MERCURSOLVOADDUCTS FROM 1-METHYL-2-(2-NITROPHENYL) CYCLOPROPANE AND THEIR TRANSFORMATIONS IN FLUOROSULFONIC ACID

Abstract

The conjugated addition reaction of mercury (II) acetate in formic acid from the corresponding 1-methyl-2-(2-nitrophenyl)cyclopropanes was used to obtain 1-formyloxy-1-(2-nitrophenyl)-2-methyl-3-chloromercurpropanes and their transformations into fluorosulfonic acid. The interaction of these adducts with FSO3H at a kinetically controlled stage gives predominantly fluorosulfonates of chloromercuric substituted N-oxo-benz[2,1]isoxazolinium ions. As these ions are kept in FSO3H at 20 °C, their protodemercuration occurs, accompanied by the formation of fluorosulfonates of nonmetallated cyclic ions. The complete conversion of fluorosulfonates of metalated ions into non-metallated ions occurs within 84 h from the moment of dissolution of the mercuric solvent adducts in fluorosulfonic acid. In the process of studying the possibilities of synthetic use of 3-chloromercuric-substituted ortho-nitrosoacylbenzenes, it was found that these compounds can easily transform into a previously unknown class of compounds - 3-vinylbenz[c]isoxazoles, which turned out to be very promising synthons. For example, they were used in the synthesis of such hard-to-reach heterocyclic compounds as 1,4-benzodiazepin-2-one dimers, in which benzodiazepinone rings are linked through C5 atoms, and the linker is a cyclobutane ring. Taking into account the fact that the transformation of mercursol water adducts into the corresponding 3-chloromercuric substituted ortho-nitrosoacylbenzenes must proceed through cyclic ions of the benzo[2,1]isoxazolinium type, certain efforts were made to obtain evidence for their formation from 1-methyl-2-mercursol water adducts of (2-nitrophenyl)cyclopropane and 1-methyl-2-(4-bromo-2-nitrophenyl)-cyclopropane in fluorosulfonic acid. Therefore, obtaining new data on the possibilities of the formation of metalated cyclic ions from mercursolvo adducts and on their stability in solutions of strong acids, on the possibilities of isomeric transformations of these ions, as well as their transformation into non-metalated analogs due to protodemercuration, is important both from a practical and theoretical point of view. For citation: Bandaev S.G., Gulov T.Y., Murodov D.S., Kabirov D.N. Mercursolvoadducts from 1-methyl-2-(2-nitrophenyl) cyclopropane and their transformations in fluorosulfonic acid. ChemChemTech [Izv. Vyssh. Uchebn. Zaved. Khim. Khim. Tekhnol.]. 2023. V. 66. N 6. P. 13-22. DOI: 10.6060/ivkkt.20236606.6761.