-
Toyokazu Kishi
1961 Volume 81 Issue 6 Pages
787-792
Published: June 25, 1961
Released on J-STAGE: February 19, 2010
JOURNAL
FREE ACCESS
α-Lipamide (IV) is obtained from α-lipoic acid (I) by application of ammonia to the reaction product of (I) and either ethyl chlorocarbonate, butyl chlorocarbonate, phosphoryl chloride, or diethyl phosphorochloridate. (IV) also forms on application of ammonia to α-lipoic anhydride (IX) or methyl α-lipoate (X). A new compound, 6, 8-dichloroöctamide (XV), was prepared by application of ammonia to methyl 6, 8-dichloroöctanoate (XI) or 6, 8-dichloroöctanoyl chloride (XIV), or to the reaction product of 6, 8-dichloroöctanoic acid (XII) and alkyl chlorocarbonate. (XV) is converted to α-lipamide (IV) by reaction with potassium thiocyanate or sodium disulfide.
View full abstract
-
Yasuyuki Suzuki
1961 Volume 81 Issue 6 Pages
792-794
Published: June 25, 1961
Released on J-STAGE: February 19, 2010
JOURNAL
FREE ACCESS
A Mannich base was obtained in 70-80% yield by stirring a mixture of 4-hydroxyisoquinoline, 35% formaldehyde solution, and dimethylamine or piperidine in methanol. The free base is unstable but its dihydrochloride is stable. Catalytic reduction of this base over palladium charcoal afforded 3-methyl-4-hydroxyisoquinoline, m. p. 179-180°, in 60-70% yield and the Mannich base was established as 3-dialkylaminomethyl-4-hydroxyisoquinoline.
View full abstract
-
Yasuyuki Suzuki
1961 Volume 81 Issue 6 Pages
795-796
Published: June 25, 1961
Released on J-STAGE: February 19, 2010
JOURNAL
FREE ACCESS
Application of the Grignard reagent to 2- or 3-alkyl-4-cyanopyridine afforded 2- or 3-alkyl(or aryl)-4-carbonylpyridine and the Bucherer reaction was attempted with these ketones. The reaction proceeded smoothly with the ketones possessing a substituent in the 2-position of the pyridine ring but the reaction did not occur at all in the ketones with a substituent in the 3-position. 4-(2-Thienylcarbonyl)-pyridine afforded the corresponding hydantoin in a low yield and the majority was recovered unchanged.
View full abstract
-
Preparation of D-Glucose 6-Phosphate and D-Galactose 6-Phosphate by the Use of Bis(2, 4-dichlorophenyl) Phosphonochloridite
Teruo Tanaka
1961 Volume 81 Issue 6 Pages
797-800
Published: June 25, 1961
Released on J-STAGE: February 19, 2010
JOURNAL
FREE ACCESS
Glycerol 1-phosphate was obtained in 72% yield by the reaction of isopropylideneglycerol and bis(2, 4-dichlorophenyi) phosphonochloridite, in the presence of a tertiary amine, oxidation of its product with
tert-butyl hydroperoxide, and final hydrolysis with an acid. In a similar manner, D-glucose 6-phosphate (in 71% yield) and D-galactose 6-phosphate (in 76% yield) were obtained respectively from 1, 2, 3, 4-tetra-O-acetyl-β-D-glucopyranose and 1, 2:3, 4-di-O-isopropylidene-D-galactopyranose. On the other hand, a 7:3 mixture of D-glucose 6-phosphate and 3-phosphate was obtained in 76% yield from 1, 2:5, 6-di-O-isopropylidene-D-glucofuranose.
View full abstract
-
The Structure and Color Reactions of Angelicone and its Related Compounds
Tsutomu Furuya, Zheng-Xyng Chen
1961 Volume 81 Issue 6 Pages
800-805
Published: June 25, 1961
Released on J-STAGE: February 19, 2010
JOURNAL
FREE ACCESS
The structure of the new coumarin compound, angelicone, isolated from the root of
Angelica schishiudo KOIDZ. (Umbelliferae), was established as 5, 7-dimethoxy-8-(3-methyl-2-butenoyl)coumarin by the acid decomposition reported in the preceding paper and by alkali decomposition reported in the present paper.
Consequently, angelicone is identical with glabra-lactone isolated from the root of
A. glabra MAKINO, and it was decided to adopt the name of angelicone as the correct designation, with glabra-lactone as an alias.
Infrared spectral analyses were made on angelicone, its alkaline decomposition product, and their related compounds. Color reaction to the Gibbs and Emerson reagent was also examined.
