The syntheses of fluorinated alkanesulfonamides and poly-(fluorinated alkanesulfonamides)

In order to synthesize poly-(fluorinated alkanesulfonamides) a series of model experiments were carried out: (1) reactions of fluorinated alkanesulfonyl fluorides with amines, (2) reactions of fluorinated alkanesulfonyl chloride with amines and (3) reactions of sodium salts of fluorinated alkanesulfonamides with alkyl iodides of fluorinated alkanesulfonic acid esters. Seventeen new fluorinated alkanesulfonamides were prepared in good yields, namely: R_FO(CF₂)₂SO₂NR¹R² (1a-h), R¹R²NSO₂R_FSO₂NR¹R² (2a-h) and [Cl (CF₂)₄O(CF₂)₂SO₂NH(CH₂)₃]₂ (3). Reaction of R_FSO₂NH₂ with equivalent amount of NaOCH₃ and methyl iodide was shown to give both the N-mono- and N,N-di-substituted amides. Consequently the N-monosubstituted alkanesulfonamides were chosen as monomers for syntheses of the poly-(fluorinated alkanesulfonamides) and two new polymers were synthesized. The effect of the condition of the polycondensation on M?_n of the polymers were discussed and elemental composition, ¹⁹F NMR, IR, M?_n, Tg, tensile strength, thermal and chemical stabilities of the polymers were measured. Several new perfluoroalkanesulfonyl chlorides CISO₂R_FSO₂Cl (4a-c) and fluorinated alkanesulfonic acid esters (6a-d) were synthesized. However, reaction of CFCl₂CF₂O(CF₂)₂SO₂F with AlCl₃ was found to give Cl₃CCF₂O(CF₂)₂SO₂F (5) instead of the expected sulfonyl chloride.     

Mono and Bisphosphonates from Perfluoro Olefins and Polyfunctional Fluoro Ketones. Syntheses,Molecular Structure and Derivatives

Perfluoroalkenyl phosphonates were formed along with Me₃SiF using CF₃CF=CF₂, CF₃CH=CF₂, F₅SCF=CF₂ or F₅SCH=CF₂ and silylated phosphites, (R¹O)₂POSiMe₃ (R¹=Et, SiMe₃). This straightforward method could be extended to perfluorobutadienes CF₂=C(R^F)C(R^F)=CF₂ (R^F F=F, CF₃). The formation of CF₃C(=O)P(=O)(OSiMe₃)₂ and further reactions to yield bisphosphonates will be described. Acetylphosphonates, R²C(=O)P(=O)(OSiMe₃)₂ (R²=CH₃, CF₃) reacted with the ketimine, CH₃C(=NiPr)Ph to give α-hydroxy-γ-imino phosphonates. Trifluoroacetylphenol and 2,6-bis(trifluoracetyl)-4-methyl-phenol have been proven to be versatile precursors for α-and γ-hydroxy phosphonates. Intermediates in these reactions were found to be cyclic λ⁵σ⁵P species.     

The reactions of perfluoro- and α,α-dichloropolyfluoroalkanesulfinates

Sodium perfluoroalkanesulfinate, R_FSO₂Na [R_F?Cl(CF₂)₄, 1a; CF₃(CF₂)₅, 1b; Cl(CF₃)₆, 1c] reacted with bromine in aqueous solution to give the corresponding sulfonyl bromide R_FSO₂Br (2a-2c) and in acetonitrile or acetic acid, to form perfluoroalkyl bromide R_FBr (3a-3c). Heating in acetonitrile at 80°C, 2a-2c were converted smoothly into 3a-3c. However, reaction of sodium α,α-dichloropolyfluoroalkanesulfinate RCCl₂SO₂Na (R?CF₃, Cl(CF₂)n, n=2, 4, 6, 5a-5d) with bromine in aqueous solution gave directly the corresponding bromoalkanes 1-bromo-1,1-dichloropolyfluoroalkane RCCl₂Br (6a-6d). In aqueous potassium iodide solution, 1a-1c, 5a and 5b also reacted with iodine to form the corresponding iodo-polyfluoroalkane 4a-4c, 7a and 7b directly. 6a and 7a underwent free radical addition to alkene readily in the presence of free radical initiator and reacted with Na₂S₂O₄ in the usual way to form α,α-dichloropolyfluoroethane sulfinate (5a). 5a was stable in strong acid, but reacted with strong base to yield 10. 5a was oxidised by hydrogen peroxide to the sulfonate 11 and reduced by zinc in dilute acid to from the α-chloro sulfinate 12.     

