YAKUGAKU ZASSHI
Online ISSN : 1347-5231
Print ISSN : 0031-6903
ISSN-L : 0031-6903
80 巻 , 5 号
選択された号の論文の40件中1~40を表示しています
  • 田村 真造
    1960 年 80 巻 5 号 p. 559-561
    発行日: 1960/05/25
    公開日: 2010/02/19
    ジャーナル フリー
    Quinoline was successfully produced in preparative yield from aniline and preformed acrolein. A glacial acetic acid solution of aniline and acrolein diacetate was added dropwise into a refluxing solution of ferric chloride and hydrochloric acid in glacial acetic acid and the mixture was refluxed for 8 hours, from which quinoline was obtained in 34.3% yield. Under similar treatment, aniline and crotonaldehyde diacetate afforded quinaldine in 50.2% yield, while aniline and methacrylaldehyde diacetate gave 3-methylquinoline in 38.7% yield.
  • 田村 真造, 工藤 忠宏, 柳原 保武
    1960 年 80 巻 5 号 p. 562-564
    発行日: 1960/05/25
    公開日: 2010/02/19
    ジャーナル フリー
    Dropwise addition of glacial acetic acid solution of o-toluidine and acrolein diacetate into the refluxing solution of ferric chloride and hydrochloric acid in glacial acetic acid afforded 8-methylquinoline in 30.9% yield. The same treatment of m- and p-toluidines respectively gave 7- and 6-methylquinolines, while o- and p-anisidines respectively gave 8- and 6-methoxyquinolines. Several kinds of other aromatic primary amines produced the corresponding quinoline derivatives but the yield of 6-nitroquinoline from p-nitroanlllne was very unsatisfactory, and 4-aminopyridine did not afford 1, 6-naphthyridlne. 4-Aminopyridine 1-oxide afforded 1, 6-naphthyridine 6-oxide in a low yield. In these reactions, ferric chloride acts as an oxidant and ferrous chloride precipitated out from the reaction mixture.
    Phenylhydroxylamine and acrolein diacetate produced quinoline by the same procedure but there was a by-product formation of a small amount of aniline in this reaction and precipitation of ferrous chloride was not observed.
  • 西海枝 東雄, 柘植 乙彦
    1960 年 80 巻 5 号 p. 565-569
    発行日: 1960/05/25
    公開日: 2010/02/19
    ジャーナル フリー
    4-Aminoacenaphthene (VI) was synthesized from 4-nitro-5-acetamidoacenaphthene (III) through 4-nitro-5-amino compound (IV) and reduction of 4-nitroacenaphthene (VI). (VI) was then derived to 4-acylamino (VII) and 4-thioacylamino (VIII) compounds, and oxidation of (VIII) with alkaline potassium ferricyanide afforded the cyclized product, thiazole compound. For this cyclized product, two isomers can be considered, 8-substituted 1, 2-dihydroacenaphtho [4, 3-d] thiazole (XII) and 4, 5-dihydroacenaphtho [4, 5-d] thiazole (XIII). In order to prove this structure, synthesis of (XIII) was attempted. (IV) was derived to 4-nitro-5-halo compound (IX) which was led to 4-nitro-5-thiol (X) or disulfide (XI) compound. Reduction of (X) or (XI) with zinc dust in acetic anhydride, followed by concurrent acetylation and dehydrative cyclization afforded the objective compound (XIII: R=CH3). It was thereby found that the above cyclized compound (VIII: R=CH3) is identical with the synthesized product, proving that the cyclized product from (XVIII) is (XIII). Ultraviolet and infrared absorption spectra of several kinds of acenaphthene compound were measured.
  • 西海枝 東雄, 柘植 乙彦
    1960 年 80 巻 5 号 p. 570-574
    発行日: 1960/05/25
    公開日: 2010/02/19
    ジャーナル フリー
    Reaction of 5-acenaphthenecarboxaldehyde (I), prepared by formylation of acenaphthene with N-methylformanilide, and thioglycolic acid, in the presence of ammonium carbonate, afforded 2-(5-acenaphthenyl)-4-thiazolidone (II) and its oxidation gave 1, 1-dioxide (III). The reaction of 5-acenaphthenyl-2-thiourea (V) and chloroacetic acid afforded 2-(5-acenaphthenylimino)-4-thiazolidone (X). An interesting fact was observed during formation of (V). Reaction of 5-aminoacenaphthene hydrochloride (IV) and ammonium isothiocyanate in aqueous solution affords the anticipated (V) but the same reaction in glacial acetic acid fails to produce (V) and 5-acenaphthenyl isothiocyanate (VI), 1, 3-bis (5-acenaphthenyl) urea (VII), and 5-acetamidoacenaphthene (VIII) are obtained. The formation mechanism for these compounds were examined in detail and it was assumed that the reaction first produces (V) which forms (VI), (VII), and (VIII) through 1, 3-bis (5-acenaphthenyl)-2-thiourea (IX). Condensation of (X) and aldehydes afforded 5-acylidene compounds (XI). Ultraviolet and infrared absorption spectra were measured in connection with these compounds.
