Acylation of thiamine with alkali gave O, S-diacylthiamine (IV) (IVa: R=p-NO2C6H4-, IVb: R=C6H5-, IVc: R=CH3-). S-Acylthiamine hydrochloride (V) (Va: R=p-NO2C6H4-, Vb: R=C6H5-) was formed by allowing a solution of (IV) in 25% ethanolic hydrochloric acid to stand. This S-acylthiamine (V) underwent S→O rearrangement in acid or alkaline medium to give O-acylthiamine (VII) (VIIa: R=p-NO2C6H4-, VIIb: R=C6H5-). From the fact that S-acylthiamine easily undergoes rearrangement to O-acylthiamine, the formation of O, S-diacylthiamine from thiamine can be explained.
1-Isonicotinoyl-2-vanillylidene hydrazine (II), vanillic acid hydrazide (III), 1-vanilloyl-2-vanillylidene hydrazine (IV), isonicotinaldehyde semicarbazone (V), 1-vanilloyl-2-isonicotinidene hydrazine (VI), and 1-isonicotinoyl-2-isonicotinidene hydrazine (VII) were prepared and their antibacterial action against H 37 Rv strain of tubercle bacilli was tested in a Kirchner medium containing 10% bovine serum. (VII) was found to be 5-10 times more effective than isonicotinic acid hydrazide. By comparing the effective dilution of these compounds, it was concluded that the reason why (II) and (VI) were somewhat effective was not due to the vanillin skeleton but to the presence of a γ-picoline ring.
1) Migration of antiserum (rabbit serum sensitized to egg albumin) and antigen (egg albumin) on the same filter paper results in the antigen-antibody reaction during migration to form a precipitate. By coloring this substance with bromophenol blue, presence or absence of an antibody can be detected. 2) Retension analysis was carried out by the migration of antiserum on a filter paper which was dried and a dilute antigen solution wetted in a direction perpendicular to the first migration, thereby effecting antigen-antibody reaction, with subsequent coloration with bromophenol blue. The portion containing the antibody (γ-globulin portion) can be easily detected because the filtration front of the antigen forms a well-defined streak or a new protein image appears. However, the present method does not offer any quantitative results.
When pantothenic acid is heated with 0.25 N hydrochloric acid for 30 minutes at 100°, it undergoes hydrolysis to form β-alanine whose colorimetric determination by the ninhydrin reaction will allow quantitative estimation of pantothenic acid. The market products of calcium pantothenate generally contain β-alanine as an impurity that it is necessary to purify and isolate pantothenic acid by paper partition chromatography before submitting such market products to the present determination method.
It seems that the ninhydrin reaction of α-amino acids and amines can be divided into two classes, as pointed out by Moubascher; one route based on the formation of hydrindantin and the other based on the formation of a Schiff base between -NH2 and ninhydrin. The reaction carried out in pyridine-water system seems to take the latter course. It follows, therefore, that the ninhydrin reduction compound, such as hydrindantin, is a requisite intermediate in the former which is not fundamentally concerned in the latter in which such reduction product merely inhibits oxidative decomposition of the reaction intermediate and accelerates the formation of the Ruhemann purple.
Catalytic syntheses of pyridine and its homologs by passing a mixed gas of acetylene, ammonia, and methanol over the catalyst of cadmium tungstate-Fuller's earth or cadmium chromate-Fuller's earth, were examined, from which the effect of reaction temperature, molar ratio of the gas mixture, space velocity, and concentration of the catalyst on the yield of pyridine was clarified. It was also found that pyridine is obtained by the use of acetaldehyde or crotonaldehyde in place of acetylene, with ammonia and methanol or formaldehyde, acrolein, or allyl alcohol in place of methanol, with acetylene and ammonia, under the same reaction conditions with the same catalyst.
