The amount of alkaloid contained in Scopolia japonica varies appreciably according to seasons in all its parts, above or below ground. The amount of alkaloid in parts above ground tends to decrease from the budding to withering period, the amount being 0.5% in January and 0.1% in June. The amount in rhizomes becomes maximum during March and April, it being 0.36%, and decreases to a minimum of 0.19% in October. The content of alkaloid in side root hairs is fairly constant throughout the year, the amount being around 0.2%, which increases slightly to 0.28% during February to March. From these facts, it is considered advisable to collect the plant just prior to and during the flowering time of March to April.
The phenomenon of polymorphism in homosulfanilamide was investigated and it was found that two different crystals can be obtained by the difference in recrystallizing conditions. Crystallographic properties were determined of these crystals.
Oxidation of p-acetaminophenyl-mercaptoacetophenone gives a corresponding sulfone compound. Its bromo compound condenses with thiourea to give thiazole compound. However, oxidation of p-acetaminophenylmercapto-acetone and acetal does not give sulfone compounds, p, p′-diacetamino-diphenyl disulfide being obtained from the latter. Bromination of the original compound also gives the same disulfide.
1) Bromination of p-acetaminobenzenesulfone-acetone was experimented under various condition s and its products were examined. 2) Bromination in cold glacial AcOH gives, first, the N-bromide, which, when recrystallized from EtOH, changes to a substance which can be assumed as 3-bromo-4-acetaminobenzenesulfone-acetone. N-bromide changes to α-bromo-α-p-acetaminobenzenesulfone-acetone (α-bromide) under the presence of water and HBr. 3) Bromination in glacial AcOH, dil. AcOH, dil. NaOH solution or in glacial AcOH under the presence of AcONa gives an α-bromide which, by recrystallization from EtOH, changes to its isomer with decompn. 197-199°. Reaction of α-bromide with thiourea gives 2-amino-4-methyl-5-p-aminobe-nzenesulfone-thiazole, mp 175-176°. but the substance with decompn. 197-199° does not react with thiourea.
In order to alleviate the irritant action of alkylresorcinols, one aldehyde radical was attached respectively to 4-ethyl-, 4-n-butyl-, 4-n-amyl-, 4-iso-amyl-, 4-n-hexyl- and 4-n-heptyl-resorcinols by Gattermann-Adams' method of phenolaldehyde synthesis. It is clear that these aldehydes are present in the p-position of the OH radical next to the alkyl group from the fact that both melting point and FeCl3 reaction of 2, 4-dihydroxy-5-ethylbenzoic acid, an oxidation product of one of the aldehydes, 2, 4-dihydroxy-5-ethylbenzaldehyde, differ from those of 2, 6-dihydroxy-3-ethylbenzoic acid synthesized by the authors previously for the determination of the position of Cl in monochloro-alkylresorcinol
There seems to be a relationship between anti-fungial action against soy sauce and anthelmintic properties. The authors examined the mold preventive action of 2, 4-dihydroxy-5-alkyl-benzaldehydes against soy sauce and found that the compounds in which the alkyl group at 5-position containing 4 or 5 C-atoms had a more powerful antiseptic power than n-propyl p-hydroxybenzoate used as a control. Compounds with alkyl group with 6 and 7 C-atoms showed less powerful antiseptic properties than n-propyl p-hydroxybenzoate although there may have been the question of solubility.
Application of paraformaldehyde and HCl-gas to nitrobenzene, o-nitrotoluene, and p- and o-nitro-chlorobenzene in conc. H2SO4 gives chloromethyl compounds with diphenylmethane compounds as by-products. The presence of 3-nitro-5-chloromethyltoluene in the chloromethyl compounds of m-nitrotoluene was assumed.
The authors assumed that vitamin B1 becomes its pyrophosphate inside the animal body and takes part in oxydo-reduction in its free base form. Therefore, air oxidation of vitamin B1 was carried out by which crystals of m.p. 239° was obtained. Its formula corresponded to C12H16ON4S2 and from its properties, its structure was assumed to be 3-(2′-methyl-4′-aminopyrimidyl-5′)-methyl-4-methyl-5-β-hydroxyethyl-thiothiazolne (2) and its synthesis was attempted as follows: To MeOH solution of 2-methyl-4-amino-5-aminomethylpyrimidine were added γ-aceto-γ-chloropropyl acetate and NH3 or (NH4)2CO3 as neutralizing agent, and OS2 was applied whereupon the reaction occurred with evolution of heat and the acetate of the above compound was obtained. This was hydrolyzed by acid or alkali and the above compound was obtained. This showed m.p. 239-240° and showed no depression of the m.p. when fused with the substance obtained from vitamin B1. It gives a hydrochloride of decompn. 243°, and picrate of decompn. 185° Acetylation with pyridine and acetic anhydride gives an acetate of m.p. 172°. Desulfurization with NaHCO3 and sublimate gives thiochrome with a good yield. This substance possesses about the equal amount of vitamin B1 activity and is assumed to play a significant part in biological reaction of vitamin B1.