  • 西海枝 東雄, 柘植 乙彦
    1960 年 80 巻 5 号 p. 575-578
    発行日: 1960/05/25
    公開日: 2010/02/19
    ジャーナル フリー
    8-Substituted 4, 5-dihydroacenaphth[5, 4-d]oxazole derivatives were prepared from 4-nitro-5-hydroxyacenaphthene (III) synthesized from 4-nitro-5-acetamido- (I) or 4-nitro-5-amino-acenaphthene (II). Reduction of (III) to form 4-amino-5-hydroxy compound (IV) was attempted but (IV) was extremely labile and was not isolated. Reduction products of 4-nitro-5-acyloxy compound (V and VI) were also labile like (IV). 8-Methyl-oxazole compound (VIII) was prepared by reductive cyclization of (III) with zinc dust in acetic anhydride but in this reaction, the diacetyl compound (IX) of (IV) was formed at the same time. In order to prepared oxazole compounds other than (VIII), (III) was reduced with stannous chloride and the chlorostannate (X) thereby formed was decomposed with sodium acetate in acetic acid, reacting with acid chloride at the same time, and the objective 8-substituted oxazole compound was finally obtained. In this case also, diacyl compounds of the corresponding (IV) were produced. Ultraviolet and infrared spectra of the compounds prepared were measured.
  • 柘植 乙彦
    1960 年 80 巻 5 号 p. 578-583
    発行日: 1960/05/25
    公開日: 2010/02/19
    ジャーナル フリー
    N-(5-Acenaphthenyl) anthranilic acids (III) were prepared by the Ullmann condensation of 5-aminoacenaphthene (I) and o-halobenzoic acid. Examinations were made on conditions for this condensation reaction and it was found that copper powder was found to have a great effect on the yield of (III). Dehydrative cyclization of (III) with conc. sulfuric acid was not effected due to sulfonation but the use of phosphoryl chloride gave the cyclized product, 7-chloro-4, 5-dihydroindeno[1, 7-bc]acridine derivative (VI). 7-Amino-4, 5-dihydroindeno[1, 7-bc]acridine derivatives were prepared by the reaction of (VI) and various amines. The reactivity of chlorine in 7-position of (VI) was found to be affected by the position and kind of other substituents present, a substituent in 10-position decreasing the reactivity and that at 9-position increasing it.
  • 西海枝 東雄, 柘植 乙彦, 田代 昌士
    1960 年 80 巻 5 号 p. 584-591
    発行日: 1960/05/25
    公開日: 2010/02/19
    ジャーナル フリー
    Conditions for the preparation of N-phenyl-5-acenaphthenylamines by decarboxylation of N-(5-acenaphthenyl) anthranilic acids (I) were examined and 7-alkyl (or aryl)-4, 5-dihydroindeno[1, 7-bc]acridine derivatives (IV) were prepared from (II) by the Bernthsen method. In this reaction, the amount of fused zinc chloride added was found to give a great effect on the yield of (IV). In the case of (IV:X=Cl, R=CH3), two isomers were isolated and their structures were determined. Condensation of active methyl in 7-position of (IV:R=CH3) and p-nitrosodimethylamine was examined and an interesting fact was observed. It was found that the presence of an alkaline catalyst (sodium carbonate, potassium carbonate, or piperidine) caused extremely poor yield, while in the presence of a mineral acid, especially hydrochloric acid, a good yield was obtained. In this case, the chief product was found to be the nitrone compound (X) and only a small amount of the anil (IX) was formed. These (IX) and (X) easily formed the 7-formyl compound (XI) by treatment with dil. hydrochloric acid. Condensation of (XI) with various amines gave Schiff bases (XII), and the acrylic acid (XIII) was prepared by the condensation of (XI) and malonic acid by the Perkin reaction. The methyl group in 7-position was found to decrease in activity in this reaction by the presence of chlorine in 10-position.
  • 高橋 三雄, 上硲 和輔, 小山 泰正, 宮村 和子
    1960 年 80 巻 5 号 p. 592-594
    発行日: 1960/05/25
    公開日: 2010/02/19
    ジャーナル フリー
    Some oxidation and reduction reactions were carried out on Shionone, a component of the root of Aster tataricus L. and it was revealed that shionone possessed isopropylidene side-chain and had saturated ring structure as the basic skeleton. Further, rotatory dispersion curves were examined and it was shown that shionone indicates a negative Cotton effect.
