Vol 60, No 8 (2024)

The reaction of triflamide with camphene in nitrile solutions in the presence of NBS and NIS has been researched. The reactions in isobutyronitrile solution give of various products: dibromide, camphenol, bromamidation product and corresponding amidines. In the reaction in benzonitrile with NBS, two isomeric benzamidines were obtained and isolated. One of them is the product of rearrangement of the camphene framework during the reaction, while in the second one the original substrate structure is retained. When using NIS as an oxidizing agent in the same solvent, a similar mixture of isomers having an iodine atom was obtained.

It has been shown for the first time that the Ti-Mg-catalyzed carbozincation reaction of N-benzyl-N-(but-3-en-1-yl)hept-2-yn-1-amine with Et₂Zn is accompanied by regio- and stereoselective formation of (Z)-1-benzyl-4-methyl-3-pentylidenepiperidine. The effect of the nature of the solvent on the Ti-Mg-catalyzed heterocyclization of N-benzyl-N-(but-3-en-1-yl)hept-2-yn-1-amine was studied. A mechanism is proposed for the studied reaction of carbozincation of N-homoallyl-substituted propargylamine with Et₂Zn in the presence of catalytic amounts of Ti(O-iPr)₄ and EtMgBr.

Alkylation of 2-(4-fluorophenyl)- and 2-(3-(trifluoromethyl)phenyl)acetonitrile with 1,4-dibrombutane gave the nitrile of the substituted phenylcyclopentane-1 carboxylic acids. Alkaline hydrolysis of the latter in ethyleneglycol corresponding acids were obtained, the interaction of acid chlorides of which with N,N-dialkylaminoalkyl- and heterylalkylamines, also with N,N-dialkylaminoalkyl- and heterylalkylalcohols, synthesized new aminoamides and aminoesters derivatives in a series of 1-(4-fluorophenyl)- and 1-(3-(trifluoromethyl)phenyl)cyclopentanecarboxylic acids. The antiarrhythmic activity of synthesized compounds has been investigated.

The mechanism of the reaction between ethyl chloride or ethyl bromide with trimethoxyphosphine in a non-polar (ε = 1) and polar medium (methanol, ε = 32.7) was studied within the density functional theory (DFT) using MOLPRO program. It was shown that the reaction occurs in 2 stages: first, a nucleophilic attack of the carbon atom by phosphorus occurs, followed by the interaction of methyl of one of the methoxy groups with the halide. The limiting stage in all cases is the second stage of the reaction, the barrier of which is approximately 1.5 times higher than the barrier of the first. The reaction barriers are lower for the reaction of ethyl bromide, while the stabilization energies of the intermediate complexes and products are almost the same for chloride and bromide. Temperature in general has little effect on the reaction profile, with the exception of entropic destabilization of the initial complex. At the same time, the usage of a polar solvent accelerates the reaction process, lowering the barriers and stabilizing the intermediates, and can be recommended for carrying out the reaction.