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1.
The reaction of o-, m-, and p-F2CCFC6H4X with SF5Br produces an intermediate adduct, F5SCF2CFBrC6H4X, which, on treatment with AgBF4, affords the first useful, high yield preparation of o-, m-, and p-F5SCF2CF2C6H4X.  相似文献   

2.
Preparation of the following new SF5-perfluoroalkyl benzene derivatives, m-SF5CF2CF2C6H4X (X=NO2, NH2, OH, I, NHCOCH3, SO2Cl, SO3H, SO3K) has been achieved. The new compounds were characterized by their respective IR, NMR and HRMS or elemental analysis.  相似文献   

3.
Preparation of the following new m-SF5CF2CF2C6H4X derivatives has been achieved: X=N3(2), Br(3), OC(O)CHCH2(4), CHCH2(5). The compounds were characterized by their respective IR, NMR, mass spectra (MS) and high resolution mass spectrometry (HRMS). An improved yield of SF5(CF2)2C6H5 (1) is also reported along with the synthesis of the polyacrylate (6) and polystyrene (7) from their respective monomers.  相似文献   

4.
The new mononuclear palladium(II) and platinum(II) [M(p-SC6F4(CF3))2(dppe)] complexes M = Pd 1a, Pt 2a; [M(o-SC6H4(CF3))2(dppe)] M = Pd 1d, Pt 2d as well as the previously known [M(SC6F5)2(dppe)] M = Pd 1b, Pt 2b and [M(p-SC6HF4)2(dppe)] M = Pd 1c, Pt 2c, have been used as metalloligands for the preparation of the heteroleptic bimetallic complexes [M2(μ-SRf)2(dppe)2](SO3CF3)2 M = Pd, Rf = p-C6F4(CF3) 3a, C6F53b, p-C6HF43c, o-C6H4(CF3) 3d; M = Pt, Rf = p-C6F4(CF3) 4a, C6F54b, p-C6HF44c and o-C6H4(CF3) 4d. Variable temperature 19F NMR experiments show that the fluorothiolate bridged bimetallic compounds are fluxional in solution whereas mononuclear complexes are not. The solid state X-ray diffraction structures of [Pd(p-SC6HF4)2(dppe)] (1c), [Pt(SC6F5)2(dppe)] (2b) and [Pt(o-SC6H4(CF3))2(dppe)] (2d) show square-planar coordination around the metal centers. The solid state molecular structure of the compound [Pt2(μ-o-SC6H4(CF3))2(dppe)2](SO3CF3)2 (4d), exhibit a planar [Pt2(μ-S)2] ring with the sulfur substituents in an anti configuration.  相似文献   

5.
A stable and storable precursor of 2-SF5-butadiene, 3-SF5-3-sulfolene, has been synthesized and its reactivity studied with several olefinic compounds. When SF5Br is added to sulfolene, 3-bromo-4-SF5-sulfolane is formed and when reacted further with silver tosylate forms 4-SF5-2-sulfolene. The 4-SF5-2-sulfolene undergoes rearrangement with silicic acid to give 3-SF5-3-sulfolene and when heated forms 2-SF5-butadiene; in the absence of a dienophile, dimerization does occur. The new 2-SF5-butadiene is a reactive diene undergoing a Diels-Alder reaction with olefinic sytems such as maleic anhydride, p-naphthoquinone, and methyl acrylate.  相似文献   