Perfluoro and polyfluoroalkanesulfonic acid: XVII. Difluoromethyl perfluoroalkanesulfonates and their reactions

In contrast to R_FSO₃CH₂R(1)(R=hydrogen, alkyl and perfluoroalkyl) and R_FSO₃CF₂R_F′ (2), the reactions of difluoromethyl perfluoroalkanesulfonates RFSO₃CF₂H (3) With nucleophiles are more complicated. Halide inos, X^? (X = F, Cl, I) and ethanol only attack the alkoxyl carbon atom, cleaving the C? O bond to give HCF₂X (4) and HCF₂OEt (5) respectively. Other reagents such as RCO₂^? (R=CH₃, CF₃), C₆H₅S^? etc. can either attack the carbon or sulfur atom of 3 to give the corresponding products of C? O and S? O bond cleavages. More basic nucleophiles RO^? (R = C₆H₅, Et) mainly abstract the proton of the HCF₂ moiety to produce difluorocarbene. Ether and benzene, which can be alkylated by methyl perfluoroalkanesulfonate, do not react with 3 under similar conditions. The reaction rate of 3 with KF is much slower than that of 1 (R = H). All these data seem to indicate that the shielding effect caused by the two fluorine atoms on the methyl carbon in 3 prevents to some extent the nucleophilic attack on this carbon, but not so completely as in 2 due to the presence of a hydrogen atom.     

Chiral Fluorinated α‐Sulfonyl Carbanions: Enantioselective Synthesis and Electrophilic Capture,Racemization Dynamics,and Structure

Enantiomerically pure triflones R¹CH(R²)SO₂CF₃ have been synthesized starting from the corresponding chiral alcohols via thiols and trifluoromethylsulfanes. Key steps of the syntheses of the sulfanes are the photochemical trifluoromethylation of the thiols with CF₃Hal (Hal=halide) or substitution of alkoxyphosphinediamines with CF₃SSCF₃. The deprotonation of RCH(Me)SO₂CF₃ (R=CH₂Ph, iHex) with nBuLi with the formation of salts [RC(Me)? SO₂CF₃]Li and their electrophilic capture both occurred with high enantioselectivities. Displacement of the SO₂CF₃ group of (S)‐MeOCH₂C(Me)(CH₂Ph)SO₂CF₃ (95 % ee) by an ethyl group through the reaction with AlEt₃ gave alkane MeOCH₂C(Me)(CH₂Ph)Et of 96 % ee. Racemization of salts [R¹C(R²)SO₂CF₃]Li follows first‐order kinetics and is mainly an enthalpic process with small negative activation entropy as revealed by polarimetry and dynamic NMR (DNMR) spectroscopy. This is in accordance with a C_α? S bond rotation as the rate‐determining step. Lithium α‐(S)‐trifluoromethyl‐ and α‐(S)‐nonafluorobutylsulfonyl carbanion salts have a much higher racemization barrier than the corresponding α‐(S)‐tert‐butylsulfonyl carbanion salts. Whereas [PhCH₂C(Me)SO₂tBu]Li/DMPU (DMPU = dimethylpropylurea) has a half‐life of racemization at ?105 °C of 2.4 h, that of [PhCH₂C(Me)SO₂CF₃]Li at ?78 °C is 30 d. DNMR spectroscopy of amides (PhCH₂)₂NSO₂CF₃ and (PhCH₂)N(Ph)SO₂CF₃ gave N? S rotational barriers that seem to be distinctly higher than those of nonfluorinated sulfonamides. NMR spectroscopy of [PhCH₂C(Ph)SO₂R]M (M=Li, K, NBu₄; R=CF₃, tBu) shows for both salts a confinement of the negative charge mainly to the C_α atom and a significant benzylic stabilization that is weaker in the trifluoromethylsulfonyl carbanion. According to crystal structure analyses, the carbanions of salts {[PhCH₂C(Ph)SO₂CF₃]Li? L }₂ ( L =2 THF, tetramethylethylenediamine (TMEDA)) and [PhCH₂C(Ph)SO₂CF₃]NBu₄ have the typical chiral C_α? S conformation of α‐sulfonyl carbanions, planar C_α atoms, and short C_α? S bonds. Ab initio calculations of [MeC(Ph)SO₂tBu]^? and [MeC(Ph)SO₂CF₃]^? showed for the fluorinated carbanion stronger n_C→σ* and n_O→σ* interactions and a weaker benzylic stabilization. According to natural bond orbital (NBO) calculations of [R¹C(R²)SO₂R]^? (R=tBu, CF₃) the n_C→σ*_{S? R} interaction is much stronger for R=CF₃. Ab initio calculations gave for [MeC(Ph)SO₂tBu]Li ? 2 Me₂O an O,Li,C_α contact ion pair (CIP) and for [MeC(Ph)SO₂CF₃]Li ? 2 Me₂O an O,Li,O CIP. According to cryoscopy, [PhCH₂C(Ph)SO₂CF₃]Li, [iHexC(Me)SO₂CF₃]Li, and [PhCH₂C(Ph)SO₂CF₃]NBu₄ predominantly form monomers in tetrahydrofuran (THF) at ?108 °C. The NMR spectroscopic data of salts [R¹(R²)SO₂R³]Li (R³=tBu, CF₃) indicate that the dominating monomeric CIPs are devoid of C_α? Li bonds.     

