ИСТИНА

In this work 7 copper-containing MOFs were studied as catalysts for the amination reaction of aryl halides. It was shown that the most effective catalytic systems are Cu-MOFs/rac-BINOL/ Cs2CO3/DMSO/110℃, which allows the formation of alkylarylamines in yields up to 85%, while they can be further increased to almost quantitative using 1.5 equiv. of amine. The possibility of successfully introducing a number of primary amines into the reaction, including adamantane-containing amines, morpholine, piperidine, substituted bromo- and iodobenzenes, was demonstrated. The repeated use of catalysts for up to 8 cycles without a significant decrease in yields was shown. Using Cu-MOFs 2-bromo-, 2-iodopyridines, as well as 3-, 5-, 6- and 8-bromoquinolines were successfully employed into the amination reaction; the yields of the target products amounted to 77%. These catalysts proved to be highly effective in the reactions of N,N'-diarylation of diamines and oxadiamines, N,N',N''-triarylation of branched tetraamines (TREN and TRPN), providing yields of target compounds over 90%. The use of Cu-MOFs made it possible to introduce substituted iodobenzenes (including ortho-substituted) to obtain N,N'-diarylation products in yields over 80%. Successful thiolation of iodobenzene with thiophenol in the presence of Cu-MOF/L2 was carried out to give diaryl sulfides in yields of up to 98%; the possibility of at least 9 recyclings of the catalyst with the retention of almost quantitative yield of the product was demonstrated. In a model reaction of iodobenzene hydroxylation with water in the presence of MOF-3/L1 the yield of phenol attained 97%, and in a similar reaction with phenol, the yield of diphenyl ether was 85%. The study of copper leaching into solution from the HKUST-1 catalyst in the amination reaction showed that at different stages of the process the degree of leaching does not exceed 1% (mass); in the case of thiolation at an early stage of the reaction, leaching reaches 50% (mass) and decreases to several percents by the end of the reaction, while in the hydroxylation reaction the degree of copper leaching increases substantially as the end of the reaction is reached. The catalytic activity of copper in solution at different degrees of its leaching was determined.