The determination method of anthraquinone derivatives in crude drugs was reported individually by Tschirch, Maurin and Daels. The author investigated these methods and developed an improved method. According to this new method, the determination values are more accurate than the values which are determined by the previous methods.
Some derivatives of p-aminomethylbenzene-sulfaminopyrimidine were synthesized by heating and fusing of p-acetaminomethylbenzene-sulfonamide and 2- or 6-chloropyrimidine in the presence of alkali carbonate.
Being interested in the physiogical proparties of coumarin-carboxylic acid derivatives, following were synthesized: Coumarin-3-carboxylic acid dimethyl amide (m.p. 145°) and its 3, 4-dihydro derivative (m.p. 75°); coumarin-3-carboxylic acid diethyl amide (m.p. 78°) and its 3, 4-dihydro derivative (b.p.7 143°); β-dimethylaminoethyl coumarin-3-carboxylate (m.p. 82°) and its 3, 4-dihydro derivative (b.p.0.3 87°, picrate, m.p. 137° (decomp.)); β-diethylaminoethyl coumarin-3-carboxylate (m.p. 68°) and its 3, 4-dihydro derivative (b.p.0.9 89°, dipicrolonate, m.p. 141° (decomp.)). Their physiological properties are still under investigation.
In order to find out the action of Achromobacter ubiquitum in the deterioration of freshness in whale carcass, the decomposing conditions of extract solution and suspension of whale meat were examined. The quantity of protein in cultural medium had no influence upon the change in the amount of volatile basic nitrogen (V.-N). In acid solution of pH 5.9-6.5, V.-N of extract solution did not increase but it increased in peptone water even in acidity. In comparing the decomposition of extract solution of autolysed whale meat with that of fresh meat, the amount of V.-N in the former began to increase rapidly again after the increase in the latter had stopped. It was assumed that this phenomenon was due to this bacteria finding another new kind of decomposable substance in the autolyzate. By the experimental results, this bacteria do not seem to be the main source in the deterioration of meat freshness. During decomposition of the extract solution, the amount of its V.-N decreased rapidly at a certain period. This was due to the production of magnesium ammonium phosphate. The organic acids produced by the decomposition of glucose (3 day culture) were a large amount of racemic lactic acid and a little of acetic acid.
Some 2, 6-lutidine derivatives were synthesized from 4-nitro-2, 6-lutidine-N-oxide. Reduction of 4-nitro-2, 6-lutidine-N-oxide in acetic anhydride with Pd-charcoal as a catalyst, results in absorption of 3mol. of hydrogen, but after that, the speed of reduction becomes slow. Addition of Pt-oxide allows a further absorption of 1mol. of hydrogen smoothly and 4-amino-2, 6-lutidine (prisms, m.p. 191-192°) was obtained. 4-Nitro-2, 6-lutidine-N-oxide was treated in alcoholic solution with sodium methoxide to yield 4-methoxy-2, 6-lutidine-N-oxide (prisms, m.p. 69-70°), catalytic reduction of which by Pd-charcoal in acetic anhydride gave 4-methoxy-2, 6-lutidine. Its ethobromide condensed smoothly with benzaldehyde or anisaldehyde in alcoholic solution with piperidine as a catalyst, giving 4-methoxy-2, 6-distyrilpyridine ethobromide (yellow needles, m.p. 249°) or 4-methoxy-2, 6-di-(p-methoxy-styril)-pyridine ethobromide (yellow needles, m.p. 250°), respectively. The corresponding N-oxide was inactive in condensation reaction with benzaldehyde.
Seasonal variation of santonin in Artemsia maritima L. was examined during June to September, 1949, in Kasukabe, Saitama Pref. Coloration of bract and tubular floret by NaOMe, number of glandular hairs, and the change in the length of bract and tubular floret were determined. Relationship between these values and the santonin content was observed. Results are given in figures and tables.
Effect of the three principles of fertilizers on the alkaloidal content of Datura Tatura L. during cultivation was examined. Although the considerable effects of lack of nitrogen and phosphate were observed, the effect caused by potash in the fertilizer seemed very slight.