The reaction of <Emphasis Type="Italic">N</Emphasis>-sulfinyltrifluoromethanesulfonamide with triethylphosphate and triethylphosphite

The reaction of N-sulfinyltrifluoromethanesulfonamide CF₃SO₂NSO with triethylphosphate and triethylphosphite results in N-(trifluoromethanesulfonyl)triethoxyphosphazene CF₃SO₂N=P(OEt)₃, which upon heating is converted into the diethyl ester of N-trifluoromethylsulfonylamidophosphoric acid CF₃SO₂NHP(O)·(OEt)₂. The latter was also prepared by alcoholysis of N-(trifluoromethanesulfonyl)trichlorophosphazene or of potassium salt of dichloroanhydride of N-trifluoromethylsulfonylamidophosphoric acid, or by the reaction of the salt CF₃SO₂NHNa with diethylchlorophosphate. Compound CF₃SO₂N=P(OEt)₃ does not rearrange into the isomeric diethyl ester of N-ethyl-N-(trifluoromethylsulfonyl)amidophosphoric acid CF₃SO₂N(Et)P(O)(OEt)₂, contrary to the statement in the literature on the easy rearrangement of phosphazenes RFSO₂N=P(OEt)₃ into amidates RFSO₂N(Et)P(O)(OEt)₂.     

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.     

Some unexpected reactions of perfluoroalkynylmagnesium halides

R_FCCMgX reacts with Ac₂O to give not only MeC(O)CCR_F but also MeC(O)CXC(R_F)C(O)Me, and with CF₃COOPr it gives CF₃C(O)CHC(OPr)R_F not CF₃C(O)CCR_F; R_FCCMgBr reacts with Cl₂ to give R_FCCBr rather than R_FCCCl, while with Br₂ R_FCCMgI similarly gives R_FCCI rather than R_FCCBr.     

Thermolyse des anhydrides perfluoroalcanesulfoniques. Mecanisme et application a la synthese des esters RFSO3RF.

