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1.
In reactions with perfluoroalkylsulfenyl chlorides (RfSCl; Rf = F3, C2F5, n-C3F7, n-C4F9) and perfluoroalkyl disulfides (RfSSRf′; Rf = Rf′ = CF3, Rf = CF3, Rf′ = C2F5) at 25°, chlorine monofluoride acts primarily as a chlorinating and fluorinating reagent to give the corresponding perfluoroalkylsulfur chloride tetrafluorides, RfSF4Cl, in good yields. However, small amounts of perfluoroalkylsulfur pentafluorides, RfSF5, 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. 相似文献
2.
《Journal of organometallic chemistry》1987,334(3):323-328
Tris(perfluoroorgano)bismuth compounds Bi(Rf)3 (Rf = CF3, C2F5, n-C3F7, n-C4F9, n-C6F13, n-C8F17, C6F5) are easily prepared in high yields from the reactions of perfluoroorganocadmium complexes with BiCl3, or BiBr3 in aprotic solvents. The perfluoroorganobismuth halides intermediates in these reactions have been detected by NMR spectroscopy. 相似文献
3.
Synthesis and Properties of Tetrakis(Perfluoroalkyl)Tellurium Te(Rf)4 (Rf = 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(Rf)4 (Rf = C2F5, C3F7, C4F9) are formed from the reaction of TeCl4 with the corresponding Cd(Rf)2 complexes. 相似文献
4.
Syntheses and Properties of Perfluoroorgano Esters of the Diethyldithiocarbamic Acid, (C2H5)2NC(S)SRf (Rf = CF3, C2F5, i‐C3F7, n‐C4F9, C6F5) Tetraethylthiuram disulfide reacts under different conditions with perfluoroorgano silver(I), AgRf, and perfluoroorgano cadmium compounds, Cd(Rf)2, to give the corresponding perfluoroorgano esters of diethyldithiocarbamic acid, (C2H5)2NC(S)SRf (Rf = 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 AgRf and Cd(Rf)2 are discussed. 相似文献
5.
A New Synthesis of Perfluoroorgano Manganese and Rhenium Compounds Pentacarbonyl perfluoroorgano manganese and rhenium compounds M(CO)5Rf (M = Mn, Re; Rf = 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(Rf)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)Rf or M(CO)3(CH3CN)2Rf are formed. 相似文献
6.
Christopher M Timperley Sally A Saunders Josef Szpalek Matthew J Waters 《Journal of fluorine chemistry》2003,119(2):161-171
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 (RFO)2P(O)SR in 13-41% yield where RF was CF3CH2, C2F5CH2, C3F7CH2 or (CF3)2CH and R was Et or n-Pr. Similarly, reaction of phosphorobromidates (RFCH2O)2P(O)Br, made by brominating the corresponding bis(fluoroalkyl) H-phosphonates, with benzenethiol gave derivatives (RFCH2O)2P(O)SPh in 43 and 46% yield where RF 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 RFO(EtO)P(O)SMe in 62-74% yield where RF 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. 相似文献
7.
《Journal of fluorine chemistry》1987,36(2):123-139
The interaction between perfluoroorgano iodides (RfI where Rf = 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 (RfRf,72–90% yield) in addition to minor quantities of the reduction products (RfH). 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 RfI 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 RfRf and RfH products. {ft*}Present address: Fluidics Inc., P.O.Box 1886, Dayton, OH 45429 U.S.A. 相似文献
8.
《Tetrahedron: Asymmetry》1999,10(14):2665-2674
Reactions of (menthyl)PH2 and H2CCHRf6 (menthyl=1R,3R,4S; Rfn=(CF2)n−1CF3) or H2CCHRf8 (AIBN, refluxing THF) give (menthyl)PH(CH2CH2Rfn) and then (menthyl)P(CH2CH2Rfn)2 (n=6, 7; n=8, 8), but with purification or other difficulties at each stage. Reactions of (menthyl)PCl2 with IMgCH2CH2Rfn give, under careful conditions, analytically pure 7 or 8 in 28–32% yields after distillation. Some Rfn(CH2)4Rfn also form. These represent the first chiral (and non-racemic) fluorous phosphines. Reactions of 7 or 8 with [Ir(COD)Cl]2 and CO give trans-[(menthyl)P(CH2CH2Rfn)2]2Ir(Cl)(CO) (n=6, 71%; 8, 51%) as analytically pure yellow oils. Their IR νCO values show the donor/acceptor properties of 7 and 8 to be intermediate between those of P((CH2)3Rf8)3 and P((CH2)4Rf8)3. The CF3C6F11:toluene partition coefficients of 7 and 8 (27°C, 78.4:21.6 and 93.7:6.3) are distinctly lower than those of P((CH2)2Rfn)3 (n=6, 98.8:1.2; n=8, >99.7:<0.3), reflecting the replacement of a linear C8–C10 group that is ca. 75–80% fluorinated by a cyclic C10 terpenyl group. Reactions of 7 or 8 with [Rh(COD)Cl]2 give [(menthyl)P(CH2CH2Rfn)2]Rh(Cl)(COD) (n=6, 69%; 8, 70%) as orange crystallizable oils. 相似文献
9.