  • 高橋 三雄, 藤多 哲朗, 小山 泰正
    1960 年 80 巻 5 号 p. 594-597
    発行日: 1960/05/25
    公開日: 2010/02/19
    ジャーナル フリー
    Enmein (I), C20H28O6, a component of Isodon japonicus and I. trichocarpus possesses two hydroxyls, a five-membered cyclic ketone, and one δ- or larger lactone. The five-membered cyclic ketone is conjugated to the terminal methylene. Hydrogenation of enmein affords two kinds of isomeric dihydro compounds (IIa and IIb). (IIb) changes to (IIa) on application of sodium borohydride in the cold. Reduction of (I) with warm sodium borohydride produces a triol (III) whose acetylation gives a triacetate. Reduction of (IIa) and (IIb) with warm sodium borohydride affords the same compound (V) whose acetylation gives a triacetate (VI). These results indicate that the isomeric compounds differ in the configuration of the hydrogen atom at the α-carbon carrying the methyl in the five-membered cyclic ketone and that (IIa) is more stable. Reduction of (IIb) with sodium borohydride is considered to produce (V) via (IIa).
  • 藤田 路一, 長沢 元夫
    1960 年 80 巻 5 号 p. 598-603
    発行日: 1960/05/25
    公開日: 2010/02/19
    ジャーナル フリー
    It was found possible to distinguish between four kinds of crude drugs containing anethole, fennel, sweet fennel, anise, and star anise from their essential oils, using infrared absorption spectra. For this purpose, anethole content and difference in coexisting components were spectrally analyzed. For the determination of anethole, characteristic absorption of a propenyl group at 961cm-1 was used. In fennel, characteristic absorption of fenchone at 1743cm-1 was used. For discrimination of anise and star anise oils, differential method was used and a good result was obtained by the use of absorption at 1371cm-1, appearing stronger in star anise oil. This absorption was considered to be due to the concerted effect of isopropyl group in cineol, terpineol, and phellandrene.
  • 三野 安
    1960 年 80 巻 5 号 p. 603-607
    発行日: 1960/05/25
    公開日: 2010/02/19
    ジャーナル フリー
    Bromination of the 3-position in 2-oxo-3-carboxy-5-(1-methyl-2-ethoxyethyl)-4-piperidineacetlc acid (III-i), in which the 1-methyl-2-ethoxyethyl and carboxymethyl groups take the cis-configuration, affords a 3-bromo compound and a new method of preparing L-α-kainic acid (XII) from it was discovered.
  • 平井 健太郎
    1960 年 80 巻 5 号 p. 608-612
    発行日: 1960/05/25
    公開日: 2010/02/19
    ジャーナル フリー
    dl-1, 2-Methylenedioxy-8, 9, 10-trimethoxyaporphine (III) and dl-1, 2, 8, 9, 10-pentamethoxyaporphine (IV) were prepared and their characteristic ultraviolet absorption spectra (Fig. 1) were clarified. As by-products of the Pschorr reaction, benzylisoquinolinetype bases were isolated as dl-1-(2, 3, 4-trimethoxybenzyl)-2-methyl-6, 7-methylenedioxy-1, 2, 3, 4-tetrahydroisoquinoline (XVIII) and dl-1-(2, 3, 4-trimethoxybenzyl)-2-methyl-6, 7-dimethoxy-1, 2, 3, 4-tetrahydroisoquinoline (XXIV).
  • 北村 為男
    1960 年 80 巻 5 号 p. 613-616
    発行日: 1960/05/25
    公開日: 2010/02/19
    ジャーナル フリー
    In the preceding paper, it was shown that the product obtained by cleavage reaction of O-methyldomesticine (I) with metallic sodium in liquid ammonia was solely a phenolic base (hydrochloride, m. p. 256°(decomp.), C18H19O2N⋅HCl) and its structure and that of its O-methylated compound (hydrochloride, m. p. 233°(decomp.), C19H21O2N⋅HCl, [α]D20+86°(90% EtOH)) were found by decomposition reactions to correspond to (II) and (III).
    In the present series of work, dl-2, 10-dimethoxyaporphine (III) was synthesized by the route shown in Chart 1 and comparison of (III) with the O-methylated cleaved base showed that the two are identical. It follows, therefore, that, since it is known that a methylenedioxy group undergoes one-sided cleavage reaction by metallic sodium in liquid ammonia to newly produce one phenolic hydroxyl, the phenolic base formed by the cleavage reaction of O-methyldomesticine (I) is known to be 2-methoxy-10-hydroxyaporphine (II). This has revealed that the methoxyl group in 1-position of the aporphine ring in (I) is completely liberated by the reaction with sodium in liquid ammonia and this is a new example rarely seen in this kind of reaction.