Perfluoroalkanesulfonic anhydrides [(R_FSO₂)₂O; R_F=CF₃,C₂F₅,C₄F₉], mixed with the parent acid, decompose thermally to give the corresponding perfluoroalkyl perfluoroalkanesulfonates (R_FSO₃R_F) with liberation of SO₂. If the perfluoroalkyl moieties in the anhydride and the acid are different, a mixture of symmetric and unsymmetric esters is obtained. An ionic bimolecular mechanism is deduced from the results, and a new easy synthesis of the symmetric perfluorinated sulfonic esters is proposed.     

Oxydation anodique de iodoperfluoroalcanes dans les acides perfluoroalcanesulfoniques. Preparation de nouveaux esters sulfoniques totalement fluores RFSO3R'F a longues chaines

Perfluorinated sulphonic esters R_FSO₃R'_F and fluorosulphates FSO₃R'_F, are easily obtained by anodic oxidation of iodoperfluoroalkanes R'_FI in perfluoroalkane sulphonic acids R_FSO₃H (R_F  CF₃, C₂F₅, C₄F₉) and fluorosulphuric acid. With di-iodo compound I(CF₂)₄I, the mono and the diester can be selectively obtained. The alkaline hydrolysis of these esters produces perfluorinated carboxylic compounds. Polyfluorinated iodide R'_FCH₂CH₂I are also oxidized in similar conditions. The mechanism of the electrolytic reaction is discussed.     

Fluorinated phosphorus compounds: Part 8. The reactions of bis(fluoroalkyl) phosphorochloridates with sulfur nucleophiles

The reactivity of bis(fluoroalkyl) phosphorochloridates to nucleophiles is summarised. Previous data and the results described here indicate that reactivities decrease in the order: amines>alcohols>thiols. The synthesis of CF₃CH₂OP(O)(SEt)₂ in 30% yield was accomplished by treating CF₃CH₂OP(O)Cl₂ with two molar equivalents of EtSH and Et₃N in ether. The chloridates (CF₃CH₂O)₂P(O)Cl and (C₂F₅CH₂O)₂P(O)Cl did not react with MeSH in ether at −78 °C or when heated with Pb(SMe)₂ in benzene. Ethanethiol and propanethiol reacted with fluorinated chloridates in the presence of triethylamine to give thiolates (R_FO)₂P(O)SR in 13-41% yield where R_F was CF₃CH₂, C₂F₅CH₂, C₃F₇CH₂ or (CF₃)₂CH and R was Et or n-Pr. Similarly, reaction of phosphorobromidates (R_FCH₂O)₂P(O)Br, made by brominating the corresponding bis(fluoroalkyl) H-phosphonates, with benzenethiol gave derivatives (R_FCH₂O)₂P(O)SPh in 43 and 46% yield where R_F was CF₃ and C₂F₅, respectively. Treatment of the chloridothiolate Cl(EtO)P(O)SMe, prepared in two steps from triethyl phosphite, with fluoroalcohols and triethylamine in ether gave species R_FO(EtO)P(O)SMe in 62-74% yield where R_F was CF₃CH₂, C₂F₅CH₂, C₃F₇CH₂ or (CF₃)₂CH. The reactions of bis(trifluoroethyl) phosphorochloridate with 2-mercaptoethanol, 3-mercaptopropanol and ethane-1,2-dithiol gave several unexpected products whose structures were tentatively assigned.     

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.     

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.     

Studies on sulfinatodehalogenation: IV. The sulfinatodebromination of primary perfluoroalkyl bromides and perfluoroalkylene α, ω-dibromides

