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On the Bacteriostatic Activity of Compounds related to 4H-1-Benzothiopyran-4-one 1, 1-Dioxide
Toshio Nambara, Yoshio Takemori, Setsuko Okamoto
1961 Volume 81 Issue 1 Pages
1-7
Published: January 25, 1961
Released on J-STAGE: February 19, 2010
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In order to test the bacteriostatic activity, some compounds related to 4
H-1-benzothiopyran-4-one 1, 1-dioxide, a kind of isoster of 1, 4-naphthoquinone, were prepared as illustrated in Chart 1. Contrary to expectations, none of these compounds showed strong activity
in vitro against
Mycobac. tuberculosis and
E. coli. It is supposed that the redox potential of quinones plays an important rôle in their bacteriostatic activity.
The half-wave potentials of some typical derivatives were measured by polarography. It was clarified that these compounds, which possessed 3-oxopropenylsulfonyl (-CO-CH=CH-SO
2-) structure, showed comparatively positive reduction potential. This result agreed with the fact that 2-(phenylthio)thiochroman-4-one 1, 1-dioxide was easily produced from 3-bromo-4
H-1-benzothiopyran-4-one 1, 1-dioxide and thiophenol in alkaline medium.
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(3). Cleavage of 1, 6-Dimethoxy-3, 8-dimethyldibenzo-p-dioxin
Yasuo Inubushi, Keiichi Nomura
1961 Volume 81 Issue 1 Pages
7-12
Published: January 25, 1961
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Cleavage reaction with sodium in liquid ammonia was examined with 1, 6-dimethoxy-3, 8-dimethyldibenzo-
p-dioxin (I), which possesses a methyl group in the position
para to the ether linkage. One of the two cleaved products was found to be 2-hydroxy-4, 5′-dimethyl-6, 3′-dimethoxydiphenyl ether (II) and the other, 2, 2′-dimethoxy-4, 4′-dimethyl-6, 6′-dihydroxybiphenyl (III). The presence of this methyl group in the
para-position was found to inhibit the progress of normal cleavage reaction, resulting in increased formation of (III). The yield of (II) was found to increase by lowering the reaction temperature and by addition of ammonium chloride during the reaction. This conclusion agrees with the result obtained in the previous work.
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Masao Tomita, Toshimitsu Ujiie
1961 Volume 81 Issue 1 Pages
13-17
Published: January 25, 1961
Released on J-STAGE: February 19, 2010
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Examination was made on the cleavage reaction of dibenzofuran (II), phenoxathiin (III), thianthrene (IV), and 2, 7-dimethylthianthrene (V) with alkali metal in liquid ammonia and results thereby obtained are listed in Table I. The ether linkage in dibenzofuran (II) is comparatively difficult to be cleaved and reduction of the ring takes place preferably when ammonium chloride is added. In phenoxathiin (III), the sulfur linkage is cleaved first to form
o-phenoxybenzenethiol and a mercapto group is newly formed in the
ortho-position, making it difficult for subsequent cleavage of the ether linkage, as in the case of 2-hydroxydiphenyl ether. In the case of thianthrene (IV) and dimethylthianthrene (V), however, the two sulfur linkages are easily cleaved, forming two moles of thiophenol.
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Synthesis of 1-Deoxy-1-p-toluidino-4, 5-O-isopropylidene-D-fructopyranose and 2, 3-O-Isopropylidene-D-erythrose
Setsuzo Tejima, Yoneshiro Oketani
1961 Volume 81 Issue 1 Pages
18-21
Published: January 25, 1961
Released on J-STAGE: February 19, 2010
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Treatment of 1-deoxy-1-
p-toluidino-D-fructose (N-
p-tolyl-D-isoglucosamine) (I) with a mixture of acetone and conc. sulfuric acid afforded 1-deoxy-l-
p-toluidino-4, 5-O-isopropylidene-D-fructopyranose (II), m.p. 123-124°, whose periodate oxidation gave 2, 3-O-isopropylidene-4-O-(N-
p-tolylglycyl)-D-erythrose (VIII) as a syrup. Hydrolysis of (VIII) with alcoholic potassium hydroxide produced 2, 3-O-isopropylidene-D-erythrose (X) and the potassium salts of N-
p-tolylglycine. Deacetonation of (X) with Amberlite IR-120 (H
+) gave D-erythrose. The yield of (X) and (XII) was 43% and 36%, respectively, from D-glucose.
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Rapid Determination of Small Quantities of Iron
Shigeru Shimomura
1961 Volume 81 Issue 1 Pages
22-26
Published: January 25, 1961
Released on J-STAGE: February 19, 2010
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In photometric titration of iron (II) ion with potassium permanganate in sulfuric acidity, the equivalence point can be determined as the cross point of two straight lines if the spectrophotometer is set between 280 and 300mμ. Since the extinction of titanium (III) and titanium (IV) ions is far smaller than that of iron (III), titration of iron (III) with potassium permanganate, with addition of excess titanium (III) sulfate, followed by photometric titration at 280-300mμ, would give a curve in which the distance between the first and second break would correspond to the amount of iron. This method will make it possible to determine a minute amount of iron of 0.1-1mg. in 50cc. of a sample taken into the titration cell. Moreover, this eliminates the conventional reduction procedure by merely adding titanium (III) sulfate, and this method is more rapid and sensitive than the existing method when handling a large number of samples containing about the same amount of iron.