  • 萩庭 丈寿, 原田 正敏
    1960 年 80 巻 5 号 p. 617-619
    発行日: 1960/05/25
    公開日: 2010/02/19
    ジャーナル フリー
    Examinations were made on Bupleurum falcatum and B. sachalinense on their hemolytic values, antifebrile effect on fever produced in a rabbit by mixed vaccine of typhoid and paratyphoid, and effect on some hepatic functions in a rabbit with acute hepatic disorders caused by carbon tetrachloride. Some examinations were made on the difference between these two plants. There was no great difference between the two in hemolytic values. Neither showed any marked effect in antifebrile action and against hepatic functions. It was thereby found that the presence or absence of effect should be tested by some other method.
  • 柴田 承二, 原田 正敏, ブディダルモ ウィダグド
    1960 年 80 巻 5 号 p. 620-624
    発行日: 1960/05/25
    公開日: 2010/02/19
    ジャーナル フリー
    Quantitative examinations were made on the papaverine-like spasmolytic action of various flavonoids and anthraquinones, using excised small intestine of mice. Papaverine was used as the standard and acetylcholine as the contraction agent, and the potency ratio so found is shown in Table I. It was found that some of these compounds had the same or stronger effect than the standard papaverine. It was also observed that the introduction of a large group like sugar into the molecule or increased solubility of a molecule caused decrease in spasmolytic acitivity. Preliminary tests were carried out on some sample with excised trachea of guinea pigs but only far weaker effect than the standard papaverine was observed.
  • 棚瀬 弥一郎, 下村 滋
    1960 年 80 巻 5 号 p. 625-628
    発行日: 1960/05/25
    公開日: 2010/02/19
    ジャーナル フリー
    Photometric titration of potassium iodide at 290mμ was found to give different equivalence according to the acid added.
    1) When titrated with potassium permanganate, 2cc. of 0.001M KI corresponds to 1cc. of 0.002M KMnO4 in sulfuric, phosphoric, and acetic acidity, while a breaking point is present at the point of 1cc. 0.001M KI≡1cc. 0.002N KMnO4 in hydrochloric acidity.
    2) When titrated with potassium iodate, the breaking point is present at the point of 5cc. 0.001M KI≡1cc. 0.001M KIO3 in sulfuric and phosphoric acidity, and at the point of 0.001M KI≡1cc. 0.001M KIO3 in hydrochloric acidity.
    However, the determined values comes out lower when titration is carried out in hydrochloric acidity. It is therefore considered to be the most suitable to carry out titration with potassium permanganate in sulfuric acidity in determination of potassium iodide in the presence of chloride, bromide, and iodide ions, and with potassium iodate in sulfuric acidity when determining potassium iodide in the presence of chlorine and bromine ions, iodine, and Ethanol
  • 内藤 武男, 長瀬 脩
    1960 年 80 巻 5 号 p. 629-631
    発行日: 1960/05/25
    公開日: 2010/02/19
    ジャーナル フリー
    18-Methoxy-15, 16, 17, 18, 19, 20-hexadehydroyohimbane (VII) was prepared from 4-me-thoxyhomophthalic anhydride and tryptamine through (III), (IV), (V), and (VI), according to the general method for synthesis of hexadehydroyohimbane, and reduction of the E-ring in (VII) was examined. Reduction of (VII) with metallic sodium in liquid ammonia and tert-butanol gave a tetradehydro compound (VIII) and its treatment with hydrochloric acid afforded dl-18-oxo-15(20)-yohimbene (IX). In order to prove the position of double bond in (IX) as at 15-20 positions, the thioketal (X) of (IX) was refluxed with Raney nickel in ethanol to effect desulfurization and the structure of (IX) was established by its derivation to the known compound, dl-15(20)-yohimbene (XI).
  • 内藤 武男, 長瀬 脩
    1960 年 80 巻 5 号 p. 632-634
    発行日: 1960/05/25
    公開日: 2010/02/19
    ジャーナル フリー
    Reduction of dl-18-oxo-15(20)-yohimbene (I) with sodium borohydride in methanol afforded two kinds of dl-18-hydroxy-15(20)-yohimbene (II) considered to have different steric configuration of the hydroxyls. Reduction of the double bond present between the D- and E-rings in the main product was examined. This reduction was found to be difficult but was finally effected by heating with Raney nickel in ethanol and the product was derived to dl-18-hydroxyalloyohimbane (III). Reduction of the tosylate (IV) of (III) with lithium aluminum hydride afforded dl-alloyohimbane (V) and the structure of (III) was established. Some examinations were also made on the steric configuration of the hydroxyl at 18-position.
