N. Yu. Adonin

Fluorine-Containing Heterocycles: XIX.* Synthesis of Fluorine-Containing Quinazolin-4-ones from 3,1-Benzoxazin-4-ones

Reactions of fluorine-containing 3,1-benzoxazin-4-ones with ammonium acetate, hydrazine, and heteroaromatic amines gave new 3H-, 3-amino-, and 3-hetarylquinazolin-4-ones, respectively. Differences in the conditions of formation of benzoxazinones from anthranilic acids with different fluorination patterns and in the reactions of fluorinated 3,1-benzoxazinones with nitrogen-centered nucleophiles were revealed.

New approach to the synthesis of tris(perfluoroalkyl)borane adducts with dialkylamines

A convenient synthetic approach to the adducts (CnF2n+1)3BNHR2 (n = 2–4, 6; R = Me, Et) was developed, based on the reaction of lithium perfluoroalkyls with dichloro(dialkylamino)boranes at temperatures below −90°C. The target products can be synthesized with preparative yields of 50–90%.

Activation of C-F bonds in ionic liquids catalyzed by nickel complex compounds

A nickel complex-catalyzed hydrodefluorination of acet(pentafluoroanilide) with zinc in ionic liquids resulted in the corresponding 2,3,4,5-tetrafluoro, 3,4,5-trifluoro, and 3,4-difluoro derivatives. The influence of the ionic liquid nature and the reaction conditions on its selectivity were studied, a possibility of the multiple reuse of the ionic liquids as the reaction media was demonstrated.

Iminodiacetic acid synthesis in a microchannel reactor

The synthesis of iminodiacetic acid (IDA) by diethanolamine (DA) dehydrogenation over a Cu/ZrO2 catalyst in a microchannel rector has been investigated and has been compared to the same synthesis in an autoclave. The output capacity of the microchannel reactor per unit volume of the reaction zone and per unit weight of the catalyst is 4.38 (g IDA)/(cm3 h) and 0.49 (g IDA)/(g Cat h), respectively, while the corresponding output capacities of the autoclave are 0.018 (g IDA)/(cm3 h) and 0.46 (g IDA)/(g Cat h). A kinetic analysis has demonstrated that IDA synthesis proceeds in two steps, yielding N-(2-hydroxyethyl)glycine as an intermediate product. A formal two-step kinetic scheme has been proposed, and the apparent rate constants of the reaction steps have been calculated. These rate constants for the synthesis in the microchannel reactor are several orders of magnitude higher than the corresponding constants for the synthesis in the autoclave. The output capacity per unit volume of the reaction zone for the microchannel reactor is two orders of magnitude higher than for the autoclave. This is evidence that the process in the submillimeter-sized channels is markedly intensified owing to the high heat and mass transfer efficiency.

Perylene derivatives formation in reaction of 3-bromobenzanthrone and 4-bromonaphthalic acid derivatives with a reduction system NiCl2-2,2′bipyridyl (or 1,10-phenathroline)-Zn

The reaction of 3-bromobenzanthrone and 4-bromonaphthalic acid derivatives with a reduction system NiCl2-2,2′bipyridyl (or l,10-phenathroline)-Zn gives rise to compounds containing perylene fragment. Under similar conditions was established a possibility to transform substituted l.l′-binaphthyls into the corresponding perylene derivatives.

Reactions of aromatic compounds with xenon difluoride

Reactions of substituted benzenes C6H5R (R = Me, F, Cl, Br, CF3, NO2) with xenon difluoride in the presence of boron trifluoride–diethyl ether complex in weakly acidic (1,1,1,3,3-pentafluorobutane) and weakly basic media (acetonitrile) have been studied. These reactions lead to the formation of fluorobenzene derivatives FC6H4R (isomer mixture) together with isomeric difluorobenzenes and fluorinated and non-fluorinated biphenyls. The results have been compared with previously reported data obtained in other solvents using other catalysts.