V. V. Avrorin

Ion-molecular reactions of free phenylium ions, generated by tritium β-decay with group V–VII elements

Abstract Generation of free phenylium ions, obtained by tritium β-decay and their ion-molecular reactions with Group V–VII elements are described. The elaborated nuclear–chemical method has been used for the synthesis of tritium-labeled organic derivatives containing these Group V–VII elements.

Preparation of fused n-phenyl-substituted pyridinium derivatives by direct phenylation with nucleogenic phenyl cations

The direct phenylation of a nitrogen atom has been carried out for the first time in fused pyridine derivatives by ion-molecular interaction of nucleogenic phenyl cations with acridine and phenanthridine. N-Phenylacridinium and -phenanthridinium compounds, which are sensitive markers for biological investigations, were obtained labeled with tritium.

The reaction of direct phenylation by nucleogenic cations as a method of synthesis of unknown or complicated tritium labeled compounds

As a result of ion-molecular reactions of nucleogenic phenyl cations, generated by tritium β-decay in polytritiated benzene, with nucleophilic centers of investigated substrates the direct phenylation has been realized at first time and unknown tritium labeled aromatic derivatives of polyvalent fluorine together with the different N-phenyl substituted pyridinium compounds which are important syntones for biological and medical investigations have been synthesized.

Pathways of ion–molecular interactions of nucleogenic phenyl cations with the nucleophilic centers of picolines

Background The nuclear-chemical method brought unique opportunity for synthesis of unknown and hardly available organic compounds. Presence of tritium labeling allows one-step preparation of radioactive markers for the investigation of chemical and biological processes. Methods The ion–molecular reactions of nucleogenic phenyl cations with 4-picoline have been carried out. The phenyl cations were generated by spontaneous tritium β-decay within the tritium-labeled benzene. Both additions to the nitrogen and substitutions about the aromatic ring were able to be studied simultaneously. Results Unusual substitutions on both the α- and β-positions of the ring system have been revealed. Conclusion By unknown direct phenylation of nitrogen atom tritium-labeled N-phenylpicolinium derivatives, perspective biological markers have been synthesized.

Radiochemical Study of Gas-Phase Reactions of Nucleogenic Diethylgermyl Cations with Dibutyl Ether and 1-Butanol

Reactions of tritium-labeled free diethylgermyl cations with dibutyl ether and 1-butanol in a gas phase were studied by the radiochemical method. Mechanisms of the corresponding ion-molecular reactions were suggested, and the most probable paths of the cation (C2H5)2TGe+ conversion into other isomeric forms were shown.

Synthesis of arylhalonium compounds [including (4-methylphenyl) phenylfluoronium] by the nuclear–chemical method

Abstract The nuclear–chemical method has been used for the synthesis of previously unknown multivalent fluorine derivatives, namely (4-methylphenyl)phenylfluoronium. The synthesis includes the ion-molecular reaction of free phenyl cations generated by tritium β-decay with 4-methylhalobenzenes. The influence of the halogen atom (F, Cl, Br, I) as well as effects of the methyl substituent on the yields of the corresponding halonium compounds have been investigated.

Ion-molecular reactions of free phenylium ions, generated by tritium β-decay with bidentate arenes

Abstract Generation of free phenylium ions, obtained by tritium β-decay and their ion-molecular reactions with bidentate arenes are described. The elaborated nuclear-chemical method has been used for the synthesis of tritium labeled organic derivatives using halobenzenes. Two alternative pathways for interaction of the phenylium ion with the bidentate arene, addition to the lone pair of the halogen or substitution on the aromatic ring, were revealed.

Synthesis of phenylsilocane tritium-labeled at the benzene ring

A strategy for synthesis of the 2-phenyl-2-hydro-1,3-oxa-6-aza-2-silacyclooctane doubly tritium-labeled (2,4- or 2,6-) at the benzene ring has been elaborated. The products are sources of the silyl cations having the atrane structure.

Investigation of the phenylation of methyl-quinolines using tritium-labeled nucleogenic phenyl cations

The phenylation of methylquinolines by nucleogenic phenyl cations was studied. This reaction led to a product mixture through electrophilic addition and electrophilic substitution, with composition depending on the methyl substituent position. In the case of 4-methylquinoline, the electron-donating methyl group in the para position markedly increased the yield of N-phenylquinolinium derivative, while the low yield of the quinolinium salt in the case of 8-methylquinoline was due to the two factors - low basicity of the nitrogen atom in comparison to 4-methylquinoline and steric hindrance by the methyl group, which led to predominant electrophilic substitution.

Synthesis of diethylditritiumstannane Et2SnT2, a generator of stannylium cations

In recent decades tricoordinated cations of heavy elements of the 14-th group of the Periodic table, R3M (M = Si, Ge, Sn) are objects of intense study [1–4]. Despite the fact that the existence of R3M cations in gas phase was proved convincingly, their identification in the condensed phase remains a challenge. This is due to the unique ability of the heavy elements of 14th group to expand their coordination sphere in the reactions with the nucleophiles of any kind. Recent progress in this area relates to the development of the chemistry of anions with extremely low nucleophilicity, such as carborane anion [CB11X12], X = halogen, H [5], borane dianion [B12X12], X = Cl, Br [6], perfluorotetraalkylborates [B(C6F4X)4], X = F, SiR3 [7]. Use of such anions, solvents with low nucleophilicity, and suitable methods of generating allowed, finally, to synthesize and characterize some tricoordinated cations R3M. So, the tin cations of low coordination were obtained in two ways: by splitting a Sn–C bond in tetraorganylstannanes [8] and by the addition of an R cation to stannylene [9]. cations. The method is based on the use of the processes of tritium β-decay in the tritium-labeled stannanes.