定実験結果とその考察
稻垣 勳, 久田 末雄, 小川 宗治, 野呂 征男, 石原 利克
1956 年 76 巻 11 号 p.
1265-1268
発行日: 1956/11/25
公開日: 2010/02/19
ジャーナル
フリー
Qualitative potency tests by the
in vivo assay method for anthelmintic power for tapeworms were carried out with 14 kinds of acyl and alkyl derivatives of phloroglucinol and methylphloroglucinol, 4 kinds of C-acyl derivatives of dimedone, 3 kinds of dimethone (aldomedone), 4 kinds of filicinic acid derivatives, 15 kinds of crude drugs, crude drug preparations, and plant principles, 6 kinds of pigments, and 7 miscellaneous substances. The results obtained are listed in Tables I to IV and some summarized considerations on the results were made.
抄録全体を表示
-
安江 政一, 加藤 義成
1956 年 76 巻 11 号 p.
1269-1271
発行日: 1956/11/25
公開日: 2010/02/19
ジャーナル
フリー
The decomposition of phenolphthalein in glacial acetic acid and red phosphorus was carrried out and reaction mechanism was considered for the formation of phenol, 2, 4-diiodo- and 2, 4, 6-triiodophenol, 2-(3, 5-diiodo-4′-hydroxybenzyl)benzoic acid (I), m. p. 210°, 2-hydroxyanthracene (II), m. p. 191.5-193°, and 1, 2, 3, 4-tetrahydroanthracene (III), m. p. 103.5°, as the products. In order to facilitate isolation and purification, 3, 5-dinitrobenzoates of
o- and
p-iodophenol, 2, 4-diiodophenol, and 2, 4, 6-triiodophenol were prepared. Of these,
p-iodophenol melted at 65°, differing from m. p. 92° given in the literature.
抄録全体を表示
-
イオン交換クロマトグラフィー並びに焔光分光光度法による酸性泉中のナトリウム, カリウムイオンの定量法
益子 安
1956 年 76 巻 11 号 p.
1272-1275
発行日: 1956/11/25
公開日: 2010/02/19
ジャーナル
フリー
Good results were obtained in the determination of sodium and potassium ions in acidic spring water by the following procedure. A sample water containing about 3m. eq. of cation was accurately measured, passed through a column (1×15cm) of Amberlite IR-120 resin (H-R type), the column was eluted with 0.5
N hydrochloric acid, and the eluaee, discarding the first 10cc., was collected exactly in a measuring flash of 50-cc. and 100-cc. capacity. The amount of sodium and potassium ions was determined by flame sepectrophotometer. This allowed determination with small errors.
抄録全体を表示
-
D-グルコサミンのアセタール誘導体について
秋谷 七郎, 大澤 利昭
1956 年 76 巻 11 号 p.
1276-1279
発行日: 1956/11/25
公開日: 2010/02/19
ジャーナル
フリー
Several kinds of new acetal derivatives, including N-benzoxycarbonyl-D-glucosamine, were synthesized and the position of acetal bonding was proved to be 4=6-in all of these compounds. Deamination of one of these acetal derivatives, 4, 6-ethylidene-3-methyl-methyl-α(or β)-D-glucosaminide with sodium nitrite in weak acetic acidity resulted in facile decomposition of the methyl and glucosaminide bonding and anhydration between C
2 and C
5 positions to form 2, 5-anhydro-4, 6-ethylidene-3-methyl-D-mannose.
抄録全体を表示
-
5-Amino-5-deoxy-1,2-isopropylidene-D-xylofuranoseの合成と脱アミノ化反応について
秋谷 七郎, 大澤 利昭
1956 年 76 巻 11 号 p.
