Fluorinated phosphorus compounds: Part 6. The synthesis of bis(fluoroalkyl) phosphites and bis(fluoroalkyl) phosphorohalidates

Reaction of phosphorus trichloride with tert-butanol and fluoroalcohols gave bis(fluoroalkyl) phosphites (R_FO)₂P(O)H in 42-89% yield, where R_F=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 (R_FO)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.     

Fluorinated tropylium ions in the mass spectra of some polyfluoroaromatic compounds

The most prominent ion in the mass spectra of C₆F₅CH₂X (X ? H, Br, CH:CH₂, COCl, and CH₂C₆F₅) is C₇F₅H₂⁺, formulated as the pentafluorotropylium cation. This ion is also found, in an amount comparable to the parent ion, in the spectrum of (C₆F₅)₂CH₂. The heptafluorotropylium cation is found similarly in the spectrum of C₆F₅CF₃. The mass spectra of (C₆F₅)₂CHBr and [(C₆H₅)₂CH]₂ exhibit an ion C₁₃F₁₀H⁺ as the base peak, which is probably a pentafluorophenylpentafluorotropylium cation. The alcohol (C₆F₅)₂CHOH shows loss of C₆F₅, followed by 2H, as a major breakdown pathway. The mode of formation, and the subsequent fragmentation, of the major ions in these spectra, are discussed.     

Preparation of CF3COCl: investigation of operating parameters

The preparation of CF₃COCl through reaction between CF₃CCl₃ and SO₃ was investigated with particular reference to the following operating parameters: catalyst type and concentration, molar ratio C₂Cl₃F₃/SO₃ and composition of the isomeric mixture CF₃CCl₃/CClF₂CCl₂F.Such preparation was first investigated either batchwise or semi-continuously, in order to define at best the above parameters. It was then effected continuously on proper equipment, which allowed to separate the CF₃COCl at a degree of purity adequate to its direct use in the preparation of trifluoroacetic compounds.     

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.     

单氢钌配合物与水和2,2,2-三氟乙醇的作用机理

利用原位¹H和³¹P NMR对单氢钌配合物TpRu(PPh₃)(CH₃CN)H [Tp＝hydrotris(pyrazolyl)borate]与H₂O和酸性HOCH₂CF₃的反应进行了研究, 结果显示相应的反应产物分别是TpRu(PPh₃)(CH₃CN)(OH) 和TpRu(PPh₃)(CH₃CN)(OCH₂CF₃). 观察到反应过程中Ru-H…HOH和Ru-H…HOCH₂CF₃分子间的氢键作用. 提出了生成TpRu(PPh₃)(CH₃CN)(OH)和TpRu(PPh₃)(CH₃CN)(OCH₂CF₃)的不同作用机理. 在水存在下, TpRu(PPh₃)(CH₃CN)H 与H₂O反应, 经过中间体TpRu(PPh₃)(H₂O)H和TpRu(PPh₃)(OH)(η²-H₂)生成产物TpRu(PPh₃)(CH₃CN)(OH). 而TpRu(PPh₃)(CH₃CN)H与酸性HOCH₂CF₃反应时, 单氢配体被质子化形成中间体[TpRu(PPh₃)(CH₃CN)- (η²-H₂)](OCH₂CF₃), 进而转变成产物TpRu(PPh₃)(CH₃CN)(OCH₂CF₃). TpRu(PPh₃)(CH₃CN)(OCH₂CF₃)与H₂作用, 经中间体TpRu(PPh₃)(HOCH₂CF₃)H生成TpRu(PPh₃)(η²-H₂)H.     

Bis(fluoroalkyl)acrylic and methacrylic phosphate monomers, their polymers and some of their properties

Ten fluoromonomers of structure (R_FO)₂P(O)OCH₂CH₂OC(O)CRCH₂ were made in 30-64% yield by treating the chloridates (R_FO)₂P(O)Cl with HOCH₂CH₂OC(O)CRCH₂ in chloroform in the presence of triethylamine [R_F=CF₃CH₂, C₂F₅CH₂, C₃F₇CH₂, C₄F₉CH₂, C₄F₉CH₂CH₂ or C₆F₁₃CH₂CH₂; R  H or Me]. The chloromonomer (CCl₃CH₂O)₂P(O)OCH₂CH₂OC(O)CHCH₂ was obtained analogously in 29% yield. Polymerisation of the acrylate monomers, but not the methacrylate monomers, could be effected using α-azoisobutyronitrile as a radical initiator. Acrylic polymers having CF₃CH₂O, CCl₃CH₂O and C₆F₁₃CH₂CH₂O side-chains were obtained as translucent rubbers. Specimens of cotton fabric were treated with solutions of the polymers, and average water and oil repellency ratings measured. Fabric coated with the polymer with the C₆F₁₃CH₂CH₂O side-chain afforded protection from penetration of the test liquids. Treated fabrics were subjected to the limiting oxygen index (LOI) test according to BS EN ISO 4589-2 (1999): this test determines the point at which a material just burns in a volumetric flow of oxygen and nitrogen. The treated fabrics were more fire-resistant (LOI 22-29%) than the untreated fabric (LOI 18%). Fabric coated with the CCl₃CH₂O-based polymer can be considered fire-retardant (LOI 29%). The fluoromonomers were tested for anti-acetylcholinesterase activity and were found to be poor enzyme inhibitors; they are predicted to possess low acute toxicity.     