γ-Aceto-γ-chloropropyl acetate and CS2 were applied, under the presence of NH3, to 2-ethyl-4-amino-5-aminomethylpyrimidine, 2-benzyl-4-amino-5-aminomethylpyrimidine and 2-methyl-4-hydroxy-5-aminomethylpyrimidine, and subequent hydrolyses gave 3-(2′-ethyl-4′-aminopyrimidyl-5′)-methyl-4-methyl-5-β-hydroxyethyl-thiothiazolone (2), decompn. 225°; 3-(2′-benzyl-4′-aminopyrimidyl-5′)-methyl-4-methyl-5-β-hydroxyethyl-thiothiazolone (2), decompn. 224°; and 3-(2′-methyl-4′-hydroxypyrimidyl-5′)-methyl-4-methyl-5-β-hydroxyethyl-thiothiazolone (2), m.p. 206-208°, respectively. Desulfurization of the first two compounds gives respective thiochromine compounds. 2′-Ethyl compound possesses far stronger vitamin B1 action than vitamin B1.
Six kinds of bacteria were isolated from well-water and their metabolic abilities were tested against benzoic, p-hydroxybenzoic, salicylic, m-hydroxybenzoic, anisic, piperonylic, p-nitrobenzoic, phenylacetic, cinnamic, o-coumaric and dl-mandelic acids. These 6 kinds of bacteria each possessed different metabolic ability which were different from those of 23 kinds of bacteria reported previously.
Continued cultivation is possible with KT3, KT30 and KT38 with NH3 as the source of nitrogen, and β-phenylpropionic acid for KT3 and KT38, γ-phenylbutylic acid for KT30 and δ-phenyl-n-valeric acid for KT30 and KT38 as the sole sources of carbon, respectively.
Starting with diethylaminoacetone, 1-diethylamino-2-chloro-2-allylpropane was prepared to which C-allylguaiacol was condensed to give the corresponding phenolalkyl ether. The methylene oxide ring of safrol was cleaved by Grignard reagent whereby formed phenols and 2-allyl-4-methoxyphenol passed into basic phenolalkyl ethers.
2, 2′-Diamino-4, 4′-diphenyl-5, 5′-dithiazolyl sulfone was synthesized by bromination of phenacyl sulfide in CHCl3 to dibromophenacyl sulfide, condensed with thiourea to 2, 2′-diamino-4, 4′-diphenyl-5, 5′-dithiazolyl sulfide which was oxidized to sulfone compound by H2O2 after acetylation and then hydrolyzed with HCl. From this fact, the position of Br was determined. An attempt to carry out this synthesis by the oxidation of phenacyl sulfide to the sulfone compound, its bromination to the dibromo compound and condensation with thiourea was not successful. The mechanism of this reaction and its product are now under study.
Diphenyl ether-4-acetic acid was synthesized from diphenyl ether-4-carboxylic acid by the application of Arndt-Eistert reaction and in good yield. The acid chloride obtained by the application of SOCl2 to diphenyl ether-4-carboxylic acid is led to diazoketone by the action of diazomethane to crystals of decompn. 69°. The decomposition of this ketone in EtOH with AgNO3 in NH3-alkaline state gives crystals of diphenyl ether-4-acetamide, m.p. 172°, which is decomposed by alkali into the acetic acid, white plates, m.p. 78-79°.
Application of formaline and HCl-gas in glacial AcOH solution of diphenyl ether under the presence of ZnCl2 gives 4, 4′-dichloromethyl-diphenyl ether, m.p. 64°, white, scaly crystals with the formula of C14H12OCl2. This gives a methyl ester of m.p. 154° by methylation of the acid obtained by oxidation with KMnO4. This compound was determined by the mixed fusion with dimethyl diphenyl ether-4, 4′-dicarboxylate. This proves the fact that the chloro-methylation occurs in the 4, 4′-position of diphenyl ether nucleus. This dichloromethyl derivative can be led to dicyanomethyl derivative and then decomposed by 50% H2SO4 to 4, 4′-diphenyl ether-4, 4′-diacetic acid, m.p. 207-208°, which gives a formula of C16H14O5 by analysis and corresponds to the objective substance.