Zur Kenntnis der Sulfensäurefluoride CF3SF und CF2ClSF sowie deren Dimeren

The Sulfenic Fluorides CF₃SF and CF₂CISF and their Dimers The reactions of R_fSCl (R_f = CF₃, CF₂Cl) with HgF₂ and AgF give R_fSF and the dimer product R_fSF₂SR_f in high yield and various ratios, in contrast, activated KF leads only to R_fSF in low yield. A complex of transition metal and sulfenic halide as an intermediate step is discussed for the dimerisation. As liquid CF₃SF₂SCF₃ disproportionates into CF₃SF₃ and CF₃SSCF₃ and the hydrolysis of CF₃SF₂SCF₃ gives the stable compound CF₃S(O)SCF₃ · PF₃ reacts with R_fSF as well as with R_fSF₂SR_f to R_fSPF₄. The products of the spontaneous decomposition of CF₂ClSF were investigated. I.r., n.m.r., and mass spectra are reported and discussed. It was possible to carry out vapour pressure measurements of CF₂ClSF.     

Über die Umsetzung von NN-Dihalogenperfluoralkanaminen mit Schwefel und Schwefelderivaten

Reactions of NN-Dihaloperfluoroalkaneamines with Sulfur and Sulfur Derivatives Reactions of NN-Dihaloperfluoroalkaneamines R_fNX₂ (R_f = CF₃, C₂F₅; X = Cl, Br) with S₈, S₄N₄ and A = SX₂ (A = R_fN, O) are described. The products isolated are: Sulfurdihalideimides R_fNSX₂ (R_f = CF₃, C₂F₅; X = Cl, Br), Sulfurdiimides R_fNSNR_f and Bis(sulfurdiimido)sulfides (R_fNSN)₂S(R_f = CF₃, C₂F₅). Thionylimides R_fNSO were not obtained in preparative quantities.     

Metal complexes of fluorophosphines : III. Some oxidative addition reactions of a rhodiumtrifluorophosphine complex

Some oxidative addition reactions of (CH₃)₅C₅Rh(PF₃)₂ with various iodine compounds are described. Iodine reacts with (CH₃)₅C₅Rh(PF₃)₂ in benzene at room temperature to give the deep red crystalline diiodide (CH₃)₅C₅Rh(PF₃)I₂. The perfluoroalkyl iodides R_fI (R_f = CF₃, C₂F₅, n-C₃F₇, and n-C₇F₁₅) react with (CH₃)₅C₅Rh(PF₃)₂ in benzene at room temperature to give the orange to deep red (CH₃)₅C₅Rh(PF₃)(R_f)I (R_f = CF₃, C₂F₅, n-C₃F₇, and n-C₇F_l5). The IR and proton and fluorine NMR spectra of these new (pentamethylcyclopentadienyl)rhodium-trifluorophosphine complexes are discussed.     

Synthesen und Eigenschaften von Tetrakis(perfluoralkyl)tellur Te(Rf)4 (Rf = CF3, C2F5, C2F5, C3F7, C4F9)

Synthesis and Properties of Tetrakis(Perfluoroalkyl)Tellurium Te(R_f)₄ (R_f = CF₃, C₂F₅, C₃F₇, C₄F₉) Te(CF₃)₄ is obtained from the reaction of Te(CF₃)Cl₂ with Cd(CF₃)₂ complexes as a complex with e. g. CH₃CN, DMF. It is a light and temperature sensitive hydrolysable liquid. The reaction with fluorides yields the complex anion [Te(CF₃)₄F]⁻, with fluoride ion acceptors the complex cation [Te(CF₃)₃]⁺. With traces of water an acidic solution is formed. Te(CF₃)₄ acts as a trifluoromethylation reagent. The reaction with XeF₂ gives hints for the formation of Ye(CF₃)₄F₂. Properties and NMR spectra are discussed. The much more stable complexes of Te(R_f)₄ (R_f = C₂F₅, C₃F₇, C₄F₉) are formed from the reaction of TeCl₄ with the corresponding Cd(R_f)₂ complexes.     

