Darstellung und charakterisierung von CF2ClSF3 und CF2ClS(O)F

The fluorination of CF₂ClSCl with AgF₂ yields CF₂ClSF₃ together with CF₃SF₃ and CF₃SF₅. CF₂ClSF₃ is also formed when CF₂ClSCl reacts with BrF₃ which is adsorbed at HgF₂. CF₂ClS(O)F results from the mild hydrolysis reaction of CF₂ClSF₃ with glass walls. The new compounds were characterised by their NMR and mass spectra, CF₂ClS(O)F also by its IR spectrum. The volatilities of the compounds were derived from codistillation diagrams. - Furthermore, previously unreported mass spectra of CF₃SF₃ and CF₃SF₅ are given.     

Darstellung und Eigenschaften von Trifluormethylmercaptothiophosphoryldichlorid

Preparation and Properties of Trifluoromethylmercaptothiophosphoryldichloride The reaction of CF₃SP(O)Cl₂ with SPCl₃ leads to a CF₃S-chlorine exchange and gives CF₃SP(S)Cl₂ in 50% yield. A controlled hydrolysis of CF₃SP(O)Cl₂ affords CF₃SP(O)(OH)₂, that cannot be isolated as such, but it condenses to CF₃SP(O)(OH)O? [P(SCF₃)(O)? O]_nP(O)(OH)SCF₃. On the other hand, CF₃SP(S)Cl₂ reacts with water to yield H₃PO₄, CF₃SH, S₈, and HCl. CF₃SP(X)Cl₂ reacts with alcohols to give CF₃SP(X)(OR)₂ [R = CH₃, C₂H₅, n-C₃H₇, CH(CH₃)₂, n-C₄H₉ and for X = O, R = C₆H₅, too]. The formation of semi-esters CF₃SP(X)Cl(OR′) could be proven for X = O, R′ = CH₃, C₆H₅ and for X = S, R′ = R. While CF₃SP(O)(OC₂H₅)₂ rapidly decomposes into SCF₂ and FP(O)(OC₂H₅)₂, the other compounds and primarily CF₃SP(O)(OCH₃)₂ and CF₃SP(S)(OR)₂ ar stable. The reaction between CF₃SCl and CH₃SPCl₂ results in CF₃SCH₂SPCl₂ and that between CF₃SP(O)Cl₂ and AlCl₃ gives [CF₃SP(O)Cl]⁺[AlCl₄]^?. Physical and spectroscopical data are given for the newly formed compounds.     

Die Synthese von CF3TeTeCF3 und Reaktionen mit den Elementen Hg,Cd, Cu und Ag

The Preparation of CF₃TeTeCF₃ and Reactions with the Elements Hg, Cd, Cu, and Ag (CF₃)₂Te₂ is a main product of the photochemical reaction of (CF₃)₂Te with e.g. furan and can be separated in more than 40% yield. It quantitatively reacts with mercury and cadmium to give the new compounds (CF₃Te)₂Hg and (CF₃Te)₂Cd, respectively. With copper some CF₃? Cu compounds are formed, whereas with silver no reaction takes place.     

Konfiguration und konformation von methyl- und aminylradikalen mit CF3S-substituenten

From the hyperfine ESR-splitting patterns of, $\text{a(}{}^{13}\text{C}{}_{\mathrm{\gamma }}\text{), a(}{}^{14}\text{N}\text{)}\text{and}\text{a(}{}^{19}\text{F}\text{)}$ it is concluded that the radicals (CF₃S)₃C·, (CF₃S)₂HC·, (CF₃S)H₂C·, (CF₃S)₂N· and (CF₃S)₃Si· are planar π-radicals existing in a nearly fully staggered conformation. The force which promotes the staggered conformation arises from conjugative delocalization between the 2 p_z-unpaired electron and the p-type lone pair on the sulfur atoms of the CF₃S-groups, causing a stabilization of the radicals. The electronegative CF₃-group decreases the extent of conjugative electron delocalization.Whereas fluorine atoms adopt equivalent positions in the radicals the staggered conformation implies inequivalence of the protons in CF₃SCH₂.     

