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1.
Gerd-Volker Rschenthaler 《无机化学与普通化学杂志》1981,479(8):158-164
Reactions of ClS[OCH(CF3)2]3 and S[OCH(CF3)2]2 with Phosphorus(III) Derivatives The sulfurane ClS[OCH(CF3)2]3 reacts with Me3P to give the phosphonium salt [Me3POCH(CF3)2]+Cl?, in the case of (MeO)3P products of an Arbuzov reaction are found: (MeO)2P-(:O)OCH(CF3)2 and MeCl; the sulfurane is reduced to the sulfoxylate S[OCH(CF3)2]2. The cyclic phosphite FP[OC(CF3)2C(CF3)2O] and P[OCH(CF3)2]3 furnish derivatives of pentacoordinated phosphorus upon reaction with ClS[OCH(CF3)2]3. The sulfoxylate S[OCH(CF3)2]2 oxidises Me3P, (MeO)3P and P[OCH(CF3)2]3 to form R3P? O and R3P? S (R = Me, OMe, OCH(CF3)2). The ether (CF3)2CHOCH(CF3)2 is isolated, too. 相似文献
2.
On Sn[OCH(CF3)2]2 and Sn(OCH2CF3)2 (n = 1, 2) The sulfoxylates S[OCH(R)CF3]2, 1 and 2 and the disulfides S2[OCH(R)CF3]2, 5 and 6 (R = CF3, H) are obtained by reacting SCl2 or S2Cl2, respectively, and the lithium alcoxides LiOCH(R)CF3. Chlorine and compound 2 give ClS(O)OCH2F3 and CF3CH2Cl, whereas the sulfur-sulfur bound is cleaved in 5 and 6 furnishing SCI2, 1 and 2 , respectively. The 19F n.m.r. spectrum of 5 and the 1H n.m.r. spectrum of 6 are interpreted in terms of hindered rotation about the sulfur-sulfur axis. 相似文献
3.
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
4.
A. Moghimi H. R. Khavassi A. H. Benvidi M. Vojdani N. Faghihimoghaddam 《Journal of the Iranian Chemical Society》2011,8(4):958-964
Synthesis of two salts involving CH2O spacer between the imidazole nitrogen and hexafluoroisopropyl group in the fluorous imidazolium cations is reported. Such an insertion would result in the formation of ??-ammonium ether. The two fluorous imidazolium salts involve one or two -CH2OCH(CF3)2 groups attached to the imidazole nitrogen atoms. These products were synthesized from the reaction between methyimidazole and imidazole as nucleophiles and sevochlorane, ClCH2OCH(CF3)2, as electrophile, in different molar ratios. The resulting products have been characterized by 1H, 13C, and 19F NMR and FTIR spectroscopy. Also, the single crystal X-ray diffraction analysis for the symmetrically substituted imidazolium product is presented. The preliminary animal tests indicated no anesthetic property but the two tested salts were found to behave as calmative. 相似文献
5.
The Cl‐atom‐initiated oxidation of two esters, ethyl formate [HC(O)OCH2CH3] and ethyl acetate [CH3C(O)OCH2CH3], has been studied at pressures close to 1 atm as a function of temperature (249–325 K) and O2 partial pressure (50–700 Torr), using an environmental chamber technique. In both cases, Cl‐atom attack at the CH2 group is most important, leading in part to the formation of radicals of the type RC(O)OCH(O?)CH3 [R = H, CH3]. The atmospheric fate of these radicals involves competition between reaction with O2 to produce an anhydride compound, RC(O)OC(O)CH3, and the so‐called α‐ester rearrangement that produces an organic acid, RC(O)OH, and an acetyl radical, CH3C(O). For both species studied, the α‐ester rearrangement is found to dominate in air at 1 atm and 298 K. Barriers to the rearrangement of 7.7 ± 1.5 and 8.4 ± 1.5 kcal/mole are estimated for CH3C(O)OCH(O?)CH3 and HC(O)OCH(O?)CH3, respectively, leading to increased occurrence of the O2 reaction at reduced temperature. The data are combined with those obtained from similar studies of other simple esters to provide a correlation between the rate of occurrence of the α‐ester rearrangement and the structure of the reacting radical. © 2010 Wiley Periodicals, Inc. Int J Chem Kinet 42: 397–413, 2010 相似文献
6.
