In previous reports, the authors showed results of experiments on growth inhibition tests of 12 kinds of acylamino acid against Staphylococci (Terashima strain) and in the present expt., same tests were made with 17 kinds of acylamino acids. Results were as follows: (1) Growth inhibition increases in the following order. Lauryl-dl-alanine (1, 000-2, 000); lauryl-dl-α amino-n-butyric acid (2, 000); lauryl-dl valine (4, 000); lauryl-dl-phenylalanine (16, 000-32, 000). (2) Laurination of amino acid is more effective than caprinylation. Benzoylation is ineffective. (3) o-Laurylamino-benzoic acid is effective at 16, 000-32, 000 dilution but due to its insolubility, m-laurylamino-benzoic acid is ineffective even at 2, 000 dilution.
A mold from Penicillium No. 176 strain, which was being cultured for the production of penicillin, was isolated and systematic analysis of its chemical properties were made. Ergosterol, a red, basic dyestuff of d-mannit, m.p. 170-180° (decompn.), and neutral oily substance, C36H64O4, b.p 0·02 140 to 145° were found. Catalytic reduction of the oily substance gave crystalline derivative, C36H72O4, m.p. 33.5°. It was revealed that both ergosterol and d-mannit are also produced by Penicllium No. 233 with similar yields.
d-Citronellal and d-citronellic acid were fed to rabbit and from its urine was recovered a substance identical with dihydro-Hildebrandt acid. On the other hand, feeding l-rosinic acid gave its optic antipode.
It has been found that the synthetic method of obtaining mercapto-vitamin B1 by the condensation of N-(2-methyl-4-aminopyrimidyl-5-methyl)-dithiocarbamate and the acetate of γ-aceto-γ-chloropropyl alcohol will proceed smoothly by using this alcohol itself. At the same time, a by-product is always obtained during this reacion.
During the condensation reaction in the synthesis of mercapto-vitamin B1, a by-product of decompn. 277-278°, C7H8N4S, is always obtained. This was proved to be 2-thio-7-methyl-1, 2, 3, 4-tetrahydro-1, 3, 6, 8-benzotetrazine.
Action of acetyl chloride on 2-methoxy- or 4-methoxy-diphenyl ether, under the presence of anhydrous aluminum chloride, gives diacetyl derivatives but, in the case of 3-methoxy-diphenyl ether, triacetyl derivative is principally formed and, similar to the case of 4-methoxy derivative, methyl radical of the methoxyl radical isolates, forming phenol.
6-Chloro-4-ethylresosrcinol, 6-chloro-4-n-butylresorcinol and 6-chloro-4-isoamylresorcinol were prepared by blowing-in the calculated amount of chlorine with carbon tetrachloride as a solvent. Determination of the position of chlorine will be explained in a later report.
2-Amino-4-phenyl-5-p-tolylmercapto-acetophenone (I) was obtained by the condensaion of bromo-p-tolylmercapto-acetophenone and thiourea, and then (I) oxidized as acetate. 2-Amino-4-phenyl-5-p-tolylsulfone-thiazole was obtained by the condensation of bromo-or chloro-p-tolylsulfone-acetophenone and thiourea.
Spiculisporic acid, first isolated by Clutterbuck, Raistrick and Rintoul as metabolic product of glucose by Penicillium spiculisporum Lehman, was first shown to be the lactone of γ-hydroxy-β, δ-dicarboxypentadecoic acid but, later, Asano and Kameta decided that it was a lactone of γ-hydroxy-γ, δ-dicarboxypentadecoic acid. Present experiment showed that strain “KT 21” of a rod-shaped bacterium isolated from the soil of a drain near the Kanazawa Medical University, grows excellently in a synthetic medium containing spiculisporic acid as the sole source of carbon and ammoniak as the sole source of nitrogen, at 25°C, and could be cultivated for six generations. For this culture, spiculisporic acid can be replaced by p-hydroxybenzoic acid or phenylacetic acid acid as a source of carbon.