View full abstract
-
Transformations of Cardenolides by Microörganisms. (1). Formation of 7β-Hydroxydigltoxigenin by Rhizopus arrhizus
Hiroshi Ishii, Yoshio Nozaki, Tamotsu Okumura, Daisuke Satoh
1961 Volume 81 Issue 6 Pages
805-808
Published: June 25, 1961
Released on J-STAGE: February 19, 2010
JOURNAL
FREE ACCESS
Microbiological oxidation of digitoxigenin (I) by
Rhizopus arrhizus gives a kind of monohydroxydigitoxigenin (IIa) which does not agree with either digoxigenin, gitoxigenin, or sarmentogenin. Since (IIa) forms a diacetate, it is not 11β-hydroxydigitoxigenin and since the bis-dehydro compound (IV) obtained by oxidation of (IIa) with chromium trioxide is not digoxigenone, (IIa) does not have a hydroxyl in 12-position. Infrared spectrum of (IV) suggests the presence of two six-membered ring carbonyls and this suggests that the new hydroxyl introduced into (IIa) is not in D-ring. Since the ultraviolet spectrum and ferric chloride reaction of (IV) do not indicate the presence of α- or β-diketone, the new hydroxyl cannot be in the A-ring. Treatment of (VI) with hydrochloric acid does not cause isomerization to the 5α compound, which denies 3, 6-diketone structure for (IV). These experimental results suggest that the newly introduced hydroxyl is in 7-position.
The presence of α, β-unsaturated ketone in the anhydro compound (V) of (IV) is indicated by its ultraviolet spectrum and this satisfies the above assumption. Application of carbonyl chloride to the 3-dehydro compound (IIIa) of (IIa) afforded 7β, 14β-carbonate (VI) and (IIa) was established as 7β-hydroxydigitoxigenin.
View full abstract
-
1-Arylamino-1-deoxy-D-glucuronamide and its Structure
Yasuo Nakajima
1961 Volume 81 Issue 6 Pages
809-811
Published: June 25, 1961
Released on J-STAGE: February 19, 2010
JOURNAL
FREE ACCESS
1-Arylamino-1-deoxy-D-glucuronamide was prepared from D-glucuronamide and arylamine and 1-arylamino-1-deoxy-2, 3, 4-tri-O-acetyl-D-glucuronamide (III) obtained by its acetylation was found to be the same as that obtained from 1, 2, 3, 4-tetra-O-acetyl-D-glucuronamide (α- and β-forms) (IV) and 1-bromo-l-deoxy-2, 3, 4-tri-O-acetyl-α-D-glucuronamide (V). It was revealed from these facts that (II) is an N-glucopyranoside with a pyranose ring.
View full abstract
-
Amadori Rearrangement
Yasuo Nakajima
1961 Volume 81 Issue 6 Pages
811-814
Published: June 25, 1961
Released on J-STAGE: February 19, 2010
JOURNAL
FREE ACCESS
Amadori rearrangement reaction was carried out on D-glucuronamide and arylamine and the amide of 1-arylamino-1-deoxy-D-fructouronic acid was obtained as crystals. The amide of 1-
p-anisidino-1-deoxy-D-fructouronic acid was obtained as two kinds of inter-convertible crystals which were found from their infrared spectra to be the carbonyl type and the lactol type with a furanose ring.
View full abstract
-
Synthesis of N-(2-tert-Aminoalkyl)propionanilides having Hydroxyl on the Benzene Ring
Noboru Shigematsu
1961 Volume 81 Issue 6 Pages
815-819
Published: June 25, 1961
Released on J-STAGE: February 19, 2010
JOURNAL
FREE ACCESS
As a general rule in analgesics, when a hydroxyl is introduced in the benzene ring, the potent compound has
m-hydroxyl against the quaternary carbon bonded directly to the benzene ring. N-(2-
tert-Aminoalkyl)propionanilides, possessing a hydroxyl in the benzene ring, were prepared and their analgesic action was examined. As a result, it was revealed that the most potent compound also has a hydroxyl in
meta position against the tertiary nitrogen bonded directly to the benzene ring when in the
meta position.
View full abstract
-
Volatile Substance in Copper-N-Ethylidene-DL-threonine Chelates
Yoshishige Sato, Tadao Takahashi, Sataro Imado, Norio Sugimoto
1961 Volume 81 Issue 6 Pages
819-823
Published: June 25, 1961
Released on J-STAGE: February 19, 2010
JOURNAL
FREE ACCESS
Application of acetaldehyde to threonine-copper chelate gives two kinds of crystals, α and β. In order to elucidate their structure and properties, measurement with thermobalance was carried out. Weight-loss curve at the time of heating of the substance showed ca. 9.5% loss in both α- and β-crystals, and this decrease was found to correspond to 2 moles of water of crystallization. The fact was also confirmed by recovery of the original weight by application of water vapor to the substance with decreased weight caused by heating. Dissociation pressure did not show a great value and dissociation energy was found to be similar to that of crystal water. Analysis of the volatile matter produced on heating showed it to be water.
View full abstract
-
Infrared Absorption Spectra of Copper-N-Ethylidene-DL-threonine Chelates
Yoshishige Sato, Keishi Kotera, Sataro Imado, Norio Sugimoto
1961 Volume 81 Issue 6 Pages
824-827
Published: June 25, 1961
Released on J-STAGE: February 19, 2010
JOURNAL
FREE ACCESS
In order to elucidate the chemical structure of two forms, α- and β-crystals, of threonine-copper-acetaldehyde compound, infrared spectral comparison was made on their anhydrates and rehydrated compound. The infrared absorption of the anhydrite showed the same spectrum in both forms. The anhydrite of β-crystal, when water vapor was allowed to be absorbed up to 0.4 specific pressure, showed the same spectrum as that of the β-crystal but when more water was allowed to be absorbed and then desorbed, its infrared spectrum was the same as that of the α-crystal. This showed that the β-crystal easily transited to the α-crystal in the presence of excess water. The ligand in both crystals is a Schiff base with acetaldehyde bonded to the amino group, the crystals possess two moles of water of crystallization, and their chemical structure is the same. The difference in their infrared absorption spectra was assumed to be due merely to the difference in crystal structure.