6.
Compound [Fe2(μ-CO)2(CO)25-C9H7)2] (1) reacts with aryllithium reagents, ArLi (Ar = C6H5, p-CH3C6H4, p-CF3C6H4) followed by alkylation with Et3OBF4 to give the diindenyl-coordinated diiron bridging alkoxycarbene complexes [Fe2{μ-C(OC2H5)Ar}(μ-CO)(CO)25-C9H7)2] (2, Ar = C6H5; 3, Ar = p-CH3C6H4, 4, Ar = p-CF3C6H4). Complex 4 reacts with HBF4 · Et2O at low temperature to yield cationic bridging carbyne complex [Fe2(μ-CC6H4CF3-p)(μ-CO)(CO)25-C9H7)2]BF4 (5). Cationic 5 reacts with NaBH4 in THF at low temperature to afford diiron bridging arylcarbene complex [Fe2{μ-C(H)C6H4CF3-p}(μ-CO)(CO)25-C9H7)2] (6). The reaction of 5 with NaSC6H4CH3-p under the similar conditions gave the bridging arylthiocarbene complex [Fe2{μ-C(C6H4CF3-p)SC6H4CH3-p}(μ-CO)(CO)25-C9H7)2] (7). Complex 5 can also react with carbonylmetal anionic compounds Na[M(CO)5(CN)] (M = Cr, Mo, W) to produce the diiron bridging aryl(penta-carbonylcyanometal)carbene complexes [Fe2{μ-C(C6H4CF3-p)NCM(CO)5}(μ-CO)(CO)25-C9H7)2] (8, M = Cr; 9, M = Mo; 10, M = W). The structures of complexes 4, 6, 7, and 10 have been established by X-ray diffraction studies.  相似文献   

7.
Fluorinated organodifluoroboranes RfBF2 are in general suitable reagents to transform XeF2 and RIF2 into the corresponding onium tetrafluoroborate salts [RfXe][BF4] and [R(Rf)I][BF4], respectively. (4-C5F4N)BF2 and trans-CF3CFCFBF2 which represent boranes of high acidity form no Xe-C onium salts in reactions with XeF2 but give the desired iodonium salts with RIF2 (R = C6F5, o-, m-, p-C6FH4). The reaction of (4-C5F4N)BF2 with XeF2 ends with a XeF2-borane adduct. C6F5Xe(4-C5F4N), the first Xe-(4-C5F4N) compound, was obtained when C6F5XeF was reacted with Cd(4-C5F4N)2. We describe the synthesis of (4-C5F4N)IF2 and reactions of (4-C5F4N)IF2 and C6F5IF2 with (4-C5F4N)BF2. Analogous to [(4-C5F4N)2I][BF4] and [C6F5(4-C5F4N)I][BF4] aryl(perfluoroalkenyl)iodonium salts [R(R′)I][BF4] were obtained from RIF2 (R = C6F5, o-, m-, p-C6FH4) and R′BF2 (R′ = trans-CF3CFCF, CF2CF). The gas phase fluoride affinities pF of selected fluoroorganodifluoroboranes RfBF2 and their hydrocarbon analogs are calculated (B3LYP/6-31+G*) and discussed with respect to their potential to introduce Rf-groups into hypervalent EF2 bonds. Four aspects which influence the transformation of hypervalent EF2 bonds (E = Xe, R′I) under the action of Lewis acidic reagents RAFn−1 (A = B, P; n = 3, 5) into the corresponding [RE][AFn+1] salts are presented and the important role of the acidity is emphasized. Fluoride affinities may help to plan the introduction of organo groups into EF2 moieties and to expand the types of acidic reagents. Thus C6H5PF4 with a pF value comparable to that of RfBF2 compounds is able to introduce the C6H5 group into RIF2 (R = C6F5, p-C6FH4).  相似文献   

8.
Addition of pentafluorothio bromide, SF5Br, to ethyl propiolate results in an 1:1 adduct, SF5CHCBrC(O)OC2H5, and a small amount of a 1:2 adduct. The former is converted by reduction to the corresponding β-SF5-acrylic ester, SF5CHCHC(O)OC2H5. Treatment of SF5CH2CBr(CH3)C(O)OCH3 with base produces methyl-β-SF5-methacrylate, SF5CHC(CH3)C(O)OCH3. The preparation and characterization of these new compounds are described.  相似文献   