  • 石黒 武雄, 森田 善夫, 村井 博
    1960 年 80 巻 5 号 p. 635-639
    発行日: 1960/05/25
    公開日: 2010/02/19
    ジャーナル フリー
    Oxidation of methyl isobutyl ketone was carried out by catalytic vapor-phase reaction, electrolysis, with potassium permanganate, with hypohalogenous acid, and by electrolytic haloform reaction. The fatty acids produced were examined by paper chromatography and possibility of preparing isovaleric acid by this method was examined. Catalytic vapor-phase oxidation failed to give any acid component, while permanganate and electrolytic oxidation chiefly produced isobutyric and acetic acids. Oxidation of isovalerylacetone, the acetylated product of methyl isobutyl ketone, with potassium permanganate afforded isovaleric acid in 88% yield. Isovaleric acid was also obtained in 65-87% yield by oxidation with hypohalogenous acid, and also by electrolytic haloform reaction with current efficiency of 64.8%, especially by the use of 17.8% potassium bromide as the electrolytic solution, at 6-9°, current of 2A, DA 8.83A/dm2, and voltage of 5.2V, and electrolysis carried out by maintaining the electrolytic solution at pH 9.6-11.5 by continuous neutralization with hydrochloric acid.
  • 高橋 酉蔵, 里田 勲, 福井 富次郎, 松尾 義治, 山本 泰男, 奥村 英夫
    1960 年 80 巻 5 号 p. 639-646
    発行日: 1960/05/25
    公開日: 2010/02/19
    ジャーナル フリー
    Preparation of the dimethylamide derivatives of N-(4-antipyrinyl) alanine and N-arylalanine was reported in the preceding paper in connection with their solubility in water and pharmacological action. In the present series of work, simpler derivatives were synthesized in connection with relationship between these compounds and structure of hydantoin-cleavage type. Compounds synthesized were the dimethylamides (I, X) of N-antipyrinylglycine, dimethylamides (XVII to XXI) of N-arylglycine and their related compounds, dimethylaminoethyl esters (XII and XIII) of N-antipyrinylglycine, dimethylamides (XXV, XXVI, and XXVII) of N-substituted N-dimethylaminoacetylglycine, and dimethylamides (XXVIII to XXXIII) of N-substituted N-acylglycine. Some of these compounds were found to have good solubility.
    Recrystallization of N, N-dimethyl-2-(N-phenylacetamido) acetamide (XXIX) afforded two kinds of crystals and they were found to be dimorph from infrared spectra.
  • 高橋 酉蔵, 速水 正明
    1960 年 80 巻 5 号 p. 646-650
    発行日: 1960/05/25
    公開日: 2010/02/19
    ジャーナル フリー
    Acetylacetamidoacetone was synthesized from glycine by the Dakin-West reaction and the acetamidoacetone obtained from it were converted to 2, 5-dimethyloxazole. Methiodide and ethiodide of the oxazole were prepared by application of methyl or ethyl iodide. Fusion of these quaternary salts with diphenyl-type formamidine and bipyridyl-type formamidine afforded the aminovinyl-type dyes. Pharmacological test was carried out on rabbit skin with 3, 5-dimethyl-2-(5-bromo-2-pyridylamino)-vlnyloxazolium iodide. The dye was administered as an ointment or injection and comparison was made with non-treated control group on burnt skin and measurement of inorganic salts in the blood, examining the changes and recovery of healthy, normal state.
  • 高橋 酉蔵, 速水 正明
    1960 年 80 巻 5 号 p. 651-655
    発行日: 1960/05/25
    公開日: 2010/02/19
    ジャーナル フリー
    Twenty kinds of styryl-type dyes were synthesized with 2, 5-direthoxyoxazole methiodide and ethiodide as the parent compounds and by condensation of various aromatic aldehydes, one in ethanol solution with piperidine as the addition agent and the other in acetic anhydride as the dehydration-condensation solvent. These styryl-type dyes and the aminovinyl-type dyes reported earlier*1 were submitted to antibacterial tests. It was thereby found that aminovinyl-type dyes are generally stronger than the styryl-type dyes in antibacterial power, with N-ethylated compounds stronger than N-methylated compounds. Dyes with a substituent in the para-position of the additional ring had stronger antibacterial action than the dyes without such substituent.
  • 小寺 啓司
    1960 年 80 巻 5 号 p. 655-658
    発行日: 1960/05/25
    公開日: 2010/02/19
    ジャーナル フリー
    Infrared absorption spectra were measured of a mixture of p-benzoquinone containing phenol or hydroquinone in various ratios. An equal mixture of these two components in nonpolar solvent was found to form a molecular compound of 1 mole each of these two components from the shift of infrared absorption band. In this case, νC=O and δC-H bands of p-benzoquinone shift to a lower wave number and the absorptions were in approximately the same position in the case of either phenol or hydroquinone. It follows, therefore, that p-benzoquinone in these mixtures takes the same electronic state. On the other hand, infrared absorption spectra of a mixture of p-benzoquinone and phenol or hydroquinone in various ratios, taken in Nujol, showed a shift of both νC=O and δC-H in p-benzoquinone due to electron charge. The shift of δC-H absorption is completed in a mixture at a certain ratio so that further increase in the amount of phenol or hydroquinone does not cause any change in the position of δC-H absorption band while that of νC=O alone undergoes shift. This was considered to be due to the receipt of proton from phenol or hydroquinone by p-benzoquinone after completion of electron charge. From such a fact, it was assumed that the so-called quinhydrone-type double compound is formed by acceptance of an electron on the one hand and proton on the other by deviation of electron charge due to quinonoid resonance in the quinone.