Treatment of silver salts with ammonia is the usual method in isolating the iodine and chlorine ions but such a method necessitates decomposition of each silver salt separately after treatment with ammonia, which is somewhat tedious in analytical procedures. A method of isolation using the difference in the solubility of the cuprous salt of each ion was examined and it was thereby found that a sufficiently satisfactory results are obtained except when the concentration of the chloride is extremely small. If this isolation method can be carried out quantitatively, qualitative estimation of each ion, in the presence of both halogen ions, can be made more simply than by the silver salt method. Moreover, such method of isolation can possibly be utilized for the quantiative determination of each ion in the presence of the two halogen ions or of each element in organic compounds possessing both iodine and chlorine in their molecule.
The bulbs of Allium Togasii Hara, A. Rosenbachianum, A. fistulosum L. var. gigantium Makino, A. fistulosum L. var. caespitosum Makino, Nothoscordum fragrans Kunth., Brodiaca uniflora Baker, and A. albopilosum were treated with thiamine and the allithiamine homologs thereby obtained as the reaction products were derived to Salkylmercapto-L-cysteine, isolated, and detected by paper chromatography. It was observed that, in the case of A. victorialis L. var. platyphyllum Hulten, A. tuberosum Rottle, and A. Bakari Regel, the amount of allithiamine homologs formed varied slightly with the time and location of collecting.
It has been found that potassium thiocyanate or iodide possessed the action of preventing oxidation of trans-π-oxocamphor. This is not due to the inhibition of the catalytic action of the copper ion present but to the inhibition of the chain-reaction of oxidation by decomposition of the peracid. In such a case, KCNS changes to CN-- and SO4-- in the solution, and KI to the halogen, thereby decreasing the peracid. The preventive action of KCNS is due to its sulfur atom and similar effect can be detected in thiourea and thiosemicarbazide but not in KCN, KCNO, urea, and semicarbazide.
Toxicity and analgesic action of the various aromatic acid esters of 1-alkyl-(aralkyl, aryl)-2-dialkylaminomethylcyclohexanol were examined. Of these derivatives, 1-ethyl-and 1-isopropyl-1-benzoxy-2-dimethylaminomethylcyclohexane hydrochloride showed somewhat powerful analgesic action.
In order to study the configuration of a lactone ring, several alantolactone derivatives were derived to γ-keto acids by the oxidation of the stable γ-lactone with anhydrous chromic acid in pyridine. From the characteristics of the butenolides obtained by the treatment of these γ-keto acids with acetic anhydride, the structure of natural alanto-lactones was assumed.
Electrophoresis was carried out on antipyrine, aminopyrine, and sulpyrine for a definite period, using a buffer solution of a definite pH and in a definite range of temperatures, and the determination was made from the position, shape, and color of the pherogram colored with a reagent. The apparatus used was the Tiselius' apparatus partly modified by the writers (cf. Fig. 1), which gave smaller effect of heat generation (cf. Table I). Relationship between the migration distance and electric pressure or time was found to be linear, as shown in Figs. 2 and 3, but the migration distance and temperature were not in linear relationship (cf. Table II). The relationship between the component of the buffer solution and migration distance is shown in Table III. Relation of pH values, as indicated in Figs. 4, 5, 6, and 7, showed the maximum at pH 3-4. When the electrophoresis is carried out under these conditions, antipyrine and aminopyrine migrate to the cathodic side, while sulpyrine migrates toward the anodic side. The limit of detection by bromine gas was 1γ each of antipyrine and aminopyrine, and 2γ of sulpyrine. Aminopyrine containing some occluded antipyrine was found to be separately identified up to the limit ratio of 5000:1.