1280-1282
発行日: 1956/11/25
公開日: 2010/02/19
ジャーナル
フリー
5-Amino-5-deoxy-1, 2-isopropylidene-D-xylofuranose (IV) was synthesized by the catalytic reduction of 1, 2-isopropylidene-trihydroxy-D-xyloglutaric dialdehyde phenylhydrazone (II) and by heating 1, 2-isopropylidene-5-tosyl-D-xylofuranose (III) with methanolic ammonia. The tosyl group in (III) is affected by the steric effect of the adjacent furanose ring, compared to that in 1, 2-isopropylidene-6-tosyl-D-glucofura nose and shows far stronger resistance to ammonia. Deamination of (IV) with an excess of sodium nitrite in the presence of an equivalent amount of hydrochloric acid afforded 5-chloro-5-deoxy-1, 2-isopropylidene- (VI) and 1, 2-isopropylidene-D-xylofuranose (VII), indicating that the deamination of (IV) is not accompanied with the formation of a propylene oxide ring, as in the reaction of (III) and sodinm methoxide.
抄録全体を表示
-
Aryl-β-D-glucopyranosiduronic Acidの合成
塚元 久雄, 浜名 政和, 加藤 敬太郎, 黒田 健
1956 年 76 巻 11 号 p.
1282-1287
発行日: 1956/11/25
公開日: 2010/02/19
ジャーナル
フリー
Methyl (aryl-tri-O-acetyl-β-D-glucopyranosid)uronates were synthesized by heating under a reduced pressure methyl tetra-O-acetyl-β-D-glucopyranuronate with β-naphthol, phenol,
m-cresol, hydroquinone as the phenols, in the presence of
p-toluenesulfonic acid. This reaction gave a fairly good yield and the Helferich-Shishido method as a general method of synthesizing glycosides was sufficiently utilizable for the synthesis of β-D-glucopyranosiduronate. Examinations were also made on the syntheses of methyl D-glucopyranuronate, the intermediate of the foregoing synthesis, and its acetate, and ethyl α-D-glucopyranuronate was obtained as its crystalline ester, and derived to its tera-O-acetate.
抄録全体を表示
-
Stephania capitata SPRENGのアルカロイド その5 Stephanineの構造
白井 秀明, 織田 範一
1956 年 76 巻 11 号 p.
1287-1289
発行日: 1956/11/25
公開日: 2010/02/19
ジャーナル
フリー
The structural formula (III) proposed for stephanine by the present writer had been questioned by Manske from the point of biogenesis of aporphine-type bases and, therefore, 1-methoxy-5, 6-methylenedioxyphenanthrene (II) was prepared by the Pschorr's phenanthrene synthesis. It was thereby proved beyond doubt that (II) was completely identical with the phenanthrene compound obtained by the Hofmann degradation of stephanine. From such experimental evidences, the writer again forwards the structural formula 1-methoxy-5, 6-methylenedioxyaporphine (III) for stephanine.
抄録全体を表示
-
菊地 愼太郎
1956 年 76 巻 11 号 p.
1290-1292
発行日: 1956/11/25
公開日: 2010/02/19
ジャーナル
フリー
Coloration reactions of several substances having an imidazoline ring were examined with various reagents based on sodium nitroprusside. Sodium pentacyanoammine-ferroate (PAF) and the reagent for Weber's guanidine determination, with the amount of alkali modified were found to color well by forming a colored complex with imidazoline and a reddish violet to blue color of extreme stability was formed which was detectable enough even with 5 γ/cc. of the sample. The PAF was better in the point of intensity and stability of the color produced, durability of the reagent, and simplicity of procedures. The modified Weber reagent is more useful than PAF when a trace of free acid or alkali is present in the sample since its effect is slight. These reagents either do not color with structurally similar imidazole and purine derivatives or show a slight orange brown color in highly concentrated solution.
抄録全体を表示
-
含硫化合物の酸化成績体について その2
高林 昇
1956 年 76 巻 11 号 p.