  • 小寺 啓司
    1960 年 80 巻 5 号 p. 659-661
    発行日: 1960/05/25
    公開日: 2010/02/19
    ジャーナル フリー
    Infrared absorption spectra of a mixture of 1, 4-naphthoquinone and phenol, hydroquinone, or 1, 4-naphthohydroquinone in various molar ratios were measured in Nujol and cyclohexane. The spectra of mixtures with phenol in various ratios in liquid or solid state exhibited three absorptions of νC=O, one of which agreed with that of 1, 4-naphthoquinone. This fact suggests that, differing from the mixture of p-benzoquinone and phenol, there does not seem to be complex formation and formation of a molecular compound must be assumed. The mixtures with hydroquinone or 1, 4-naphthohydroquinone gave characteristic spectra differing from the spectra of each individual component in equimolar ratios and formation of a complex was recognized from their absorptions. The complex of 1, 4-naphthohydroquinone and 1, 4-naphthoquinone colored dark violet and absorption of νC=O appeared in the lowest wave number. However, these complexes showed absorption band of 1, 4-naphthoquinone in cyclohexane, so that the complex was considered to be dissociated into their molecular compound and 1, 4-naphthoquinone. It was thereby learned that the molecular compound is far more labile than that of p-benzoquinone series.
  • 小寺 啓司
    1960 年 80 巻 5 号 p. 662-664
    発行日: 1960/05/25
    公開日: 2010/02/19
    ジャーナル フリー
    2-Methyl-1, 4-naphthoquinone-sodium hydrogensulfite adduct (menadione sodium bisulfite) is used as the vitamin K3 preparation. This compound, in solid state, undergoes coloration with passage of time, from yellow to red, and the most marked colors reddish violet. The cause of this coloration was proved to be the formation of a solid complex between 2-methyl-1, 4-naphthoquinone, produced by liberation of sulfurous acid from the above compound, and its reduction product, 2-methyl-1, 4-naphthohydroquinone. Infrared absorption spectra were measured of a mixture of these two components in various ratios and the displacement of absorption bands of νO-H, νC=O, and δ′C-H was examined. It was thereby learned that the complex responsible for the coloration is composed of 1 mole of 2-methyl-1, 4-naphthoquinone and 2 moles of 2-methyl-1, 4-naphthohydroquinone, and that the complex dissociated in nonpolar solvents into the two components.
  • 根来 玄忠, 三木 知憲, 上田 省吾
    1960 年 80 巻 5 号 p. 665-669
    発行日: 1960/05/25
    公開日: 2010/02/19
    ジャーナル フリー
    In order to understand the solubility phenomena of monocarboxamides of pyridine and pyrazine by application of the regular solution theory, heat of sublimation was calculated from molecular effusion method (Table II). The samples were purified by low-pressure sublimation at temperatures below the melting point and absence of any changes in crystal system before and after sublimation was confirmed through X-ray diffraction (Table III). However, pyrazine-monocarboxamide shows, even below its melting point but above 160°, a crystal system different from that of the starting material or that below 160°, and this suggests phase rearrangement (cf. Part II of this series). Heat of evaporation of three kinds of picolylamine, corresponding to acid amide, was measured by molecular effusion method (Table V) and the degree of its reaction was found to be in the decreasing order of 2-, 4-, and 3-, as in the case of acid amides. From the difference of these values, energy of one hydrogen bond of NH…O was presumed (Table VI).
  • 根来 玄忠, 三木 知憲, 上田 省吾, 真田 隆幸, 岡田 隆三
    1960 年 80 巻 5 号 p. 670-673
    発行日: 1960/05/25
    公開日: 2010/02/19
    ジャーナル フリー
    A recording adiabatic calorimeter was made on trial and heat of fusion was measured (Table I). The melting curve (Fig. 4) of pyrazine-monocarboxamide shows a shoulder at around 160°, prior to reaching the melting point, and suggests the presence of a transition point. This point was also mentioned in Part I of this series.