View full abstract
-
X-Ray Studies on Polymorphism of Copper-N-Ethylidene-DL-threonine Chelate
Sataro Imado
1961 Volume 81 Issue 6 Pages
828-832
Published: June 25, 1961
Released on J-STAGE: February 19, 2010
JOURNAL
FREE ACCESS
trans-Bis (N-ethylidene-DL-threoninato) copper (II) dihydrate comes in α- and β-form crystals, both melting at 202-203° with decomposition. The α-form crystal is a monoclinic holohedral class and the β-form crystal belongs to the triclinic holohedral class, the α-form crystal having
C2h-2/m and β-form,
Ci-1. These crystals were proved to be polymorphic forms by their comparative examination through X-ray powder and chemical methods.
View full abstract
-
The Crystal and Molecular Structure of Copper-N-Ethylidene-DL-threonine Chelate (α-Form)
Sataro Imado
1961 Volume 81 Issue 6 Pages
832-836
Published: June 25, 1961
Released on J-STAGE: February 19, 2010
JOURNAL
FREE ACCESS
In order to determine the structure of
trans-bis(N-ethylidene-DL-threoninato)copper (II) dihydrate (α-form), X-ray crystal analysis was carried out on a single crystal, chiefly on (010) face, using Patterson and Fourier projection. This crystal has two molecules in unit lattice, is a monoclinic, and its space group is
P21/c. The dimensions of the monoclinic cell are:
a=11.41 Å,
b=7.26 Å,
c=10.63 Å, β=100°. From the electron density projection obtained from structural analysis, this chelate was found to have OH and COOH groups coordinating to the copper atom in a square planar and its ligand is a Schiff base with N-ethylidene group.
View full abstract
-
On the Crystal and Molecular Structure of Copper-N-Ethylidene-DL-threonine Chelate (β-Form)
Sataro Imado
1961 Volume 81 Issue 6 Pages
837-840
Published: June 25, 1961
Released on J-STAGE: February 19, 2010
JOURNAL
FREE ACCESS
The structure of β-form of
trans-bis (N-ethylidene-DL-threoninato) copper (II) dihydrate was presumed by the use of Patterson projection, P
(UV). This crystal has one molecule in unit lattice and a projection close to that of electron density was obtained, making it easy to analyze its structure. The crystal is a triclinic, its space group is P1, and lattice constants are:
a=9.90Å,
b=8.91Å,
c=5.54Å; α=102°, β=100°, γ=74°. The structure model obtained from crystal analysis of the α-form was found to place each atom at the maximum position on
P(VU) merely by correcting slightly the inclination angle against (001) face. These facts showed that the chemical structure of β-form crystal is the same as that of the α-form.
View full abstract
-
Iron (II) Chelates of N-Alkylidene-α-amino Acids containing OH or SH Groups
Sataro Imado
1961 Volume 81 Issue 6 Pages
841-845
Published: June 25, 1961
Released on J-STAGE: February 19, 2010
JOURNAL
FREE ACCESS
Present series of work was carried out in order to prepare a hematopoietic with amino acid derived to iron (II) chelate. As reported in Parts I to V,
trans-bis(N-ethylidene-DL-threoninato) copper (II) dihydrate is a special kind of a chelate with OH and COOH coordinated to the copper atom. This suggested that the same chelate may be formed with bivalent iron and examinations were made. It was thereby found that, of the requisite amino acids, α-amino acids possessing OH or SH group formed a stable chelate with iron (II). From its chemical properties and ultraviolet and infrared absorption spectra, this iron (II) chelate was assumed to have two molecules each of N-alkylidene-α-amino acid with OH or SH group and water molecule as the ligands, and coordinated with OH or SH and COOH groups.
View full abstract
-
Yuzo Nakamura
1961 Volume 81 Issue 6 Pages
846-850
Published: June 25, 1961
Released on J-STAGE: February 19, 2010
JOURNAL
FREE ACCESS
1) Conditions necessary for the strongest specific coloration were examined for application of anthrone reagent to aqueous solution containing 50γ of D-glucose and 50γ of L-tryptophan, and the amount of reagent to be used, concentration of the reagent, and period of heating were determined.
2) In optimal conditions and in the presence of an equal amount of D-glucose and L-tryptophan, the optical density was found to become the maximum at 530mμ.
3) Optical density was measured in a solution of equal amounts of L-tryptophan and several kinds of sugars other than D-glucose. The result same as that described in (2) was obtained with hexoses and D-fructose showed the greatest absorbance.
4) Quantitative ratio of L-tryptophan and sugar in the sample solution was changed and variation in the absorbance at 530mμ was measured. When the amount of L-tryptophan was made constant and the amount of D-fructose varied, absorbance increased linearly in proportion to the increase of sugar but when the amount of D-fructose was made constant and the amount of L-tryptophan varied, absorbance did not increase proportionally unless the amount of L-tryptophan was twice that of D-fructose.
