Methyl (2-chloroethyl-2, 3, 4-tri-O-acetyl-β-D-glucopyranosid) uronate (II) was prepared by the reaction of methyl 1-bromo-1-deoxy-tri-O-acetyl-α-glucopyranuronate and 2-chloroethanol, in the presence of silver carbonate, Treatment of II with methanolic ammonia afforded 2-chloroethyl β-D-glucopyranosiduronamide (III) which agreed with the product obtained from 1-bromo-1-deoxy-tri-O-acetyl-α-glucopyranuronamide (V). Treatment of II with trimethylamine solution gave 2-aminoethyl β-D-glucopyranosiduronic acid trimethyl betaine (XV). 2-Alkylaminoethyl β-D-glucopyranosiduronamides (VI to X) were obtained by the application of various amines to III. It was found that application of dimethylamine solution to II produced 2-dimethylaminoethyl β-D-glucopyranosiduronic acid (XVI), N, N-dimethyl (2-chloroethyl-β-D-glucopyranosid) uronamide (XVIII), and N, N-dimethyl (2-dimethylaminoethyl-β-D-glucopyranosid) uronamide (XIX), and their structure was established.
The Koenig-Knorr reaction of tri-O-acetyl-1-bromo-1-deoxy-α-D-glucopyranuronic acid and 2-chloroethanol was found to produce three compounds; 2-chloroethyl tri-O-acetyl-β-D-glucopyranosiduronic acid (II), 2-hydroxyethyl (2-chloroethyl tri-O-acetyl-β-D-glucopyranosid) uronate (V), and 1-O-(2-chloroethyl tri-O-acetyl-β-D-glucopyranosiduronoyl) tri-O-acetyl-β-D-glucopyranuronic acid (VIII). Reaction of tetra-O-acetyl-D-glucopyranuronic acid and acetylated halogen-sugar derivatives in acetone, in the presence of silver carbonate, afforded the corresponding ester-type disaccharides and examinations were made on the stability of these compounds in aqueous ammonia.
Examinations were made on the fluorescence ability of the reaction mixture of phthalaldehyde and amines in various media and it was found that only aromatic primary amines showed fluorescence in acid medium. Sulfanilamide, sulfisoxazole, sulfisomezole, and sulfadimethoxine showed stable blue fluorescence, with maxima at 434, 425, 425, and 422mμ, respectively, through this reaction. By the use of the wave lengths of maximum fluorescence, fluorometric determination of sulfanilamides with phthalaldehyde was established. This method has high sensitivity and is simple in procedure. From the reaction of phthalaldehyde and sulfanilamides, corresponding 2-(p-sulfamoyl-phenyl) phthalimidines were isolated and it was found that the fluorescent substances formed in this method are these phthalimidines.
Phenylphthalimidines, possessing substituents like hydroxyl, methoxyl, chlorine, bromine, iodine, sulfonilamide, carboxyl, and nitro group in the phenyl ring, and 2-(1-naphthyl) phthalimidine and 2-(2-naphthyl) phthalimidine were prepared and their fluorescence ability was examined. Fluorescence of 2-phenylphthalimidines requires the conjugation of phthalimidine ring and phenyl group, and there is a great contribution of ionic resonance structure. Extension of the conjugate system increases fluorescence ability while interference of planar configuration by steric hindrance decreased or completely inhibited fluorescence. This fluorescence ability is affected by the electronic character of the substituent in the phenyl ring; increased electron-donating nature of the substituent resulted in the red shift of the maximum wave length and decrease in fluorescence intensity, while increased electron-accepting nature of the substituent resulted in the blue shift of the maximum wave length and increase in fluorescence intensity. Introduction of a nitro group completely inhibited fluorescence ability of 2-phenylphthalimidine.
2-Phenyl-5, 6-methylenedioxyphthalimidines were prepared from 4, 5-methylenedioxyphthalaldehyde and ring-substituted anilines. These phthalimidines showed fluorescence and the effect of solvents, substituents, and steric state on their fluorescence was the same as those on 2-phenylphthalimidines reported earlier, and their fluorescence intensity was stronger than that of the corresponding 2-phenylphthalimidines. Based on these facts, fluorometric determination of sulfanilamides with 4, 5-methylenedioxyphthalaldehyde was established. This method is more sensitive than the one using phthalaldehyde as the reagent and is hardly affected by the presence of aliphatic amines, aromatic secondary and tertiary amines, or ortho-substituted aromatic primary amines.
Hydrolysis of hydrochlorothiazide (I) in alkaline solution was examined. Hydrochlorothiazide was hydrolyzed to 4-amino-6-chloro-m-benzenedisulfonamide (II) and formaldehyde which was converted to methanol and formic acid. These reactions are represented as the reversible consecutive reaction. I⇔II+HCHO 2HCHO→CH3OH+HCOOH The rate for all reactions was determined and the rate constants checked with analog and digital computers.