There has been no incidence of the reduction of organic compounds with lithium amalgam and, therefore, such reduction with 1% lithium amalgam was carried out on various organic compounds. For example, reduction of carbon-carbon double bond was effected on cinnamic acid and cinnamaldehyde, yielding dihydrocinnamic acid and cinnamic alcohol. Acetophenone, as an example of carbonyl compounds, chiefly yielded a pinacone compound by this reduction, while acetone was recovered unchanged. As the nitrogenous compounds, oxime, azobenzene, and Schiff base yielded the corresponding amine, hydrazobenzene, and secondary amine, while nitriles were recovered unchanged. Reduction of nitrobenzene yielded aniline and azobenzene. It may be concluded that the activity of lithium amalgam is not different from sodium amalgam although the reaction of the former is much milder and it is interesting to note that nitriles are not reduced and ketones are comparatively indifferent to reduction.
Since 1-thienylisoquinoline derivatives, analogs of papaverine, possessed some analgesic action, three kinds of 1-thienylisoquinoline derivatives were synthesized by the condensation of 2-thienylacetyl chloride with three kinds of amines, α-methyl-β-methoxy-β-(3, 4-methylenedioxyphenyl)-ethylamine, α-methyl-β-(3, 4-methylenedioxyphenyl)-ethylamine, and homoveratrylamine to the corresponding amides which were submitted to the usual isoquinoline cyclization. The physiological action of these compounds are being examined.
Since formaldehyde is formed during the ninhydrin reaction of ephedrine, adrenaline, sarcosine, and methylbenzylamine, the ninhydrin reaction of these secondary amines was assumed to occur by the liberation of the primary amine. It follows, therefore, that the rate of coloration of such secondary amines is dependent on the ease or difficulty of the liberation of the primary amines.
1) The substance of m.p. 235°, obtained by heating 1-carbamylthiosemicarbazide (I) or 1-(N-phenylcarbamyl)-thiosemicarbazide (II) with acetic anhydride and followed by hydrolysis with hydrochloric acid, is 2-amino-5-methyl-1, 3, 4-thiadiazole, and not 2-amino-5-hydroxy- or 2-amino-2, 5-endoxy-2, 3-dihydro-1, 3, 4-thiadiazole as Guha pointed out. 2) When the substance of m.p. 177° is obtained by heating (I) or (II) with conc. hydrochloric acid, there is no formation of the isomer of m.p. 235° as a by-product, as was stated by Janniah-Guha, and such crystals cannot be obtained by the acetylation of the substance of m.p. 177° followed by hydrolysis, only recovering the original crystals of m.p. 177°. 3) It is assumed that the so-called transition of the crystals of m.p. 177° to those of m.p. 235° is an error arising from the use of a mixture of the substance of m.p. 177° and thiosemicarbazide for such experiments.
Various kinds of mono-substituted piperazines were quite easily obtained by reacting piperazine with methyl formate or formamide, to 1-formylpiperazine, derived to 1-formyl-4-substituted piperazine, and followed by hydrolysis.
Formation of a piperazine ring by the fusion of morpholine salts and amine hydrochlorides was examined. The reaction was found to proceed comparatively well with the hydrochloride of aromatic amines, such as aniline, at 220-240°, to give phenylpiperazines, as in the case of diethanolamines. In the case of ammonium chloride and hydrochloride of aliphatic amines, higher temperature was necessary, which effected partial dealkylation and the yield of piperazines were not so good.
In order to examine the tuberculostatic activity, 2-benzylidenehydrazono-5-substituted 1, 3, 4-thiadiazoles were prepared by reacting several aromatic aldehydes with 2-hydrazino-5-substituted 1, 3, 4-thiadiazoles. The latter was obtained from 2-nitrosoamino-5-substituted 1, 3, 4-thiadiazoles by its reduction, or cyclization of benzoyldithiocarbazinic acid ester in conc. sulfuric acid to 2-alkylthio-5-phenyl-1, 3, 4-thiadiazole, which was oxidized to the 2-alkylsulfonyl compound, and finally reacted with hydrazine hydrate.