View full abstract
-
Zensaku Fujinaga, Bumpei Negishi, Miyako Ohmoto
1961 Volume 81 Issue 6 Pages
851-855
Published: June 25, 1961
Released on J-STAGE: February 19, 2010
JOURNAL
FREE ACCESS
In order to prepare water-soluble derivatives of Phenobarbital and to examine their pharmacological activity, the compounds listed in Table I were prepared from the sodium salt of phenobarbital, using the reaction routes A, B, and C in Chart 1. Results of pharmacological tests on these synthesized compounds are shown in Table II.
View full abstract
-
Shinzo Tamura
1961 Volume 81 Issue 6 Pages
855-860
Published: June 25, 1961
Released on J-STAGE: February 19, 2010
JOURNAL
FREE ACCESS
The quinoline containing radioactive carbon, obtained by the reaction of aniline and acrolein [3-
14C] diacetate, was derived through its 1-oxide to carbostyryl, oxidized with potassium permanganate to kynuric acid, and hydrolyzed into oxalic acid and anthranilic acid. The radioactive carbon was found to be in oxalic acid. This has revealed that the synthesis of quinoline from aniline and acrolein was effected by the mechanism (a) in Chart 1.
The reaction of quinoline synthesis from aromatic primary amines and acrolein diacetate is affected by the acidity of the reaction mixture and the yield varies through the maximum with increasing acidity, In the case of
p-nitroaniline, with weaker basicity than aniline, the optimal acidity is higher than that of aniline and this phenomenon can be explained by detailed analysis of the mechanism (a) shown in Chart 1.
View full abstract
-
Syntheses of Some Methoxymethylphenazines
Hirotaka Otomasu, Kei Yoshida
1961 Volume 81 Issue 6 Pages
861-864
Published: June 25, 1961
Released on J-STAGE: February 19, 2010
JOURNAL
FREE ACCESS
Nitration of 1-methylphenazine 5-oxide (I) with potassium nitrate and sulfuric acid at a low temperature gives a mononitro compound (II), m. p. 210°. Refluxing of (II) with methanolic potassium hydroxide results in substitution of the nitro group with methoxyl and 1-methyl-
x-methoxyphenazine 5-oxide (III) is formed. Polarization effect of the N-oxide group in (I) is assumed to appear at 3-, 7-, and 9-positions and synthesis of 1-methylphenazines with the methoxyl in 3-, 7-, or 9-position was attempted.
The Wohl-Aue reaction of
p-anisidine and
m-nitrotoluene afforded 1-methyl-7-methoxyphenazine (VI), m. p. 147°, and its N-oxide (VII), m. p. 182°. The same reaction of
o-anisidine and
m-nitroanisole gave (VII) and 1-methyl-9-methoxyphenazine (IX), m. p. 164°, that of
o-anisidine and
m-nitrotoluene afforded (I) alone, and the reaction of
o-nitroanisole and
m-toluidine, (IX) alone. (VI) and (IX) did not agree with 1-methyl-
x-methoxyphenazine (IV), m. p. 152°, obtained by deoxygenation of (III). Condensation of 3-methyl-4-nitroanisole and aniline was attempted in order to obtain a 3-methoxy compound but the objective compound was not obtained. Consequently, (IV) cannot be compared directly but it was assumed to be a 1-methyl-3-methoxy derivative since it did not agree with either of the known samples of 1-methoxy-6-methyl- and 1-methoxy-4-methylphenazines.
View full abstract
-
New Color Reaction of Codeine and Morphine and its Application to Colorimetric Determination. (1)
Hiroshi Sakurai
1961 Volume 81 Issue 6 Pages
865-869
Published: June 25, 1961
Released on J-STAGE: February 19, 2010
JOURNAL
FREE ACCESS
Oxidation of codeine and morphine with ceric ammonium nitrate and application of 2, 4-dinitrophenylhydrazine results in orange-red coloration. Thebaine, narcotine, and papaverine color yellowish to this reaction and can therefore be discriminated from the former two. Limit of detection is 1.5γ/0.05cc. In quantitative determination, interfering thebaine, narcotise, and papaverine must be removed. The procedure for determination of codeine is as follows: One cc. of aqueous solution of codeine (30-240 γ/cc.) is placed in a 5-cc. measuring flask, 2cc. of water is added, and the mixture is allowed to stand in crushed ice (0 to 2°) for 5 minutes. To this solution, 1cc. of 0.6% ceric ammonium nitrate (in
N sulfuric acid), which had been stood in crushed ice for 5 minutes, is added, mixed well, and allowed to stand at that temperature for 25 minutes. To this mixture, 0.5cc. of 0.6% 2, 4-dinitrophenylhydrazine solution is added, the flask is removed from the ice bath, and allowed to stand at room temperature for 20 minutes. The mixture is diluted to 5cc. with water, shaken well, and transferred to a glass-stoppered centrifuge tube. Ten cc. of isoamyl acetate is added to the tube, shaken 100 times, and centrifuged for 3 minutes. Isoamyl acetate layer is discarded, 5cc. of fresh isoamyl acetate is added, and treated in the same manner. Absorbancy of the aqueous layer is measured at 500mμ. A blank test is carried out with the same reagent and in the same manner, using 1cc. of water in place of the test solution, and used as the control.