  • 根来 玄忠
    1960 年 80 巻 5 号 p. 674-679
    発行日: 1960/05/25
    公開日: 2010/02/19
    ジャーナル フリー
    Solubility of picolinamide, nicotinamide, isonicotinamide, and pyrazincarboxamide in water, alcohols, acetic esters, chloroform, and isoöctane at 0° and 25° (or at 30° or 38°) was measured by analytical method using ultraviolet absorption (Tables II and III). On the other hand, from the heat of sublimation and heat of fusion of these solutes, reported in Parts I and II of this series, solubility parameter was calculated (Table VI) and the values were compared with the values of solubility calculated by application of the regular solution theory (Table VII). The calculated values were smaller than found values and the two values were almost in disagreement, but the order of solubility was in good agreement with measured order and the fact that the pairs of picotinamide and pyrazincarboxamide, and nicotinamide and isonicotinamide, showed similar behavior all indicate that, as far as the measurement is limited to qualitative steps, consideration by the regular solution theory has a certain amount of significance.
  • 朝日 豊
    1960 年 80 巻 5 号 p. 679-683
    発行日: 1960/05/25
    公開日: 2010/02/19
    ジャーナル フリー
    Phenazine-1-carboxylic acid (I) and its amide (II) show two-step, one-electron reduction wave at below pH 2. Its 1st wave is accompanied by an anomalous wave considered to be due to adsorption of to the electrode and relationship between concentration and peak height of A. C. polarography satisfies adsorption isotherm. At pH 2-13, this two-step wave becomes one-step and is treated as the two-electron, two-proton reduction wave. In weak acidity, they also indicate anomalous wave like riboflavin. Reduction potential of monosubstituted phenazines showed E-effect of the substituent in the order of COON>CONH2>H>OH. From these polarographic behaviors, it is considered that the semiquinone compounds of (I) and (II) are stable only in strong acidity and may act as a respiratory catalyst of Pseudomonas aeruginosa.
  • 朝日 豊
    1960 年 80 巻 5 号 p. 684-688
    発行日: 1960/05/25
    公開日: 2010/02/19
    ジャーナル フリー
    α-Lipoic acid shows a two-electron, two-proton reduction wave to dlhydrolipoic acid in its polarogram and the wave is divided into two steps by adsorption phenomenon. The 1st wave nears a constant value by increasing the concentration but the total wave-height is proportional to concentration. When a rotating platinum electrode is used, an oxidation wave appears at E1/2+0.8V vs. N. C. E. α-Lipoic acid shows three A. C. polarographic waves. The 1st wave is Ep+0.02V and corresponds to adsorption of α-lipoic acid, the 2nd wave corresponds to the 1st wave in D. C. and is due to electrolysis and desorption, and the 3rd wave is considered to be due to desorption of dihydrolipoic acid. β-Lipoic acid shows reduction wave accompanied by an adsorption wave and this is due to a four-electron, four-proton reduction to dihydrolipoic acid, An A. C. polarographic wave is obtained at the potential corresponding to the D. C. adsorption wave. β-Lipoic acid is easily hydrolyzed by alkali to form mercaptosulfinoöctic acid and loses reduction wave. The polymer of α-lipoic acid does not show a reduction wave and undergoes depolyrnerization by alkalis. The reduction wave of α-lipoic acid is deformed by the detergent, Tween 20, but its effect is the smaller, the lower the pH. α-Lipoic acid and thiamine propyl disulfide can be determined separately but at the same time in a 0.02% solution of Tween 20 at pH 2.
  • 朝日 豊
    1960 年 80 巻 5 号 p. 688-692
    発行日: 1960/05/25
    公開日: 2010/02/19
    ジャーナル フリー
    Thiosemicarbazide (T) shows anodic wave due to the reaction with mercury when using a dropping mercury electrode. At pH below 5, E1/2+0.01V, diffusion current constant KD=2.05 (μA⋅mM-1 mg-2/3⋅sec1/2), and n=1, and above pH 5, E1/2=+0.36-0.07 pH, KD=8.23, and n=4. These facts were confirmed through microcoulometry, controlled potential electrolysis, and amperometric titration with mercury or silver nitrate. This polarographic method is used for determination of thiosemicarbazide and does not interfere in the determination of thiosemicarbazones. With rotating platinum electrode, thiosemicarbazide shows further oxidation wave at the positive potential. In acid solution, thiosemicarbazide reacts with equimolar amount of mercury nitrate but immediately undergoes decomposition to mercury and a mercuric complex [T2Hg]2+ [NO3-]2. This complex was isolated and from its infrared spectra, it was found that thiosemicarbazide is coordinated to mercury not by N and N but by N and S. In alkalinity, thiosemicarbazide reacts with 4 moles of mercury nitrate to form mercury sulfide, mercury-amino complex, and nitrogen.
  • 井上 正敏, 齋藤 隆子
    1960 年 80 巻 5 号 p. 693-696
    発行日: 1960/05/25
    公開日: 2010/02/19
    ジャーナル フリー
    In order to examine thermal change of organic medicinals during heating, a very simple differential thermal analyzer was devised, utilizing the large temperature-resistance characteristics of a thermister. An AC voltage was applied to the thermister and voltage deviation between thermisters on the objective control substance and sample sides was amplified and measured. Sodium chloride was used as the standard and the amount taken was 300mg. of both sodium chloride and sample. Temperature rise was of 1°/min., and 1V was applied to the bridge. Thermal analyses were carried out on citric acid, sodium citrate, and calcium lactate as the hydrated organic medicinals and they all indicated distinct heat absorption by liberation of the water of crystallization. It was also observed that calcium lactate absorbed heat on transiting to amorphous state after liberation and evaporation of the water of crystallization.