Stable polyfluorinated bis- and tris-(alkoxy)methyl cations were prepared by the reaction of the corresponding difluoroformals (RfO)2CF2 (Rf = -CH2CF3, -CH(CF3)2, -CH2CF2Cl) with an excess of SbF5. Although the cation (CF3CH2O)2CF+ (1a) is stable at ambient temperature, the chlorinated analog (ClCF2CH2O)2CF+ (3a) can be generated only at low temperature in SO2ClF solvent and rapidly decomposes at ambient temperature. Although the salt [(CF3)2CHO]2CF+SbnF5n+1− (2a) is slightly more stable than the salt of cation 3a, at ambient temperature it undergoes rapid disproportionation with formation of equal amounts of [(CF3)2CHO]3C+SbnF5n+1− (2b) and CF3OCH(CF3)2 (2c). Stable solid salt 2b (n = 2) was isolated and fully characterized by 1H, 19F and 13C NMR spectroscopy and its structure was confirmed by single crystal X-ray diffraction. 相似文献
7.
Radical polyaddition of bis(α-trifluoromethyl-β,β-difluorovinyl) terephthalate [CF2C(CF3)OCOC6H4COOC(CF3)CF2] (BFP) with silsesquioxanes was investigated in order to produce a polymer possessing silsesquioxane moiety in polymer main chain. 1,3,5,7,9,11,13,15-octakis(dimethylsilyloxy)pentacyclo[9.5.1.13,9.15,15.17,13]octasiloxane (T8S) with BFP successfully afforded a polymer bearing a molecular weight of about 2.5×105. The polymer obtained were soluble in usual organic solvent such as methanol, tetrahydrofuran and chloroform. In order to get some information on the polyaddition reaction mechanism, model reactions of 2-benzoxypentafluoropropene [CF2C(CF3)OCOC6H5] (BPFP) with dimethylphenylsilane, [(CH3)2SiHC6H5], BPFP with 1,1,3,3-tetramethyldisiloxane {[(CH3)2SiH]2O}, and BFP with dimethylphenylsilane were carried out. The mechanism that the radical abstracts a hydrogen from silane compounds followed by the addition of perfluoroisopropenyl groups was proposed. 相似文献
8.
Structure and mechanism of thermal and photochemical reactions of radical cations of methyl n-propyl ether (MPE) were studied in irradiated freonic matrices CFCl3, CF2ClCFCl2, and CF3CCl3 at 77 K. The quantum chemical calculations of the structure of radical cations and products of their transformations were carried out with methods based on the density functional theory (DFT). Experimental and calculation results show that the MPE radical cations are characterized by substantial delocalization of spin density to the propyl group. The action of light on the MPE radical cations in a CF3CCl3 matrix at 77 K results in intramolecular rearrangement yielding the distonic radical cation .CH2CH2CH2(OH+)CH3. It was found that the primary MPE radical cations underwent irreversible transformation to CH3CH2CH2OCH
2
.
radical as a result of an ion-molecule reaction that occurred in a CF2ClCFCl2 matrix upon heating the sample to 110–120 K or in a CFCl3 matrix upon increasing the solute concentration.Translated from Khimiya Vysokikh Energii, Vol. 39, No. 2, 2005, pp. 105–113.Original Russian Text Copyright © 2005 by Belevskii, Feldman, Tyurin.This revised version was published online in April 2005 with a corrected cover date. 相似文献
9.
By pyrolyzing di-t-butyl peroxide over the temperature range of 405–450 K in the presence of hexafluoroacetone the kinetics of the addition reaction (1), CH3 + (CF3)2CO→; (CF3)2C(?)CH3, have been studied. Detailed analyses have shown that the principal product of the adduct radical, (CF3)2C(?)CH3, is CF3COCH3 from reaction (2), (CF3)2C(?)CH3 → CF3COCH3 + CF3. The rate constant of the addition reaction was determined to be k1(dm3/mol·s) = (1.1 ± 4.0) + 109 exp(-(3680 ± 480)/T) over the temperature range 405–450 K, based on the value k3 = 2.2 × 1010 dm3/mol·s for reaction (3), 2CH3 → C2H6. The results are discussed in relation to existing data for radical additions to carbonyl groups. 相似文献
10.