Synthese et reactivite des F-alkyl sulfures et sulfones actives

In this paper we report syntheses of F-alkyl compounds such as R_FC₂H₄S(O)_nCH₂Z (with n=0,2 and Z=H,Ø(C₆H₅),COØ,COOEt,COCH₃,CN). Using the carbanionic reactivity of these compounds, we would like to use them as precursors of surfactants, grafting hydrophilic functions on the carbons α or α′ to the sulfur atom. The compounds were not very reactive. Alkylation or acylation on this site could only be obtained with a ‘pseudo malonic’ CH₂ (R_FC₂H₄SO₂CH₂Z with Z=COØ, COOEt,COCH₃,CN). Only methyl iodide and acetyl chloride led to positive results.     

New types of asymmetrical bromonium salts [RF(RF′)Br]Y where RF and/or RF′ represent perfluorinated aryl, alkenyl, and alkynyl groups

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 R_F′BF₂ (R_F = 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 R_F′BF₂·NCMe (R_F = C₆F₅, CF₃C≡C) on reactions aside to bromonium salt formation are discussed. Reactions of C₆F₅BrF₂ with Alk_F′BF₂ in PFP gave mainly C₆F₅Br and Alk_F′F (Alk_F′ = C₆F₁₃, C₆F₁₃CH₂CH₂), presumably, deriving from the unstable salts [C₆F₅(Alk_F′)Br]Y (Y = [Alk_F′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 [C_nF_2n+1C≡C(R_F)Br][BF₄] slowly added HF when dissolved in aHF and formed [Z-C_nF_2n+1CFCH(R_F)Br][BF₄].     

Darstellung von polyfluororganotrichlorsilanen

The following substances could be prepared by Grignard reactions or by conversions with trichlorosilane: C₆F₅CH₂CHCH₂, C₆F₅(CH₂)₃SiCl₃, CF₃(CF₂)₉CH₂CHCH₂, CF₃(CF₂)₇(CH₂)₂SiCl₃, CF₃(CF₂)₁₁(CH₂)₃CHCH₂ und CF₃(CF₂)₁₁(CH₂)₅SiCl₃.They were characterized by spectroscopical and microanalytical methods.     

Synthesis and properties of gemini-type hydrocarbon-fluorocarbon hybrid surfactants

Gemini-type hybrid surfactants with two fluorocarbon chains connected through a hydrocarbon spacer, F(CF₂)_m(CH₂)₂CH(OSO₃Na)(CH₂)_nCH(OSO₃Na)(CH₂)₂(CF₂)_mF [Fm(Hn)FmOS, m = 4, 6; n = 5, 6, 7, 8)], were synthesized and their surface chemical properties were examined with the aim to have highly functional and highly water-soluble fluorinated surfactants when compared with the conventional fluorinated surfactants. Comparisons of the surface chemical properties of the synthesized gemini-type hybrid surfactants with those of monounit-type hybrid surfactants, F(CF₂)_m(CH₂)₂CH(OSO₃Na)(CH₂)_nH [FmEHnOS, m = 4, 6; n = 3, 5)], revealed that gemination causes a remarkable lowering (about 1/100) in cmc value while it produces little changes in Krafft point (below 0 °C) and surface tension at cmc (γ_cmc).     

Atmospheric pressure deposition of F‐doped SnO2 thin films from organotin fluoroalkoxide precursors

Five tributyltin fluoroalkoxides Bu₃SnOR_f [R_f = CH(CF₃)₂ ( 1 ), CH₂CF₃ ( 2 ), CH₂C₂F₅ ( 3 ), CH₂(CF₂)₃CF₂H ( 4 ), CH₂CH₂F ( 5 )] were synthesized and assessed as precursors for the APCVD of F‐doped SnO₂. O₂ is required as co‐reagent to produce hard, well‐adhered coatings. Of the precursors assessed, 5 gave the best film incorporating 1.52 atom% fluorine, showing some (200) preferred orientation, resistivity of 1.30 × 10^?3 Ω cm and 0.42% haze. Copyright © 2008 John Wiley & Sons, Ltd.     