Perfluoralkyljod-verbindungen: Darstellungen und eigenschaften von CF3JO,CF3JOF2 und CF3JO2

Perfluoroalkyl iodine compounds: preparations and properties of CF₃IO, CF₃IOF₂, and CF₃IO₂. The trifluoromethyl iodine compounds CF₃IO, CF₃IOF₂, and CF₃IO₂ are formed from the reactions of CF₃I, CF₃IF₂ or CF₃IF₄ with ozone or silicon dioxide respectively. Their preparartions, properties, ¹⁹F-nmr spectra, and ir spectra are described.     

Trifluormethylselenyl-Verbindungen des N,P und As

Trifluoromethylselenyl Compounds of N, P, and As The reaction of CF₃SeBr with NH₃ leads, depending on conditions, to (CF₃Se)_nNH_3?n, where n = 1, 2 or 3. CF₃SNCO reacts with CF₃SeNH₂ to give CF₃SNHCONHSeCF₃, and (CF₃Se)₃N with P(C₆H₅)₃ provides CF₃SeN ?P(C₆H₅)₃. (CF₃Se)₃E (where E = P, As) is formed by the reaction of Hg(SeCF₃)₂ with EBr₃ in CS₂. Analogously, from Hg(SeCF₃)₂ and P₂J₄ in CS₂ (CF₃Se)₂PP(SeCF₃)₂ is obtained that contains (CF₃Se)₃P as a contamination. While reacting C₆H₅PJ₂ or C₆H₅P(J)(J)C₆H₅ with Hg(seCF₃)₂ respectiverly C₆H₅P(SeCF₃)₂ is formed. The latter can be also obtained from (C₆H₅P)₅ and CF₃SeSeCF₃. IR, ¹⁹F, ³¹P, ⁷⁷Se NMR, and MS data are given.     

Hexa-, hepta- und octafluortrimethylamin

The electrofluorination of N(CH₃)₃ yields, along with fragmentation and recombination products and N(CF₃)₃ (I), minor quantities of the hitherto unknown compounds (CF₃)₂ NCF₂H (II), CF₃N(CF₂H)₂ (III) and N(CF₂H)₃ (IV). I –IV have been isolated and characterized by their ¹H, ¹³C and ¹⁹F nmr and their E I and C I mass spectra.     

Pseudohalogenverbindungen. XX. Perfluorierte alkan- und phenylsulfonylpseudohalogenide

The pseudohalide CF₃SO₂NCO has been synthesized by means of a new reaction involving trifluoromethanesulphonamide and chlorosulphonylisocyanate. This method may be used for preparing other perfluorinated alkanesulphonyl-, arenesulphonyl- and alkanecarbonyl-amides. Reactions of CF₃SO₂NCO with alcohols, thiols, phenols and amines lead to the corresponding carbonic acid esters, thio-esters, phenyl esters and ureas. Reactions with carbonic acids, aldehydes and dimethylsulphoxide gave CO₂ and the corresponding acid amides, azomethines and imino-dimethylsulphurane. Under pressure at 160°C, CF₃SO₂NCO reacts with phosphorus pentasulphide to give the previously unknown compound CF₃SO₂NCS; with phosphorus pentachloride under the same conditions, CF₃SO₂NCCl₂ is formed.     

Darstellung und chemische Eigenschaften von N-Trifluormethylthiophosphaniminen

Preparation and Chemical Properties of N-Trifluoromethylthiophosphaneimines In n-hexane (CF₃S)₃N and (C₆H₅)₃As react to CF₃SN?As(C₆H₅)₃ and CF₃SSCF₃. With (RO)₃P (CF₃S)₃N forms CF₃SSCF₃ and CF₃SN?P(OR)₃ (R = C₆H₅, CH₃, C₂H₅). While CF₃SNP-(OC₆H₅)₃ is stable up to 100°C the other Phosphaneimines rearange to (R′O)₂P(O)N(R′)SCF₃ (R′ = CH₃, C₂H₅). Hydrolysis leads to ROH and (RO)₂P(O)N(H)SCF₃. Only for R = C₆H₅ in addition (C₆H₅O)₂P(O)NH₂ is formed. Physical data and nmr spectra of the newly prepared substances are presented.     