9.
Treatment of [BzPh3P][AuCl2] with [Hg(x-C6H4NO2)2] (x = o, m, or p) gives anionic gold(I) complexes of the type [BzPh3P][Au(R)Cl](R = o-, m- or p-C6H4NO2, Bz = C6H5CH2). The chloro ligand in [Au(o-C6H4NO2)Cl]? can be replaced by bromo or iodo ligands by use of NaBr or NaI. The anions [Au(R)Cl]? react with neutral monodentate ligands, L, to give neutral mononuclear complexes [Au(R)L] (R = o-C6H4NO2, L = PPh3, AsPh3; R = m-C6H4NO2, L = PPh3) and with 1,2-bis(diphenylphosphino)ethane (dpe) to give [Au2(R)2(dpe)] (R = o-C6H4NO2). The corresponding [Au(p-C6H4NO2)Cl]? reacts with PPh3 or AsPh3 to give mixtures containing [AuClL]. The anionic ortho-nitrophenylgold(I) complex is much more stable than its meta- or para-nitrophenyl isomers. These are thought to be the first reports of nitrophenylgold(I) complexes.  相似文献   

10.
It has been found that treatment of SF5-alkyl halides, especially SF5(CH2)2Br, with silver salts such as CH3C(O)OAg, p-CH3C6H4SO3Ag, CF3SO3Ag and AgNO3 provides convenient pathways for preparing the following ester compounds: SF5CH2CH2R (R = CH3COO, TosO, CF3SO3, NO3), SF5(CH2)3OTos, and SF5(CF2)4(CH2)2OAc. Important derivatives prepared from these esters include SF5(CH2)2OH; SF5(CF2)4(CH2)2OH. Several alkenes SF5C(Br)CH2 and SF5CH2(COOCH3)CCHC(O)OCH3 are obtained using silver salts. The use of alkali metals salts with SF5(CH2)3Br is studied and yields SF5(CH2)3I; also, a pathway has been developed that extends for SF5(CH2)3− the chain by two-carbon atoms and also produces the first SF5-containing malonic acid.  相似文献   

11.
Inhibition of photosynthetic electron transport (PET) in spinach chloroplasts by nineteen 2-benzylsulphanylbenzimidazoles (BZA) was studied. BZA were found to inhibit photosynthetic electron transport (PET) and for their inhibitory efficiency, electronic properties of the R substituent on the benzyl moiety are decisive. The PET inhibiting activity of the studied BZA expressed as IC50 varied in the range from 28.5 ??M (R = 3,5-(CF3)2) to 394.5 ??M (R = 2,4-(NO2)2). For compounds with R = H, 4-CH3, 3-CH3, 3-OCH3, 4-F, 3-F, 4-Cl, 3-Cl, 2-Cl, 4-Br, 3-Br, 3,4-F2, 3,4-Cl2, 3-CF3, 3,5-(CF3)2 linear increase of the inhibitory activity with the increasing value of the substituent??s ?? constant up to 0.86 was observed. Further increase of the ?? constant resulted in a sharp activity decrease of the corresponding compounds (R = 2-F-6-Cl, 2-NO2, 3,5-(NO2)2, 2,4-(NO2)2). Using EPR spectroscopy and an artificial electron donor diphenyl carbazide it was found that the site of BZA action in the photosynthetic apparatus is situated on the donor side of PS 2, prior to the Z·/D· intermediate.  相似文献   

12.
A series of previously unknown asymmetrical fluorinated bis(aryl)bromonium, alkenyl(aryl)bromonium, and alkynyl(aryl)bromonium salts was prepared by reactions of C6F5BrF2 or 4-CF3C6H4BrF2 with aryl group transfer reagents Ar′SiF3 (Ar′ = C6F5, 4-FC6H4, C6H5) or perfluoroorganyl group transfer reagents RF′BF2 (RF = C6F5, trans-CF3CFCF, C3F7C≡C) preferentially in weakly coordinating solvents (CCl3F, CCl2FCClF2, CH2Cl2, CF3CH2CHF2 (PFP), CF3CH2CF2CH3 (PFB)). The presence of the base MeCN and the influence of the adducts RF′BF2·NCMe (RF = C6F5, CF3C≡C) on reactions aside to bromonium salt formation are discussed. Reactions of C6F5BrF2 with AlkF′BF2 in PFP gave mainly C6F5Br and AlkF′F (AlkF′ = C6F13, C6F13CH2CH2), presumably, deriving from the unstable salts [C6F5(AlkF′)Br]Y (Y = [AlkF′BF3]). Prototypical reactivities of selected bromonium salts were investigated with the nucleophile I-and the electrophile H+. [4-CF3C6H4(C6F5)Br][BF4] showed the conversion into 4-CF3C6H4Br and C6F5I when reacted with [Bu4N]I in MeCN. Perfluoroalkynylbromonium salts [CnF2n+1C≡C(RF)Br][BF4] slowly added HF when dissolved in aHF and formed [Z-CnF2n+1CFCH(RF)Br][BF4].  相似文献   

