Reactions of nucleophilic substitution involving solid organic halogen compounds under shear deformation at high pressure

Abstract

Under conditions of shear deformation and high pressures (SD+HP), reactions of nucleophilic substitution were studied: 1) the replacement of aliphatic halogen atom with alkaline metal halides (halo-substituted aliphatic carboxylic acids, 1-bromoadamantane); 2) the replacement of halogen atom in aromatic nucleus (halobenzoic acids, dihalobenzenes) with halogen of salt; 3) the replacement of aliphatic halogen with hydroxyl (hydrolysis in a solid phase); 4) the replacement of halogen with amino group under deformation of the samples of ammonium α-halocarboxylates to give the corresponding amino acids. It was found that the exchange of the halogen atoms bonded with aliphatic carbon is most intensive in the mixtures of alkaline metal iodides with bromo-substituted acetic and propionic acids: the exchange reaction in these mixtures is observed even during grinding in the mortar. Unlike the liquid phase, under conditions of SD+HP exchange of the halogen atom of the aromatic nucleus with alkaline metal halides, proceeds successfully, and the reactivity of halides increases in the series Na < K < Rb < Cs. Under SD+HP, 1-Br-adamantane reacts with water to form 1-adamantanol. A high reactivity of the water adsorbed by the reagents is observed.