Yu.L. Yagupolskii

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)Bru200a·u200a2u200aCH3CN, Cd(CF3)2u200a·u200a2u200aCH3CN 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)Bru200a·u200a2u200aCH3CN 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. n n n nCarbenoide Reaktionen von Trifluormethylelement-Verbindungen. 5. Difluormethylierungen von Aminen mit Zn(CF3)Bru200a·u200a2u200aCH3CN, Cd(CF3)2u200a·u200a2u200aCH3CN und dem System Bi(CF3)3/AlCl3 n n n nDie Reaktionen von Zn(CF3)Bru200a·u200a2u200aCH3CN, Cd(CF3)2u200a·u200a2u200aCH3CN 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)Bru200a·u200a2u200aCH3CN 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.

Phenylbis(fluorosulfonyl)- and phenylbis(trifluoromethylsulfonyl)-methyliodonium triflates

Abstract Phenyliodonium bis(fluorosulfonyl)methylide ( I ) and phenyliodonium bis(trifluoromethylsulfonyl)methylide ( II ) are converted to triflates of phenylbis(fluorosulfonyl)- ( III ) and phenylbis(trifluoromethylsulfonyl)-methyliodonium ( IV ), respectively, by the addition of equimolar amounts of trifluoromethanesulfonic acid in CH 2 Cl 2 . The existence of these triflates has been confirmed by 19 F NMR spectroscopy. Reactions between the iodonium salts III and IV and nucleophilic reagents such as thiophenol derivatives, thiocyanates, nitrites and cyanates result in the formation of strong CH acids, i.e. trisubstituted methanes HC(SO 2 R) 2 Nu, Rue5fbF, CF 3 , formed as tetrabutylammonium salts.

Phenyl- and diphenylpolyfluoroolefin epoxides

Abstract The epoxides of α,β,β-trifluorostirene (1), α,β-difluoro-β-chlorostirene (2), 1-phenylperfluoropropene (3) and trans-α,β-difluorostilbene (4) were prepared by oxidation of corresponding ethylenes by oxygene in presence of chlorine under UV-irradiation Investigation of electronic properties of difluorochlorovinyl and difluorochloroepoxiethyl groups has shown their electron accepting nature. The interaction of (1) and (2) with water leads to the formation of phenylglyoxyl fluoride, and the heating of (4) with water gives benzil. The isomerization of (1) and (2) under the action of triethyl amine yields phenyldifluoro- and phenylfluorochloro-acetyl fluorides. Under the action of CsF compounds (1) and (2) are transformed into corresponding ketones. The heating of (4) with gives α-bromo-α-fluorobenzylketone.

Hexaethyltriaminophosphazomethane — a convenient agent for synthesis of TAP+ HF−2 and CH acids difluoromethylation

Abstract Highly basic hexaethyltriaminophosphazomethane 1 reacts easily with HF to give tetraaminophosphonium hydrogen difluoride, TAP + HF − 2 2 . High thermal stability (up to 150°C) and solubility of 2 in organic solvents make possible its application as a soft source of nucleophilic F − ion. Base 1 proved to be a convenient agent for :CF 2 generation under unhydrous conditions. For example, the difluorometylation of N -acetylaminodiethylmalonate followed by hydrolyses and decarboxylation leads to β,β-difluoroalanine in a high yield.

Phenyliodonium ylides stabilized by FSO2- and CF3SO2- groups

Abstract Phenyliodoniumbis(fluorosulfonyl)methylide 1 and phenyliodoniumbis (trifluoromethylsulfonyl)methylide 2 were obtained by the following scheme: Photochemical reaction of compound 1 with benzene catalyzed by copper (II) acethylacetonate yields phenylbis(fluorosulfonyl) methane. Organic derivatives of V and VI groups elements undergo under the same conditions re-ylidation. Some other electrophile catalyzed reactions between the ylides 1 and 2 and nucleophilic reagents have also been investigated.

Fluoro-containing oxosulfonium ylides-derivatives of alkylsulfonyl fluorides and alkylperfluoroalkylsulfones aci-form

Abstract Recent results of a systematic study of a new reaction-pyrolysis of phenyldiazonium salts stabilized by the anions of strong and superstrong CH-acids H n C(SO 2 R F ) − 3− n , R F ue5fbF, Alk F , are discussed The reaction is due to the phenyl cation attack to the O-atom of one fluoro-containing sulfonyl group of the C-anion. Chemical properties and structure peculiarities of the novel oxosulfonium ylides will be presented.

Latest trends in the introduction of fluorine-containing anions into organic molecules

Abstract Recent progress in investigations of the reactivity of the CF3SiMe3/TASF system, amido- and alkylamidophosphites to different type of electrophiles will be reported. The processes developed make it possible to introduce into organic molecules a range of fluorinated anions of a broad spectrum of nucleophilicity. The possible mechanism of the reactions, and spectral and single crystal X-ray data of the compounds obtained are discussed.