A Convenient Route to Tetraalkylammonium Perfluoroalkoxides from Hydrofluoroethers

Hydrofluoroethers are shown to alkylate tertiary amines readily under solvent‐free conditions, affording valuable tetraalkylammonium perfluoroalkoxides bearing α‐fluorines. The reaction of R_FCF₂? OCH₃ (R_F=CF₂CF₃, CF₂CF₂CF₃, and CF(CF₃)₂) with NR¹R²R³ produces twenty new α‐perfluoroalkoxides, [(CH₃)NR¹R²R³][R_FCF₂O] under mild conditions. These α‐perfluoroalkoxides are easy to handle, thermally stable, and can be used for the perfluoroalkoxylation of benzyl bromides.     

Ethylene/α‐olefin copolymerization with bis(β‐enaminoketonato) titanium complexes activated with modified methylaluminoxane

Copolymerizations of ethylene with α‐olefins (i.e., 1‐hexene, 1‐octene, allylbenzene, and 4‐phenyl‐1‐butene) using the bis(β‐enaminoketonato) titanium complexes [(Ph)NC(R₂)CHC(R₁)O]₂TiCl₂ ( 1a : R₁ = CF₃, R₂ = CH₃; 1b : R₁ = Ph, R₂ = CF₃; and 1c : R₁ = t‐Bu, R₂ = CF₃), activated with modified methylaluminoxane as a cocatalyst, have been investigated. The catalyst activity, comonomer incorporation, and molecular weight, and molecular weight distribution of the polymers produced can be controlled over a wide range by the variation of the catalyst structure, α‐olefin, and reaction parameters such as the comonomer feed concentration. The substituents R₁ and R₂ of the ligands affect considerably both the catalyst activity and comonomer incorporation. Precatalyst 1a exhibits high catalytic activity and produces high‐molecular‐weight copolymers with high α‐olefin insertion. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 6323–6330, 2005     

Metallkomplexe mit biologisch wichtigen Liganden. CLVII [1] Halbsandwich‐Komplexe mit Isocyanoacetylaminosäureestern und Isocyanoacetyldi‐ und tripeptidestern („Isocyano‐Peptide”︁)

Metal Complexes of Biologically Important Ligands, CLVII [1] Halfsandwich Complexes of Isocyanoacetylamino acid esters and of Isocyanoacetyldi‐ and tripeptide esters (?Isocyanopeptides”?) N‐Isocyanoacetyl‐amino acid esters CNCH₂C(O) NHCH(R)CO₂CH₃ (R = CH₃, CH(CH₃)₂, CH₂CH(CH₃)₂, CH₂C₆H₅) and N‐isocyanoacetyl‐di‐ and tripeptide esters CNCH₂C(O)NHCH(R¹)C(O)NHCH(R²)CO₂C₂H₅ and CNCH₂C(O)NHCH(R¹)C(O)NHCH (R²)C(O)NHCH(R³)CO₂CH₃ (R¹ = R² = R³ = CH₂C₆H₅, R² = H, CH₂C₆H₅) are available by condensation of potassium isocyanoacetate with amino acid esters or peptide esters. These isocyanides form with chloro‐bridged complexes [(arene)M(Cl)(μ‐Cl)]₂ (arene = Cp*, p‐cymene, M = Ir, Rh, Ru) in the presence of Ag[BF₄] or Ag[CF₃SO₃] the cationic halfsandwich complexes [(arene)M(isocyanide)₃]⁺X^? (X = BF₄, CF₃SO₃).     

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.     

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.     

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.     

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.     

Surface properties and structure of organofluorosilicon polymers based on organotrialkoxysilanes R<Superscript>F</Superscript>OCH<Subscript>2</Subscript>Si(OR<Superscript>F</Superscript>)<Subscript>3</Subscript>

The hydrolysis of trifunctional alkoxysilanes R^FOCH₂ Si(OR^F)₃, where R^F = CH₂CF₃, CH₂CF₂CF₃, CH₂CF₂CF₂CF₃, or CH₂CF₂CF₂CF₂CF₃, during the action of atmospheric moisture in the presence of 3-aminopropyltriethoxysilane under mild conditions yields new ladderlike polysiloxanes. Their structure is studied via ¹H NMR spectroscopy, GPC, TGA, and AFM. Polymer coatings prepared on their basis are found to be low-energy and hydrophobic. The total surface energy and polarity of the surface of polysiloxane films decrease, while their hydrophobicity increases with lengthening of the fluoroorganic substituent at the silicon atom.     

Ein Neuer Syntheseweg für Perfluororganomangan- und -rhenium-Verbindungen

A New Synthesis of Perfluoroorgano Manganese and Rhenium Compounds Pentacarbonyl perfluoroorgano manganese and rhenium compounds M(CO)₅R_f (M = Mn, Re; R_f = CF₃, C₂F₅, C₃F₇, C₄F₉, C₆F₁₃, C₆F₅) are formed as colourless solids or liquids in good yields from the reactions of M(CO)₅Br with Cd(R_f)₂ complexes in CH₂Cl₂ either in the presence of stoichiometric amounts of Ag[BF₄] or catalytic amounts of CuI. In the presence of e. g. CH₃CN the mono or disubstituted complexes M(CO)₄(CH₃CN)R_f or M(CO)₃(CH₃CN)₂R_f are formed.     