A strain “KT 22”, a rod-shaped bacterium isolated from human feces, can be cultivated in a synthetic medium containing benzoic acid as the sole source of carbon, and ammoniak as the sole source of nitrogen, at 25°C, for 3 generations. It was found that in a four-day incubation of strain “KT 22” at 25°C, no visible growth of the bacteria can be seen in synthetic media containing any one of the following: p-oxybenzoic, salicylic, m-oxybenzoic, anisic, piperonylic, p-nitrobenzoic, phenylacetic, cinnamic and o-coumaric acids or coumarin. A strain “KT 23”, a rod-shaped bacterium isolated from dried persimmons, can be cultivated in a synthetic medium containing p-oxybenzoic acid as the source of carbon and ammoniak as the sole source of nitrogen, at 25°C, for three generations. “KT 23” produces a water soluble pigment which diffuses through the medium a yellowish-green pigment. Four-day incubation of the strain “KT 23” at 25°C, showed that no visible growth of the bacteria can be seen in synthetic media containing any one of the following: benzoic, salicylic, m-oxybenzoic, anisic, piperonylic, p-nitrobenzoic, phenylacetic, cinnamic and o-courmaric acid or coumarin. It was found that, in the cultivation of “KT 22” and “KT 23”, either acetic, succinic or citric acids can be used excellently as a source of carbon.
Two methods of synthesizing 2-amino-4-methyl-5-p-tolylsulfone-thiazole are described. In halogenation of p-tolylsulfone-acetone, α-p-tolylsulfone-α′-halogen-acetone is obtained if ether, glacial acetic acid or benzene is used as a solvent but, α-p-tolylsulfone-α-halogen-acetone is obtained if alkaline aqueous solution is used. By the condensation of either of these substances and thiourea, corresponding sulfone-thiazole compound is obtained. Bromination or chlorination of p-tolylmercapto-acetone in glacial acetic acid or ether gives α-halogen-α-tolylmercapto-acetone and condensation of the latter with thiourea gives thiazole compound which can be acetylated and later oxidized to sulfonethiazole compound.
In the lowering of freshness of tail meat of a whale (Balaenoptera) at room temperature, it was found that the amount of volatile basic nitrogen and Formol titrated nigrogen both increase regularly with passage of time and the rate of increase was great. The increse of non-protein nitrogen and trimethyl amine nitrogen was comparatively small and no change was observed in the amount of trimethyl amine-oxide nitrogen. At the beginning of putrefaction amount of volatile basic N per 100g sample was 30.2mg, nonprotein N 500mg; Formol titrated N 136mg; and trimethyl amine N 0.45mg. A comparison of percentage freshness and the amounts of volatile basic N and Formol titrated N at the time of the dissection of a sperm whale, showed that both N gradually but distincly increase with the lowering of freshness between 90%-70% freshness but below 70%, the amount of volatile basic N increases rapidly. As a result of these experiments it has been shown that the freshness of a whale meat could be evaluated by the determination of volatile basic N or Formol titrated N.
Flavone glucoside isolated from the leaves of Salix gymnolepis Lev. et Vnt. was proved, from its melting point, analytical values, aglucone derivative and determinations of absorption spectra of the glucoside and the aglucone, to be luteolin-7-glucoside.
The authors experimented with the relation between the position and number of chlorine substitution in naphthol and toxicity against mice. It was found that the toxicity decreased considerably by the substitution of chlorine at para position to OH radical, the decrease being at maximum when the number of Cl substituent is one. In vitro test of 4-chloro-1-hydroxynaphthalene showed this compound to be the best insecticide among chloronaphthol compounds. The chlorine compounds of naphthoquinone possessed low insecticidal action but had a powerful toxicity against higher animals so that unless a compound of excellent insecticidal power can be found, this group of compounds do not seem to be practicable. Observations on the relations between anthelmintic properties and OH radical showed that acylation of OH radical to remove irritation was of no avail and that free OH radical was necessary in such a compound.
Nitro-, amino- and sulfanilamide compounds of chloronaphthol and its acyl derivatives were synthesized in order to observe insecticidal powers of naphthalene compounds. Improvement was made in the method of synthesizing 1-chloro-2-hydroxynaphthalene.
