A thermal study of hydrated lanthanide heptafluorobutyrates

Several hydrated lanthanide salts of heptafluorobutyric acid have been prepared and characterized.Hydration studies have shown the compounds to exist in various hydration states across the series. Powder X-ray diffraction studies support the existence of variable hydration states in that three distinct crystalline forms exist. Infrared analysis revealed two types of structures to be present. Upon dehydration of the lighter rare earth hydrates to intermediate dihydrates, all of the compounds showed similar structures. Decomposition was found to be exothermic. The volatile decomposition products were identified by infrared analysis and found to consist of CO, CO₂, CF₃CF₂COF and CF₃CF₂CF₂COF. The amounts of each gas were found to be dependent on the decomposition temperature. The non-volatile decomposition products were identified by powder X-ray diffraction and found to consist of LnF₃, LnOF and Ln₂O₃.     

A new method for the preparation of perfluorocarboxylic acids

The reaction of both primary perfluoroalkyl iodides and bromides containing 3 ∼ 12 carbon atoms [CF₃(CF₂)_nX, n = 2 ∼ 11, X = Br, I] with a Rongalite-NaHCO₃ reagent in aqueous dipolar aprotic solvents, such as DMF or DMSO, has been investigated. The reaction gave sodium perfluorocarboxylates [CF₃(CF₂)_n-1CO₂Na, n = 2 ∼ 11] in 51 – 86 % yields, and these were transformed to the respective perfluorocarboxylic acids [CF₃(CF₂)_n−1CO₂H, n = 2 ∼ 11] by treatment with sulfuric acid. This provides a new method for the synthesis of perfluorocarboxylic acids.     

Triflic acid promoted synthesis of polycyclic aromatic compounds

The triflic acid (CF₃SO₃H) promoted cyclizations of 2-styrylbiaryls are found to be useful for the synthesis of polycyclic aromatic compounds, including functionalized derivatives of polycyclic aromatic compounds and heterocyclic systems. The reaction involves cationic cyclization followed by an elimination of benzene from the intermediate product.     

Synthesis of Aryl-Manganese(III) Fluoride Complexes via α-Fluorine Elimination from CF3 and Difluorocarbene Generation

We report the synthesis of cyclometalated monoaryl Mn^III fluoro complexes using bis(trifluoromethyl)zinc reagent, Zn(CF₃)₂(DMPU)₂, under mild conditions via a reaction pathway that involves initial transmetalation followed by α-fluorine elimination. The formation of difluorocarbene in these reactions was detected by trapping experiments. Such facile difluorocarbene generation from Mn^III results in moderate enhancement of difluoropropanation and difluoropropenation of alkenes and alkynes using Zn(CF₃)₂(DMPU)₂ at lower temperature (20–60 °C) and short reaction time, suggesting potential application of manganese(III) perfluoroalkyl complexes as reactive species for carbene transfer reactivity.     

Super-Hydrophobic,Stable, and Swelling Nanoporous Solid Strong Acid

Super-hydrophobic solid strong acid with superior thermal stability and unique swelling properties has been synthesized by sulfonation of nanoporous polydivinylbenzene (PDVB) with super-acid of trifluoromethanesulfonic acid (TFMSA). The resultant PDVB–HOSO₂CF₃ has a well developed system of nanopores, superhydrophobic surface character and strong acid sites, and could be used as a highly efficient solid acid for catalyzing production of biodiesel and fine chemicals via transesterification, esterification and acylation. In terms of activity PDVB–HOSO₂CF₃ is superior to various solid acids such as SBA-15-SO₃CF₃, Nafion, Amberlyst 15, SBA-15-Ar-SO₃H and H form USY. The preparation of PDVB–HOSO₂CF₃ offers the way to develop new kind of porous solid acid with strong acid strength and regulated wettability.     

(CF3)2Cd·D und (CF3)2Zn·D: neue reagenzien für difluorcarben-reaktionen [1]

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.     

Synthesis and repellent properties of vinylidene fluoride-containing polyacrylates