Solvents effects in reactions between perfluoroalkyliodides and cadmium

The interaction between perfluoroorgano iodides (R_fI where R_f = F(CF₃)₂C(CF₂CF₂)₃, n-C₆F₁₃,n-C₈F₁₇, F(CF₃)₂COCF₂CF₂,F(CF₃)₂CO(CF₂CF₂)₄ andC₂H₅OC(O)(CF₂CF₂) with cadmium in an acetonitrilesolvent media produces primarily the coupled products (R_fR_f,72–90% yield) in addition to minor quantities of the reduction products (R_fH). On the other hand ICF₂CF₂I and C1CF₂CFC1I, by a 1,2-dehalogenation reaction, form the olefins CF₂ = CF₂ and CF₂ = CFC1, respectively, as the principal products. The interaction of R_fI compounds with cadmium in other solvent media, e.g. diethyl ether. tetrahydrofuran (THF), N,N-dimethylformamide (DMF), and bis(2-methoxyethyl)ether(diglyme) were examined and found to produce a different ratio of R_fR_f and R_fH products. {ft*}Present address: Fluidics Inc., P.O.Box 1886, Dayton, OH 45429 U.S.A.     

Perfluororganocadmium-verbindungen als sehr wirksame perfluoralkylierungs- und perfluorphenylierungsmittel zur darstellung von perfluororganozinn- und -blei-verbindungen [1]

Perfluoroorgano tin and lead compounds can be prepared in high yields from the reactions of (CH₃)₃SnOCOCF₃ and (CH₃)₃Pb(OCOCF₃) with perfluoroorgano cadmium complexes. (CH₃)₃SiOCOCF₃ reacts with (CF₃)₂Cd complexes — probably via the intermediate (CH₃)₃SiCF₃ and CF₂ elimination — to form (CH₃)₃SiF and CF₃CdOCOCF₃ complexes. While the reaction of (CF₃)₂Cd·D with (CH₃)₃SnONO₂ yields CF₃NO as the only volatile product, (R_f)₂Cd·D (R_f  C₂F₅, iC₃F₇) forms R_fCdONO₂·D and (CH₃)₃SnR_f. The preparations and properties of the partly new compounds as well as the n.m.r. spectra are described.     

Synthesis of fluorine-containing symmetrical N,N-alkylidene bisamides

Fluorine-containing N,N-alkylidene bisamides RCH(NHCOR_f)₂ (R: H, Aryl; R_f: CF₃, CF₂Cl, 2,6-C₆H₃F₂) are conveniently prepared in good yields by the reaction of corresponding aldehydes with fluorine-containing amides (R_fCONH₂) in the presence of fluoroalkanesulfonic acids R_f′SO₃H(R_f′: CF₃, HCF₂CF₂, ICF₂CF₂OCF₂CF₂).     

Novel ammonium hexafluoroarsenate salts from reaction of (CF3)2NH,CF3N(OCF3)H,CF3N[OCF(CF3)2]H,CF3NHF and SF5NHF with the strong acid HF/ASF5.

Reactions of the fluorinated amines (CF₃)₂NH, CF₃N(OCF₃)H, CF₃N[OCF(CF₃)₂]H, CF₃NHF and SF₅NHF with the strong acid HF/AsF₅ form the corresponding ammonium salts R_f¹R_f²NH₂⁺AsF₆^? and R_fNFH₂⁺ AsF₆^? in high yield. [R_f¹=CF₃, R_f²=CF₃, CF₃O, (CF₃)₂CFO; R_f=CF₃, SF₅] The colorless crystalline solids are stable for prolonged periods at 22°C in sealed FEP containers. They have dissociation pressures at 22°C ranging from ～5 torr (R_fNFH₂⁺ AsF₆^?) to ～50 torr [CF₃N(OCF₃)H₂⁺AsF₆^?]. ¹⁹F NMR and Raman spectroscopy were used to identify the compounds.     

Some fluorinated heterocyclic and acyclic derivatives of chlorocarbonylsulfenyl chloride

For the first time, fluorinated oxathialones, polyfluoroalkylchlorothioformates, chlorocarbonylpolyfluoroalkylsulfenate esters, a chlorocarbonylhexafluoroisopropylidenimino sulfenate, and a 5-tri-fluoromethyl-2-oxo-1,3,4-oxathiazole were synthesized by reacting chlorocarbonylsulfenyl chloride with R_fC(O)CH₂C(O)R′ (R_f = CF₃; R'= CF₃, OC₂H₅), R_fO^-Li⁺ (R_f = CF₃CH₂, (CF₃)₂C=N^-Li⁺ and CF₃C(O)NH₂. Perfluorosuccinic acid and mercury(II) trifluoroacetate with ClC(O)SCI gave their respective anhydrides.     