The methods of Piloty (1901, 1903), Kuhn (1935), and Lillevik (1942) for the synthesis of porphirindin (reagent for the thiol radical) were examined. It was thereby confirmed that the oily substance formed as a by-product during the derivation of α-hydroxyaminoisobutyro ethyl iminoether (III) to the isobutyroamidine (IV) is the free base of the acid amide (XII). It was found that a larger amount of this oily product is formed when the reaction is not carried out under anhydrous conditions or when the reaction temperature is raised above the normal.
In order to examine antibacterial action, eight kinds of diphenyl ether-carboxylic acid hydrazide derivatives and their glucosyl derivatives were synthesized. The compounds prepared were diphenyl ether-2-, -3-, and -4-carboxylic acid hydrazides, -4, 4′-dicarboxylic acid hydrazide, 4-methoxydiphenyl ether-2′-, -3′-, and -4′-carboxylic acid hydrazides, and 2-methoxydiphenyl ether-5, 4′-dicarboxylic acid hydrazide.
Twelve kinds of diphenyl ether-carboxylic acid hydrazide derivatives and glucosyl derivatives of some of those, with nitro or amino radical substituted in the phenyl ring, were prepared. The compound synthesized were 4-nitro- and 4-aminodiphenyl ether-2′-, -3′-, and 4′-carboxylic acid hydrazides, and 3-nitro- and 3-aminodiphenyl ether-2′-, -3′-, and 4′-carboxylic acid hydrazides.
Twenty-one kinds of glycerol ethers (15 of them new compounds) were prepared and their pharmacological action examined. Of the compounds prepared, 3-(o- and 3-(m-benzyloxyphenoxy)-1, 2-propanediol were found to possess anticonvulsant action against electric shock stronger than that of Myanesin, with a larger safety margin (LD50/ED50), but were insoluble in water. Anticonvulsant action of 3-(m-dimethylaminophenoxy)-1, 2-propanediol against electric shock was about equal to that of Myanesin and its safety margin was the largest among the compounds tested, with good solubility in water.
A new esterification was attempted by the application of the borate of alcohols with organic acids and effecting an exchange reaction. By reacting phenyl, salicyl, p-cresyl, guaiacyl, butyl, and benzyl borates, phenyl, p-cresyl, guaiacyl, butyl, and benzyl acetates, phenyl, guaiacyl, butyl, and benzyl benzoates, phenyl, p-cresyl, and guaiacyl cinnamates, and p-cresyl, butyl, and benzyl phenylacetates, were prepared in approximately 50-70% yield. Salicylic acid esters could not be prepared by this method.
1) In the nihydrin reaction, ornithine, lysine, cadaverine, and hexamethylenediamine form Ruhemann purple corresponding to one amino radical and this is assumed to be due to the ring formation of the amine aldehyde expected to be formed during the course of this reaction. 2) In spite of the fact that γ-aminobutyladehyde diethylacetal gives positive ninhydrin reaction, it shows a negative reaction after treatment with N hydrochloric acid. This is thought to endorse the foregoing assumption. 3) Octa- and decamethylenediamines form Ruhemann purple corresponding to two amino radicals. 4) The rate of Ruhemann purple formation in ethylenediamine is very low and this is assumed to be due to the formation of an entirely different condensate by the reaction of ethylenediamine and ninhydrin.
Theophylline, theobromine, and caffeine can be potentiometrically titrated in anhydrous acetic acid solution with perchloric acid by glass-calomel electrodes. The determination can be made with an accurary of 0.4%. These compounds are titrated as one molar equivalent. It has been known that theophylline and theobromine can be titrated as an acid in anhydrous alkaline solvent, but not caffeine. According to the titration curves (cf. Fig. 1), the basicity of theophylline and caffeine is similar but that of theobromine is weaker. The methyl derivatives of xanthine will be titrated as a base by the basicity of the nitrogen atom in 9-position of the purine nucleus. A mixture of caffeine and sodium benzoate or salicylate is titrated at the two neutralization points. The first endpoint indicates the basicity of the salt, and the second, caffeine in the mixture. As the basicity of potassium or ammonium salts is stronger than that of sodium salts in anhydrous acetic acid, the mixture of caffeine and potassium or ammonium salts can be titrated more accurately than the mixture of caffeine and sodium salts. These bases cannot be titrated directly with crystal violet, malachite green, or methyl violet as the indicator but they can be determined by back tritration with basic titrants such as potassium or sodium carbonate, potassium hydrogen phthalate, or pyridine in anhydrous acetic acid.
