Natalya V. Kirij

Bi(CF3)3/Cu(OCOCH3)2 — a new system for the synthesis of 2-trifluoromethylcycloalkan-1-ones, trifluoromethylanilines and phenyl(trifluoromethyl)sulfane

Abstract Bi(CF 3 ) 3 reacts in the presence of equimolar amounts of Cu(OCOCH 3 ) 2 and 1-morpholinocyclopentene to give 1-morpholino-2-trifluoromethylcyclopentene in 83% yield. This compound as well as intermediately formed 1-morpholino-2-trifluoromethylcyclohexene can easily be converted into the corresponding cycloketones (78 and 41% yield) using the Swarts procedure. In absence of a copper(II) source, no reactions were observed. The reaction of the system Bi(CF 3 ) 3 /Cu(OCOCH 3 ) 2 with N , N -diethylaniline gave an 1.7: 1 isomer mixture of 2-trifluoromethyl and 4-trifluormethyl- N , N -diethylanilines in 48% yield. With tetrabutylammonium thiophenolate, mixtures of phenyl(trifluoromethyl)sulfane and diphenyldisulfane were obtained. Mechanisms are discussed.

Difluoromethylation of Amines with Zn(CF3)Br · 2 CH3CN, Cd(CF3)2 · 2 CH3CN and the System Bi(CF3)3/AlCl3

The reactions of Zn(CF3)Br · 2 CH3CN, Cd(CF3)2 · 2 CH3CN or Bi(CF3)3/AlCl3 with tertiary amines lead to the formation of quaternary ammonium salts of the general formula [R3NCF2H]X. The reaction of 4-N,N-dimethylaminopyridine with Zn(CF3)Br · 2 CH3CN yields (N-difluoromethyl)-4-N,N-dimethylaminopyridinium bromide. Bi(CF3)3/AlCl3 reacts with 1,4-diazabicyclo[2.2.2]octane to form a mixture of mono- and bis(difluoromethylammonium) salts. Carbenoide Reaktionen von Trifluormethylelement-Verbindungen. 5. Difluormethylierungen von Aminen mit Zn(CF3)Br · 2 CH3CN, Cd(CF3)2 · 2 CH3CN und dem System Bi(CF3)3/AlCl3 Die Reaktionen von Zn(CF3)Br · 2 CH3CN, Cd(CF3)2 · 2 CH3CN oder Bi(CF3)3/AlCl3 mit tertiaren Aminen fuhren zur Bildung von quarternaren Ammoniumsalzen der allgemeinen Formel [R3NCF2H]X. Bei der Reaktion von 4-N,N-Dimethylaminopyridin mit Zn(CF3)Br · 2 CH3CN entsteht N-(Difluormethyl)-4-(N,N-dimethylamino)pyridiniumbromid. Bi(CF3)3/AlCl3 reagiert mit 1,4-Diazabicyclo[2.2.2]oktan zu einem Gemisch aus Mono- und Bis(difluormethylammonium)-Salzen.

Synthesis and characterization of aryl(trifluoromethyl)bismuth compounds (R-C6H4)3-nBi(CF3)n [R=H, 4-CH3, 4-CF3, 3-F, 4-F; n=1 and 2] and the reactions of (C6H5)3-nnBi(CF3)n [n=0–3] with benzoylpyridinium chloride

Abstract The partly new derivatives (R-C 6 H 4 )BiBr 2 and (R-C 6 H 4 ) 2 BiCl (R=4-CH 3 , 4-CF 3 , 3-F, 4-F) have been prepared from the redistribution reactions of the corresponding triarylbismuth compounds with BiBr 3 and BiCl 3 , respectively. Metathesis reactions of these substrates with Cd(CF 3 ) 2 complexes yielded the new aryl(trifluoromethyl)bismuth compounds (R-C 6 H 4 ) 3- n Bi(CF 3 ) n ( n = 1 and 2). The mono(trifluoromethyl) derivatives are quite stable towards dismutations, whereas the bis(trifluoromethyl) compounds rapidly redistribute to give (R-C 6 H 4 ) 2 Bi(CF 3 ) and Bi(CF 3 ) 3 . Comparative reactions of (C 6 H 5 ) 3- n ,Bi(CF 3 ) n with benzoylpyridinium chloride showed that the mixed derivatives preferentially transfer the phenyl group to yield benzophenone. Reactions of R 3 Bi with benzoylpyridinium chloride selectively give the corresponding phenone in good yield.

Carbenoid reactions of trifluoromethylelement compounds. Part 6. Syntheses and characterization of difluoromethylphosphonium, arsonium and stibonium compounds from reactions of triorganopnicogens with Zn(CF3)Br·2D and Bi(CF3)3

Abstract (Difluoromethyl)triorganopnicogenium tetrachlorobismuthates are isolated in moderate to very good yields from the reactions of several R 3 E derivatives(E=P, As) with the reagent Bi(CF 3 ) 3 /AlCl 3 . (Difluoromethyl)triorganopnicogenium bromides are obtained from room temperature reactions of R 3 E(E=P, As, Sb) with Zn(CF 3 )Br·2CH 3 CN. The compounds were characterized by their NMR and mass spectra and by comparison with literature data.

The first alkyl bismuthates: tris(trifluoromethyl)fluoro- and tetrakis(trifluoromethyl)-bismuthate

Tris(trifluoromethyl)bismuth reacts with flourides ions and intermediately generated trifluormethyl anions to form the first representatives of hithero unknow fluroalkylbismuthates: tris(trifluromethyl)fluoro- and tetrakis(trifluoromethyl)-bismuthates.