The reaction of perfluoro-2,4-dialkyloxolanes with anhydrous aluminum chloride

Several kinds of perfluoro-2,4-dialkyloxolanes (A), having such alkyl groups as R_fR′_fCF₃ (2a); R_fC₂F₅, R′_fCF₃ (3a); R_fCF₃, R′_fC₂F₅ (4a); R_fR′_fC₂F₅ (5a); R_fCF₃, R′_fnC₃F₇ (6a) on the 2 and 4 positions of the oxolane ring, respectively, were treated with AlCl₃ in a heterogeneous reaction to give the corresponding perfluoro-2,5,5-trichloro-2,4-dialkyloxolanes (B). For purposes of comparison, the respective reactions of perfluoro-2-methyl-oxolane (la), perfluoro-2-n-butyloxolane (7a), and perfluoro-2, 5-dimethyloxolane (8a) with AlCl₃ were also conducted. An increasingly higher reaction temperature was needed for the reaction of A with AlCl₃ to give B as the carbon number of A increased. Cis- and trans-perfluoro-4-chloro-2,4-dimethyl-γ-butyrolactones (2c) were obtained from the hydrolytic reactions of cis- and trans-perfluoro-2,5,5-trichloro-2,4-dimethyloxolanes (2b), respectively, with fuming H₂SO₄. Physical properties and ¹⁹F nmr data are given for these new compounds.     

Fluorination of perfluoroalkylsulfenyl chlorides,perfluorodialkyl disulfides and perfluorodialkyl sulfides with chlorine monofluoride

In reactions with perfluoroalkylsulfenyl chlorides (R_fSCl; R_f = F₃, C₂F₅, n-C₃F₇, n-C₄F₉) and perfluoroalkyl disulfides (R_fSSR_f′; R_f = R_f′ = CF₃, R_f = CF₃, R_f′ = C₂F₅) at 25°, chlorine monofluoride acts primarily as a chlorinating and fluorinating reagent to give the corresponding perfluoroalkylsulfur chloride tetrafluorides, R_fSF₄Cl, in good yields. However, small amounts of perfluoroalkylsulfur pentafluorides, R_fSF₅, are also obtained. A mixture of the cis and trans isomers of bis(trifluoromethyl)sulfur tetrafluoride and of trifluoromethyl pentafluoroethylsulfur tetrafluoride has been formed by the reaction of the corresponding bis(perfluoroalkyl) sulfides and chlorine monofluoride. The new perfluoroalkylsulfur chloride tetrafluorides are colorless, unpleasant smelling liquids. The infrared, mass and ¹⁹F NMR spectral data, as well as thermodynamic and elementary analysis data, are given for the new compounds.     

Fluoroalcohols as solvents for aliphatic polyamides

Some fluoroalcohols have been prepared by free-radical addition of methanol, ethanol and isopropanol to fluoroolefins as C₃F₆, CFHCFCF₃, (CF₃)₂CFCFCFCF₃, H(CF₂)₄CFCF₂, The general reaction is (1) R_fCFCF₂ + RR′CHOH = R_fCFHCF₂CRR′OH where R_f is a fluoroalkyl group, R and R′ are H or CH₃. NMR data of these alcohols are reported. 2,2,3,4,4,4-hexafluorobutanol (HFB) shows the best solvent ability among the compounds of this class. Its properties and solvent power have been evaluated and compared to the ones of trifluoroethanol (TFE) and hexafluoroisopropanol (HFIP). Some toxicological data related to HFB, TFE and HFIP are also reported.Owing to their strong tendency to form hydrogen bonds, fluoroalcohols are excellent solvents for polymeric materials which possess receptive sites for hydrogen bonding formation. The bonding power of the OH has been investigated by IR and NMR Spectroscopy on amide-group containing substrates. The properties and the correlations observed have pointed out that HFB may be usefully used as solvent for some aliphatic polyamides as Nylon 6.The polymer-solvent system Nylon 6-HFB has been studied and the constants of Mark-Houwink equation determined.     