Fluorinated phosphorus compounds: Part 9. The reactions of bis(fluoroalkyl) phosphorochloridates with oxygen nucleophiles

Twenty nine bis(fluoroalkyl) phosphates (R_FO)₂P(O)OR were prepared in 18-75% yield by treating phosphorochloridates (R_FO)₂P(O)Cl, where R_F was HCF₂CH₂, HCF₂CF₂CH₂, H(CF₂)₄CH₂, C₂F₅CH₂, C₃F₇CH₂, (CF₃)₂CH, (FCH₂)₂CH and (CH₃)₂CF₃C with methanol, ethanol, propanol and isopropanol in diethyl ether in the presence of triethylamine. The bulky chloridate [(CH₃)₂CF₃CO]₂P(O)Cl reacted with methanol, ethanol and propanol, but not with isopropanol - even on heating in the presence of the catalyst 4-dimethylaminopyridine - due to steric hindrance at phosphorus. The relative reactivities of three of the chloridates decreased in the order [(CF₃)₂CHO]₂P(O)Cl > [(FCH₂)₂CHO]₂P(O)Cl > [(CH₃)₂CF₃CO]₂P(O)Cl. Also described is the synthesis of phosphates (CF₃CH₂O)₂P(O)OCH₂R, where R = CH₂Br, CH₂Cl, CH₂F and CHF₂, and diphosphates [H(CF₂)_nCH₂O]₂P(O)OCH₂(CF₂)₂CH₂OP(O)[OCH₂(CF₂)_nH]₂, where n = 1, 2 and 4.     

Protonation of the Dodecahydro-<Emphasis Type="Italic">closo</Emphasis>-Dodecaborate Anion in CH<Subscript>3</Subscript>CN/CF<Subscript>3</Subscript>COOH

The behavior of the [B₁₂H₁₂]^2– anion in CH₃CN, CF₃COOH, and the CH₃CN/CF₃COOH system is studied by IR spectroscopy. Based on the IR spectroscopy data correlated with the data obtained when studying the protonation processes of boron cluster anions [B₆H₆]^2– and [B₁₀H₁₀]^2–, the possibility to prepare the protonated form of the closo-dodecaborate anion, namely monoanion [B₁₂H₁₃]^–, is concluded in CF₃COOH and the CH₃CN/CF₃COOH system. In the IR spectra of salts of the protonated forms of anions [B_nH_n]^2– (n = 6, 10, 12) in solutions and Nujol mulls, a high-frequency shift of the ν(BH) absorption bands is observed as compared with the spectra of salts of non-protonated anions Cat₂[B_nH_n] (Δν = 70–100 cm^–1).     

Synthese de materiaux polymers transparents - Partie II Synthese et polymerisation d'acrylates et de methacrylates d'halogenoalkyle

Several fluorinated and chlorofluorinated acrylates and methacrylates were synthesized from the alcohols R_FCH₂OH with R_F=CCl₃, CHClCH₂CCl₃, (CF₂CFCl)_nCl, (C₂F₄)_nH, CF₃, C₇F₁₅ and C₆F₁₃CH₂. The corresponding polymers were also studied for their application as transparent polymeric materials. For this purpose the refractive indices n²⁰_D of the monomers and the polymers were measured as were the Tg values of the polymers. A study of their infrared spectra shows to what extent these products could be utilized taking into consideration their absorption in the long wavelength range between 0.85 and 1.50 m. The refractive indices of these polymers, which are reduced when increasing the number of fluorine atoms in the molecule, and that of the Tg measured between 50 and 70° C for the fluorinated methacrylates, indicate a potential use of these polymers as sheathing materials for optical fibres.     

Synthesis of thiols,disulfides, and sulfonic acids containing trichloromethyl,dichloro vinyl,and carboxy groups

Summary Starting from...-tetrachloroalkanes, trichloroalkenes of structure CCl₂=CH(CH₂)_nCl, and-chloro carboxylic acids, we obtained ithio, mercapto, and sulfo compounds and some of their derivatives of structure; [CCl₃(CH₂)₄]₂S₂; [CCl₂=CH(CH₂)₃]₂S₂; [ROOC(CH₂)₄]₂S₂ (in which ); CCl₃(CH₂)₄SCl; CCl₃(CH₂)_nSH (in which n=4,6,8); CCl₂=CH(CH₂)₃SH; ROOC(CH₂)₄SH (in which R=H, C₂H₅); CCl₃(CH₂)_nSO₃Na (in which n=4,6,8); C₂H₅OOC(CH₂)₄SO₃Na.     