Dielectric properties of aluminum stearate in benzene solution were studied. It has been shown that the dielectric loss is due both to the direct-current conductivity and to the relaxation phenomena. Both the dielectric constant and loss decreased with the increase of stearate/aluminum ratio and they varied with aging after dissolution. It was found that the Cole-Cole's circular arc law holds for the complex dielectric constants of aluminum soaps. From the Cole-Cole's circular arc law and also, the method of Williams and Ferry, distribution functions of relaxation time were calculated. The mean relaxation time of mono-soap thus obtained was about the same as that of di-soap, and was greater than that of 1.5-soap. On the basis of these results on dielectric properties, it has been concluded that the mono-soap, as well as the di-soap, forms a kind of aggregate in benzene solution, and the aggregate of mono-soap is probably globular in contrast to the aggregate of di-soap which is believed to be linear.
The present experiments were undertaken in order to clarify the biological activity of N-dl-mevalonoyl-β-alanine, a new compound and an isomer of pantothenic acid. In the present series of work, condensation of dl-mevalonic lactone (I) and β-alanine ethyl ester (II) was carried out by heating in dehyd. ethanol at 65° for 30 minutes and the objective N-dl-mevalonoyl-β-alanine ethyl ester (III) was obtained as a crude product. This product was purified through column chromatography using Silica Gel Q-23 (Wako) and a purified product (III) was obtained as a colorless, hygroscopic, viscous liquid, in 51% yield calculated from I.
N-dl-Mevalonoyl-β-alanine synthesized in the present series of work is an isomer of d-pantothenic acid and was therefore tested for its biological activity using three kinds of lactobacillus, Lactobacillus arabinosus, L. casei, and L. fermenti. In the incubation medium not containing pantothenic acid, a high concentration of N-dl-mevalonoyl-β-alanine was able to replace pantothenic acid in promoting bacillary growth. This growth-promoting activity seemed to be a characteristic activity of mevalonoyl-β-alanine molecule because such activity was not found in either dl-mevalonic acid or β-alanine, which might be produced by the hydrolysis of mevalonoyl-β-alanine. In the medium containing pantothenic acid, N-dl-mevalonoyl-β-alanine showed weak antagonism against pantothenic acid on the growth of L. casei and L. fermenti, but not of L. arabinosus.
The growth of Escherichia coli mutant No. 229, which requires d-pantothenic acid, was found to be promoted by a high concentration of synthesized N-dl-mevalonoyl-β-alanine in a medium not containing pantothenic acid. In E. coli mutant No. 3020, requiring d-pantothenic lactone, its growth was strongly promoted by pantothenic acid than by its lactone, which could both be replaced by synthesized N-dl-mevalonoyl-β-alanine or dl-mevalonic lactone. E. coli mutant No. 229, cultured in a medium containing a high concentration of mevalonoyl-β-alanine, and E. coli mutant No. 3020, cultured in a medium containing a high concentration of mevalonic lactone or mevalonoyl-β-alanine, did not revert to their original strain, E. coli o-20. In the E. coli mutant No. 229, antagonism of mevalonoyl-β-alanine against pantothenic acid in the medium containing the latter was not observed. Similarly, in E. coli mutant No. 3020, antagonism of mevalonoyl-β-alanine against pantothenic lactone was not observed in a medium containing the latter lactone.
Synthesized N-dl-mevalonoyl-β-alanine of larger molecular weight showed stronger growth-promoting action against Lactobacillus heterohiochii, which requires d-mevalonic acid, than the synthesized dl-mevalonic lactone of smaller molecular weight. Microbiological activity of mevalonoyl-β-alanine against L. heterohiochii resembles to its activity against Escherichia coli mutant No. 3020 and is assumed to be characteristic to its molecule rather than to dl-mevalonic acid produced by its hydrolysis.
From the experiment of the Magnus method using an isolated hind gut of the crayfish, the antagonism between acetylcholin (ACh) and 4-aminobutyric acid (GABA) was tested, according to the technique of the drug-action curve analysis. From these results, it is suggested that the hind gut of the crayfish may have two receptor systems R1 and R2, to ACh, and that the antagonism between ACh and GABA includes the two non-competitive types to R1 or R2, respectively.
Reduction of ethyl 2-methyl-9, 10-dimethoxy-1, 2, 3, 4, 6, 7-hexahydro-11bH-benzo [a] quinolizine-3-carboxylate (VIII) gave the carbinol derivative (IX), which was also recognized as the methiodide (XII). Condensation of IX with phenyl isocyanate in benzene afforded the urethan (X) as crystals, m.p. 195-197°.
The leaves of Lyonia ovalifolia var. elliptica, supplied from the eastern part of, Japan, contain astilbin and quercitrin, and those supplied from the western part lack astilbin, but there are some exceptions. Small amount of isoengelitin, which seems to be an isomerised product of engelitin, was detected from the methanol extract of the leaves.