Application of cupric or potassium thiocyanate and bromine to 2-aminopyridines does not yield pyridothiazole ring, but the same reaction on 2, 6-diaminopyridines and 3 (5)-aminopyridines yields pyridothiazole rings. Corresponding pyridothiazoles were synthesized from 2-hydroxy-5-aminopyridine, 2-alkyloxy-5-aminopyridines and 2, 5-diaminopyridine. 2-Amino-3-nitropyridine was converted into 2-hydroxy-3-nitro-5-bromopyridine, reduced to 2-hydroxy-3-amino-5-bromopyridine and, by heating with acetic anhydride, it was cyclized to pyridoxazole.
Since the report of Vongerichten, in 1899, on the coloration of pyridine by α-dinitrochlorobenzene, many authors have discussed on this subject. This coloration is not only limited to α-dinitrochlorobenzene, but can also be made by other halogen compounds and sulfone chloride (cf. Table II). The coloration is not specific to pyridine, but is also produced by pyridine homologs. o-Nitrobenzene sulfochloride, however, was affected only by pyridine as shown in Table I. The limit of identification was 0.01%. As to the mechanism of coloration, as shown by the absorption spectrum of Fig. 1, the coloration is not related to the reacting chloride. It seems to be the coloration produced by the formation of enol-glutacone aldehyde as assumed by Baumgarten.
1) The authors examined the essential oil of Cyperus microsia Steud. to compare with that of Cyperus rotundus L. previously studied. 2) As a result, caryophyllene and cadinol were found as the chief components. 3) Besides, a large amount of cadinene was also detected. As the principal constituent, cadinol, easily liberates its hydroxyl, forming cadinene during processing, it was doubtful whether cadinene was contained originally in the plants.
In order to synthesize γ-acetyllactic ester, the raw material to obtain dihydroresorcinol by cyclization, it was found that there are two effective methods, as follows. 1) By the condensation of methylene acetoacetic ester and malonic ester to γ-acetyl-α, γ-carbethoxylactic ester in a good yield, which is saponified by hydrochloric acid to γ-acetyl-lactic acid, follwed by esterification. 2) γ-Acetyl-γ-carbethoxybutyronitrile, obtained by the condensation of acetoacetic ester and acrylonitrile, is saponified by alcoholic sulfuric acid to γ-acetyllactic ester.
Supersonic waves have been found to effect the promotion of chemical reactions, as well as oxidation of chemical substances and destruction of macro-molecules. By acidic saccharification of starch under the radiation of supersonic waves, production of maltose was recognized even at a temperature below 60°. Further, in the reaction producing acetone-glucose from acetone and glucose with sulfuric acid as the condensation agent, the yield is increased in a shorter time by radiation of supersonic waves than only by shaking.
Observations were made on the unfermentable sugar produced from glucose by the action of acid, changing concentration of glucose, concentration of acid and reaction temperature. 1) There is an equilibrium between glucose and the unfermentable sugar, which can be shown by the following equation: K=[biose]⋅[H2O]/[glucose]2 Where [glucose], [biose] and [H2O] represent the respective concentrations, in mol./l., of glucose, unfermentable sugar and water at the time of the equilibrium. 2) The equilibrium constants at 100°, 80° and 60° are 1.84 (mean), 1.51 and 1.20, respectively. 3) The thermochemical equation between glucose and the unfermentable sugar can be shown by: 2C6H12O6⇔C12H22O11+H2O-2.90K cal. As this reaction is endothermic reaction, the equilibrium tends to move to the right and increases the production of the unfermentable sugar as the temperature rises. 4) The equilibrium constant derived from van't Hoff's equation at 120° is 2.32. It corresponds exactly to the experimental value obtained by the use of 0.5 N-sulfuric acid solution on 10% glucose by heating at 120° for 90 minutes (the reaction was assumed to have reached to equilibrium approximately).
The production of unfermentable sugar from glucose, which has been explained by the theory of chemical equilibrium was certified by the kinetic mechanics, to follow the equation. 2C6H12O6⇔C12H22O11+H2O The velocity constants for the production of unfermentable sugar from 0.5N, 1.0N and 2.0N sulfuric acid solutions of 10% glucose, determined at 100°, are 2.77×10-3, 3.30×10-3 and 8.94×10-3, respectively. The constants increased with the increase of acid concentration but no relationship seemed to exist between them that can be shown by a simple equation. The reaction velocity constants in 0.5 N-sulfuric acid solution of 5%, 10% and 20% glucose are 2.61×10-3, 2.86×10-3 and 2.95×10-3, respectively. The relationship between the concentration of glucose and velocity constant can be shown by the following equation k1×104=0.215p+25.65 where p represents concentration of glucose in weight percentage, and k1 the constant.