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Hideo Tani, Kunio Fukushima
1961 Volume 81 Issue 1 Pages
27-31
Published: January 25, 1961
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Infrared spectra of cyanopyridine derivatives having various substituents were examined. The C≡N stretching absorption of the nitrile bonded directly to the ring appears at 2239±4cm
-1, while that of cyanomethylpyridine derivatives appear at 2257±4cm
-1. Introduction of an electron-attracting group into the ring shifts the C≡N stretching absorption to a higher wave-number region, with marked decrease in its intensity. This absorption band splits into two in 2- and 3-cyano-pyridine 1-oxide, appearing respectively at 2237 and 2245cm
-1 and at 2241 and 2249cm
-1. The C≡N stretching absorption in 4-cyanopyridine 1-oxide derivatives shifts to a lower wave number than those of 4-cyanopyridine derivatives, with marked increase in their intensity. Relationship between the Hammet's σ value and wave number, molecular extinction coefficient, and integrated absorption intensity is generally linear. The wave number and intensity of C≡N stretching absorption in 2- and 4-cyanopyridine 1-oxides are markedly different from those of 2- and 4-cyano-pyridines, indicating that the electron-donating property of the N-O bond in 4-cyano-pyridine 1-oxide is considerable, and appropriateness of this fact is also suggested by the result of nitration reaction of pyridine 1-oxide.
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Solubilization of Vitamins A and D. (7). Viscosity of Aqueous Solution solubilized with Sucrose Monoesters
Hiroyuki Mima, Mitsuo Kato
1961 Volume 81 Issue 1 Pages
32-36
Published: January 25, 1961
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Solubilization of vitamin A-alcohol, -acetate, and -palmitate, and ergocalciferol in water by mixing with sucrose monomyristate results in different viscosity of the solubilized solution according to the kind of solubilizates when the ratio of sucrose myristate to water is kept constant and concentration of the solubilizates is varied. In vitamin A-alcohol and ergocalciferol, relative viscosity increases with increasing concentration until the solution becomes turbid and the viscosity then falls. On the other handy viscosity of the solubilized solution hardly changes with increasing concentration of vitamin A-palmitate and -acetate. This phenomenon is assumed to be connected with polarity of the solubilizates. Viscosity of the solution in which lauryl alcohol has been solubilized is similar to the former and that of cetane is similar to the latter. The fact that the viscosity of a solution in which polar substance has been solubilized shows a maximum at a certain concentration of the solubilizate has already been observed in other surface-active agents and the foregoing phenomenon is assumed to be related to the structure of solubilized micelle formed by sucrose myristate and the substance to be dissolved.
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Solubilization of Vitamins A and D. (8). Solubilization with Raffinose Fatty Acid Esters
Hiroyuki Mima, Mitsuo Kato, Masaru Yotsuzuka
1961 Volume 81 Issue 1 Pages
37-40
Published: January 25, 1961
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In order to solubilize vitamins A and D for fortification of foodstuff, substances which are allowed for use in foodstuff, such as sucrose ester, must be used as a solubilizing agent. However, some of sucrose esters suited for solubilization have unpleasant odor or taste and their use is limited. In order to improve this point, raffinose esters were prepared, and their properties and solubilization power were examined. Raffinose palmitate, oleate, and myristate are practically odorless and tasteless, dissolve well in water, and are able to solubilize vitamins A and D to form a transparent solution, thereby showing that they have solubilization power equal to the known solubilizing agents such as Tweens. Oral and parenteral toxicity of these raffinose esters showed that the former is very small and their possible use for foodstuff was suggested. However, these esters were fairly toxic by intravenous injection and this was assumed to be due to their hemolytic action, same as that of sucrose esters. Aqueous solution of vitamins A and D solubilized with raffinose ester is stable and does not become cloudy on heating.
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Toyoharu Mizuma, Masanao Shimizu, Shigeshi Toyoshima
1961 Volume 81 Issue 1 Pages
40-43
Published: January 25, 1961
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Assuming that antiviral compounds might be obtained by introduction of a higher alkyl group into the structure of barbituric acid, 28 compounds of this series were prepared and their
in vivo effect against Nakayama strain of Japanese B encephalitis virus was examined in mice. It was thereby found that the compound effective on this virus are 3-methyl-5-propyl-, 3-allyl-, 3-benzyl-5-methyl-, and 3-butyl-5-methyl-5-lauryl-barbituric acids, and 3-benzyl-5-ethyl-5-phenyl- and 3-benzyl-5, 5-diethyl-barbituric acids.