1293-1296
発行日: 1956/11/25
公開日: 2010/02/19
ジャーナル
フリー
Oxidation of 3-alkoxy (or phenoxy)-6-alkyl (or phenyl) thiopyridazines with 30% hydrogen peroxide and potassium permanganate in acetic acid or the latter in sulfuric acid afforded mono-, di-, or trioxides. There seemed to be a regularity between the ease or difficulty of oxidation and the kinds of substituent present, the electron acceptor suppressing oxidation and electron donator accelerating it. Ultraviolet absorption spectra of the oxides showed that sulfides possessed the strongest absorption and substances assumed to be an N-oxide exhibited strong absorption in the longer wave length region.
抄録全体を表示
-
求核的置換反応について
高林 昇
1956 年 76 巻 11 号 p.
1296-1299
発行日: 1956/11/25
公開日: 2010/02/19
ジャーナル
フリー
3-Alkoxy (phenoxy)-6-alkyl (phenyl) thiopyridazines were prepared by various routes of synthesis and their nucleophilic displacement was examined, with sodium methoxide, phenoxide, phenosulfide, potassium hydrogen sulfide, and hydrazine hydrate. Cyclization of 3-phenoxy- and 3-methylsulfonyl-6-hydrazinopyridazines by heating with 80% formic acid afforded 6-phenoxy- and 6-methylsulfonyl-
s-triazolo-[4, 3-
b] pyridazines. 6-Ethoxy- and 6-alkylthio-
s-triazolo [4, 3-
b] pyridazines were also prepared.
抄録全体を表示
-
2-γ-Pyridyl-1,3,4-oxadiazol-5-one関連化合物の合成及び抗菌作用 その1
谷山 兵三, 安井 凡平, 内田 譽
1956 年 76 巻 11 号 p.
1300-1303
発行日: 1956/11/25
公開日: 2010/02/19
ジャーナル
フリー
In order to examine whether the antibacterial mechanism of 2-γ-pyridyl-1, 3, 4-oxadiazol-5-one (I), prepared by Smith and reported to possess a strong antitubercular activity, is due to isonicotinic acid hydrazide (INAH) formed from it or to the 1, 3, 4-oxadiazol-5-one ring, 2-γ-pyridyl-4-phenyl-(II) and 2-(N-oxy-γ-pyridyl)-1, 3, 4-oxadiazol-5-one (III) were prepared. (II), (III), and
m- and
p-dimethylamino, nitro, amino, and hydroxy derivatives of 2-phenyl-1, 3, 4-oxadiazol-5-one (IV) were submitted to antibacterial tests but except for (I), the antibacterial activity of these compounds were very weak. This proves that the antibacterial factor is not the oxadiazolone ring but INAH.
These compounds tested were prepared by the reaction of phosgene with carboxylic acid hydrazides. Application of phosgene to
m- and
p-nitrobenzoic acid hydrazides and reduction of the cyclized product afforded the amino compound, whose diazotization followed by decomposition gave the hydroxyl compound. These amino and hydroxyl compounds were also obtained directly by the application of phosgene to the corresponding amino- and hydroxy-benzoic acid hydrazides.
抄録全体を表示
-
谷山 兵三, 三好 文彦, 榊原 榮一, 内田 譽
1956 年 76 巻 11 号 p.
1304-1307
発行日: 1956/11/25
公開日: 2010/02/19
ジャーナル
フリー
In order to prepare chemotherapeutic with speciality of species, L-cystyl or L-cysteinyl derivatives listed in Tables I and II were prepared and all were submitted to antibacterial tests with
Mycobacterium tuberculosis,
Escherichia coil,
Staphylococcus aureus, and
Bacillus subtilis. These compounds were prepared by de Vigneaud's cystine peptide synthesis, starting with benzoxycarbonyl-L-cystine, which was derived to the acid chloride with phosphorus pentachloride, reacted with basic compounds such as aromatic amines, hydrazine, and carboxylic hydrazides, and the condensation product was reduced with sodium in liquid ammonia, with subsequent liberation of the benzoxycarbonyl group. It is interesting that, whereas the cystine derivatives with amino group substituted with benzoxycarbonyl group do not show practically any antitubercular action, with the exception of isonicotinoyl condensate (XI) and phenylhydrazine condensate (XII), the liberation of this benzoxycarbonyl group to form a free amino group results in a tremendous increase in the antibacterial activity. L-Cystine di-
p-phenetidide suppressed the growth of tubercle bacilli in a concentration of 3-10 γ/cc. and bis (benzoxycarbonyl)-L-cystine bis (isonicotinoylhydrazide) (XI) showed antibacterial action against Staphylococci in 5γ/cc. concentration.