In the presence of thebaine, the test solution is heated with
N hydrochloric acid, basified with sodium hydroxide, and shaken with chloroform to transfer codeine into the chloroform layer.
In the presence of narcotine and papaverine, the test sample is dissolved in 0.2% tartaric acid, shaken with chloroform, and the aqueous layer is submitted to determination of codeine as above.
View full abstract
-
New Color Reaction of Codeine and Morphine and its Application to Colorimetric Determination. (2)
Hiroshi Sakurai
1961 Volume 81 Issue 6 Pages
869-872
Published: June 25, 1961
Released on J-STAGE: February 19, 2010
JOURNAL
FREE ACCESS
Examinations ware made on the analysis of morphine by ceric ammonium nitrate-2, 4-dinitrophenylhydrazine method. The limit of detection by this method is 1.5γ/0.05cc. Thebaine and papaverine interfere in this determination and both must be removed by a simple separation procedure. Narcotine did not affect the resulting data but there is a fear of its having caused secondary reaction, so that its separation was also examined. The procedure for this determination is the same as that described for codeine, with ceric ammonium nitrate as 0.4% solution and period of reaction at 20 minutes. When codeine is present, the test solution is shaken with chloroform in the presence of sodium hydroxide, and morphine is determined with the aqueous layer, codeine with the chloroform layer. When thebaine is present, morphine is determined with the aqueous layer obtained by treatment as above. When both narcotise and papaverine are present, they are separated by treatment as in the case of codeine, and morphine is then determined.
View full abstract
-
Precipitation and Color Reaction of 5, 6- and 6, 7-Dihydroxy-1, 4-naphthoquinone with Metal Ions
Ushiho Matsumoto, Yûzô Nagase
1961 Volume 81 Issue 6 Pages
873-877
Published: June 25, 1961
Released on J-STAGE: February 19, 2010
JOURNAL
FREE ACCESS
Precipitation and coloration reaction of 5, 6-dihydroxy-1, 4-naphthoquinone (I) and 6, 7-dihydroxy-1, 4-naphthoquinone (II) with metal ions were examined and their limit of identification was sought. Of 26 kinds of common metal ions, (I) underwent sensitive precipitation and coloration with Ag
+, Hg
2+, Cu
2+, and Fe
3+ at pH 1 and formed precipitates or chelates at pH 5 with those ions and Al
3+ and Cr
3+, (I) produced color with Sn
4+ and Sb
3+ at pH 1-5. (II) reacted sensitively with Al
3+ at pH 1-5, somewhat insensitively with Fe
3+ at pH 5-8, and somewhat sensitively with Bi
3+, Sn
4+, and Sb
3+ at pH 1, but (II) did not produce any precipitate. Patio of bonding between (II) and Sn
4+ or Bi
3+ in acid solution was measured by the continuous variation method and the composition of Sn
4+: (II) of 1:1 and Bi
3+: (II) of 1:2 was indicated.
View full abstract
-
Enteric Coating. (1). Acrylic and Methacrylic Acid Derivatives
Isamu Utsumi, Tadao Ida, Shoji Takahashi
1961 Volume 81 Issue 6 Pages
878-882
Published: June 25, 1961
Released on J-STAGE: February 19, 2010
JOURNAL
FREE ACCESS
In order to obtain synthetic high polymer enteric coating agent, various copolymers of methyl acrylate, acrylic acid, methyl methacrylate, and methacrylic acid were synthesized. These polymers were examined for their solubility in simulated gastric and enteric juice, permeability of water vapor through the film, and their viscosity and disintegrability were measured. Their availability as enteric coating agent was also examined and comparative examinations were made with shellac and cellulose acetate phthalate. It was thereby found that excellent enteric coating agent is found in methyl acrylate-acrylic acid system containing 9-42 molar % of free acid, methyl methacrylate-methacrylic acid system with around 70 molar % of free acid, and methyl acrylate-methacrylic acid system with 19-52 molar % of free acid. These polymers were also found to have better water vapor permeabilty and disintegrability than shellac or cellulose acetate phthalate.
View full abstract
-
Synthesis of Related Compounds of 2-Phenylbutyric Acid
Koji Oka
1961 Volume 81 Issue 6 Pages
882-888
Published: June 25, 1961
Released on J-STAGE: February 19, 2010
JOURNAL
FREE ACCESS
Two Arndt-Eistert reactions were carried out on 3-phenylvaleric acid to prepare 5-phenylheptanamide. The Reformatsky reaction of propiophenone and ethyl 2-bromopropionate, followed by dehydration and reduction afforded a mixture of two isomers of 2-methyl-3-phenylvaleric acid, which were successfully separated by chromatography through silica gel. Attempted stereospecific preparation of one of the isomers alone failed. Each isomer was submitted to two Arndt-Eistert reactions and the corresponding ethyl 4-methyl-5-phenylheptanamide was obtained. The Reformatsky reaction of indanone and ethyl 2-bromopropionate, followed by dehydration, saponification, and catalytic reduction afforded only one isomer (XIIIa) of α-methyl-1-indanacetic acid. In this case, reduction with sodium and ethanol gave a mixture of two isomers and recrystallization of this mixture from petroleum ether afforded the other isomer (XIIIb). Two Arndt-Eistert reactions of (XIIIa) afforded 4-methyl-butyramide but this reaction did not take place in the case of (XIIIb), being accompanied by isomerization. α-Ethyl-5, 6, 7, 8-tetrahydro-2-naphthaleneacetonitrile (XVIII) was obtained from 5, 6, 7, 8-tetrahydro-2-naphthaleneacetonitrile and ethyl bromide. (XVIII) was derived to its methyl ester by the action of hydrogen chloride gas in methanol and its dehydrogenation reaction over palladium-carbon afforded α-ethyl-2-naphthaleneacetic acid, while saponification of (XVIII) afforded α-ethyl-5, 6, 7, 8-tetrahydro-2-naphthaleneacetic acid.