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Toyoharu Mizuma, Yasuo Minaki, Shigeshi Toyoshima
1961 Volume 81 Issue 1 Pages
44-47
Published: January 25, 1961
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In order to find better antiviral compounds than PANS-610, 15 compounds of alkyl N-acetylnaphthionate and 16 compounds of N-alkyl-4-acetamido-1-naphthalenesulfon-amide related PANS-610 were prepared and their
in vitro and
in vitro activity against the Nakayama strain of Japanese B encephalitis virus were examined. However, the decyl, undecyl, and dodecyl derivatives of the two series of compounds were found to have only
in vitro activity weaker than PANS-610.
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Toyoharu Mizuma, Yasuo Minaki, Shigeshi Toyoshima
1961 Volume 81 Issue 1 Pages
48-50
Published: January 25, 1961
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It has been reported that some organophosphorus compounds possess antimitotic property and it was thought that antiviral compounds might be obtained by introduction of a higher alkyl group into the structure of such compounds. Thus, 16 compounds of N-alkyl-P, P-bis(1-aziridinyl)phophinic amides were prepared and their
in vitro activity was examined with the Nakayama strain of Japanese B encephalitis virus. N-Nonyl and N-decyl derivatives found to have
in vitro activity against the virus, almost equal to that of PANS-610.
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Toyoharu Mizuma, Yasuo Minaki, Shigeshi Toyoshima
1961 Volume 81 Issue 1 Pages
51-53
Published: January 25, 1961
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It has been found that several compounds of N-alkyl-P, P-bis(1-aziridinyl)phosphinic amide series have
in vitro antiviral activity and, therefore, 12 compounds of Alkyl P, P-bis(1-aziridinyl)phosphinate series were prepared and their
in vitro activity tested against the Nakayama strain of Japanese B encephalitis virus. N-Decyl, N-undecyl, and N-dodecyl derivatives were found to be effective against this virus.
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Experiments on o-Aminophenol Conjugates in Urine of Rabbits following Oral Administration of o-Aminophenol
Takeo Ohtaki
1961 Volume 81 Issue 1 Pages
53-58
Published: January 25, 1961
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o-Aminophenol was given orally to a rabbit and substances in the urine originating from the aminophenol were examined. The presence of
o-aminophenol,
o-amino-phenyl glucosiduronic acid,
o-aminophenyl hydrogensulfate, and
o-acetamidophenol were confirmed by individual isolation. 1-
o-Hydroxyanilino-1-deoxyglucuronic acid was not isolated directly but its presence was proved indirectly, while
o-hydroxy-phenylsulfamic acid and 3-aminophenoxazin-2-one were not detected. Quantitative examination of these substances in the urine after oral administration of 1g. of
o-aminophenol showed that approximately 7.6% of the administered aminophenol was excreted
per se, 26% as
o-aminophenyl glucosiduronic acid, 18% as
o-aminophenyl hydrogensulfate, and 1.2% as
o-acetamidophenol.
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Reaction of Acetophenone or Thioacetophenone and Aromatic Primary Amines in the Presence of Sulfur
Haruo Saikachi, Takuzo Hisano
1961 Volume 81 Issue 1 Pages
59-63
Published: January 25, 1961
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Reaction of acetophenone with aromatic primary amines, in the presence of sulfur, failed to afford the anticipated phenylthioacetanilides, differing somewhat from the reaction of heterocyclic compounds, and only phenylacetanilides were obtained. In order to examine this reaction, the same reaction was carried out with thioacetophenone, sulful, and aniline, from which only 2, 4-diphenylthiophene (XXII) and a small amount of styrene (XXIV) were obtained. Desulfurization reaction gave 1, 3-diphenylbutane (XXIII) from (XXII) and 2, 3-diphenylbutane (XXVI) from thioacetophenone. These experiments have given interesting example that the reaction of thioacetophenone and aromatic primary amines is preceded by complicated condensation reaction of thioacetophenone molecule itself. The foregoing 2-phenylacetanilides were derived by the usual process into 2-phenylthioacetanilides and 2-benzylbenzothiazoles.
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New Substitution of Thiopicolinanilide-type Compounds. (1)
Haruo Saikachi, Takuzo Hisano
1961 Volume 81 Issue 1 Pages
64-68
Published: January 25, 1961
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Reaction of active methyl group and aromatic primary amines, in the presence of sulfur, easily affords the compounds of thioanilide-type and benzothiazole type. Examinations were made on the behavior of thioanilide-type compounds during this reaction and a new kind of substitution reaction was found to take place.
The reaction of thiopicolinanilide (I) and aniline afforded N, N′-diphenylpicolinamidine (II) which was proved by synthesis through a different route. In order to obtain a mixed-type amidines by the same procedure, thiopicolinanilide was reacted with aromatic primary amines carrying electron-releasing group in the
para-position but, contrary to expectations, formation of mixed-type amidines was not observed and a substituted products were obtained. A small amount of 6-substituted 2-(2-pyridyl) benzothiazoles was also obtained.