13.
The thermal reaction of chiral 2-phenyl-4-(p-X-phenyl)-5-(p-Y-phenyl)-4-tert-butyldimethylsilylperoxy-4H-isoimidazoles (5b: X = CF3, Y = OMe; 5c: X = CF3, Y = F) was carried out in DMSO. The chiral 2-phenyl-5-(p-X-phenyl)-5-(p-Y-phenyl)-5H-imidazol-4-ones (4b: X = CF3, Y = OMe; 4c: X = CF3, Y = F) were quantitatively obtained in 50-60% enantiomer excess (ee). The mechanism for the reaction was proved to be stereoselective 1,5-phenyl migration. Although the sigmatropic 1,5-phenyl migration should be thermally allowed according to the Woodward-Hoffmann rule, the migration actually includes a stepwise process.  相似文献   

14.
Vibrationally resolved electronic spectra of heteroclusters C6H6-SF6 and C6H6-(SF6)2 were studied in the spectral regions near the S0-S1, 0 0 0 and 6 0 1 transitions of the benzene monomer. A nonvanishing 0 0 0 vibrational band has been observed for C6H6-SF6 with a C3v symmetry. For both clusters we have determined the ionization potentials as well as the binding energies in the electronic ground state and the ionization state. The fragmentation of larger clusters (C6H6)n(SF6)m is restricted to the loss of SF6 molecules while the emission of C6H6 molecules have not been observed.  相似文献   

15.
Some new bimetallic carboxylates of tin and germanium with general formula where R1 = m-CH3C6H4, p-CH3C6H4, C6H5, R2 = o-CH3C6H4, p-CH3C6H4, o-CH3OC6H4, C6H5, CH3, have been prepared by the condensation reaction of diethyltin oxide and triarygermyl(substituted)propanoic acid in 1:2 mole ratio, respectively, and characterized by multinuclear (1H, 13C, 119Sn) NMR, 119mSn Mössbauer and IR spectroscopy. The X-ray crystal structure of the ligand I4 [(C6H5)3GeCH(o-CH3OC6H4)CH2COOH] delineate four coordinated germanium atom with a peculiarity of having a molecule of solvent (CHCl3). The chiral center in the synthesized compounds was identified on the basis of 1H NMR data and measurements of angle of rotations.  相似文献   

16.
The application of DFT computational method (B3LYP/6-311++G(d,p)) to mono- and poly(CF3)substituted naphthalene derivatives helps to study changes in the electronic properties of these compounds under the influence of 11 substituents (-Br, -CF3, -CH3, -CHO, -Cl, -CN, -F, -NH2, -NMe2, -NO2, and -OH) to confront substituent effects in naphthalene with an analogous situation in benzene. This paper shows the dependencies of theoretically calculated SESE (Substituent Effect Stabilization Energy) values on empirically determined, well-defined Hammett-type constants (σp, σm, R, and F). Described poly(CF3)substituted derivatives of naphthalene are, so far, the most sensitive molecular probes for the substituent effects in the aromatic system. The presence of the trifluoromethyl groups of such an expressive nature significantly increases the sensitivity of the SESE to changes caused by another substitution. Further, the more -CF3 groups are attached to the naphthalene ring, the more sensitive the probe is. Certain groups of probes show additivity of sensitivity: the obtained sensitivity relates to the sum of the sensitivities of the mono(CF3)substituted probes.  相似文献   