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, (Rf)2Cd·D (Rf C2F5, iC3F7) forms RfCdONO2·D and (CH3)3SnRf. The preparations and properties of the partly new compounds as well as the n.m.r. spectra are described. 相似文献
10.
Several kinds of perfluoro-2,4-dialkyloxolanes (A), having such alkyl groups as RfR′fCF3 (2a); RfC2F5, R′fCF3 (3a); RfCF3, R′fC2F5 (4a); RfR′fC2F5 (5a); RfCF3, R′fnC3F7 (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. 相似文献
11.
A series of fluorinated β-diketones, RfC(O)CH2C(O)Rf′ (Rf=C6F13, Rf′=CF3; Rf=Rf′=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. 相似文献
12.
Christopher M. Timperley Robert E. ArbonSally A. Saunders Matthew J. Waters 《Journal of fluorine chemistry》2002,113(1):65-78
Reaction of phosphorus trichloride with tert-butanol and fluoroalcohols gave bis(fluoroalkyl) phosphites (RFO)2P(O)H in 42-89% yield, where RF=HCF2CH2, H(CF2)2CH2, H(CF2)4CH2, CF3CH2, C2F5CH2, C3F7CH2, (CF3)2CH, (FCH2)2CH, CF3(CH3)2C, (CF3)2CH3C, CF3CH2CH2, C4F9CH2CH2 and C6F13CH2CH2. Treatment of these with chlorine in dichloromethane gave the bis(fluoroalkyl) phosphorochloridates (RFO)2P(O)Cl in 49-96% yield. The chloridate (CF3CH2O)2P(O)Cl was isolated in much lower yield from the interaction of thionyl chloride with bis(trifluoroethyl) phosphite. Heating the latter in dichloromethane with potassium fluoride and a catalytic amount of trifluoroacetic acid gave the corresponding fluoridate (CF3CH2O)2P(O)F in 84% yield. Treatment of bis(trifluoroethyl) phosphite with bromine or iodine gave the bromidate (CF3CH2O)2P(O)Br and iodidate (CF3CH2O)2P(O)I in 51 and 46% yield, respectively. The iodidate is the first dialkyl phosphoroiodidate to have been isolated and characterised properly—its discovery lags behind the first isolation of a dialkyl phosphorochloridate by over 130 years. The fluoroalkyl phosphoryl compounds are generally more stable than known unfluorinated counterparts. 相似文献
13.
Francis B. Dudley George H. Cady Alden L. Crittenden 《Journal of mass spectrometry : JMS》1971,5(8):953-957
Negative ion mass spectra are reported for the compounds (CF3CO)2O, (C2F5CO)2O, (C3F7CO)2O, C3F7C(F)(CF3)2, n-C6F14, CF3COCL, (CF3)2CO, BF3, N2F4 and SiF4. 相似文献
14.
Christopher M. Timperley Sue Kirkpatrick Mark Sandford Matthew J. Waters 《Journal of fluorine chemistry》2005,126(6):902-906
Treatment of bis(fluoroalkyl) phosphites (RFCH2O)2P(O)H, where RF was CF3 or C2F5 with sulfur in pyridine at 80 °C gave salts of structure [(RFCH2O)2P(O)SH]NC5H5 in 90 and 88% yield, respectively. The salts reacted with alkyl iodides in acetonitrile at 50 °C to furnish bis(fluoroalkyl) S-alkyl phosphorothiolates (RFCH2O)2P(O)SR, where R was Me, Et, n- and i-Pr (when RF = CF3) and Me (when RF = C2F5). Yields ranged from 21 to 57%. Bis(trifluoroethyl) S-methyl phosphorothiolate (CF3CH2O)2P(O)SMe underwent fluorination by silver(I) fluoride in acetonitrile at room temperature to yield the phosphorofluoridate (CF3CH2O)2P(O)F in 75% yield. Tris(fluoroalkyl) phosphorothionates (RFCH2O)3P = S, where RF was CF3, C2F5 and C3F7, were prepared in 30-34% yield by heating the tris(fluoroalkyl) phosphites (RFCH2O)3P and sulfur to 200 °C in a sealed tube for 8 h. 相似文献
15.
