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.     

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.     

Nitroxide chemistry. Part XVII [1]. Reaction of bistrifluoromethyl nitroxide with some halogenoalkanes and related alkenes

The mono (bistrifluoromethylamino-oxy)alkanes (CF₃)₂NOCXYZ (X = Y = F, Z = Cl; X = H, Y = F or Cl, Z = CH₃; X = Y = F, Z = CH₃; X = H, Y = Cl or Br, Z = CF₃; X = Cl, Y = Br, Z = CF₃) have been synthesised by treatment of appropriate halogenoalkanes, CHXYZ, with bistrifluoromethyl nitroxide. The 1,2-bis(bistrifluoromethylamino-oxy)alkanes (CF₃)₂NOCH₂CXYON(CF₃)₂ were obtained as by-products in the reactions involving the ethanes CH₃CHXY (X = H, Y = F or Cl; X = Y = F); these products, like their analogues (CF₃)₂NOCHFCF₂ON(CF₃)₂ and (CF₃)₂NOCH₂CCl₂ON(CF₃)₂, were also prepared $\text{via}$ attack of bistrifluoromethyl nitroxide on the corresponding ethenes.     

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.     

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.     

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.     

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.     

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).     

The preparation of perfluorinated carboxylic esters and perfluoro carbonates

Aliphatic perfluorinated carboxylic esters have been prepared by two methods; (i) the reaction of the potassium salt of perfluoro 3-ethyl pent-3-ol, KOC(C₂F₅)₃, with perfluoro acid chlorides R_fCOCl, to yield perfluorinated esters of composition R_fCOOC(C₂F₅)₃, and (ii) the reaction of carbonyl chloride or thionyl chloride with a mixture of the potassium salt KOC(C₂F₅)₃ and perfluoro acid salts of the general formula KOCOR_f in a polar solvent. The product ester has the composition R_fCOOC(C₂F₅)₃, and in this instance carbon dioxide or sulphur dioxide is liberated during the reaction. A qualitative study of the thermal decomposition of a perfluoro ester has been made.A tertiary perfluoro carbonate of composition [(C₂F₅)₂CF₃CO]₂CO has been prepared by the reaction of phosgene with the potassium salt KOC(C₂F₅)₂CF₃ in a polar solvent. The intermediate acid chloride (C₂F₅)₂CF₃COCOCl can be isolated.     

Studies on fluoroalkylation and fluoroalkoxylation: 8. Palladium(0)-catalyzed addition reaction of fluoroalkyl iodides with alkynes

Fluoroalkyl iodide R_fI [R_F=(CF₂)_nCl, n=2, 4, 6; CF₃(CF₂)_n, n=1, 3; H(CF₂)₄] reacted with alkyne (CH≡CC₄H₉; CH≡CSiMe₃; CH≡CC₆H₅) in the presence of catalytic amounts of tetrakis (triphenylphosphine) palladium (0) to give a mixture of E and Z-fluoroalkylated adduct. The reaction could not be catalyzed by dichloro-bis(triphenylphosphine)palladium (II) and fluoroalkyl complex of palladium (II). 2-Nitro-2-nitrosopropane partly suppressed the reaction. It is believed that the reaction proceeds through a free radical intermediate rather than fluoroalkyl complex of palladium (II).     

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.     

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.     

Mass spectra of perfluoroalkyl and perfluoroalkylether nitriles and acyl halides

Electron impact fragmentation patterns were obtained for perfluoroalkylether nitriles, C,F,O[CF(CF₃)CFIO]ICF(CF₃)CN (x = 1 and 2), perfluoroalkylether acyl halides, CSF,OCF(CF,)-CF₂OCF(CF₃)COX (X = F and Cl), n-perfluorooctanonitrile and n-perfiuorooctanoyl chloride. The perfluoroalkyl and perfluoroalkylether nitriles afforded ions characteristic of the nitrile function. The major fragment from the acyl chlorides was the [COClJ]+ ion; the presence of chlorine was evidenced also by rearrangement ions of the general form [R_fCl] t. The perfluoroalkylether compounds appeared to undergo a typical fragmentation governed by the cleavage of the carbon-oxygen bond.     