Fluorinated polyacrylats with side group containing vinylidene fluoride (VDF) units (CF₃(CF₂)_n (CH₂CF₂)_m, n = 3, 5; m = 1, 2) were successfully synthesized. The water and oil repellency properties of these polymers are similar to those of fluorinated polyacrylate with side group containing long perfluorooctyl group (CF₃(CF₂)₇). The thermal telomerization of CF₃(CF₂)₅I and CF₃(CF₂)₃I with vinylidene fluoride (VDF) provided CF₃(CF₂)₅CH₂CF₂I (1b) and CF₃(CF₂)₃CH₂CF₂CH₂CF₂I (1c), respectively. The addition of 1b with ethylene followed by hydrolysis gave CF₃(CF₂)₅CH₂CF₂CH₂CH₂OH (2b). Treatment of 1c with ethyl vinyl ether in the presence of Na₂S₂O₄ followed by reduction produced CF₃(CF₂)₃CH₂CF₂CH₂CF₂CH₂CH₂OH (2c). Fluoroacrylates 3b-d were prepared by acrylation of the corresponding fluoroalcohols 2b-d. The semi-continuous process emulsion co-polymerization of 3a-d with octadecyl acrylate and 2-hydroxylethyl acrylate initiated by (NH₄)₂S₂O₈ in the presence of a mixture emulsifiers of polyoxyethylene(10)nonyl phenyl ether (TX-10) and sodium lauryl sulfate provided stable latexes 4a-d, respectively. The water and oil repellency properties of 4b (R_f: CF₃(CF₂)₅CH₂CF₂) and 4c (R_f: CF₃(CF₂)₃CH₂CF₂CH₂CF₂) containing vinylidene fluoride (VDF) units were similar to those of 4a (R_f: CF₃(CF₂)₇) containing long perfluoroalkyl group and much better than those of polymer 4d (R_f: CF₃(CF₂)₃) with short perfluoroalkyl chain. Thus, polyacrylates containing vinylidene fluoride units showed promising aspects as the alternatives to the currently used water and oil repellent agents with long perfluoroalkyl chains.     

Electron structure and reactivity of organofluorine compounds. 4. AMI calculations of anion radicals of primary,secondary, and tertiary perfluoroalkyl chlorides,bromides, and iodides

Calculations were carried out using the semiempirical quantum chemical AMI method for anion radicals (AR) of the perfluoroalkyl halides (R_FX): CF₃X, CF₃CF₂X, (CF₃)₂-CFX, and (CF₃)₃CX for X=Cl, Br, and I. All the AR's studied are thermally stable. The electron affinity of the perfluoroalkyl halides, and consequently, the thermal stability of their AR's increases in the series from F-methyl to F-tertbutyl halides and from the chlorides to bromides and iodides. During formation of an AR the spin density is preferentially localized on the * orbital of the C–X bond which leads to an increase in the distance between these atoms. Dissociation of the AR of tert-perfluorobutyl iodide to a perfluorocarbanion and an I atom is thermodynamically more favorable than dissociation with formation of a perfluoroalkyl radical and I^–.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 5, pp. 1064–1068, May, 1990.     

Synthesis and properties of carbosilane dendrimers with perfluorohexyl groups in the outer layer of the molecular structure

Branched perfluorohydrosiloxane with CF₃CF₂CF₂C(CF₃)₂(CH₂)₃ groups at the silicon atom was synthesized by a sequence of chemical reactions. The resulting compound was used as a modifying agent for carbosilane dendrimers of the 3rd and 6th generations. Dendrimers with perfluorohexyl terminal groups in surface layer are characterized by a complex of physicochemical methods. It is demonstrated that due to the branching of perfluoroalkyl terminal groups, obtained carbosilane dendrimers are soluble in organic and inorganic media. Differences in the solubility of small and large dendrimers are caused by the formation of the outer fluoride shell of different densities.     

Perfluoro-4-methyl-1,3-dioxole: a new monomer for high-Tg amorphous fluoropolymers

A 4-Chloro-5-trifluoromethyl-2,2,4-trifluoro-1,3-dioxolane (1) was synthesised by reaction of CF₂(OF)₂ with CF₃CHCFCl; the elimination of HCl from (1) in basic conditions led to the formation of dioxole perfluoro-4-methyl-1,3-dioxole (2). Both these synthetic steps gave the corresponding product in high yield.A new synthetic route for the preparation of CF₃CHCFCl, starting from CF₂ClBr and CH₂CF₂, together with some examples of polymerisation products obtained by reaction of dioxole (2) with fluoroolefins are also reported.     

Reactions of mesomeric fluorocarbanions with acid anhydrides. Transformation of trifluoromethyl groups into fluorocarbonyl and perfluoroacyl groups

It was found that the reaction of mesomeric fluorocarbanions of the CF₃$\text{C}\text{θ}$XCOY type with benzoic anhydride leads to the loss of benzoyl fluoride and the formation of mesomeric carbanions of the FCO$\text{C}\text{θ}$XCOY type. In a similar reaction with perfluorocarboxylic acid anhydrides, besides a CF₃→COF transformation, further change of COF into COR_F is observed, leading to the formation of salts containing mesomeric anions of the R_FCO$\text{C}\text{θ}$XCOY type, which, upon acidification, give 1,1- -bis(perfluoroacyl)-2,2,2-trifluoroethanes CF₃CH(COR_F)₂ , tris- (perfluoroacyl)methanes (R_FCO)₃CH and bis(trifluoroacetyl)- acetic ester (CF₃CO)₂CHCOOMe. It has been shown that perfluoroalkyl groups in β-diketones and β,β′-triketones may hinder enolization despite their electron-attracting effect.     