View full abstract
-
Configuration of 2-Methyl-3-phenylvaleric Acid
Koji Oka
1961 Volume 81 Issue 6 Pages
889-892
Published: June 25, 1961
Released on J-STAGE: February 19, 2010
JOURNAL
FREE ACCESS
Reaction of propiophenone and ethyl succinate in
tert-butanol, in the presence of potassium
tert-butoxide, at below 10° afforded the half ester of 4-ethyl-4-phenylitaconic acid. The dibasic acid obtained by its saponification formed an anhydride with conc. sulfuric acid from which the ethoxycarbonyl and phenyl groups in the half ester are in
trans. This
trans-configuration was also revealed by comparison of ultraviolet absorptions of the half-ester of 4-ethoxy-4-phenylitaconic acid. One-sided addition of hydrogen to this half ester, its Hunsdiecker reaction, and reductive substitution of the bromine compound thereby formed with hydrogen, followed by saponification afforded
threo-2-methyl-3-phenylvaleric acid.
View full abstract
-
Synthesis of erythro-2-Methyl-3-phenylvaleric Acid
Koji Oka
1961 Volume 81 Issue 6 Pages
892-894
Published: June 25, 1961
Released on J-STAGE: February 19, 2010
JOURNAL
FREE ACCESS
The Reformatsky reaction of α-acetoxypropiophenone and ethyl 2-bromopropionate afforded 2-methyl-3-phenyl-4-methyl-
Δ2-butenolide (I) as crystals. Catalytic reduction of (I) gave 2-methyl-3-phenyl-4-hydroxyvaleric acid γ-lactone (II), whose alkaline saponification resulted in partial isomerization to form a hydroxy acid (III), a mixture of stereoisomers. Warming of (III) in pyridine completed the isomerization and only one kind of γ-lactone (IX) was obtained, without contamination of an isomer. Saponifcation of (IX) afforded a hydroxy acid (III′) without being accompanied by isomerization. Methylation of (III′) with diazomethane to the methyl ester (IV′) and application of tosyl chloride to it in pyridine afforded the tosylate (V). Application of phenylmethanethiol to (V) to form the benzylthio compound (VI) and its desulfurization and saponification finally afforded
erythro-2-methyl-3-phenylvaleric acid stereospecifically.
View full abstract
-
Synthesis of 2-(Morpholinocarbonylmethyl)-3-phenylvaleric Acid
Koji Oka
1961 Volume 81 Issue 6 Pages
895-896
Published: June 25, 1961
Released on J-STAGE: February 19, 2010
JOURNAL
FREE ACCESS
4-Ethyl-4-phenylitaconic acid was catalytically reduced to 2-(1-phenylpropyl)succinic acid and the reaction product of its anhydride and morpholine was identical with 2-(morpholinocarbonylmethyl)-3-phenylvaleric acid, prepared from the silver salt of 3-ethoxycarbonyl-4-phenylhexanoic acid according to the method of Salmon-Legagneur and Saudan. This fact indicates that the reaction of unsymmetric anhydride and amine took place by addition of the amine to the carbonyl with less substituent on the α-carbon atom. There seemed to be no change in the configuration throughout the whole course of this reaction.
View full abstract
-
Polarization Titration by Direct or Alternating Current with Different Electrode Surfaces Area
Katsuaki Morisaka
1961 Volume 81 Issue 6 Pages
897-902
Published: June 25, 1961
Released on J-STAGE: February 19, 2010
JOURNAL
FREE ACCESS
Two electrodes of equal surface area are usually used for polarization titration and redox titration by D. C. and A. C. polarization methods was attempted with two electrodes of different surface area. Titration curve becomes distorted in D. C. polarization method and this is analyzed from controled current polarography. The titration curve in A. C. polarization method is almost the same as that in the use of minute electrodes and it was found that a D. C. titration curve is obtained by the commutating effect. In either case, a clear end-point is indicated in the titration curve.
View full abstract
-
Nobuo Tanaka, Kiyoshi Harada, Setsuho Takino (née Sugawara)
1961 Volume 81 Issue 6 Pages
903-907
Published: June 25, 1961
Released on J-STAGE: February 19, 2010
JOURNAL
FREE ACCESS
Tetracaine and procaine undergo decomposition in an aqueous solution respectively into
p-butylaminobenzoic acid and
p-aminobenzoic acid. The compounds are more stable in acid range than in alkalinity and the extent of their decomposition cannot be measured correctly from the lowering of ultraviolet absorption alone. It was found that extraction of a sample at around the isoelectric point of
p-butylamino-or
p-aminobenzoic acid was the most effective in extracting these products and this was utilized for their determination (Charts 1-4).