Efficient Cu‐catalyzed Atom Transfer Radical Addition Reactions of Fluoroalkylsulfonyl Chlorides with Electron‐deficient Alkenes Induced by Visible Light

Fluoroalkylsulfonyl chlorides, R_fSO₂Cl, in which R_f=CF₃, C₄F₉, CF₂H, CH₂F, and CH₂CF₃, are used as a source of fluorinated radicals to add fluoroalkyl groups to electron‐deficient, unsaturated carbonyl compounds. Photochemical conditions, using Cu mediation, are used to produce the respective α‐chloro‐β‐fluoroalkylcarbonyl products in excellent yields through an atom transfer radical addition (ATRA) process. Facile nucleophilic replacement of the α‐chloro substituent is shown to lead to further diverse functionalization of the products.     

Action des perfluoroalkylcuivre(I) sur les perfluoroalkylethylenes

A series of new polyfluorinated dienes 3, containing the novel -CFCHCHCF-, pattern has been synthesized (50–70% yields) by reacting perfluoroalkyl iodides with perfluoroalkyl-ethylenes in the presence of copper. The monoalkenes R_fCFCHCH₂CF₂R′_f and the saturated compounds R_fCF₂CH₂CH₂CF₂R′_f were obtained by varying the experimental conditions. The ¹H and ¹⁹F NMR spectra are analysed and the reaction mechanism is discussed.     

Aromatic compounds with new fluorine-containing substituents

The introduction of strong electron-accepting fluorine-containing substituents into the aromatic moiety gives compounds with unique properties. Determination of the electronic nature of the grouping (R_f)₂PO in arylbis(perfluoroalkyl)-phosphine oxides has shown that this substituent is comparable with R_fSO₂, one of the most electron-accepting groups.A general principle is proposed for the construction of the new superstrong electron-accepting substituents by the replacement of oxygen atoms for trifluoromethylsulfonylimino groups. For example, when the oxygen atoms in CF₃SO and CF₃SO₂ groups are replaced by CF₃SO₂N=, new stable and even more electron-accepting substituents are formed. The grouping CF₃S(O)=NSO₂CF₃ corresponds to two nitro groups. A similar increase in electron-accepting ability is observed in groupings derived from other elements by replacement of oxygen atoms by the CF₃SO₂N= group.     

Unexpected formation of N-fluoroalkaneacyl anilides from the reactions of fluoroalkanesulfonyl azides with nitrobenzene and its derivatives

The thermal reactions of fluoroalkanesulfonyl azides R_fCF₂SO₂N₃1 with nitrobenzene and its derivatives XC₆H₄NO₂ (X=H, F, Cl, CF₃) gave the unexpected N-fluoroalkaneacyl anilides R_fCONHC₆H₄X (X=H, Cl, F, CF₃) in addition to fluoroalkanesulfonyl amides R_fCF₂SO₂NH₂. Under the same reaction conditions, however, nitrobenzene containing an electron-donating group RC₆H₄NO₂ (R=CH₃, OCH₃) reacted with 1 affording the corresponding N-fluoroalkanesulfonyl anilides R_fCF₂SO₂NHC₆H₃(NO₂)R. Other electron-poor benzene derivatives, such as benzaldehyde, benzoate, and acetophenone C₆H₅Y(Y=CHO, COCH₃, CO₂CH₃) all gave the meta-substituted N-fluoroalkanesulfonyl anilides R_fCF₂SO₂NHC₆H₄Y.     