Palladium‐Catalyzed Cascade CH Trifluoroethylation of Aryl Iodides and Heck Reaction: Efficient Synthesis of ortho‐Trifluoroethylstyrenes

A palladium‐catalyzed selective C? H bond trifluoroethylation of aryl iodides has been explored. The reaction allows for the efficient synthesis of a variety of ortho‐trifluoroethyl‐substituted styrenes. Preliminary mechanistic studies indicate that the reaction might involve a key Pd^IV intermediate, which is generated through the rate‐determining oxidative addition of CF₃CH₂I to a palladacycle; the bulky nature of CF₃CH₂I influences the reactivity. Reductive elimination from the Pd^IV complex then leads to the formation of the aryl–CH₂CF₃ bond.     

Transition metal-catalyzed formation of CF3-substituted α,β-unsaturated alkene and the synthesis of α-trifluoromethyl substituted β-amino ester

A new transition metal-catalyzed formation of CF₃-substituted α,β-unsaturated alkenes through the ylide intermediate from the reaction between methyl 3,3,3-trifluoro-2-diazopropionate 1 and aryl aldehydes has been developed. Further transformation of the alkene affords the α-trifluoromethyl substituted β-amino ester, a valuable intermediate in the synthesis of fluorine-containing amino acids with potential biological application.     

Aromatic compounds with new fluorine-containing substituents

The introduction of strong electron-accepting fluorine-containing substituents into the aromatic moiety gives compounds with unique properties. Determination of the electronic nature of the grouping (R_f)₂PO in arylbis(perfluoroalkyl)-phosphine oxides has shown that this substituent is comparable with R_fSO₂, one of the most electron-accepting groups.A general principle is proposed for the construction of the new superstrong electron-accepting substituents by the replacement of oxygen atoms for trifluoromethylsulfonylimino groups. For example, when the oxygen atoms in CF₃SO and CF₃SO₂ groups are replaced by CF₃SO₂N=, new stable and even more electron-accepting substituents are formed. The grouping CF₃S(O)=NSO₂CF₃ corresponds to two nitro groups. A similar increase in electron-accepting ability is observed in groupings derived from other elements by replacement of oxygen atoms by the CF₃SO₂N= group.     

Palladium‐Catalyzed Cascade C?H Trifluoroethylation of Aryl Iodides and Heck Reaction: Efficient Synthesis of ortho‐Trifluoroethylstyrenes

A palladium‐catalyzed selective C H bond trifluoroethylation of aryl iodides has been explored. The reaction allows for the efficient synthesis of a variety of ortho‐trifluoroethyl‐substituted styrenes. Preliminary mechanistic studies indicate that the reaction might involve a key Pd^IV intermediate, which is generated through the rate‐determining oxidative addition of CF₃CH₂I to a palladacycle; the bulky nature of CF₃CH₂I influences the reactivity. Reductive elimination from the Pd^IV complex then leads to the formation of the aryl–CH₂CF₃ bond.     

Pentafluoroethylsilicic Acids

Pure anhydrous hexafluorosilicic acid (H₂[SiF₆]) is a still elusive species, although its existence in aqueous solutions is well documented. Desiccation inevitably leads to decomposition to form tetrafluorosilane and hydrogen fluoride. An oxonium hexafluorosilicate turned out to not be stable at room temperature. Partial substitution of the fluorine atoms with strong electron‐withdrawing perfluoroalkyl groups results in substantial stabilization of the corresponding fluorosilicic acids. Mono‐ and bis(pentafluoroethyl)‐substituted fluorosilicic acids were prepared through conversion of the respective halosilanes (Si(C₂F₅)_nX_4?n, with X=Cl, Br) with aqueous HF, and were obtained as colorless solids. They can be stored at room temperature for several months without decomposition, and thus are the first examples of stable fluorosilicic acids.     