Δ-3 α-hydroxycholenic acid (III) and Δ-3 α-hydroxycholadienic acid (VIII), important intermediates for 11-hydroxysteroids, were prepared by an extremely simple method. Application of bromine to methyl 3α-acetoxy-12-oxocholanate (I′), obtained from desoxycholic acid, gave the 11-bromo compound (II′) which was submitted to the Wolff-Kischner-Minlon reduction to (III). Similar treatment of methyl 3α, 7α-diacetoxy-12-oxocholanate (V), obtained from cholic acid, to 11α-bromo compound and its reduction as above gave (VIII).
Diethyl- and dimethylamides of isocoumarin-3- and -4-carboxylic acids were submitted to catalytic reduction to obtain their 3, 4-dihydro compounds. Hypnotic action of these new compounds were tested with mice, using Bromural as a control but none of the compounds showed any marked activity. These acid chlorides and β-diethyl- or β-dimethylaminoethanol furnished the anticipated esters whose catalytic reduction also gave 3, 4-dihydro compounds. Four kinds of these amino esters were oily substances which were paralytic to the tongue.
Several derivatives of nonylpyrazoles were synthesized in order to examine their antimicrobial properties but none were found to be more effective than nonylpyrazole. It might be concluded that the pyrazole itself is toxic towards bacteria and fungi, and that further examination of pyrazole derivatives offers lekelihood of discovering markedly effective compounds.
The specific coloration of 1, 8-dihydroxyanthrone derivatives and p-nitrosodimethyl-aniline in pyridine solution was utilized in separtory detecting several kinds of anthrones, especially their 1, 8-dihydroxy derivatives. It was also found that this procedure can be used as a means in studying the component of plants. The choice of the developing agents and Rf values of various anthrone derivatives are respectively shown in Tables I and II. Distribution of 1, 8-dihydroxyanthrone derivatives in plants were examined by the present method, one-dimensional ascending method of paper chromatography (developer: methanol-saturated cyclohexane; coloration agent: ammonia), and with the simplified method using circular filter papers, and some interesting observations were gained (cf. Table III).
The specific new coloration reaction of hydroxyanthrone derivatives was further extended and a micromethod for the separatory determination of 1, 8-dihydroxy-anthrone and -anthraquinone derivatives was established. To the pyridine solution of 1, 8-dihy-droxyanthrone derivatives, 0.1% pyridine solution of p-nitrosodimethylaniline is added and the colored solution thereby obtained is measured with the Beckman spectrophotometer. The detection curve is linear, showing possibility of quantitative determination (5-25γ/cc.). In this case, the presence of excess of the reagent, hydroxyanthraquinones, flavonoids, and sugars does not interfere with the measurement. By the concurrent use of this method and that of determination of hydroxyanthraquinones (Shibata: This Journal, 72, 1311 (1952)), seasonal variation in the content of chrysophanol, chrysophanol anthrone, emodin, and emodin anthrone in the fresh and dried fruits of Rhamnus dahurica Pall. var. nipponica Mak. was examined (cf. Figs. 6-9).