The velocity constant of reaction in the production of unfermentable sugar from glucose was determined by varying temperatures. 1) The velocity constants of 0.5 N-sulfuric acid solution of 10% glucose at 80° and 60° are 1.68×10-4, and 2.24×10-5, respectively. 2) These values, together with the values determined at 100° given in the 4th Report satisfy the Arrhenius' equation. 3) The activation energy calculated from the Arrhenius' equation is 29, 700cal. 4) The velocity constant calculated from the Arrhenius' equation at 120° is 1.78×10-2. The experimental values of unfermentable sugar obtained by the reaction for 15, 45 and 90 minutes coincide well with calculated values based on the velocity constant and the equiribrium constant at 120° described in the 3rd report.
The domestic, edible shellfish, Asari, Venerpis Semidecussata Reeve, collected in winter and transported to the laboratory, taking about one week, was treated with hot water. When the shells were opened, the juice was taken out and analysed. Succinic acid was detected from the portion precipitating by lead acetate, and taurine, tyrosine and leucine from the monoamino acid portion. From the volatile basic portion were obtained ammonia and trimethylamine, from purine portion, adenine, hypoxanthine, from arginine portion, arginine, and from lysine portion, glycocoll betaine, N-methylpyridinium hydroxide. Further, a small amount of histidine was detected in the histidine portion, and two kinds of unknown base were obtained from the arginine portion giving a picrate, m.p. 230-235° (decomp.), and of m.p. 222-225°, and two unknown from the lysine portion, giving aurates of m.p. 91-93° and of m.p. 165-167°.
Following the 1st Report on the results of analyses of aqueous extract of a shellfish, Venerpis Semidecussata Reeve, the residual meat (muscles and internal organ) were cut into fine pieces, digested with water, and its aqueous solution analysed. The amount of nitrogen-containing compounds other than volatile amines and arginine in this water solution was less than that of the extract reported previously, especially in the amount of taurine, glycocoll betaine and monoamino acids. Compounds detected in the aqueous solution were: ammonia, trimethylamine, xanthine, adenine, hypoxanthine, arginine, glycocoll betaine, histidine, guanine, tyrosine, taurine. N-Methylpyridinium hydroxide was not detected. Unknown bases obtained were one from the lysine portion giving an aurate of m.p. 138-140°, and one from arginine portion giving a picrate of m.p. 222-225°, which was found to be identical with the one from the aqueous extract reported previously.
Results of analysis on the aqueous extract of a shellfish, Venerpis semidecussata Reeve, collected during the spring was compared with that of winter as reported previously. The most remarkable difference was in the amount of arginine, the amount from the spring one being as much as four times that of the winter one. Generally, arginine exists as arginine phosphate in ordinary invertebrate animals in which it is expended for the muscle movement, and it is natural that the amount of arginine should increase in the spring. The amount of glycocoll betaine increased in winter. The amount of the sample used was far smaller than those used in experiments reported in I and II. The basic compounds detected in the present analysis were: adenine, guanine, arginine, glycocol-betaine, taurine, histidine, trimethylamine and ammonia.
The domestic shellfish, Setashijimi, Corbicula sandai Reinhardt, gathered in the middle of November, was soaked in hot water and the aqueous digest was separated and analyzed when the shells opened. Adenine, hypoxanthine, histidine, arginine, glycocolbetaine, N-methyl-pyridinium hydroxide, trimethylamine, ammonia, taurine and succinic acid were isolated. At the same time, from lysine portion, an unknown base, giving an aurate of m.p. 134° and a picrate of m.p. 190-191°, was isolated. A seasonal change in the extract component was examined by the analyses of nitrogen of various forms in the extracts of samples collected in November, January and March. The amount of total nitrogen-containing compounds was found larger in winter, and the amount of arginine was the largest in the spring. Throughout the four seasons, the amount of basic substances in the extract of Corbicula sandai was larger than that of monoamino acids, which was also found in the extract of Anodonta and seems to be the common property in fresh-water shellfish.