《Journal of fluorine chemistry》1986,34(2):191-200
The isocyanate RfCH2NCO (Rf=CF3(C2F5)2C)reacts under strongly acidic conditions to form the salt RfCH2NH3(+)HSO4(−)(1) which yields, on treatment with sodium nitrite the diazaoalkane RfCHN2 (3). Dissolution of (1) in D.M.S.O. gives, by a remarkable decomposition reaction, the alkane RfH (2). Reaction of (3) with excess sodium nitrite affords the isocyanate RfNCO (4) which is stable to water,but which reacts with ammia to give the urea RfNHCONH2 (5); this latter was not readily hydrolysed .Photolysis of (3) yields the diazadiene RfCHNNCH Rf (7). Thermolysis of (3) alone afforded the diazadiene (7), but reaction in the presence of copper (II) perchlorate afforded (7) and the aldehyde RfCHO (6) 相似文献
16.
Reactions of NN-Dihaloperfluoroalkaneamines with Sulfur and Sulfur Derivatives Reactions of NN-Dihaloperfluoroalkaneamines RfNX2 (Rf = CF3, C2F5; X = Cl, Br) with S8, S4N4 and A = SX2 (A = RfN, O) are described. The products isolated are: Sulfurdihalideimides RfNSX2 (Rf = CF3, C2F5; X = Cl, Br), Sulfurdiimides RfNSNRf and Bis(sulfurdiimido)sulfides (RfNSN)2S(Rf = CF3, C2F5). Thionylimides RfNSO were not obtained in preparative quantities. 相似文献
17.
Perfluoroorgano Tellurium Compounds: New Investigations on the Preparation of Te(Rf)2 and CH3TeRf (Rf = C2F5, C3F7, C6F5) Methyl(perfluoroorgano) tellurium and bis(perfluoroorgano) tellurium compounds are synthesized in high yields from the photochemical or the thermal reactions of (CH3)2 Te with perfluoroorgano iodides in the presence of (C2H5)3N. They are isolated in pure states. Another general method for the preparation of bis(perfluoroorgano) tellurium is the thermal reaction of TeCl4 with bis(perfluoroorgano) mercury. The preparations and properties of the partially new compounds are described. 相似文献
18.
The nascent vibrational energy distributions of the HF? formed in the reactions of a series of partially fluorinated alkanes (RFH; RF = CH2F, CHF2, CF3, C2F5, C3F7, and C7F15) with electronically excited oxygen atoms O(21D2) have been determined by measuring the appearance times of stimulated emissions from various vibration–rotation transitions in a grating-tuned optical cavity. The vibrational energy contents of the HF formed in these reactions were found to be considerably greater than statistically expected. These reactions are believed to occur via vibrationally excited short-lived α;-fluorinated alcohols (RFOH?), formed by insertion of the O(21D2) atoms into C? H bonds. The observation of nonstatistical energy partitioning in the above reactions is in clear contrast to the result obtained from the O(21D2) + CF3CH3 reaction that produces the β-fluorinated alcohol CF3CH2OH, from which the HF product carries a near statistical vibrational energy distribution. A mechanism for HF? formation in these very exothermic reactions is presented. 相似文献
19.
Perfluoroalkyl iodide RfI [Rf = (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 (RfC6H4Y). 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. 相似文献
20.
Mary F. Mahon Kieran C. Molloy Joanne E. Stanley David W. H. Rankin Heather E. Robertson Blair F. Johnston 《应用有机金属化学》2005,19(5):658-671
Nine organotin fluorocarboxylates RnSnO2CRf (n = 3, R = Bu, Rf = CF3, C2F5, C3F7, C7F15; R = Et, Rf = CF3, C2F5; R = Me, Rf = C2F5; n = 2, R = Me, Rf = CF3) have been synthesized; key examples have been used to deposit fluorine‐doped SnO2 thin films by atmospheric pressure chemical vapour deposition. Et3SnO2CC2F5, in particular, gives high‐quality films with fast deposition rates despite adopting a polymeric, carboxylate‐bridged structure in the solid state, as determined by X‐ray crystallography. Gas‐phase electron diffraction on the model compound Me3SnO2CC2F5 shows that accessible conformations do not allow contact between tin and fluorine, and that direct transfer is therefore unlikely to be part of the mechanism for fluorine incorporation in SnO2 films. The structure of Me2Sn(O2CCF3)2(H2O) has also been determined and adopts a trans‐Me2SnO3 coordination sphere about tin in which each carboxylate group is monodentate. Copyright © 2005 John Wiley & Sons, Ltd. 相似文献