Trifluoronitrosomethane reacts with bis(trifluoromethyl)phosphine to give (CF3)2P(O)N(OH)CF3 and a small amount of (CF3)2NOH. On the other hand, the reactions with tris(trifluoromethyl)phosphine and bis(trifluoromethyl)chlorophosphine afford (CF3)2NOP(O)CF3N(CF3)2 and (CF3)2NP(O)(CF3)Cl respectively. Isomerisation of may be involved as found for the isomerisation of the phosphine, (CF3)2NOP(CF3)2, to the phosphoryl compound, (CF3)2NP(O)(CF3)2. Mechanisms for the above reactions are discussed. 相似文献
(CF3)2AsX (X = F, Cl) give at elevated temperatures substitution reactions with (CF3)2NO to afford (CF3)2NOAs(CF3)X and (CF3)2NOCF3. The formation of addition products at low temperatures to give [(CF3)2NO]2As(CF3)2X, followed by elimination reactions at elevated temperatures to give the final products provide for the first time direct evidence for the mechanisms of the substitution reactions. With (CF3)2AsBr, bromine was initially displaced to afford (CF3)2NOAs(CF3)2, followed by addition reactions to give [(CF3)2NO]3As(CF3)2. 相似文献
The reactions between bis(trifluoromethyl)nitroxyl and CF3PX2 (where X = F, Cl, Br and CN) in 2:1 molar ratio give addition products, [(CF3)2NO]2P(CF3)X2. The bromo and cyano products are unstable. The former decomposes at room temperature to give bromine and perfluoro-2-azapropene, and the latter yields predominantly (CF3)2NOCF3. With CF3PI2, iodine displacement occurs to afford [(CF3)2NO]2PCF3. On the other hand, P(CN)3 affords [(CF3)2NO]3PO, (CF3)2NON(CF3)2 and paracyanogen. Mechanisms for these reactions are proposed. 相似文献
Cleavage of the E-P bond in compounds of the type (CF3)2EPh2(E = P, As) is achieved by polar [HBr, (CF3)2EI, (CH3)3SnH, (CF3)2AsH] and non-polar [Br2, Mn2(CO)10] substances. Exchange reactions are possible with (CF34)E2 and P2F4 leading to the unsymmetrical compounds (CF3)2PPF2, (CF3)2AsPF2, (CF3)2PAs(CF3)2, F2PPH2, (CF3)2AsPH2. The reaction of (CF3)2PPH2 with Mn2(CO)10 gives the new binuclear complex Mn2(CO)8PH2P(CF3)2 and Mn2(CO)8[P(CF3)2]2. The hitherto unknown compound (CF3)2AsPF2 is obtained by the reaction of (CF3)2AsPH2 with P2F4. Adducts of (CF3)2PPH2 with B2H6 and (CH3)3N, respectively, are discussed. Investigation of the reaction route and characterization of most of the reaction product is based on 1H and 19F NMR spectral data. 相似文献
The insertion of (CF3)2CO into the PH bond of MenH3?nP yields MenH2?nPC(CF3)2OH and MenH1?nP[C(CF3)2OH]2 (n=O, 1), respectively [1]. MeP[C(CF3)2OH]2 rearranges giving the diphosphine [MePOCH(CF3)2]2 and the phosphorane MeP[OCH(CF3)2]4. Me2PH reacts with (CF3)2CO forming several products, e.g. MePF[OCH(CF3)2]2 and Me2PPMe2 [1]. The phosphines tBu(R)PH(R=Me, tBu), however, add (CF3)2CO giving rise to the phosphinites tBu(R)POCH(CF3)2, which furnish stable phosphonium salts upon treating with MeI. (CF3)2CO inserts into the SH bond of RSH to yield RSC(CF3)2OH (R=H,Me,Ph), which were reacted with MeI, too. Reacting SCl2 with LiOCH(CF3)2 gives S[OCH(CF3)2]2 which is oxidised by chlorine to the sulfurane ClS[OCH(CF3)2]3 [2]. The sulfurane is able to transfer (CF3)2CHO groups to phosphorus (III) compounds, e.g. P[OCH(CF3)2]3 and Me3P yielding P[OCH(CF3)2]5 and [Me3POCH(CF3)2]+Cl?. ClS[OCH(CF3)2]3 gives a stable salt upon reaction with SbCl5, like ClP[OCH(CF3)2]4. The mechanisms for these reactions are discussed. 相似文献