Zur Bildung und Stabilität von Difluormethylenphosphoranen,R3P⊕-C̄–F2

Inhaltsübersicht. Die Reaktion von Difluorhalogenmethanen, CF₂X₂, mit Phosphanen, R₃P, in Gegenwart von Metallen und Carbonylverbindungen, R″R′CO, führt zur Bildung geminaler Difluorolefine, R″R′C=CF₂. Die sorgfältige Untersuchung der Einzelschritte dieser komplexen Reaktion zeigt, daß intermediär Difluorhalogenmethylphosphoniumhalogenide, [R₃P–CF₂X]X, und Difluormethylenphosphorane, R₃P^⊕ – c?^?-F₂, gebildet werden. Die Phosphoniumsalze sind stabil und können als kristalline Substanzen isoliert werden. Durch Metalle oder Phosphene werden sie zu den instabilen Difluormethylenphosphoranen reduziert. Diese zersetzen sich beim Fehlen geeigneter Reaktionspartner in Phosphan und Difluorcarben, CF₂. Ihre Bildung durch Addition von CF₂ an R₃P ist nicht möglich. Mit Halogenwasserstoffen bilden sie Difluormethylphosphoniumsalze, [R₃P-CHF₂]X. Formation and Stability of Difluoromcthylene Phosphoranes, R₃P^⊕ —c?F₂ In the presence of metals and carbonyl compounds, R″R′CO, the reaction of difluoro-halomethanes, CF₂X₂, with phosphanes, R₃P, leads to the formation of geminal difluoroolefins, R″R′C=CF₂. Our investigations have proved that difluorohalomethylphosphonium halides, [R₃P–CF₂X]X, and difluoromethylene phosphoranes, R₃P^⊕–C??F₂, are formed intermediately. The phosphonium salts are stable. They can be isolated as crystalline substances. They are reduced by metals or phosphanes forming unstable difluoromethylene phosphoranes as intermediates. These decompose into phosphane and difluorocarbene, CF₂, if suitable reactants are absent. Their reaction with hydrogen halides, HX, yields difluoromethylphosphonium salts, [R₃P–CHF₂]X. The formation of difluoromethylene phosphoranes by addition of CF₂ to R₃P is not possible.     

2-Hydroperfluoropropyl azide—a versatile reagent for the oxidative fluorination of organic compounds of trivalent phosphorus

2-Hydroperfluoropropyl azide CF₃CHFCF₂N₃, 1 , an inexpensive, readily available, and stable (easy to store) compound, is suggested as an effective fluorinating reagent for different classes of trivalent organophosphorus compounds in accordance with the general scheme R₃P → R₃PF₂. Generally, the reactions are performed without solvent, the highly volatile CF₃ CHFCN being the main by-product. The fluorination is usually an exothermic process, but slight heating is necessary in the case of alkyldifluorophosphites. The unusual Arbuzov rearrangement, accompanied by isomerization of an isobutyl or neopentyl group into a tert-group, ROPF₂ → t-R′POF₂, under the action of a catalytic amount of 1 , was observed.     

Studies on fluoroalkylation and fluoroalkoxylation: 2. Perfluoroalkylation of aromatics with perfluoroalkyl iodides in the presence of copper

Perfluoroalkyl iodide R_fI [R_f = (CF₂)_nO(CF₂)₂SO₂F, n = 2, (a); n = 4, (b); (CF₂)₄Cl, (c)] reacted with substituted benzene C₆H₅Y (Y = alkyl, OCH₃, CF₃, F, Cl, Br, I) in the presence of copper in acetic anhydride to give the corresponding mixture of isomeric disubstituted benzene (R_fC₆H₄Y). The conversion and yield depend on both the amount of copper used and nature of substituent. The likely explanation is that the reaction may involve a free radical process. The perfluoroalkyl radical can be trapped by cyclohexene, isopropylbenzene and styrene. Using DMSO in place of acetic anhydride as a solvent the reaction takes a different course, it is believed that the reaction in DMSO proceeds through a perfluoroalkylcopper intermediate.     

Synthese und Eigenschaften von Diethyldithiocarbaminsäureperfluororganylestern, (C2H5)2NC(S)SRf (Rf = CF3, C2F5, i‐C3F7, n‐C4F9, C6F5)

Syntheses and Properties of Perfluoroorgano Esters of the Diethyldithiocarbamic Acid, (C₂H₅)₂NC(S)SR_f (R_f = CF₃, C₂F₅, i‐C₃F₇, n‐C₄F₉, C₆F₅) Tetraethylthiuram disulfide reacts under different conditions with perfluoroorgano silver(I), AgR_f, and perfluoroorgano cadmium compounds, Cd(R_f)₂, to give the corresponding perfluoroorgano esters of diethyldithiocarbamic acid, (C₂H₅)₂NC(S)SR_f (R_f = CF₃, C₂F₅, i‐C₃F₇, n‐C₄F₉, C₆F₅), and metal diethyldithiocarbamates, AgSC(S)N(C₂H₅)₂ and Cd[SC(S)N(C₂H₅)₂]₂. The mechanisms of the reactions with AgR_f and Cd(R_f)₂ are discussed.