According to such a result, in order to clarify the order of substitution by the effect of
para-substituent in the amines, reactions were carried out in various combinations and the order of substitution by this reaction was found to be as follows:
H
2N- -COOC
2H
5<H
2N- H
2N- -CH
3<H
2N- -OCH
3<H
2N- -OC
2H
5<H
2N- -OC
3H
7This order of substitution agrees with the order of electron-donating nature of the substituent
para to the amino group in benzene ring and the Hammett's rule would probably apply in this case.
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New Substitution of Thioanilide-type Compounds. (2)
Takuzo Hisano
1961 Volume 81 Issue 1 Pages
69-72
Published: January 25, 1961
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The substitution reaction confirmed in thiopicolinanilide was examined in N-phenylthioisonicotinamides, thiobenzanilides, and thioacetanilides, in order to extend the range of this reaction. It was thereby found that this substitution reaction is not instigated by the effect of nitrogen atom in the pyridine ring but is a general reaction for thioanilide-type compounds. Examinations were also made to see if this reaction also occurs in oxaanilide-type compounds, having oxygen atom in place of sulfur atom, but the substitution reaction was found not to occur in the case of phenylacetanilides, benzanilides, picolinanilides, and acetanilides. It follows, therefore, that this is a substitution reaction characteristic to thioanilide-type compounds.
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On the Sulfisoxazole N-Glucuronide
Toyozo Uno, Masao Kono
1961 Volume 81 Issue 1 Pages
72-76
Published: January 25, 1961
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Examinations were made on the formation of sulfisoxazole N-glucuronide, one of the biological metabolites of sulfisoxazole. The increased excretion of N-glucuronide into the urine after oral administration of sulfisoxazole and further increase in the N-glucuronide by the combined use of glucuronolactone were observed. Formation of sulfisoxazole N-glucuronide was recognized in the aqueous solution, blood, and urine when allowed to stand at 37° for 8 hours after addition of sulfisoxazole and glucuronic acid. It was also found that addition of sulfisoxazole to normal urine and allowing this to stand at 37° for 8 hours resulted in increased formation of the N-glucuronide and this was accompanied with the corresponding decrease of approximately equal amount of free glucuronic acid. From these results, it is pointed out that bioformation of sulfisoxazole N-glucuronide is non-enzymatic as well as being enzymatic, and the effect of (administered) glucuronolactone on detoxication of sulfisoxazole is chiefly acceleration of N-glucuronide-type detoxication process.
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Determination of Propylamine Antihistamines in Pharmaceutical Preparations
Masayoshi Horioka, Hiromi Ishioka
1961 Volume 81 Issue 1 Pages
76-79
Published: January 25, 1961
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Method of assay for antihistamines in official formularies is difficult when used for assay of preparations and the values obtained are often inaccurate. The colorimetric determination of organic bases by the sulfophthalein dyes was applied to the assay of antihistamines of propy famine series and a good result was obtained by the use of Bromocresol Green and Bromothymol Blue. At the same time, effect of substances blended in the preparations was also examined and it was found that chlorpheniramine maleate (I) alone can be selectively determined by the use of Bromothymol Blue and ethylene dichloride when aminopyrine is compounded in (I) and by the use of Bromocresol Purple or Bromophenol Blue and benzene when ephedrine hydrochloride is compounded in (I).
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Chemical Kinetic Studies on Aqueous Solution of Diphenhydramine Hydrochloride
Hisashi Nogami, Masayoshi Horioka
1961 Volume 81 Issue 1 Pages
79-83
Published: January 25, 1961
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It has been found that diphenhydramine undergoes fairly rapid decomposition in the presence of a strong acid and, in order to find its decomposition in gastric juice and its stability in a preparation, kinetic studies were made of its decomposition in aqueous solution. Diphenhydramine is hardly decomposed in alkaline solution. The decomposition in acid solution was found to be due to hydrolysis of the ether linkage and the reaction velocity constants were calculated at 40.0°, 50.0°, 59.6°, and 95.0°, between pH 0.7 and pH 4.7. It was found that this decomposition is a pseudofirst-order reaction and that it was catalyzed by hydrogen ion in the range of pH measured. The hydrogen ion catalytic constant,
kH, could be represented by the following equation:
kH=8.63×10
15⋅e-23, 900/
RT (L./mole/hr.)
Rates of decomposition during digestion in the stomach, during sterilization at pH 5.5, and during storage were calculated from the above equation and all were found to be below 0.4%, negligible from the point of compounding. It is assumed, therefore, that the rapid decomposition of diphenhydramine in the body is mainly due to their decomposition in the organs and tissues.
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The Mechanism of Desulfurization Reaction of Bis(p-nitrobenzyl) Disulfide with Hydrazine Hydrate and the Reaction of Disulfide with various Amines
Tetsuji Kametani, Seiichi Takano, Keiichiro Fukumoto, Yuriko Takayanag ...