1) Paper chromatography of dioscin and several of its allied compounds was examined. It was thereby found that by the use of developing solvent and coloring agents listed in Table I, isolation and detection of dioscin was possible and that some assumptions could also be made on the presence of a minute amount of other new saponins. 2) This method of paper chromatography was carried out on the water-insoluble saponins from Dioscorea nipponica, D. gracillima, and D. tenuipes, described in the previous report, on the dioscin sample of Tsukamoto and Ueno, on each of the (A), (B), and (C) fractions from the chromatographic purification of these samples, and on purified saponins. It was thereby found that both the crude products and the samples were chiefly dioscin but contained a minute amount of unknown substance. The saponin from D. gracillima was found to contain, besides the above, a small amount of a new substance. Each of the (A) fractions was composed only of dioscin, while the (B) fraction from D. gracilliama was composed of the new substance. The purified products were all found to be pure dioscin.
A mixed vapor of allyl alcohol or allylamine and ammonia was passed over the catalyst of cadmium phosphate or cadmium tungstate and Fuller's earth, at 350-400°, and β-picoline was obtained as the chief product, with 3, 5-lutidine as the by-product. The mixed vapor of acetylene and allylamine passed over the cadmium phosphate-Fuller's earth catalyst gave pyridine. A mixed vapor of acetylene, ammonia, and acetone passed over the catalyst of cadmium and chromium tungstate or cadmium and lead chromate on Fuller's earth, at 400°, gave 2, 4, 6-collidine in a good yield, with mesitylene and mesityl oxide as the by-products. Formation of pyridine was extremely small when the vapor of N-methylpyrrole was passed over the catalyst of cadmiun phosphate-Fuller's earth at 400°.
Evidence that o-aminophenol is conjugated with sulfuric acid in vivo was presented by the successful isolation of potassium o-aminophenylsulfate as colorless plates, m.p. 225°, from the urine of tuberculosis patients receiving o-aminophenol by oral administration.
Effect of phenol, p- and o-nitrophenols, and resorcinol on glycolysis and succinic acid dehydrogenation of the live bacterial suspension of Escherichia coli strain S was examined and following results were obtained. 1) Only the non-dissociating type of phenols inhibited respiration of the bacteria. 2) At the concentration that inhibits succinic acid dehydrogenation of live bacterial suspension, the phenols do not affect the aerobic or anaerobic glycolysis. 3) The succinic acid dehydrogenase obtained from the cell-free extract of E. coli by decomposition with supersonic waves seemed to be less affected by these chemicals than the live bacterial suspension.
3-Methyl-6, 7-methylenedioxy-Py-tetrahydroisoquinolines substituted in the 2-position were prepared by the reaction of 2, 3-methylenedioxy-5-(β-bromopropyl)-6-bromomethyl-benzene and methylamine, p-nitroaniline, ethyl p-aminobenzote, or 4-methyl-2-aminothiazole.
Theoretically, two isomers should be present in sulfanilylguanidine by the manner of bonding between sulfanilyl radical and guanidine. Synthetic and analytical studies were carried out on sulfanilylguanidine by taking the guanidine radical as =N =N C=N″-, and its imino-type derivative, N″-acetylsulfanilyl-N′-acetylguanidine, CH3CONH-C6H4-SO2N=C NH2 NHCOCH3 as the α-form, and its isomer, the amino-type derivative, N-acetylsulfanilyl-N′-acetylguanidine, CH3CONH-C6H4-SO2NH=C NH NHCOCH3 as the β-form. The α-form isomer was prepared from N4-acetylsulfanilylguanidine possessing the α-bonding, and the β-form from the guanidine salt of acetylsulfanilic acid. It was found that the α-form derivative liberated two molecules of ammonia by mild alkaline decomposition, while the β-form derivative liberated three molecules of ammonia. Since this decomposition was quantitative when barium hydroxide was used as the decomposition agent, Kjeldahl method was utilized in establishing a separatory quantitative determination of α-and β-bonding. Absorption spectra of these two isomers indicated that α-form showed the absorption bands in the longer wave length region than the β-form.
Solubility of diene-strol, hexestrol, diethylstilbestrol, and their ester- and ether-type derivatives into aqueous solution of various surface active agents was measured. Some of these estrogens possessing a free hydroxyl showed a high solubility while those with all the hydroxyls substituted showed low solubility.