  • 高橋 三雄, 藤多 哲朗, 小山 泰正
    1960 年 80 巻 5 号 p. 696-697
    発行日: 1960/05/25
    公開日: 2010/02/19
    ジャーナル フリー
    Of the two kinds of isomeric dihydro compounds produced by hydrogenation of enmein, the higher-melting substance was submitted to rotatory dispersion measurement and a multiple Cotton-effect curve was obtained. From the large amplitude, the presence of a five-membered cyclic ketone was confirmed.
  • 高橋 三雄, 石正 成一, 小山 泰正
    1960 年 80 巻 5 号 p. 698-699
    発行日: 1960/05/25
    公開日: 2010/02/19
    ジャーナル フリー
    The partial oxidation of sophoradiol (olean-12-ene-3β(e), 7α(a)-(or 22β(a))-diol) with chromium trioxide-pyridine complex affords sophoraon-3-ol. Analysis of its rotatory dispersion curve confirmed the appropriateness of the conclusion*1 that, of the two hydroxyls in sophoradiol, one is at C-3 and the other should be at C-22 or C-7.
  • 中島 靖夫, 川田 稔
    1960 年 80 巻 5 号 p. 700-702
    発行日: 1960/05/25
    公開日: 2010/02/19
    ジャーナル フリー
    D-Glucuronolactone [14C] was prepared from uniformly labeled D-glucose[14C] through 1, 2-isopropylidene-D-glucose and calcium 1, 2-isopropylidene-D-glucuronate. Autoxidation was effected by the use of platinum-carbon catalyst. Radiochemical yield of D-glucuronolactone[14C] to D-glucose[14C] was 45.5%.
  • 塚本 赳夫, 由比 顕之介
    1960 年 80 巻 5 号 p. 702-704
    発行日: 1960/05/25
    公開日: 2010/02/19
    ジャーナル フリー
    3, 5-Dibromosalicylaldehyde, whose suitability as colorimetric agent for determination of aliphatic amines was reported in the preceding paper, was used for determination of 5 kinds of aliphatic amines and its practicability was confirmed. This reagent makes it possible to determine aliphatic primary amines in the range of concentration of the amine of 2-100γ/cc. at pH 5.1 of the coloring solution, measured at 434mμ.
  • 伊藤 一男
    1960 年 80 巻 5 号 p. 705-707
    発行日: 1960/05/25
    公開日: 2010/02/19
    ジャーナル フリー
    Alkaloids contained in the tree bark of Michelia compressa MAXIM. (Magnoliaceae) (Japanese name ‘Ogatama-no-ki’) were examined. Oxyacanthine, a biscoclaurine-type base, was obtained as the tertiary base, and the berberine-type bases, berberine, palmatine, and jatrorrhizine, and aporphine-type base, magnoflorine, were isolated as the water-soluble quaternary bases.
  • 亀田 幸雄, 松井 勝彦, 堀田 良子
    1960 年 80 巻 5 号 p. 707-708
    発行日: 1960/05/25
    公開日: 2010/02/19
    ジャーナル フリー
    Facile racemization occurs by heating to 160-165° N-benzoyl-p-nitro-D-phenylalanine, α, ε-di-N-benzoyl-D-lysine, α-N-acetyl-ε-N-benzoyl-L-lysine, N-benzoyl-D-methionine, N-benzoyl-D-phenylalanine, and N-acetyl-D-tryptophan and they produce the corresponding acylated DL-amino acids.
  • 荒田 義雄
    1960 年 80 巻 5 号 p. 709-711
    発行日: 1960/05/25
    公開日: 2010/02/19
    ジャーナル フリー
    The condensate (I) of 2, 5-lutidine and formaldehyde was heated with potassium hydroxide to form the vinyl compound (II). whose catalytic reduction afforded (IV). On the other hand, catalytic reduction after chlorination of (I) with thionyl chloride gave (IV). The N-oxide of (IV) was treated with acetic anhydride and hydrolyzed to (VII). Chlorination of (VII) with phosphoryl chloride and application of ethyl malonate to its product (VIII) in the presence of sodium gave the malonate (IX). Hydrolysis and heating of (IX) gave (X) which was derived to its ester (XI) by treatment with ethanol and sulfuric acid.
  • 中込 孟也
    1960 年 80 巻 5 号 p. 712-713
    発行日: 1960/05/25
    公開日: 2010/02/19
    ジャーナル フリー
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