17.
Full geometry optimizations were carried out on singlet and triplet states of α-substitued divalent five-membered rings XC4H3M (X = -NH2, -OH, -CH3 -H, -CH3, -Br, -Cl, -F, -CF3 and -NO2; M = C, Si and Ge) by B3LYP method using 6-311++G** basis set. Thermal energy gaps, ΔEs-t; enthalpy gaps, ΔHs-t; Gibbs free energy gaps, ΔGs-t, between singlet (s) and triplet (t) states of above structures were calculated using the GAUSSIAN 03 program. The ΔGs-t of XC4H3C was changed in the order: X = -Cl > -Br > -CH3 > -H > -CF3 > -F > -NO2 > -OH > -NH2. The changes of ΔGs-t for XC4H3Si and XC4H3Ge were in the order: X = -NH2 > OH > F > Cl > Br > CH3 > H > CF3 > NO2. The relationship between all the parameters such as different energy types, geometry parameters, natural bonding orbital (NBO) charge at atoms, HOMO and LUMO energies, chemical hardness (η), chemical potential (μ), dipole Moment (D), electrophilicity (ω) and the maximum amount of electronic charge, ΔNmax, was presented and discussed.  相似文献   

18.
The interactions of cyclic trinuclear copper {[3,5-(CF3)2Pz]Cu}3 and silver {[3,5-(CF3)2Pz]Ag}3 complexes with polyhedral borate anions [B10H10]2− and [B12H12]2− in solvents of low-polarity were studied using IR spectroscopy (190-290 K). Two types of complexes were found in solution: {[((3,5-CF3)2PzM)3][BnHn]}2− and {[((3,5-CF3)2PzM)3]2[BnHn]}2− (M = Ag, Cu; n = 10, 12). The stability constants of these complexes were determined from IR-spectra.  相似文献   

19.
The rates of solvolysis of 2 - aryl - exo - 5,6 - trimethylene - exo - and endo - 2 - norbornyl p-nitrobenzoates (7 and 8, respectively) with representative substituents [p-CH3O, p-CH3, H, m-CF3, p-CF3, and 3,5-(CF3)2] were determined in 80% aqueous acetone and compared with those of the parent 2-aryl-exo- and endo-2-norbornyl p-nitrobenzoates (5 and 6, respectively). The rate ratios for the endo-p-nitrobenzoates (68) are essentially constant and close to unity for these substituents, indicating that the perturbation of the trimethylene bridge toward the C2-position is virtually negligilbe. The rate ratios for the exo-p-nitrobenzoates (57) can also be regarded as invariant over the reactivity range studied. The exo/endo rate ratios (78) are 246 (p-CH3O), 196 (P-CH3), 129 (H), 80 (m-CF3), 90 (p-CF3), and 89 [3,5-(CF3)2], being similar to the corresponding 56 rate ratios. The solvolyses of these p-nitrobenzoates (7 and 8) afford predominantly ( > 97%) exo-alcohols. Since the secondary exo-5,6-trimethylene-2-norbornyl system, with its low exo/endo rate ratio, 11.2, is known to solvolyse without significant σ-participation, the tertiary derivatives should also undergo solvolysis without σ-participation. Consequently, the similarities in the solvolytic behaviors between the two systems (5 vs 7; 6 vs 8) strongly support the previous conclusion that σ-participation is unimportant in the solvolysis of 5.  相似文献   

20.
A series of reactions between SF5CF2CF2I and SF5(CF2)4I with F2CCF2 was carried out in an effort to find the most effective methods for chain-extension. Also, for the first time, SF5(CF2)8I and SF5(CF2)10I have been prepared and isolated. The reaction conditions for the addition of H2CCH2 were also investigated. A determination of the crystal structure of the SF5(CF2)4CH2CH2I has been carried out: the crystal system is monoclinic, with space group P2(1)/n and a=23.465(5) Å; b=6.0971(12) Å; c=44.892(9) Å; α=90°; β=99.38(3)°; γ=90°; Z=20.  相似文献   

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