1961 Volume 81 Issue 1 Pages
83-88
Published: January 25, 1961
Released on J-STAGE: February 19, 2010
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An interesting desulfurization reaction was discovered by the formation of hydrazone (III) by the reaction of bis(
p-nitrobenzyl) disulfide (I) and hydrazine hydrate. As a supplementary means for examining this reaction mechanism, reaction of (I) with other basic substances was examined and it was found that the oxime (XIII) and semicarbazone (XIV) were also formed with hydroxylamine and semicarbazide. As to the mechanism of this reaction, it was assumed, from the evolution of hydrogen sulfide and ammonia, and resistance of bis(
p-nitrobenzyl) sulfide (VI) to desulfurization, that (I) forms thioaldehyde compound (XI) and thiol (XII), the former (XI) reacts with hydrazine to form the hydrazone (III) and hydrogen disulfide, and the thiol (XII) formed at the same time gradually changes into the disulfide (I), causing the chain reaction to progress, chiefly forming a hydrazone (III). It was also observed that various amines, such as methylamine, ethylamine, trimethylamine, aniline, and pyridine, also undergo similar desulfurization reaction but the reaction rate was slow in this case and the yield of the product was so poor that only a few of the products were identified. Further examinations are under way.
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Synthesis of 2-Acyl-4-alkylpyridine
Nobushige Nishimoto, Tatsumi Nakashima
1961 Volume 81 Issue 1 Pages
88-92
Published: January 25, 1961
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2-Acylpyridines (acyl=CH
3CO, C
2H
5CO, C
3H
7CO, C
4H
9CO) with alkyl (methyl or ethyl) in the 4-position were prepared by the following route: 2, 4-Lutidine 1-oxide was submitted again to rearrangement by the Boekelheide method to 4-methylpicolin-aldehyde (B), oxidized with silver oxide, and esterified to ethyl 4-methylpicolinate (C). The Claisen condensation of (C) to (D) and ketonic decomposition of (D) afforded 2-acetyl-4-methylpyridine (I). Application of methyl, ethyl, or butyl iodide to (D) and ketonic decomposition of the respective products afforded 2-propionyl- (II), 2-butyryl- (III), and 2-valeryl-4-methylpyridine (IV). Application of methyl iodide to 4-ethylpyridine 1-oxide and reaction of the resultant 1-methoxy-4-ethylpyridinium iodide (E) with potassium cyanide gave 4-ethyl-2-pyridinecarbonitrile (F). Application of the Grignard reagents obtained from methyl iodide, ethyl bromide, propyl iodide, and butyl iodide to (F), afforded 2-acetyl- (V), 2-propionyl- (VI), 2-butyryl- (VII), and 2-valeryl-4-ethylpyridine (VIII).
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Quantitative Determination of 5α-Cholestan-3α-ol by Infrared Spectrum
Yoshio Kozaki, Minako Makiguchi, Yuzo Nagase, Shigeo Baba
1961 Volume 81 Issue 1 Pages
93-96
Published: January 25, 1961
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Determination of 5α-cholestan-3α-ol (I) was carried out by the use of its absorption at 1002cm
-1 in its infrared spectrum (Fig. 2) as the key band, in chloroform solution and as KBr pellet. From the route of its synthesis, (I) was expected to be contaminated with cholesterol (II), 5α-cholestan-3β-ol (III), and 5β-cholestan-3-one (IV), and their effect on the determination of (I) was also examined. Presence of (II) and (IV) was found not to affect the determination but (III) was found to interfere, and, therefore, determination of (I) in a mixture of (I) and (II) was attempted. As the results indicated in Tables I and II show, the standard deviation presumed according to the method of Youden was 0.55% by the solution method and 0.58% by the pellet method.
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Synthesis of Arylsulfone Derivatives
Kaoru Kondo, Takanori Hayazaki
1961 Volume 81 Issue 1 Pages
97-100
Published: January 25, 1961
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N-(
p-Methoxyphenyl)glycine ethyl ester and N-(
p-ethoxyphenyl)glycine ethyl ester were each reacted with benzenesulfonyl or
p-toluenesulfonyl chloride in pyridine to form N-(
p-alkoxyphenyl)-N-(arylsulfonyl)glycine ethyl esters (II) and these were reacted with hydrazine to form N-(
p-alkoxyphenyl)-N-(arylsulfonyl)glycine hydrazine (III). Application of arylsulfonyl chloride to (III) or N-(
p-alkoxyphenyl)glycine hydrazide (V) in pyridine affords 1-[N-(
p-alkoxyphenyl)-N-(arylsulfonyl)glycyl]-2-(arylsulfonyl)hydrazine (IV). Reaction of (V) and arylsulfonyl chloride in dehyd. ethanol affords (IV) and 1-[N-(
p-alkoxyphenyl)glycyl]-2-(arylsulfonyl)hydrazine (VI). Further application of arylsulfonyl chloride to (VI) in pyridine affords (IV).
