Aminomethylation of trifunctional 2.5-dihydroxyacetophenone (2.5-DHA) and 2.4-dihydro¬xy¬aceto-phenone (2.4-DHA) by free primary and secondary amines in the presence of formaldehyde has been conducted for the first time. It has been established that 2.5-DHA is aminomethylated with secondary heterocyclic amines - piperidine and morpholine and with aqueous formaldehyde solution in alcohol medium at 500C. The reaction proceeds simultaneously via all three functions forming stable C,O-substitution products − β-amino-2-aminomethoxy-4-aminomethyl-5-hydroxypropiophenones. The aminomethylation reaction of 2.4-DHA proceeds by phenolic function only under the action of methylene bis-amines piperidine and morpholine in absolute alcohol at 200C with the formation of 2.4-dihydroxy-3-aminomethylacetophenones. Aminomethylation of 2.4-DHA with primary aromatic amines - n-to¬luidine and n-anisidine proceeds in absolute alcohol under the action of formaldehyde in the form of paraform in the presence of catalytic amounts of KOH at 500C. The reaction products are 3.4-dihydro-2H-1.3-benzoxazines. 2.5-DHA does not react with primary aromatic amines and formaldehyde. The composition and structure of compounds synthesized have been established according to the data of ele¬mental and spectral methods of analysis
The complexation of tungsten (VI) with an azo compound synthesized from para-tret-butylphenol (2-hydroxy-5-Tr-butylphenol-4-nitro-asobenzene) has been studied spectrophoto¬metrically. The optimum pH values of the solution are 2.0-3.0. The maximum light absorption of the complexes in n-butanol is in the range 460-470nm, and that of the reagent at 360-370; complex formation is accompanied by a bathochromic shift. The spectrophotometric characteristics of the complex have been calculated and the composition of the complex was determined by various methods. Using the equilibrium shift and isomolar series methods it has been found that the W:R ratio is 1:2. By the Sommer method it has been found that during complex formation one proton is released from each reagent molecule. The complex stability constant βk = 9.04·108 and the complex formation reaction equilibrium constant (4.2·104) have been calculated by the method of Komar. The molar absorption coefficient is (3.44.2).104. The graduation diagram is linear at a tungsten concentration of 1.0-10 µg/ml, n-butanol has been used as an extractant. A single extraction with n-butanol 97% of tungsten as a complex is extracted. Methods of extraction-atomic-absorption and extraction-photometric determination of tungsten have been developed and the influence of a number of extraneous ions on the determination of tungsten has been revealed. The correctness of the results obtained has been controlled by analysing the State Standard Alloy Reference Materials
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