Atmospheric pressure deposition of F‐doped SnO2 thin films from organotin fluoroalkoxide precursors

Five tributyltin fluoroalkoxides Bu₃SnOR_f [R_f = CH(CF₃)₂ ( 1 ), CH₂CF₃ ( 2 ), CH₂C₂F₅ ( 3 ), CH₂(CF₂)₃CF₂H ( 4 ), CH₂CH₂F ( 5 )] were synthesized and assessed as precursors for the APCVD of F‐doped SnO₂. O₂ is required as co‐reagent to produce hard, well‐adhered coatings. Of the precursors assessed, 5 gave the best film incorporating 1.52 atom% fluorine, showing some (200) preferred orientation, resistivity of 1.30 × 10^?3 Ω cm and 0.42% haze. Copyright © 2008 John Wiley & Sons, Ltd.     

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.     

Chemical transformation of bis((perfluoroalkyl)sulfonyl)methanes and 1,1,3,3‐tetraoxopolyfluoro‐1,3‐dithiaycloalkanes

Halogenation of the potassium or silver salts of bis((trifluoromethyl)sulfonyl)methane(CF₃SO₂)₂CH₂ and its cyclo analogues (CF₂)_nSO₂‐CH₂SO₂CF₂ with N‐fluoro‐bis((trifluoromethyl)sul‐fonyl)imine (CF₃SO₂)₂NF, chlorine or bromine gave good yields of the corresponding α‐halo disulfones (CF₃SO₂)₂CHX and (CF₂)_nSO₂CHXSO₂CF₂ (X: F, Cl, Br; n = 1,2). Some chemical transformations of these fluorinated α‐halo‐disulfones are described. © 1999 John Wiley & Sons, Inc. Heteroatom Chem 10: 147–151, 1999     

Die ersten CF3-substituierten organyl(chlor)silane

The three component reaction (Et₂N) ₃P/CF₃Br/ R_nSiCl_4-n (n = 1,2,3; RCH₃,Ph) gives CF₃-substituted organyl(chloro)silanes for the first time. Their genesis will be elucidated.     

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.     

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.     

Synthesen und NMR‐Untersuchungen von Salzen mit den neuen Anionen [PtXn(CF3)6‐n]2— (n = 0 ‐ 5, X = F,OH, Cl,CN) und die Kristallstrukturanalyse von K2[(CF3)2F2Pt(μ‐OH)2PtF2(CF3)2]·2H2O

Syntheses and NMR Spectroscopic Ivestigations of Salts containing the Novel Anions [PtX_n(CF₃)_6‐n]^2— (n = 0 ‐ 5, X = F, OH, Cl, CN) and Crystal Structure of K₂[(CF₃)₂F₂Pt(μ‐OH)₂PtF₂(CF₃)₂]·2H₂O The first syntheses of trifluoromethyl‐complexes of platinum through fluorination of cyanoplatinates are reported. The fluorination of tetracyanoplatinates(II), K₂[Pt(CN)₄], and hexacyanoplatinates(IV), K₂[Pt(CN)₆], with ClF in anhydrous HF leads after working up of the products to K₂[(CF₃)₂F₂Pt(μ‐OH)₂PtF₂(CF₃)₂]·2H₂O. The structure of the salt is determined by a X‐ray structure analysis, P2₁/c (Nr. 14), a = 11.391(2), b = 11.565(2), c = 13.391(3)Å, β = 90.32(3)°, Z = 4, R₁ = 0.0326 (I > 2σ(I)). The reaction of [Bu₄N]₂[Pt(CN)₄] with ClF in CH₂Cl₂ generates mainly cis‐[Bu₄N]₂[PtCl₂(CF₃)₄] and fac‐[Bu₄N]₂[PtCl₃(CF₃)₃], but in contrast that of [Bu₄N]₂[Pt(CN)₆] with ClF in CH₂Cl₂ results cis‐[Bu₄N]₂[PtX₂(CF₃)₄], [Bu₄N]₂[PtX(CF₃)₅] (X = F, Cl) and [Bu₄N]₂[Pt(CF₃)₆]. In the products [Bu₄N]₂[PtX_n(CF₃)_6‐n] (X = F, Cl, n = 0—3) it is possibel to exchange the fluoro‐ligands into chloro‐ and cyano‐ligands by treatment with (CH₃)₃SiCl und (CH₃)₃SiCN at 50 °C. With continuing warming the trifluoromethyl‐ligands are exchanged by chloro‐ and cyano‐ligands, while as intermediates CF₂Cl and CF₂CN ligands are formed. The identity of the new trifluoromethyl‐platinates is proved by ¹⁹⁵Pt‐ and ¹⁹F‐NMR‐spectroscopy.     

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.     

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).     

On the reactions of dimethylsulfoxide with acyl fluorides - pummerer rearrangements and formation of monofluoromethyl esters

In stoichiometry-dependent reactions, dimethylsulfoxide (DMSO) reacts with acyl fluorides, R_fC(O)F (R_f = F, CF₃), to yield CH₃SCH₂F and R_fC(O)OCH₂F, while CH₃SCH₂Cl and FC(O)OCH₂Cl are obtained with COClF. Oxalyl difluoride, C₂O₂F₂, reacts with DMSO to give CH₃SCH₂F and FCH₂OCH₂F.     

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.