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Syntheses of Schiff Base
Kaoru Kondo, Takanori Hayazaki
1961 Volume 81 Issue 1 Pages
101-104
Published: January 25, 1961
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The corresponding 1-[(N-
p-alkoxyphenyl)glycyl]-2-benzylidenehydrazines (II) were obtained by condensation of N-(
p-methoxyphenyl)- or N-(
p-ethoxyphenyl)glycine hydrazide (I) with salicylaldehyde,
p-nitrobenzaldehyde,
m-nitrobenzaldehyde,
p-chlorobenzaldehyde, 3-nitro-4-chlorobenzaldehyde, piperonal,
p-(dimethylamino)benzaldehyde,
p-acetamidobenzaldehyde, and
p-aminobenzaldehyde, in ethanol containing acetic acid. Similarly, treatment of N-(
p-methoxyphenyl)- and N-(
p-ethoxyphenyl)-N-(benzenesulfonyl)glycine hydrazide (III) with the foregoing aromatic aldehydes afforded 1-[N-(
p-alkoxyphenyl)-N-(benzenesulfonyl)glycyl]-2-benzylidene hydrazines (IV). Reaction of (II), other than 1-[N-(
p-alkoxyphenyl)glycyl]-2-(
p-aminobenzylidene)-hydrazine (II), with benzenesulfonyl chloride in pyridine also afforded (IV). Reaction of benzenesulfonyl chloride with (II) and 1-[N-(
p-alkoxyphenyl)-N-(benzenesulfonyl)-glycyl]-2-(
p-aminobenzylidene)hydrazine in pyridine gave 1-[N-(
p-alkoxyphenyl)-N-(benzenesulfonyl)glycyl]-2-(
p-benzenesulfonamidobenzylidene)hydrazine, and application of hydrazine hydrate to 1-[N-(
p-alkoxyphenyl)-N-(benzenesulfonyl)glycyl]-2-(
p-acetamidobenzylidene)hydrazine and 1-[N-(
p-alkoxyphenyl)glycyl]-2-(
p-acetamidobenzylidene)hydrazine respectively gave (III) and (I).
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The Structure of N-(p-Methoxyphenyl)glycine Hydrazide Derivatives
Kaoru Kondo, Takanori Hayazaki, Harue Nakajima
1961 Volume 81 Issue 1 Pages
105-108
Published: January 25, 1961
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1-[N-(
p-Methoxyphenyl)glycyl]-2-isopropylidenehydrazine (II), obtained by the reaction of N-(
p-methoxyphenyl)glycine hydrazide (I) and acetone, reverts to the original (I) by treatment with hydrazine hydrate. Heat treatment of (II) in ethanol containing a small amount of hydrochloric acid does not afford the anticipated (I) but an unknown substance (V) is obtained which, on reaction with benzenesulfonyl chloride, changes into the compound (VI) containing a benzenesulfonyl group. From the qualitative reactions, elemental analytical values, and determination of molecular weight of these substances, (V) was assumed to be 1, 2-bis[N-(
p-methoxyphenyl)glycyl]hydrazine and (VI), 1, 2-bis[N-(
p-methoxyphenyl)-N-(benzenesulfonyl)glycyl]hydrazine.
On the other hand, application of thionyl chloride to the ethyl ester of N-(
p-methoxyphenyl)-N-(benzenesulfonyl)glycine to form the acid chloride and its reaction with N-(
p-methoxyphenyl)-N-(benezenesulfonyl)glycine hydrazide (IV) gives (VI). Reaction of (IV) and monochloroacetyl chloride to form 1-[N-(
p-methoxyphenyl)-N-(benzenesulfonyl)glycyl]-2-(chloroacetyl)hydrazine and its reaction with
p-anisidine gives 1-[N-(
p-methoxyphenyl)-N-(benzenesulfonyl)glycyl]-2-[N-(
p-methoxyphenyl)glycyl]hydrazine which also produces (VI) by reaction with benzenesulfonyl chloride.
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Masao Tomita, Jun-ichi Kunitomo, Sugako Kikuchi (née Mat ...
1961 Volume 81 Issue 1 Pages
108-113
Published: January 25, 1961
Released on J-STAGE: February 19, 2010
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Cleavage reaction of norcoralydine (I) by application of metallic sodium in liquid ammonia affords one kind of a phenolic base (cleaved base A), whose hydrochloride melts at 249-250° with decomposition. The same reaction with metallic lithium in place of sodium, under exactly the same conditions, affords two kinds of phenolic bases, the same cleaved base A and another base B of m. p. 232-234°. Of these cleaved bases, base A was found to be 11-hydroxy-2, 3, 10-trimethoxy-5, 6, 13, 13a-tetrahydro-8
H-dibenzo [
a,
g] quinolizine (II) by its synthesis through the route shown in Chart 1. The cleaved base B was found identical with 2, 10-dimethoxy-3, 11-dihydroxy-5, 6, 13, 13a-tetrahydro-8
H-dibenzo[
a,
g] quinolizine (III) which had earlier been synthesized by the present writers.
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Masao Tomita, Jun-ichi Kunitomo
1961 Volume 81 Issue 1 Pages
113-115
Published: January 25, 1961
Released on J-STAGE: February 19, 2010
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Cleavage reaction of laudanosine (IV) by metallic lithium in liquid ammonia, using dehyd. dioxane as a solvent, results in the demethylation of methoxyl in 3′-position of benzyltetrahydroisoquinoline ring to form the phenolic base, laudanine (V). When the same reaction is carried out in tetrahydrofuran as a solvent, with increased amount of metallic lithium used, the reaction progresses further to demethylation of the methoxyl in the 6-position as well, forming 4′, 7-O, O-dimethyllaudanosoline (VI).