Antiseptic power of chloronaphthols against soy sauce were tested and it was found that 4-chloro-1-hydroxynaphthalene and 1-chloro-2-hydroxynaphthalene acetate possessed strong antiseptic power which were far stronger than that of p-hydroxybenzoic acid esters. Growth inhibitory action of chloronaphthols against various microorganisms were tested and it was found that substitution by chlorine in naphthol increased such inhibitory action but the number of substituent was limited to one atom which imparted maximum action and the increase of chlorine atoms decreased germicidal strength. Although substitution with chlorine atom increased germicidal action, polysubstituent of chlorine and keto-compounds in which OH has been oxidized, are assumed to possess decreased germicidal action due probably to changes in physical properties. It has been found that the germicidal and anthelmintic properties of a compound went more or less in parallel, so that, if a compound having germicdal powers but having weak toxicity against higher animals could be found, it might be possible to find an excellent anthelmintics among them.
Although Chargaff has not made any investigation regarding separation of bonded lipoid in diphtherial bacteria, the authors saponified this lipoid and obtained reddish-brown pigment of carotene series, m.p. 184°, from non-saponifiable substance. From the saponified portion were obtained lauric acid, m.p. 44°, myristic acid, m.p. 54°, palmitic acid, m.p. 63°, stearic acid, m.p. 68°, and cerotic acid, m.p. 78°, which were all identified by mixed fusion with authentic compounds. As unsaturated acids, palmito-oleic acid was obtained which was identified by comparison with standard compound as dihydroxy-palmito-oleic acid, m.p. 130°. Dihydroxyacetone, m.p. 695° (dibenzoate, m.p. 125°) was obtained from the aqueous solution which was also identified by mixed fusion. From the aqueous solution was also obtained yellow crystals, m.p. 140°, which was assumed to be phenylhydrazone of hexose, and colorless crystals, m p. 110° (semicarbazone, decompn. 168°), C6H13NO5, which coincides with d-glucosamine. Evaporation of aqueous solution by conc. hydrochloric acidity, isolation by Jones-Foremarr method gave two portions, one being C6H13NO2, m.p. 293-295°, and the other, C5H9NO4, m.p. 202°, which were identified as leucine and glutamine, respectively.
Fatty acid obtained by the saponification of fats in diphterial bacteria, named by Chargaff as diphtheric acid, is an unsatuated acid, C35H68O2, m.p. 35-36°, which is catalytically reduced to dihydrodiphtheric acid, C35H70O2, m.p. 95° (anilide, m.p. 73°). Oxidation of diphtheric acid by KMnO4 gives dihydroxydiphtheric acid, C35H70O4, m.p. 46°, which is further oxidized by sulfuric acid and sodium bichromate to cerotic acid, m.p. 78°, and 8-keto-nonic acid, m.p. 40.5° (semicarbazone, m.p. 134.5°), the latter being identified by synthesis. Cleavage of this acid must be at a point where two OH radicals are situated next to each other which were oxidized, i.e. oxidative cleavage of the double bond in diphtheric acid. It follows, therefore, that the structure of diphtheric acid can be shown by CH3-(CH2)24-CH=C-(CH2)6-COOH.
Some of the alkylselenazole homologs can be synthesized directly from nitriles (including cyanic acid), α-halogenketone, dichloro-ether or chloracetal and hydrogen selenide. The yield can considerably be increased by the addition of a suitable condensation agent. Such reactions can be expected to give universality against alkylthiazole homologs.
Chemical properties of alkylselenazole homologs can be compared to those of corresponding alkylthiazole homologs but there is a great deal of difference in the degree of activity. C2-Position of selenazole is less active to nucleophilic reagents than C2 in thiazole but the activity of C5 to electrophilic reagent is remarkably greater. Selenazole ring is more easily cleaved than the thiazole ring and various derivatives of the former are also more easily decomposed compared to those of thiazole.
Chemical properties of 2-amino-4-methylselenazole can be assumed to resemble the corresponding thiazole compound although selenazole ring is more easily cleaved. The amino radical in this compound cannot be so easily diazotized as with general aromatic primary amines.