Fluorieren mit Trifluormethylhypochlorit CF3OCl. Darstellung und Kristallstrukturanalyse von Trifluormethyliodtetrafluorid CF3IF4

Fluorinate with Trifluoromethylhypochlorite CF₃OCl. Preparation and Crystal Structure Determination of Trifluoromethyliodine Tetrafluoride CF₃IF₄ The preparation of Trifluoromethyliodine tetrafluoride (CF₃IF₄), from Trifluoromethyliodide (CF₃I) with Trifluoromethylhypochlorite (CF₃OCl), and the crystal structure of CF₃IF₄ at 172(1) K is described. CF₃IF₄ crystallizes in the monoclinic space group P2₁/c with a = 762.2(7) pm, b = 842.9(10) pm, c = 856.4(7) pm, β = 99.65(7)° with four formula units per unit cell.     

Die NMR-Spektren von CF3I,CF3IF2 und CF3IF4

The NMR Spectra of CF₃I, CF₃IF₂, and CF₃IF₄ The ¹⁹F-NMR and ¹³C-NMR spectra of CF₃I, CF₃IF₂ and CF₃IF₄ were recorded in acetonitrile solution. The chemical shifts of the CF₃-groups are strongly dependent on the oxidation state of the iodine atom. With increasing oxidation state the resonances of the CF₃-groups in the ¹⁹F-NMR spectra are characteristically shifted to high field, whereas in the ¹³C-NMR spectra a characteristic shift to low field is measured. The absolute value of the coupling constants ¹J(¹⁹F? ¹³C) increases with increasing oxidation state from 344 Hz (CF₃I) via 354 Hz (CF₃IF₂) to 359 Hz (CF₃IF₄).     

über die Reaktionen von CH3OCl,CF3OCl,CF3OF und CF3OH mit dem supersauren System HF/MF5 (M = As,Sb) Darstellung und Charakterisierung von CH3OCl(H)+MF6− und CF3OCl(H)+MF6−

On the Reactions of CH₃OCl, CF₃OCl, CF₃OF, and CF₃OH with the Superacid System HF/MF₅ (M = As, Sb). Preparation and Characterization of CH₃OCl(H)⁺MF₆^? and CF₃OCl(H)⁺MF₆^? The preparation of the chlorine oxoniumsalts CH₃OCl(H)⁺MF₆^? and CF₃OCl(H)⁺MF₆^? by protonation of CH₃OCl and CF₃OCl in the superacid solution of HF/MF₅ (M = As, Sb) is described. However CF₃OF and CF₃OH have not been protonated under the same conditions. In the case of CF₃OH the formation of F₂CO · MF₅ is observed. The novel compounds are characterized by nmr- and vibrational spectroscopy.     

Über die Umsetzung von Pertluorisobuten mit Thiazylfluorid und Thiazyltrifluorid

On the Reaction of Perfluoro Isobutene with Thiazylfluoride and Thiazyltrifluoride From thiazylfluoride (1) and perfluoro-isobutene (2) (CF₃)₃C? N?S?N? S? C(CF₃)₃ (4) isr formed in the presence of CsF. With NSF₃NSF₂C(CF₃)₃ (8) is obtained, which isomerizes above 100°C to (CF₃)₃CNSF₂ (9). In contrast to 9, with fluoro Lewis-acids 8 forms 1:1 adducts (CF₃)₃CSF₂N · MF₅ (M = As, Sb (10a), (10b)). In 50% aqueous KOH 9 hydrolyses to give the amine (CF₃)₃CNH₂.     

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.     