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A Note on the N-Acetylation of Sulfanilamide
Kitiji Enoki
1961 Volume 81 Issue 1 Pages
116-119
Published: January 25, 1961
Released on J-STAGE: February 19, 2010
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Dissociation constants of 10 kinds of sulfanilamides (I to XIV) were measured and it was observed that a large dissociation constant means that N
1-acetyl derivative is easily obtained, i.e, it is one of the factors for selective acetylation of N
1-position. Ultraviolet absorption spectra of acetyl derivatives of sulfanilamides were examined and some regularity was found to be present.
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A Note on the Rearrangement of N1-Acetylsulfanilamides
Kitiji Enoki
1961 Volume 81 Issue 1 Pages
120-122
Published: January 25, 1961
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The reaction whereby the acetyl group in N
1-position undergoes rearrangement to N
4-position in N
1-acetyl-N
1-(3, 4-dimethyl-5-isoxazolyl) sulfanilamide (I), N
1-acetyl-N
1-(5-methyl-3-isoxazolyl) sulfanilamide (III), and N
1-acetyl-N
1-(2-phenyl-3-pyrazolyl)-sulfanilamide (IV) is considered to be an intermolecular rearrangement since the reaction of sulfanilamide (VII) with (I) produces N
4-acetyl-N
1-(3, 4-dimethyl-5-isoxazolyl)-sulfanilamide (II), N
4-acetylsulfanilamide (VIII), and N
1-(3, 4-dimethyl-5-isoxazolyl) sulfanilamide (IX), and the same products are similarly obtained from (III) and (VII). The fact that N
4-acetyl-N
1-(3, 4-dimethyl-5-isoxazolyl) sulfanilamide is obtained in a good yield from N
1, N
4-diacetyl-N
1-(3, 4-dimethyl-5-isoxazolyl) sulfanilamide (XI) and (IX), and that a similar reaction takes place with N
1, N
4-diacetyl-N
1-(5-methyl-3-isoxazolyl)-sulfanilamide (XII) indicate that this rearrangement reaction is preceded by the formation of (IX) from 2 moles of (I) and one mole of (XI), and (XI) thereby formed acetylates the N
4-position of (IX) to produce two moles of (II). It is assumed that, in the case of (III) and (IV), the acetyl group in N
1-position undergoes rearrangement to N
4-position by a similar mechanism.
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The Reactions of Acetoacetic Ester Derivatives with N4-Acetylsulfanilamide
Kitiji Enoki
1961 Volume 81 Issue 1 Pages
122-125
Published: January 25, 1961
Released on J-STAGE: February 19, 2010
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N-(
p-acetamidobenzenesulfonyl)-2-methylthioacetamide (IX) was prepared from methyl 2-methylthionoacetoacetate (V) and N
4-acetylsulfanilamide (III), and reactivity of 2-methylacetoacetimidic ester (I), 2-methylacetoacetic ester (II), and (V) with (III) was examined. The reactivity was thought to be in the descending order of (I), (V), and (II). Effect of α-alkyl group in acetoacetic ester (VI) in the condensation of (III) and derivatives of (VI) was examined and the reaction was found to become difficult as the number of carbon atoms in the α-alkyl increased. Further, effect of various alcohols in the solvent on the condensation of (I) and (III) was examined and the yield of condensation was found to increase as the polarity became larger.
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Investigation of Photochemical Conversion on Unsaturated Fatty Acid by Gas Chromatography
Kazuta Kitahara
1961 Volume 81 Issue 1 Pages
126-129
Published: January 25, 1961
Released on J-STAGE: February 19, 2010
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Photochemical change of methyl oleate, linoleate, and linolenate was examined by gas chromatographic procedure described in the preceding report. Determination standard of these acids, when exposed to direct sunlight, showed a change which appeared as a peak same as in the case of the ozonide of these acids. This change did not occur at all in the absence of oxygen and the light of 3200-5000 Å was found to give the greatest photochemical change. Velocity of photochemical change under the same conditions of sunlight irradiation was found to be approximately proportional to the square of the number of double bonds in unsaturated fatty acids. It was thereby concluded that the position of this unsaturated bond becomes the factor for acceptor element for attack of oxygen molecule.
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Analysis of Radix Asiasari by Infrared Spectrophotometry
Motoo Nagasawa
1961 Volume 81 Issue 1 Pages
129-138
Published: January 25, 1961
Released on J-STAGE: February 19, 2010
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Xi-xin is a crude drug using a subterranean portion of a few plants of
Asiasarum genus (Asaraceae family). The most important of its component has been reported as methyleugenol which makes up about 50% of its essential oil but this was found to vary greatly according to habitat of the plant. Some plants contained safrole, eucarvone, and 1, 8-cineol as the chief components. Xi-xin oil from Manchurian plant was proved to contain elemicin, an isomer of
cis-asaron.