抄録全体を表示
-
Alkylpyridine類の酸化
杉本 典夫, 釘田 博至, 田中 雅
1956 年 76 巻 11 号 p.
1308-1310
発行日: 1956/11/25
公開日: 2010/02/19
ジャーナル
フリー
The known process of oxidation of active methylene or methyl in alkylpyridines is the oxidative rearrangement of their 1-oxides with selenium dioxide or with acetic anhydride. It was found that the oxidation of alkylpyridines and their 1-oxides with chromium trioxide effected oxidation in the order of β, γ, and α derivatives to form pyridyl ketone compounds in 50-15% yield. Oxidation of 5, 6, 7, 8-tetrahydroisoquinoline afforded the 8-oxo- and 5-oxo-5, 6, 7, 8-tetrahydroisoquinolines in 2:1 ratio. This reaction is rather interesting in connection with the formation of 4-oxo compound by the selenium dioxide oxidation of 1, 2, 3, 4-tetrahydroacridine found by Borsche and Hartmann.
抄録全体を表示
-
5-Aminoisoxazole類のSchiff Baseの合成並びにその還元について
加納 日出夫, 牧角 徳夫
1956 年 76 巻 11 号 p.
1311-1314
発行日: 1956/11/25
公開日: 2010/02/19
ジャーナル
フリー
In order to prepare some intermediates for pharmaceutics, a Schiff base (II) was prepared from 5-aminoisoxazole (I) and an arylaldehyde and the reduction of (II) with lithium aluminum hydride or sodium borohydride afforded the desired 5-aralkylaminoisoxazole (III) in a good yield. Reductive cleavage of (II) and (III) with Raney nickel was attempted and β-imino-N-aralkylideneamide-type compound (IV) was obtained from (II) and β-ketoaralkylamide-type compound (V) from (III). This has shown that the ring cleavage of (III) tends to be accompanied with ammonia liberation by hydrolysis. The structure of the cleavage products were confirmed as (IV) and (V) from infrared absorption spectra.
抄録全体を表示
-
田中 照夫
1956 年 76 巻 11 号 p.
1314-1318
発行日: 1956/11/25
公開日: 2010/02/19
ジャーナル
フリー
Reaction of thiamine and polyphosphoric acid affords mono-, di-, tri-, and polyphosphates as a mixture and thiamine triphosphate alone cannot be obtained. The formation ratio of each phosphate differs with the phosphorus content of the polyphosphoric acid. Separation of each phosphate by paper chromatography and direct determination of thiamine by the thiochrome photometry clarified the decomposition of thiamine diphosphate. Conditions for the separation of thiamine diphosphate by chromatography with ion exchange resin were elucidated and its synthesis facilitated.
抄録全体を表示
-
アミノ酸ヒドラチドその他の合成及び抗菌作用
堀井 善一, 村上 百合子, 田村 恭光, 内田 譽, 山村 雄一, 三木 勝治, 加藤 允彦
1956 年 76 巻 11 号 p.
1319-1321
発行日: 1956/11/25
公開日: 2010/02/19
ジャーナル
フリー
In order to examine activity against tubercle bacilli, hydrazides of 13 kinds of amino acids, thiophene-carboxylic acid derivatives, and benzothiazole-carboxylic acid derivatives were synthesized and their antibacterial action was tested.