O-Nitrosobis(trifluoromethyl)hydroxylamine gives novel reactions with tris(trifluoromethyl)-phosphine, -arsine and -stibine to affford mainly the corresponding bis(trifluoromethyl)nitroxol derivatives. Tris(trifluoromethyl) phosphine affords (CF3)2NOP(O)(CF3)2 and (CF3)2NNO. Tris(trifluoromethyl) arsine also gives (CF3)2NNO in high yield, together with smaller amounts of (CF3)2NOAs(CF3)2, CF3NCF2, COF2 and a polymeric white solid. With tris(trifluoromethyl)stibine, no oxidation nor addition reactions occurred. Instead, [(CF3)2NO]3Sb and [(CF3)NO]2SbCF3 were obtained in high yields. The stoichiometry of the reactions suggests that the additional amounts of bis(trifluoromethyl)nitroxyl groups bonded to antimony are derived from the trifluoromethyl groups bonded to antimony. Mechanisms to rationalise these reactions are proposed. 相似文献
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. 相似文献
Reactions of the fluorinated amines (CF3)2NH, CF3N(OCF3)H, CF3N[OCF(CF3)2]H, CF3NHF and SF5NHF with the strong acid HF/AsF5 form the corresponding ammonium salts Rf1Rf2NH2+AsF6? and RfNFH2+ AsF6? in high yield. [Rf1=CF3, Rf2=CF3, CF3O, (CF3)2CFO; Rf=CF3, SF5] The colorless crystalline solids are stable for prolonged periods at 22°C in sealed FEP containers. They have dissociation pressures at 22°C ranging from ～5 torr (RfNFH2+ AsF6?) to ～50 torr [CF3N(OCF3)H2+AsF6?]. 19F NMR and Raman spectroscopy were used to identify the compounds. 相似文献
During the thermal decomposition of (CF3)2Cd and (CF3)2Zn complexes primarily difluorocarbene is eliminated. The formation of CF2 is unambiguously proved by matrix i.r. spectroscopy. Both (CF3)2Cd·D and (CF3)2Zn·D are excellent CF2 sources, which can easily be prepared and handled, and which undergo CF2 reactions even at low temperature. CF2 insertion was found during the reaction of (CF3)2Te with (CH3)2Cd via the intermediate formation of a CF3Cd compound to form CH3TeCF2CH3. (CF3)2Cd·glyme reacts with (CH3)3Si(OCOCF3) to CF3Cd(OCOCF3)·glyme; during this reaction CF2 is also eliminated. 相似文献
Various preparative routes for the synthesis of (CH3)3SiP(CF3)2 are discussed. The most favourable method, reaction of (CH3)3MPH2 with HE(CF3)2, provides a good yield of (CH3)3ME(CF3)2 compounds (M = Si, Ge, Sn; E = P, As). The reaction rate is dependent on M (Si < Ge <Sn) und E (P < As). The stability and reactivity of the (CH3)3ME(CF3)2 compounds are discussed. The new compounds were characterized by NMR and IR spectra and by cleavage reactions of the M-E bond. 1H, 19F NMR and IR spectral data are reported. 相似文献
CF3I(NO3)2 is formed from the reactions of CF3IF2 or CF3IO with N2O5 as well as CF3I with ClNO3. During the reactions of CF3IF2 with N2O5 or CF3I with ClNO3 the intermediate products CF3IF(NO3) or CF3ICl(NO3) can be identified. The preparations, properties, 19F-nmr spectra and the thermal decomposition of CF3I(NO3)2 are described. 相似文献
(CF3)2ED and CF3ED2 (E = P,As) may be obtained in high yield by the reaction of (CF3)2EI and CF3EI2, respectively, with DI/Hg. 19F- and 31P-NMR spectra are reported. When compared with the H-analogues, the deuterated compounds show isotopic shifts of the 19F- and 31P-resonance signals. 相似文献