Viacheslav A. Petrov 《Journal of fluorine chemistry》2004,125(4):531-536
It was demonstrated that the reaction of 2,2-bis(trifluoromethyl)oxirane (1) with variety of alcohols could be successfully carried out under phase transfer catalysis conditions using sodium or potassium hydroxide as a base. For example, reaction of CH3OH, C2H5OCH2CH2OH, HOCH2CH2OH with one or two moles of 1 in the presence of the catalyst [(C4H9)4N+HSO4−] gives the corresponding tertiary alcohols R[OCH2C(CF3)2OH]n (n=1 or 2) in 43-53% yield, along with some O[CH2C(CF3)2OH]2. Benzyl alcohol and phenol under similar conditions are less active, producing in the reaction with 1 the corresponding adducts ArOCH2C(CF3)2OH in 31-35% yield. Fluorinated alcohols, such as CF3CH2OH, ClCF2CH2OH, HCF2CF2CH2OH have much higher reactivity towards 1 giving ring opening products in 82-97% yield. Even in the reaction of hindered hexafluoro-iso-propanol the corresponding adduct was isolated in 43% yield. Surprisingly, the reaction of iso-propanol and epoxide 1, results in the formation of O[CH2C(CF3)2OH]2 as a major product, isolated in 56% yield. Possible mechanism for the formation of the last product was proposed. 相似文献
11.
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
12.
Michaela GÖRg Ralph-Matthias Schoth Ildikó Székely Gerd-Volker Röschenthaler 《Phosphorus, sulfur, and silicon and the related elements》2013,188(1):667-670
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(RF)C(RF)=CF2 (RF 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. 相似文献
13.
Reactions of Tetrafluoro-1, 2-ethanedisulfenyldichloride with Ketones and Olefines The reaction of ClSCF2CF2SCl 1 with (CH3)3C? C(O)CH3, hexene, diacetyl, cyclobutanone, and H2C?CHC(O)CH3 leads to the cyclic and acyclic products 2 – 6 . They are destillable liquids, which have been characterized on the basis of elemental analysis, mass spectra, 19F-, 13C-, and 1H-n.m.r. spectra. The reaction mechanism will be discussed. 相似文献
14.
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
15.
《Journal of fluorine chemistry》1987,36(4):429-438
For the first time, fluorinated oxathialones, polyfluoroalkylchlorothioformates, chlorocarbonylpolyfluoroalkylsulfenate esters, a chlorocarbonylhexafluoroisopropylidenimino sulfenate, and a 5-tri-fluoromethyl-2-oxo-1,3,4-oxathiazole were synthesized by reacting chlorocarbonylsulfenyl chloride with RfC(O)CH2C(O)R′ (Rf = CF3; R'= CF3, OC2H5), RfO-Li+ (Rf = CF3CH2, (CF3)2C=N-Li+ and CF3C(O)NH2. Perfluorosuccinic acid and mercury(II) trifluoroacetate with ClC(O)SCI gave their respective anhydrides. 相似文献
16.
R. Francke R. Di Giacomo Dainis Dakternieks Gerd-Volker Rschenthaler 《无机化学与普通化学杂志》1984,519(12):141-147
Aminophosphites and Aminophosphoranes Containing the 2,2,2-Trifluoro-1-(trifluoromethyl)ethyl Grouping By the reaction of dichloroaminophosphines R2NPCl2 (R = Me, Et, SiMe3; R2 = CH2(CH2CMe2)2) and LiOCH(CF3)2 the phosphites 1 – 4 and LiCl were formed. Hexafluoroacetone reacted with 1 or 2 to give the monocyclic phosphoranes 5 and 7 . Compound 5 could also be obtained from the dichloroaminophosphosphorane 6 and LiOCH(CF3)2. The aminophosphite 2 , elementary chlorine and Li2[OC(CF3)2C(CF3)2O] or LiOCH(CF3)2 gave 7 or the acyclic phosphorane 8 , respectively. Compounds 1 – 4 exhibit two magnetically inequivalent CF3 groups in the 19F-N.M.R. spectra, the phosphoranes 5 , 7 and 8 show no ligand permutation at room temperature. 相似文献
17.