Using PTC or cosolvent, both perfluoroalkyl bromides such as Br (CF₂)₂O(CF₂)₂SO₂Na ( 1 ), Br(CF₂)₂OCF₂CO₂H ( 2 ), Cl(CF₂)₄Br ( 3 ), Cl(CF₂Br ( 4 ), n-C₆F₁₃Br ( 5 ), n-C₈F₁₇Br ( 6 ), H(CF₂)₈Br ( 7 ), α, ω-dibromides O(CF₂CF₂Br)₂ ( 8 ), Br(CF₂)₆Br ( 9 ) and Br(CF₂)₈Br ( 10 ) reacted readily with Na₂S₂O₄ in the presence of NaHCO₃ in aqueous solution to form the corresponding perfluoroalkane sulfinates NaO₂S(CF₂)₂O(CF₂)₂SO₂Na ( 11 ), NaO₂S(CF₂)₂OCF₂CO₂Na ( 12 ), Cl(CF₂)₄SO₂Na ( 13 ), Cl(CF₂)₂SO₂Na ( 14 ), n-C₃F₁₃SO₂Na ( 15 ), n-C₈F₁₇SO₂Na ( 16 ), H(CF₂)₈SO₂Na ( 17 ), α, ω-disulfinates O(CF₂CF₂SO₂Na)₂ ( 18 ), NaO₂S(CF₂)₄SO₂Na ( 19 ) and NaO₂S(CF₂)₈SO₂Na ( 20 ) in 66—97% yields. To this new and general reaction of perfluoroalkyl bromides, the name sulfinatodebromination is proposed.     

Synthesis and coordination chemistry of perfluoroalkyl-derivatised β-diketonates

A series of fluorinated β-diketones, R_fC(O)CH₂C(O)R_f′ (R_f=C₆F₁₃, R_f′=CF₃; R_f=R_f′=C₆F₁₃, C₇F₁₅), have been prepared in reasonable yields by a two-step synthesis. On reaction with appropriate metal substrates, deprotonation and concurrent coordination of the perfluoroalkyl-derivatised β-diketonate ligands affords a range of fluorous metal complexes which have been characterised by elemental analysis, mass spectrometry, IR and NMR spectroscopies. The structures of [Cu(L-L)₂(H₂O)₂] {L-L=CF₃C(O)CHC(O)C₆F₁₃, C₆F₁₃C(O)CHC(O)C₆F₁₃} and [Cu(PPh₃)₂{C₇F₁₅C(O)CHC(O)C₇F₁₅}] have been determined by single-crystal X-ray diffraction.     

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.     

Thermolyse des halogenures de perfluoroalcanesulfonyle

Perfluoroalkanesulfonyl chlorides [R_FSO₂Cl ; R_F  CF₃, C₂F₃, C₄F₉], decompose thermally to give the corresponding perfluoroalkyl chlorides with evolution of SO₂. The latter retards the reaction, but it is catalysed by copper which also inhibits the SO₂ effect. 2-methyl-2-nitrosopropane traps the perfluoroalkyl free radicals. In the presence of a perfluoroalkyl iodide [R′_FI ≠ R′_F≠R_F], other products, R_FI and R_FCl, are obtained. A free radical chain-mechanism is then suggested.On the other hand, perfluorobutanesulfonyl fluoride is very stable thermally.     

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).     

Fluorinated phosphorus compounds: Part 11. The reactions of some fluorinated amines with dialkyl and bis(fluoroalkyl) phosphorochloridates

Dimethyl phosphorochloridate reacted with R_FCH₂NH₂ in ether in the presence of Et₃N to afford (MeO)₂P(O)NHCH₂R_F, where R_F = CF₃ and C₂F₅, in 39 and 47% yield, respectively. Similar reactions with di-n-propyl and diisopropyl phosphorochloridates could be effected only with H₂NCH₂CF₃ when 4-dimethylaminopyridine catalyst was added and (n-PrO)₂P(O)NHCH₂CF₃ and (i-PrO)₂P(O)NHCH₂CF₃ were isolated in 49 and 25% yield, respectively. Treatment of POCl₃ with one molar equivalent each of H₂NCH₂CF₃ and Et₃N permitted the synthesis of Cl₂P(O)NHCH₂CF₃ in 43% yield. Bis(fluoroalkyl) phosphorochloridates (R_FO)₂P(O)Cl, where R_F = C₂F₅CH₂, C₃F₇CH₂ and (CF₃)₂CH, reacted with 2,2,2-trifluoroethylamine and 2,2,3,3,3-pentafluoropropylamine to furnish phosphoramidates (R_FO)₂P(O)NHCH₂R, where R = CF₃ or C₂F₅, in yields of 32-67%.     

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.