The fluorocarbon soluble, binuclear ruthenium(I) complexes [Ru(μ-O2CMe)(CO)2LF]2, where LF is the perfluoroalkyl substituted tertiary phosphine, P(C6H4-4-CH2CH2(CF2)7CF3)3, or P(CH2CH2(CF2)5CF3)3, were synthesized and partition coefficients for the complexes in fluorocarbon/hydrocarbon biphases were determined. Catalytic hydrogenation of acetophenone to 1-phenylethanol in benzotrifluoride at 105 °C occured in the presence of either [Ru(μ-O2CMe)(CO)2P(C6H4-4-CH2CH2(CF2)7CF3)3]2 (1) or [Ru(μ-O2CMe)(CO)2P(CH2CH2(CF2)5CF3)3]2 (2). The X-ray crystal structure of [Ru(μ-O2CMe)(CO)2P(CH2CH2(CF2)5CF3)3]2 was determined. The compound exhibited discrete regions of fluorous and non-fluorous packing. 相似文献
CF3I(OCOCF3)2 is formed from the reactions of CF3IF2 or CF3IO with trifluoroacetic anhydride at low temperature. During the reaction of CF3IF2 with (CF3CO)2O CF3IF(OCOCF3) is formed as an intermediate product. The preparation, the 19F-nmr spectra and the thermal decomposition are described. 相似文献
A new general synthesis of trifluoromethyl amines of the type, CF3N(X)H, is reported. The amines are prepared in excellent yield by the hydrolysis CF3N(X)C(O)F in the presence of NaF. The N-acyl fluorides are now available in considerable variety from the reaction of nucleophiles with the oxaziridine CF3. Six new amines have been prepared and characterized [(X=CF3O, (CF3)2CFO, CH3O, C2H5O, (CH3)2CHO and (CH3)3CO)] and improved syntheses of CF3NHF and CF3NHOC(O)CH3 are reported. The new compounds are thermally stable at 22° and are characterized by IR, NMR and physical properties. 相似文献
Synthesis of difunctional N,N′-difluoro perfluoroalkylsulfonamides, CF3SO2NFSO2(CF2)nSO2NFSO2CF3, where n=4, 6 is reported. A related compound with an oxygen linkage CF3SO2NFSO2(CF2)2O(CF2)2SO2NFSO2CF3 has also been prepared. These reagents showed good activity for electrophilic fluorination. 相似文献
The high temperature reaction of C60 with silver(I) trifluoroacetate followed by 500 °C sublimation and subsequent HPLC purification has led to the isolation of the five trifluoromethyl[60]fullerenes C60(CF3)n (n=2, 4, 6, 8, 10). Four of them have >90% compositional purity. Two of the compounds, C60(CF3)4 and C60(CF3)6, were obtained as C1-symmetry isomers with >90% isomeric purity, and a sample of C60(CF3)2 also contained ca. 15-20% of a Cs-symmetry isomer of C60(CF3)4. The new compounds were characterized by IR and EI mass spectrometry (all five compounds), NMR spectroscopy (C60(CF3)2, C60(CF3)4, and C60(CF3)6), and 2D COSY NMR spectroscopy (C60(CF3)4 and C60(CF3)6). Calculations at the AM1 and DFT levels of theory have led to the prediction of the most likely structures for C60(CF3)2, C1-C60(CF3)4, Cs-C60(CF3)4, and the two most likely structures of C1-C60(CF3)6. 相似文献
The reactions of M(CO)5X ( M = Mn, Re; X = Cl, Br, I) with E2(CF3)4 (E = P, As) between 50 and 90°C yield binuclear complexes of the type M2(CO)8E(CF3)2X with two different bridging ligands, the formation of which is influenced by M (Mn > Re), E (P > As) , and X(I > Br > Cl). The main by-product is the symmetrical system M2(CO)8[E(CF3)2]2, which is however not formed by the partial replacement of X by E(CF3)2 since this reaction requires temperatures above 120°C. The observed products can be explained by a three-step reaction path starting with the cleavage of E2(CF3)4 followed by the subtitution of a cis-CO group in the M(CO)5X component by M(CO)5E(CF3)2 and the ring closure. 相似文献
It has been found that a mixture of (CF3SO2)2CH2 and (CF3SO2)2CBr2 can be used instead of (CF3SO2)2CHBr in the radical addition to H2CCF2; the 1:1 and 1:2 adducts have been isolated and characterized. An improved synthesis of (CF3SO2)2CBr2 is also reported. 相似文献