抄録全体を表示
-
Isotetrandrineのvon Braun法によるBrCN分解
富田 眞雄, 石井 永
1956 年 76 巻 11 号 p.
1322-1323
発行日: 1956/11/25
公開日: 2010/02/19
ジャーナル
フリー
The application of cyanogen bromide by the method of van Braun to isotetrandrine (I), one of biscoclaurine-type bases, and subsequent hydrolysis gave a secondary amine, which was found to be a methine-type base (IV) formed by the cleavage of the tetrahydroisoquinoline ring.
抄録全体を表示
-
藤川 福二郎, 人長 有平, 八木 代志子, 水口 一女
1956 年 76 巻 11 号 p.
1324-1325
発行日: 1956/11/25
公開日: 2010/02/19
ジャーナル
フリー
Of the esters of
p-aminosalicylic acid, phenyl,
o-,
m-, and
p-tolyl, and
o- and
p-methoxyphenyl esters show stronger
in vitro growth inhibition against tubercle bacilli than the original acid but the trouble is that these esters are all practically insoluble in water. As a step towards making these compounds soluble in water, maleic, succinic, and phthalic anhydrides were applied to these esters in acetone and 4-maleic, 4-succinic, and 4-phthalic monoamidosalicylates were prepared. These compounds are all soluble in sodium carbonate solution.
抄録全体を表示
-
藤川 福二郎, 八木 代志子, 八木 順一, 西本 正治
1956 年 76 巻 11 号 p.
1326-1328
発行日: 1956/11/25
公開日: 2010/02/19
ジャーナル
フリー
In order to examine their antibacterial activity, corresponding hydrazones were obtained by the application of cyanoacetylhydrazine, benzoylhydrazine,
o- and
p-hydroxybenzoylhydrazine, and
p-aminobenzoylhydrazine to orcyl aldehyde, β-orcyl aidehyde, divaric aldehyde, methyl isohaematommate, isobutyl isohaematommate, 2, 4-dihydroxy-5-butyl-, -5-isoamyl-, and -5-hexylbenzaldehyde, 3-chloro-2, 4-dihydroxy-5-ethyl-, -5-butyl-, and -5-isoamylbenzaldehyde, and
d-usnic acid, possessing aldehyde or ketone group.
抄録全体を表示
-
瀧浦 潔, 瀧野 吉雄, 原田 志保子
1956 年 76 巻 11 号 p.
1328-1330
発行日: 1956/11/25
公開日: 2010/02/19
ジャーナル
フリー
Azotometry was introduced into the final process of Elek's microvolumetric determination of methoxyl group and methoxyl groups were determined in vanillin, 1, 2-diphenyl-1-methoxy-2-acetaminoethane, 1, 1, 3-trimethoxy-2-cyanopropane, 2-phenyl-4-acetovanillylidene-5-oxazolone, berberine hydrochloride, lycorenine methyl ether, and
p-methoxybenzaldehyde thiosemicarbazone. Generation of methyl iodide and apparatus and procedures for outflow followed those of Elek's method. In the final graduated absorption tube (Fig. 1), methyl iodide was converted to iodic acid with bromine-acetic acid solution and an aliquot of the acid was determined by the hydrazine azotometry. With 1-10mg. of a sample containing 1-3 methoxyl groups, such as those compounds mentioned above, 5-10 measurements are possible and accuracy was excellent. This process is assumed to be especially effective in the determination of samples with extremely small content of a methoxyl group but no experimental proof of the fact has been found yet.
抄録全体を表示
-
掛見 喜一郎, 宇野 豊三, 池上 佳彦, 平野 弘, 岩津 岳夫, 万木 庄次郎, 佐藤 大助, 和田 敬之, 奥村 保, 吉田 茂, 高 ...
1956 年 76 巻 11 号 p.
1331-1336
発行日: 1956/11/25
公開日: 2010/02/19
ジャーナル
フリー