Reactions of quadricyclane with fluorinated nitrogen-containing compounds. Synthesis of 3-aza-4-perfluoroalkyl-tricyclo[4.2.1.0]non-3,7-dienes

The cycloaddition reactions of quadricyclane (1) and polyfluorinated imines and nitriles were studied. Both (CF₃)₂CNH and (CF₃)₂CN(2-FC₆H₄) were found to have low reactivity towards 1, giving the corresponding [2 + 2 + 2] cycloadducts in a low yield. C₂F₅NCFCF₃ however, reacts with 1 rapidly, giving a mixture of two isomeric cycloadducts in a high yield. Perfluoroalkyl nitriles R_fCN (R_f = CF₃, C₂F₅, n-C₃F₇) were found to have surprisingly high reactivity to 1 producing exo-3-aza-4-(fluoroalkyl)-tricyclo[4.2.1.0^2,5]non-3,7-dienes in 56-81% yields at elevated temperature. Exo-3-aza-4-(perfluoroalkyl)-tricyclo[4.2.1.0^2,5]non-3,7-dienes rapidly react with CF₃Si(CH₃)₃ in the presence of CsF catalyst. The reaction results in addition of CF₃Si(CH₃)₃ across the CN bond of the azadienes with selective formation of only one stereoisomer of exo-3-aza-3-(trimethylsilyl)-4,4-bis(perfluoroalkyl)-tricyclo[4.2.1.0^2,5]non-7-enes. Silyl group in this compounds can be removed either by the action of tetrabutylammonium fluoride hydrate, leading to the formation of the corresponding amine after hydrolysis, or by reaction with HCl resulting in the formation of the corresponding amine hydrochloride.     

Electron structure and reactivity of organofluorine compounds. 3. Mndo and ami calculations of the ground state of perfluoroalkyl chlorides,bromides, and iodides

The semiempirical quantum chemical MNDO and AMI methods were used to determine the equilibrium geometries and electron properties of molecules of perfluoroalkyl halides (R_FX): CF₃X, CF₃CF₂X, (CF₃)₂CFX, (CF₃)₃CX for X=Cl, Br, and I. It was determined that the effective charge on the Cl atom in R_FCl is negative, positive on the I atom in R_FI, and depends on R_F for the Br atom in R_FBr. The CF₃ group can act as either an electron acceptor or donor in various perfluoroalkyl halides. The strongest C–I bond in the perfluoroalkyl halides occurs with a tertiary RF group.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 5, pp. 1059–1063, May, 1990.     

Theoretical studies of decomposition kinetics of CF3CCl2O radical

The unimolecular decomposition reaction of CF₃CCl₂O radical has been investigated using theoretical methods. Two most important channels of decomposition occurring via C–C bond scission and Cl elimination have been considered during the present investigation. Ab initio quantum mechanical calculations are performed to get optimized structure and vibrational frequencies at DFT and MP2 levels of theory. Energetics are further refined by the application of a modified Gaussian-2 method, G2M(CC,MP2). The thermal rate constants for the decomposition reactions involved are evaluated using Canonical Transition State Theory (CTST) utilizing the ab initio data. Rate constants for C–C bond scission and Cl elimination are found to be 6.7 × 10⁶ and 1.1 × 10⁸ s^?1, respectively, at 298 K and 1 atm pressure with an energy barrier of 8.6 and 6.5 kcal/mol, respectively. These values suggest that Cl elimination is the dominant process during the decomposition of the CF₃CCl₂O radical. Transition states are searched on the potential energy surface of the decomposition reactions involved and are characterized by the existence of only one imaginary frequency (NIMAG = 1) during frequency calculation. The existence of transition states on the corresponding potential energy surface is further ascertained by performing intrinsic reaction coordinate (IRC) calculation.     

Studies on sulfinatodehalogenation: III. The sulfinatodeiodination of primary perfluoroalkyl iodides and α,ω-perfluoroalkylene diiodides by sodium dithionite

Using P. T. C. or cosolvents, both perfluoroalkyl iodides such as Cl(CF₂),_nI (n=2, 4, 6, 1a-1c), H(CF₂)₈I (1d), CF₃(CF₂)_nI (n=3, 5, 7, 1e-1g), and α. ω-perfluoroalkylene diiodides such as (ICF₂CF₂)₂O (4a), I (CF₂)_nI (n=6, 8, 10, 4b-4d) reacted smoothly with sodium dithionite in aqueous solution under mild conditions to give the corresponding perfluoroalkanesulfinates Cl(CF₂)_nSO₂Na (n=2, 4, 6, 2a-2c), H(CF₂)₈SO₂Na (2d), CF₃(CF₂)nSO₂Na (n=3, 5, 7, 2e-2g), α, ω-perfluoroalky-lenedisulfinates O (CF₂CF₂SO₂K)₂ (5a), and KO₂S(CF₂)_nSO₃K (n=6, 8, 10, 6b-6d) in moderate to high yields. These sulfinates were converted to the corresponding sulfonyl chlorides by reacting with chlorine in the usual way. Thus the discovery of the new reagent renders sulfinatodeiodination a practical method for the synthesis of perfluorosulfinic and perfluorosulfonic acids and their derivatives from the corresponding perfluoroalkyl iodides.