Transaminierungen am dimethylamino-bis-(trifluormethyl)-arsin und -phosphin

The arsines and phosphines (CF₃)₂EN(CH₃)₂ (E= P or As) react with secondary amines with the formation of (CF₃)₂ENR₂ and HN(CH₃)₂. Mechanistic and steric effects associated with these reactions are discussed. The influence of the groups (CF₃)₂E on the E-N-bonding and the reaction is examined.     

Thermodynamics of vaporization of some cyclic perfluorocarbons

The temperature dependence of the saturation vapor pressure of perfluoro-meta-dimethylcyclohexane, (CF₃)₂C₆F₁₀, has been determined by the ebulliometric method in the moderate pressure range from 8.4 to 101.6 kPa. Enthalpies of vaporization have been obtained calorimetrically for perfluorobicyclo(4,4,0)dec(1,6)ene, C₁₀F₁₆, and (CF₃)₂C₆F₁₀ at T = 298.15 K. Densities of C₁₀F₁₆ have been measured in the small temperature range from 293 to 338 K. Critical parameters have been estimated from vapor pressure data and densities for the substances under study and for some mono- and bicyclo-perfluorocarbons investigated earlier. A second-order group additivity method has been applied to predict the vaporization enthalpies of some cyclic perfluorocarbons.     

Darstellung der Iminiumsalze CF3?NXCF2+MF6− (X = CH3, F und M = As,Sb) und CF3?NCl = CF2+ AsF6−

Preparation of the Iminium Salts CF₃? NX?CF₂⁺MF₆^? (X = CH₃, F and M = As, Sb) and CF₃? NCl?CF₂⁺ AsF₆^? The preparation of the iminiumsalts CF₃? NX?CF₂⁺ MF₆^? (X = CH₃, F and M = As, Sb) and CF₃? NCl?CF₂⁺ AsF₆^? is reported. The salts were characterized by NMR and infrared spectroscopy. CF₃? NCH₃?CF₂⁺MF₆^? decompose into MF₅ and (CF₃)₂NCH₃.     

Vergleich der trifluormethylierungseigenschaften von(CF3)Hg,CF3I und (CF3)2te am beispiel der reaktionen mit cyclohexen,benzol und pyridin

The trifluoromethylation reactions of (CF₃)₂Hg, CF₃I and (CF₃)₂Te with cyclohexene, benzene and pyridine are compared under similar conditions. Photochemical as well as thermal reactions result in an increase of the reactivity in the series (CF₃)₂Hg < CF₃I ? (CF₃)2Te. The yields and the kind of products vary depending on the time of irradiation and the temperature. In all cases the best yields are obtained from the thermal reactions with (CF₃)₂Te. With cyclohexene only trifluoromethylated addition products are observed. The substitution reactions with pyridine yield a mixture of isomeric trifluoromethylpyridines. (CF₃)₂Hg and CF₃I react with benzene to yield only benzotrifluoride C₆H₅CF₃. The main product of the reaction of (CF₃)2Te with benzene is also benzotrifluoride; in addition to this the disubstituted bis(trifluoromethyl)benzene isomers and trifluoromethyl- cyclohexadienes are formed. ¹H, ¹⁹F n.m.r. and mass spectra are described.     

Chlorofluorieren mit Trifluormethylhypochlorit CF3OCl. Darstellung und spektroskopische Charakterisierung von Trifluormethyliodchloridfluorid CF3I(Cl)F

Chlorofluorinate with Trifluoromethylhypochlorite CF₃OCl. Preparation and Spectroscopic Characterization of Trifluormethyliodinechloridefluoride CF₃I(Cl)F The preparation of a new iodine(III) compound, trifluormethyliodinechloridefluoride CF₃I(Cl)F, via oxidative addition of trifluoromethylhypochlorite CF₃OCl to trifluoromethyliodide CF₃I is described. The thermolabile compound has been characterized by i.r., Raman, ¹⁹F NMR, and mass spectroscopy.