On the other hand, reaction velocity was examined with tetracaine by varying the pH from 0.29 to 11.08 and it was found that, at a definite pH, the reaction is a first-order reaction and the relationship between log
kTC and pH was an acid-base catalyzed reaction, as shown in Fig. 3. This
kTC was dissolved into each elementary reaction and equation (7) was obtained. Similar experiment was carried out with procaine at pH 2.5-6.0 and the relationship between log
kPC and pH was found to be an acid-base catalyzed reaction, as shown in Fig. 5, giving equation (8).
View full abstract
-
Influence of Glucuronic Acid on Staphylococcus Hemolysin in vitro
Kenichi Akatsuka
1961 Volume 81 Issue 6 Pages
908-910
Published: June 25, 1961
Released on J-STAGE: February 19, 2010
JOURNAL
FREE ACCESS
Effect of glucuronic acid on the hemolysin of extracellular toxin from staphylococcus
in vitro was examined and its reaction mechanism was considered. Toxicity of this toxin weakened or disappeared easily on contact with glucuronic acid and the toxicity was not recovered on dialysis. Similar weakening and disappearance of toxicity was observed with glucuronamide, sodium galacturonate, and sodium pyruvate as with sodium glucuronate, but the effect of sodium gluconate and glucose was not clear. Since the toxicity of this toxin disappeared rapidly by treatment with 2, 4-dinitrofluorobenzene, free amino group in the toxin protein may be responsible for this toxicity. Therefore, weakening or disappearance of toxicity by glucuronic acid may be due to the reaction of glucuronic acid with the free amino group in the toxin protein, i.e. formation of N-glucuronide.
View full abstract
-
Influence of Glucuronic Acid on Diphtheria Exotoxin in vitro
Kenichi Akatsuka
1961 Volume 81 Issue 6 Pages
911-916
Published: June 25, 1961
Released on J-STAGE: February 19, 2010
JOURNAL
FREE ACCESS
Effect of glucuronic acid on the toxicity and antigenity of diphtheria toxin
in vitro was examined and its reaction mechanism was considered. Toxicity of this toxin weakened or disappeared easily on treatment with glucuronic acid but not its antigenity. Consequently, this change is not accompanied by marked degeneration of the protein and may be termed as the formation of a toxoid. The weakening or loss of toxicity by glucuronic acid treatment is not recovered by dialysis to remove excess glucuronic acid so that the change cannot be considered as the formation of a mere mixture or a salt, the product being a comparatively stable substance. Since the toxicity and antigenity of diphtheria toxin are lost by its treatment with 2, 4-dinitrofluorobenzene, free amino acid is thought to take part in the toxicity and antigenity of this toxin. It was found by treatment with dinitrofluorobenzene to form dinitrophenylamino acid that ε-position in lysine had a free amino group. Therefore, weakening and disappearance of toxicity of this toxin by treatment with glucuronic acid is thought to be the result of reaction between glucuronic acid and free amino group in the toxin protein molecule, i.e. formation of N-glucuronide. Toxin free of toxicity by treatment with glucuronic acid was found to contain a definite quantity of glucuronic acid which could not be removed by salting out or dialysis.
View full abstract
-
Yasuyuki Suzuki
1961 Volume 81 Issue 6 Pages
917-918
Published: June 25, 1961
Released on J-STAGE: February 19, 2010
JOURNAL
FREE ACCESS
Application of sodium sulfite to 4-chloropyridine 1-oxide and its methyl homologs afforded sodium 4-pyridine sulfonate 1-oxides. This salt turns into the free sulfonate by treatment with ion exchanger resin. Fusion of this salt with potassium cyanide afforded the corresponding 4-cyanopyridine 1-oxides and their yield was compared with that from N-oxygenation of 4-cyanopyridine with hydrogen peroxide and glacial acetic acid. The same reactions were carried out on quinolines.
View full abstract
-
Yasuo Nakajima, Masao Kuranari, Junji Ide
1961 Volume 81 Issue 6 Pages
919-921
Published: June 25, 1961
Released on J-STAGE: February 19, 2010
JOURNAL
FREE ACCESS
D-Glucuronamide (I) was derived through 1, 2, 3, 4-tetra-O-acetyl-D-glucuronamide (II) and 1-bromo -1-deoxy-2, 3, 4-tri-O-acetyl-D-glucopyranuronamide (III) to methyl 2, 3, 4-tri-O-acetyl-D-glucosiduronamide (IV). The fact that (IV) is identical with methyl 2, 3, 4-tri-O-acetyl-β-D-glucopyranosiduronamide, obtained by acetylation of methyl β-D-glucopyranosiduronamide (VI) and that (II) and (IV) satisfy the pyranose structure of Hudson's isorotation rule proved that (I) has the pyranose structure.
View full abstract
-
Motoichi Itaya, Yoshiharu Takai, Kôiti Suzuki
1961 Volume 81 Issue 6 Pages
921-923
Published: June 25, 1961
Released on J-STAGE: February 19, 2010
JOURNAL
FREE ACCESS
In the ring-alkylation of acetanilide with alcohols, the yield is lower with
sec-butanol than isopropanol. It was thereby found that this is not suitable as the method of preparation for 4′-
sec-butylacetanilide (II) and that nitration of (II) with nitric acid and acetic anhydride resulted in liberation of the
sec-butyl group, affording 4′-nitroacetanilide and not 2′-nitro-4′-
sec-butylacetanilide (IV). It was confirmed that nitration with copper nitrate (trihydrate) and acetic anhydride is the best to obtain (IV).
