Sergej Pasenok

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.

Carbenoid reactions of trifluoromethylelement compounds. Part 4. Reactions of trifluoromethylzinc bromide with enamines and methylene bases

Abstract The reactions of ZnBr(CF 3 )·2CH 3 CN with 1-morpholinocyclo-pentene and -hexene have been investigated and found to yield mixtures of two isomers of 1-morpholino-1-cyanomethyl-2-difluoromethyl-cyclopentane and -hexane, respectively. The interaction with methylene bases of nitrogen heterocycles leads to the formation of trimethinecyanine dyes. This reaction sequence includes the formation of two carbon-carbon bonds in a one-pot operation. The mechanism of the reactions is discussed.

The Reactions of Zn(CF3)Br · 2 CH3CN with Phenol, Pentafluorophenol, their Potassium and Ammonium Salts

Triphenoxymethane, tris(pentafluorophenoxy)methane, phenyl(difluoromethyl)ethers, and tetrakis(pentafluorophenoxy)ethene were prepared via carbenoid reactions of Zn(CF3)Br · 2 CH3CN and the corresponding phenol or the potassium or ammonium salts in the presence of the auxiliary acid BF3 · O(CH3)2. The products were identified by their melting and boiling points and in part by their NMR and mass spectra as well as elemental analysis. Carbenoide Reaktionen von Trifluormethylelement-Verbindungen. 3. Die Reaktionen von Zn(CF3)Br · 2 CH3CN mit Phenol, Pentafluorphenol, deren Kalium- und Ammoniumsalzen. Triphenoxymethan, Tris(pentafluorphenoxy)methan, Phenyl(difluormethyl)ether und Tetrakis(pentafluorphenoxy)ethen wurden durch carbenoide Reaktionen von Zn(CF3)Br · 2 CH3CN mit den entsprechenden Phenolen oder deren Kalium- bzw. Ammoniumsalzen in Gegenwart von BF3 · O(CH3)2 dargestellt. Die Produkte wurden anhand ihrer Schmelz- und Siedepunkte, teilweise durch ihre NMR- und Massenspektren sowie durch Elementaranalysen identifiziert.

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 of bismuthio methanides containing the RfSO2 group, (C6H5)3Bi=C(SO2Rf)2 [Rf=CF3, n-C4F9, OCH2CF2CF2H]

Abstract Bismuthio methanides (C 6 H 5 ) 3 Bi=C(SO 2 R f ) 2 (R f =CF 3 , n-C 4 F 9 , OCH 2 CF 2 CF 2 H) can be obtained as colourless solids from the sodium derivatives of the corresponding methanes with (C 6 H 5 ) 3 BiCl 2 in c. 90% yield. The compounds have been characterized by NMR spectroscopy and elemental analysis. From the NMR spectra, zwitterionic canonical structures containing Bi + −C − or Bi + −C=S−O − units may be assumed.

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.

Utilisation of ammonium and phosphonium perfluorocyclobutane ylides as fluoride anion source

Ammonium- and phosphoniumperfluorocyclobutane ylides 1 and 2, prepared from perfluorocyclobutene and tertiary amines or phosphines can be used as a masked fluoride anion source. These properties have been demonstrated in several reactions. Ylides 1 and 2 cleave C-Si or O-Si bonds, cause dimerisation of fluoroolefins or react with acid chlorides or activated aromatic compounds under halogen exchange.

New method of preparation of fluoro compounds via utilisation of ammonium and phosphonium perfluorocyclobutane ylides as fluorination reagents

Ammonium- and phosphoniumperfluorocyclobutane ylides (7–11), easily prepared from perfluorocyclobutene (1) and tertiary amines (2–4) or phosphines (5,6), smoothly react with primary or secondary alcohols (12–18) and carboxylic acids (19,20) with formation of alkyl fluorides (21–26) or acyl fluorides (27,28), respectively. A mechanism for the reaction is proposed.

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.

Diphenyl(trifluoromethyl)bismuth and phenylbis(trifluoromethyl)bismuth—new organoperfluoroalkyl derivatives of tervalent bismuth

Abstract Diphenyl(trifluoromethyl)bismuth and phenylbis(trifluoromethyl)bismuth have been synthesized from Cd(Cf 3 ) 2 2CH 3 CN and the corresponding phenylbismuth halides. The reactions of the new compounds are similar to those of tris(perfluoroorgano)bismuth compounds and mixed phenyl-akyl bismuth derivatives.