Cooperative hydrogen bonding in solution: Influence of molecule structure

Influence of cooperative interactions on IR stretching vibration frequencies of complexes CCl₃H⋯ROH⋯B (B-base), CCl₃H⋯ROH⋯O(C₂H₅)₂ and CCl₃H⋯ROH⋯ROH in proton donor solvent CCl₃H were studied.Solvent effects on OH stretching vibration frequencies of CF₃CH₂OH⋯B, ROH⋯O(C₂H₅)₂ and ROH⋯ROH complexes in aprotic solvents were calculated using earlier proposed method. Cooperativity factors in CCl₃H⋯CF₃CH₂OH⋯B complexes were determined. Obtained values were significant smaller than for CCl₃H⋯CH₃OH⋯B complexes. Also cooperativity factors for CCl₃H⋯ROH⋯O(C₂H₅)₂ and CCl₃H⋯ROH⋯ROH complexes were determined. It was demonstrated that obtained values slightly depend on length and embranchment of alkyl group in alcohol molecules. The main role in cooperative interactions plays electronic effect.     

Reaction of α,α,ω-trichloroalkenes with 1,1,1-trichloroethane and 1,1,1,3-tetrachloropropane,accompanied by rearrangement of radicals

Conclusions In the reaction of CCl₃CH₃ with CCl₂=CHCH₂CH₂CH₂Cl, and of CCl₃CH₂CH₂Cl with CCl₂= CHCH₂Cl, initiated by Fe(CO)₅+DMF, the main addition products are respectively compounds of structure HCCl₂CH(CCl₂CH₃)CH₂CH₂CHCl₂ and HCCl₂CH(CCl₂CH₂CHCl₂)CH₂C1. The formation of these compounds was explained by the isomeriza'tion of the radical-adducts CCl₂CH(CCl₂CH₃)CH₂CH₂CH₂Cl and CCl₂CH(CCl₂CH₂CH₂Cl)CH₂Cl, with migration of a hydrogen atom from the CH₂Cl groups found in the 5 position to the radical center.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 8, pp. 1857–1861, August, 1980.     

Synthesis of block cotelomers involving a perfluorinated chain and a hydrophilic chain. III. Synthesis and use of fluorinated telogens with a trichloromethyl end group

The addition by redox catalysis (CuCl or FeCl₃ with benzoin) of CCl₄ and CCl₃? CF₂? CCl₃ on pentafluorostyrene and on fluorinated allyl ether, C₆F₁₃? C₂H₄? O? CH₂? CH?CH₂ was performed. The monoaddition compounds were mainly obtained with satisfactory yields and characterized by NMR (¹³C, ¹H, and ¹⁹F). These compounds were then used as telogens in telomerization by redox catalysis of acrylamide, methyl methacrylate, and acrylic acid and in radical-initiated telomerization of N-vinyl-pyrrolidone. The chain lengths of the hydrocarbonated sequences were determined from fluorine elemental analysis. A critical investigation of correlations between DP _n and concentrations of products involved was made.     

The thiolate anion as a nucleophile Part XII. Reactions of Lead(II) Benzenethiolate

The reactions of various fluoroaromatics, C₆F_6?xH_x, and C₆F₅X (X = C₆F₆, Cl, Me, NO₂, CF₃, COCl, CH₂Br, OMe, and NH₂) with lead(II) benzenethiolate in DMF have been examined. Lead thiolate acted as an excellent source of benzenethiolate anions and displacement of fluorine, chlorine or the nitro group was observed. The new products have been characterized by elemental analysis, and NMR (H?1 and F?19), infrared and mass spectroscopy.     

Reactivity comparison for selenophen,thiophen, and their methyl derivatives via hydrogen-isotope exchange

Deuteration measurements have been made with t-C₄H₉OK and with 4 moles of CH₃COOH mixed with one mole of CF₃COOH against 2D-selenophen, 3D-selenophen, 3CH₃, 2D-selenophen and 5CH₃, 2D-selenophen. Reactivity in the selenohpen-thiopen series is examined via protophilic and electrophilic isotopic-exchange reactions. The factors for the partial exchange rates with acid and base for heterocyclics with D at position 2 and CH₃ at position 3, 4, or 5 are compared with those factors for isomers of monodeuterotoluene; it is found that the electronic effect of the CH₃ group is transmitted similarly for these heterocyclics and for the benzene ring. Reasonably good agreement is found between the relative constants for deuterium exchange in thiophen, selenophen, and methyl derivatives of these as catalyzed by alkali-metal t-butylates in dimethylsulfoxide (DMSO) and in t-butanol mixed with diethylene glycol dimethyl ether. This shows that the results with DMSO correctly characterize the reactivity in protophilic hydrogen exchange.