Tu-xi-xin is the dried root of
Hetehotropa genus of the same family and used as a substitute for Xi-xin. The chief component of its essential oil had been reported as safrole but elemicin was found to be present as the chief component in some of the crude drug.
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Experiments in Man and in Rabbit on the Relationship between Quantity of o-Aminophenol given Orally and that of Conjugated Sulfuric Acid and of O-Conjugated Glucuronic Acid excreted in Urine
Takeo Ohtaki
1961 Volume 81 Issue 1 Pages
139-140
Published: January 25, 1961
Released on J-STAGE: February 19, 2010
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Several dosage of
o-aminophenol was administered orally to human subjects and rabbits, and the amount of conjugated glucuronic acid and sulfuric acid excreted into the urine was examined. It was found that a living organism had the ability to change
o-aminophenol into O-glucuronide and ethereal sulfate according to the amount of
o-aminophenol administered but detoxication by O-glucuronide was found to take place preferentially over that of ethereal sulfate.
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Hideo Tani
1961 Volume 81 Issue 1 Pages
141-143
Published: January 25, 1961
Released on J-STAGE: February 19, 2010
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In order to examine the reaction of 3-substituted 1-methoxypyridinium salts and potassium cyanide, reaction of 1-methoxy-3-cyano-, 1, 3-dimethoxy-, and 1-methoxy-3, 5-dibromopyridinium methylsulfates with potassium cyanide was carried out in water or ethanol-water mixture. The respective reaction products thereby obtained were 2, 3-dicyanopyridine in 27.8% yield, 2, 5-dicyanopyridine in 17.6% yield, 2-cyano-3-methoxypyridine in 67.8% yield, and 2-cyano-3, 5-dibromopyridine in 70% yield.
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Alkaloids of Magnolia grandiflora L. var. lanceolata AIT
Masao Tomita, Yasuo Watanabe, Hiroshi Furukawa
1961 Volume 81 Issue 1 Pages
144-146
Published: January 25, 1961
Released on J-STAGE: February 19, 2010
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Alkaloids contained in
Magnolia grandiflora L. var.
lanceolata AIT. of North American origin were examined and the main base was found to be magnoflorine (I), one of the water-soluble quaternary bases, same as in the domestic
Magnolia gradiflora L. (Japanese name “Taisanboku”). This North American plant was found not to contain salicifoline (II) which is contained in the domestic
M. grandiflora and a new base, whose chloride melted at 203.5-207°, was found to be present.
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Quantitative Estimation by Paper Partition Chromatography
Takeo Tsukamoto, Tetsuya Komori, Yasuko Inoue
1961 Volume 81 Issue 1 Pages
146-148
Published: January 25, 1961
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In order to determine by a simple and micro-method the amino acids in protein hydrolyzate and to identify the amino acid composition in proteins, amino acids separated by paper partition chromatography were submitted to colorimetry, using the modified Ninhydrin reagent described in the preceding paper. It was thereby found that the determination is possible with an error of within 2-5% when using the calibration curve obtained by the two-dimensional, ascending chromatography. A good result was obtained by the use of Toyo Roshi No. 51 A filter paper. Actual determination using whale insulin gave approximately the same precision as the determination by the Stein-Moore method using ion exchange resin.
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Shigemi Kawahara, Hideyo Kawakami
1961 Volume 81 Issue 1 Pages
149-150
Published: January 25, 1961
Released on J-STAGE: February 19, 2010
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Catalytic hydrogenation of (diethylamino) acetonitrile was carried out over Raney nickel W-7 catalyst and without a solvent. The desired N, N-diethylethylenediamine was obtained in a yield of about 40% of the theoretical. This method was adapted to other disubstituted amino-acetonitriles and -propionitriles such as dimethylamino, morpholino, and piperidino compounds. In contrast to the experiments previously reported, relatively moderate conditions were employed for the hydrogenation and the yields were more or less improved. Raney nickel W-7 catalyst may be the most suitable for the hydrogenation of this type of compounds.
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Fukutarô Ugai, Sadao Yamaguchi
1961 Volume 81 Issue 1 Pages
151-152
Published: January 25, 1961
Released on J-STAGE: February 19, 2010
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The main alkaloids of opium, morphine, codeine, papaverine, narcotine, and dihydrocodeine, form a salt with various organic and inorganic acids. The water-soluble salts of these alkaloids have a strong bitter taste and are disliked for oral use. The artificial sweetening, saccharin, is a kind of acid and salt-formation of these alkaloids with saccharin was attained by heating a mixture of the alkaloid and saccharin in organic solvent. The salt thereby formed has a sweet taste, the sweetness of saccharin shielding the bitterness of the base, and is a water-soluble salt of uniform composition.
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Formation of Periplogenin from Digitoxigenin
Hiroshi Ishii
1961 Volume 81 Issue 1 Pages
153-154
Published: January 25, 1961
Released on J-STAGE: February 19, 2010
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