View full abstract
-
Yuzo Nakamura
1961 Volume 81 Issue 6 Pages
923-925
Published: June 25, 1961
Released on J-STAGE: February 19, 2010
JOURNAL
FREE ACCESS
The specific coloration of hexose with anthrone reagent, in the presence of tryptophan and changes in optical rotation were described in the preceding paper. The measure of optical rotation was carried out in the presence of amino acids other than tryptophan and it was found that other amino acid had almost no effect on this reaction.
View full abstract
-
Depolarized Potentials of Hexamethylenebis (trialkylammonium Halide)
Takao Iwaguchi
1961 Volume 81 Issue 6 Pages
925-927
Published: June 25, 1961
Released on J-STAGE: February 19, 2010
JOURNAL
FREE ACCESS
Some of hexamethylenebis (trialkylammonium halide) for supporting electrolyte of polarography were prepared, whose depolarized potentials (tangent potentials) were measured polarographically, being reduced at different potentials from -1.91 to -2.23 volt
vs. S. C. E.
View full abstract
-
Polarizational Titration on Argentometry with Silver Electrodes or Neutralimetry with Antimony Electrodes
Katsuaki Morisaka
1961 Volume 81 Issue 6 Pages
928-930
Published: June 25, 1961
Released on J-STAGE: February 19, 2010
JOURNAL
FREE ACCESS
As an application of A. C. polarography, silver nitrate titration with silver electrode and neutralization titration with antimony electrode were carried out. In the case of silver electrode, it is desirable that the surface area of the electrode be small, concentration of independent electrolyte be large, and the frequency be low. In the case of antimony electrode, it is desirable that the surface area of the electrode be small and frequency low, but inversely, concentration of independent electrolyte should be small. Sensitivity of both electrodes as inductive titration was not as good as that of platinum electrode. However, the two electrodes showed specific titration results and were successfully applied for A. C. polarography.
View full abstract
-
Permeability of Quinine
Ichiro Kamii, Tatsuo Tanaka, Takeo Yamabe
1961 Volume 81 Issue 6 Pages
931-933
Published: June 25, 1961
Released on J-STAGE: February 19, 2010
JOURNAL
FREE ACCESS
The object of the present work was to determine the utility of ion exchange memqrane for extraction or purification of alkaloids. The transport behavior of quinine in electrodialysis across the membrane, which was reported in the preceding paper, was particularly examined. The experiment was carried out at various pH's and current densities by the use of a five-compartment cell and following points were noted.
1) Quinine has greater permeability through weak-acid than strong-acid cation exchange membrane.
2) This permeability is maximum at about pH 3.
3) An electrodialysis of acidic aqueous extract of cinchona bark containing 2.458mg./cc., assuming all basic substances to be quinine, gives a solution which contains 4.741mg./cc., of quinine at pH 3 with 1.67A/dm
2 for one hour.
View full abstract
-
Mitsuo Takahashi, Tokuzo Ito
1961 Volume 81 Issue 6 Pages
934
Published: June 25, 1961
Released on J-STAGE: February 19, 2010
JOURNAL
FREE ACCESS
-
1961 Volume 81 Issue 6 Pages
e1a
Published: 1961
Released on J-STAGE: February 19, 2010
JOURNAL
FREE ACCESS
-
1961 Volume 81 Issue 6 Pages
e1b
Published: 1961
Released on J-STAGE: February 19, 2010
JOURNAL
FREE ACCESS
-
1961 Volume 81 Issue 6 Pages
e1c
Published: 1961
Released on J-STAGE: February 19, 2010
JOURNAL
FREE ACCESS
-
1961 Volume 81 Issue 6 Pages
e1d
Published: 1961
Released on J-STAGE: February 19, 2010
JOURNAL
FREE ACCESS
-
1961 Volume 81 Issue 6 Pages
e1e
Published: 1961
Released on J-STAGE: February 19, 2010
JOURNAL
FREE ACCESS
-
1961 Volume 81 Issue 6 Pages
e1f
Published: 1961
Released on J-STAGE: February 19, 2010
JOURNAL
FREE ACCESS
-
1961 Volume 81 Issue 6 Pages
e1g
Published: 1961
Released on J-STAGE: February 19, 2010
JOURNAL
FREE ACCESS
-
1961 Volume 81 Issue 6 Pages
e1h
Published: 1961
Released on J-STAGE: February 19, 2010
JOURNAL
FREE ACCESS
-
1961 Volume 81 Issue 6 Pages
e1i
Published: 1961
Released on J-STAGE: February 19, 2010
JOURNAL
FREE ACCESS
-
1961 Volume 81 Issue 6 Pages
e1j
Published: 1961
Released on J-STAGE: February 19, 2010
JOURNAL
FREE ACCESS
-
1961 Volume 81 Issue 6 Pages
e1k
Published: 1961
Released on J-STAGE: February 19, 2010
JOURNAL
FREE ACCESS