Reaktionen von Sulfensäurefluoriden: Synthese,Charakterisierung und NMR-Studien von Perhalogenalkylmercaptotetrafluorphosphoranen

Reactions of Sulfenic Fluorides: Synthesis, Characterization and N.M.R. Studies of Perhalogenalkylmercaptotetrafluorphosphoranes Marcaptotetrafluorophosphoranes R_fSPF₄ (R_f = CF₃, CF₂Cl) are obtained by the reaction of sulfenic fluorides R_fSF with PF₃. The compounds formed are extremely sensitive to hydrolysis. They react with H₂O yielding R_fSH, HF and POF₃ as well as with an excess of R_fSF to give PF₅ and R_fSSR_f. NMR studies were performed at various temperatures.     

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.     

Reactions of tetralouroethene oligomers Part 6. Some reactions of 4-diazo-1,1,1,2,2-pentaflouro-3-pentaflouethyl-3-triflouromethylbutane

The isocyanate R_fCH₂NCO (R_f=CF₃(C₂F₅)₂C)reacts under strongly acidic conditions to form the salt R_fCH₂NH₃⁽⁺⁾HSO₄⁽⁻⁾(1) which yields, on treatment with sodium nitrite the diazaoalkane R_fCHN₂ (3). Dissolution of (1) in D.M.S.O. gives, by a remarkable decomposition reaction, the alkane R_fH (2). Reaction of (3) with excess sodium nitrite affords the isocyanate R_fNCO (4) which is stable to water,but which reacts with ammia to give the urea R_fNHCONH₂ (5); this latter was not readily hydrolysed .Photolysis of (3) yields the diazadiene R_fCHNNCH R_f (7). Thermolysis of (3) alone afforded the diazadiene (7), but reaction in the presence of copper (II) perchlorate afforded (7) and the aldehyde R_fCHO (6)     

Free radical addition of cyclopentane and cyclohexane to halogeno derivatives of 1,2-difluoroethene

Free radical addition reactions between cyclopentane and cyclohexane and a range of difluoroalkenes, CF₂CXY (X, Y = H, F, Cl, Br) gave a series of adducts bearing difluoromethylene substituents, R-CF₂-CXYH (R = c-C₅H₉ or c-C₆H₁₁), in reasonable yield even though telomerisation and halogen transfer (when X, Y = Cl, Br) can compete. Dehydrofluorination of the adducts gave several new polyhalogenated alkenes.     

Fluorohalogeno compounds. II. Sonochemical approach to 3,3,3-trifluoropropionic acids

Fluoropropionic acids of the general formula CF₃CXYCO₂H ( X = F, Cl, Br ; Y = F, Cl, Br, H ) were obtained by the sonochemically promoted reaction of fluorohalogenoethanes CF₃CXYZ ( Z = Cl, Br ) with zinc and carbon dioxide. Penta- and tetrafluoroethanes ( X = Y = F and X = F, respectively ) gave good yields ( 35 – 47 % ) of the acids; with trifluoro derivatives the yields were substantially lower. Hydrogenolysis of the CCl and CBr bonds in CF₃CFClCO₂H and CF₃CFBrCO₂H afforded 2,3,3,3-tetrafluoropropionic acid.     

Alkoxy,amido and thiolato complexes of tris (3, 5-dimethylpyrazolyl)borato(nitrosyl) molybdenum fluoride,chloride and bromide

The complexes Mo{HB(Me₂pyz)₃}(NO)XY {HB(Me₂pyz)₃  HB(3, 5-Me₂C₃HN₂)₃; X=Y=F, Cl or Br; X=F, Y=OEt, NHMe or SBuⁿ; X=Cl, Y=NHR (R=Me Et, Buⁿ, Ph, p-MeC₆H₄), NMe₂ and SR (R=Buⁿ, C₆H₁₁, CH₂Ph, Ph); X=Br, Y=NHMe, NMe₂ and SBuⁿ} have been prepared and characterised spectroscopically. Their properties are generally similar to those of their iodo-analogues.