Philip C. Andrews Craig M. Forsyth Peter C. Junk Iryna Nuzhnaya Leone Spiccia 《Journal of organometallic chemistry》2009,694(3):373-381
The treatment of InCl3 with MOCH(CF3)2 (M = Li, Na, K) in a 1:6 stoichiometry, followed by recrystallisation results in the formation of the bimetallic “ate” complexes [Na3In(OCH(CF3)2)6(THF)3] (2) and [Li3In(OCH(CF3)2)6(THF)3] (5) from hexane, and [K3In(OCH(CF3)2)6]n (4) from a THF and toluene mixture. If a 1:3 stoichiometry is used chloride containing compounds [Na2InCl(OCH(CF3)2)4(THF)4] (1) and [KInCl2 (OCH(CF3)2)2(THF)3]n · THF (3) are obtained on recrystallisation from hexane. Treatment of GaCl3 with 6 equivalents of LiOC(CH3)2CF3 gives [LiGa(OC(CH3)2CF3)4(THF)2] (6) on recrystallisation from hexane. The protolysis reaction between In(N(SiMe3)2)3, formed in situ from (Me3Si)2NH, nBuLi and Incl3, and HOCH(CH3)CF3 results in isolation of [LiIn(OCH(CH3)CF3)3Bu]2 (7) from hexane. The structures of 2, 4, and 5 all contain the tetranuclear core InO6M3. Compounds 1 and 3 have residual chloride; 1 is a trinuclear species with two THF ligands per Na, while 3 is a linear polymer. Compound 6 has a GaO2Li four-membered parallelogram at its core. Complex 7 has a tetranuclear In2O6Li2 core and an unexpected nBu group on the In atoms. The coordination spheres of the alkali metals in 1-6 include solvated THF while 1-5 display additional close M?F interactions. 相似文献
18.
The novel alkali metal peroxide derivatives (CH3) 3COOC(CF3) 2ONa, NaOC(CF3) 2OOC(CF3) 2ONa and CF3C(O) OOC(CF3) 2ONa have been prepared through reactions of hexafluoroacetone, (CF3) 2CO, with the sodium salts of various organic hydroperoxides. These new salts are soluble in water and polar organic solvents and have been used to prepare the new covalent fluorocarbon/hydrocarbon peroxides [(CH33COOC(CF3) 2OC(O)C6H5, (CH3) 3SiOC(CF3) 2-OOC(CF3) 2OSi(CH3) 3, and (CH33COOC(CF3) 2C(O)CF3] through reaction with compounds having active halogen. Although the new peroxides are apparently less flammable and explosive than their hydrocarbon analogs, they also exhibit shorter half-lives than the parent compound (i.e., the peroxide without hexafluoroacetone insertion). 相似文献
19.
Preparation of Trifluormethylhalogen Iodate(I) Salts (CH3)4N+CF3IX? (X = F, Cl, Br) and Trifluormethyltrifluormethoxy Iodate(I) (CH3)4N+CF3IOCF3? We describe the preparation of new trifluormethyliodate(I) salts CF3IX? (X = F, Cl, Br, OCF3). (CH3)4N+CF3ICl? and (CH3)4N+CF3IBr? are obtained via addition of CF3I with the corresponded tetramethylammonium halogenide. (CH3)4N+CF3IOCF3? is synthesized by comproportionation of (CH3)4N+CF3ICl? with CF3OCl under formation of Cl2 at ?78°C. (CH3)4N+CF3IF? is formed either, through thermolysis of (CH3)4N+ CF3IOCF3? under separation of COF2, or reaction of CF3I with (CH3)4N+ OCF3?. The thermolabile compounds have been characterized by i.r., Raman, 19F-, 13C NMR spectroscopy. 相似文献
20.
The reactions of py‐hz ligands ( L1–L5 ) with Pb(CF3SO3)2?H2O resulted in some rare examples of discrete single‐stranded helical PbII complexes. L1 and L2 formed non‐helical mononuclear complexes [Pb L1 (CF3SO3)2]?CHCl3 and Pb L2 (CF3SO3)2][Pb L2 CF3SO3]CF3SO3?CH3CN, which reflected the high coordination number and effective saturation of PbII by the ligands. The reaction of L3 with PbII resulted in a dinuclear meso‐helicate [Pb2 L3 (CF3SO3)2Br]CF3SO3?CH3CN with a stereochemically‐active lone pair on PbII. L4 directed single‐stranded helicates with PbII, including [Pb2 L4 (CF3SO3)3]CF3SO3?CH3CN and [Pb2 L4 CF3SO3(CH3OH)2](CF3SO3)3?2 CH3OH?2 H2O. The acryloyl‐modified py‐hz ligand L5 formed helical and non‐helical complexes with PbII, including a trinuclear PbII complex [Pb3 L5 (CF3SO3)5]CF3SO3?3CH3CN?Et2O. The high denticity of the long‐stranded py‐hz ligands L4 and L5 was essential to the formation of single‐stranded helicates with PbII. 相似文献