1) 3, 4-Dimethylbenzoic acid, raw material for 3, 4-dimethylbenzoylsulfanilamide (Irgafen), was obtained by heating a mixture of 1 part of fenchone and 4 parts of conc. sulfuric acid, followed by the steam distillation of this reaction product, and oxidation of the oily product thereby obtained, chiefly containing 3, 4-dimethylacetophenone, with sodium hypochlorite. The yield was far better than that by the treatment of camphor in a similar manner. 2) The same treatment of borneol yielded only a small amount of an oily substance and its oxidation with sodium hypochlorite failed to give any aromatic acid.
Monochloro- and dichloro-orsellinic acid esters were prepared and their mold-preventing action in soy sauce was tested. The monochloro derivatives were equal to or better than the corresponding orsellinic acid esters while the mold-preventing action of the dichloro derivatives were found to be far lower than the corresponding orsellinic acid esters. The esters of monochloroorsellinic acid: Methyl ester, m.p. 134°; ethyl ester, m.p. 128°; propyl ester, m.p. 86°; isopropyl ester, m.p. 104°; butyl ester, m.p. 47°. Esters of dichloro-orsellinic acid: Methyl ester, m.p. 118°; ethyl ester, m.p. 158°; propyl ester, m.p. 131°; isopropyl ester, m.p. 107°; butyl ester, m.p. 81°.
N1-3, 4-Dimethylbenzoylsulfanilamide, 3, 4-dimethylsulfanilamidoisoxazole, and 6-sulfanilamido-2, 4-dimethylpyrimidine were successfully titrated in methanol-benzene mixture or pyridine, with 0.1N sodium methoxide, using thymol blue as the indicator. Analysis of variance indicated that the standard deviation of experimental error was 0.3%. The end point was more clear in pyridine solution.
1) A new substance was isolated in a pure form which was present in a small amount with dioscin in the water-insoluble saponins extracted from the rhizome of Dioscorea gracillima Miq. 2) This new substance is a diosgeninglycoside, similar to dioscin, possessing glucose and rhamnose, only the number and or arrangement of sugars were different from those of dioscin.
Following the lst report, effect of metallic ions on the coagulation by lab ferment, was comparatively examined with whole milk and milk sterilized at low and high temperatures. It was found that there was no great difference in the coagulation time by the lab ferment alone in whole milk and that sterilized at a low temperature for a short period, but a great difference was found between the whole milk and that sterilized at a high temperature. The coagulation by the lab ferment was accelerated in these three kinds of milk by the addition of calcium, manganese, or cadmium ion and the degree of such acceleration was found to be marked in the milk sterilized at a high temperature. This was considered to be due to the action of these metallic ions on milk casein to make it easier to coagulate, with concurrent activation of the lab ferment by these metallic ions.
Fungistatic and sporostatic effects of the so-called aldehydes were tested with pathogenic and non-pathogenic fungi. Against pathogenic fungi, the true aldehydes with nine to eleven carbon atoms were effective, C11-aldehyde showing the maximum effect and the effect decreasing to 1/8 in C12-aldehyde. This corresponds to the efficacy of undecylenic acid (1:64, 000 dilution) in fatty acid series. On the other hand, none of the aldehydes were so effective against non-pathogenic fungi.
O-Tosylation of the N-benzoylated compounds of dl-ephedrine, dl-ψ-ephedrine, and dl-ψ-norephedrine was carried out in pyridine by the application of p-toluene sulfochloride, under ice-chilling. However, O-tosylates were not obtained and only the salts of the O-benzoyl compounds of the corresponding diastereomers were obtained. Such facts can be explained by assuming that O-tosylation had occurred at first and then detosylation had taken place by the participation of the neighboring acyl group. During the tosylation of dl-N-benzoylephedrine, a small amount of dl-N-p-toluenesulfonyl-ψ-ephedrine O-benzoate was formed.