Composition of sterol fractions of nystatin-resistant Candida maltosa strains was determined. Using UV-spectrometry, TLC and GLC-MS it was demonstrated that resistance to nystatin is connected with the composition alterations of yeast cell sterols. Block of different stages of ergosterol biosynthesis was revealed in some mutants, viz. C-24-transmethylation, delta 8----delta 7-isomerization, 14 alpha-demethylation, C-5(6)-dehydrogenation, reduction of C-14(15) and C-24(28) double bonds.
The aim of this work was to determine the partial rate constants for the catalytic formation of 4,4-di(chloromethyl)trimethylene sulfite and to establish the controlling stage of the complex process. The choice of DMFA as catalyst during investigation of the quantitative relationships governing the substitution of the hydroxyl group by the chlorine atom was based on the fact that the reaction with triethylamine and pyridine takes place in a more complicated manner; the initially formed triethylamine and pyridine hydrochlorides accelerate substitution, i.e., autocatalysts by the reaction products is observed. The slowest stage of the complex catalytic process in the reaction of 2,2-di(chloromethyl)-1,3-propanediol with thionyl chloride in the presence of dimethylformamide is the reaction of the alcohol-catalyst donor-acceptor complex with the thionyl chloride.
The alkylation and acylation of tri(hydroxymethyl)aminomethane and tri(chloromethyl)aminomethane by methyl iodide and acetyl chloride are described. During cleavage of the quaternary ammonium base obtained by exhaustive Hofmann methylation, 1,3-dichloro-2-chloromethyl-1-propene was formed exclusively; it was also obtained from tri(chloromethyl)carbenium in a superacidic medium. The formation of the olefin was explained by competition between the two processes in the transformation of the reaction intermediate, taking place by S/sub N/1 and E1 mechanisms.