Regio- and stereoselective ring-opening reactions of epoxides with indoles and pyrroles in 2,2,2-trifluoroethanol

Aliphatic and aromatic epoxides react regio- and stereoselectively with indoles and pyrroles in 2,2,2-trifluoroethanol without the use of a catalyst or any other additive. While aromatic epoxides are selectively attacked at the benzylic position, aliphatic epoxides react at the less-substituted position. Chiral epoxides react with >99 % ee (ee=enantiomeric excess).     

Catalytic vapor-phase oxidation of 2,2,2-trifluoroethanol

The synthesis of trifluoroacetaldehyde by vapor-phase oxidation of 2,2,2-trifluoroethanol using supported vanadium catalysts was studied. Significant differences were observed in the reaction outcomes resulting from different types of catalysts. The ZrO₂- and Al₂O₃-supported catalyst demonstrated both high catalytic activity and selectivity. The addition of co-catalysts such as MoO₃ or SnO₂ improved catalytic performance (Selectivity: up to 91%; S.T.Y.: >200 g L⁻¹ h⁻¹). The experimental results on catalyst lifetime showed a marked decrease in the activity of the Al₂O₃-supported catalyst within tens of hours, while the ZrO₂-supported catalyst showed little, if any, performance alterations for 2000 h.     

Vibrational spectra and normal coordinate analysis of 2,2,2-trichloroethanol and 2,2,2-trifluoroethanol

The vibrational spectra of 2,2,2-trichloroethanol and 2,2,2-trichloroethanol and their OD deuterated analogues have been studied in argon, nitrogen and mixed argon—nitrogen matrices. The matrix spectra of the CD₂ deuterated and totally deuterated trifluoroethanol and the Raman and i.r. spectra of the liquid alcohols have also been recorded. A vibrational assignment, supported by normal coordinate analysis, is proposed for both alcohols.     

Fluoride-catalyzed hydroalkoxylation of hexafluoropropene with 2,2,2-trifluoroethanol

Trifluoroethoxylation of hexafluoropropene with 2,2,2-trifluoroethanol (TFE) were conducted using an alkali metal fluoride catalyst to produce CF₃CHFCF₂OCH₂CF₃. KF exhibited the highest yield and selectivity of CF₃CHFCF₂OCH₂CF₃, whereas LiF and NaF were inactive for the trifluoroethoxylation reaction. The same reaction also proceeded well in the presence of RbF or CsF, but yielded large amounts of olefinic and high molecular weight side products, implying that the size of alkali metal cation or the degree of MF dissociation plays an important role in determining the activity and the product composition. FT-IR and NMR experiments revealed that CsF interacts with TFE more strongly than KF through a hydrogen bonding. The experimental and spectroscopic results suggest that the degree of MF dissociation should be in the medium range for the selective production of CF₃CHFCF₂OCH₂CF₃ in high yield and selectivity.     

Catalyst-free one-pot synthesis of 1,4,5-trisubstituted pyrazoles in 2,2,2-trifluoroethanol

A simple, efficient and three component one-pot synthesis of 1,4,5-trisubstituted pyrazoles by condensation of β-dicarbonyls, N,N-dimethylformamide dimethyl acetal (DMFDMA) and hydrazine derivatives in 2,2,2-trifluoroethanol without using any catalyst and activation, is described.     

Intramolecular and liquid structure of 2,2,2-trifluoroethanol by X-ray diffraction

Intramolecular and liquid structure of 2,2,2-trifluoroethanol (TFE) have been investigated by x-ray diffraction at 25°C. The structural parameters for the skeleton of the molecules in the liquid phase are similar to those in the gas phase. The conformers of TFE molecules in the liquid phase are discussed. The O...O distance at about 284 pm and additional F...O one at about 302 pm were found to be characteristic for the first neighbor interactions. Various models (dimers and trimers) have been examined for analyzing the first neighbor structure. The liquid structure was explained in terms of small clusters consisting of two to three molecules rather than of a more extended polymeric network.Central Research Institute for Chemistry of the Hungarian Academy of Sciences, Budapest, P. O. Box 17, H-1525, Hungary.     

Use of the hexane-2,2,2-trifluoroethanol system in partition chromatography

The use of the hexane-2,2,2-trifluoroethanol heterophase system of solvents in partition chromatography is characterized. Gas-chromatographic retention indices and partition coefficients are used for the identification of organic compounds in this technique. The partition coefficients of compounds from 12 homologous series were measured in this heterophase system, and parameters for their group identification were calculated. The examples of the use of this system for solving different analytical problems are considered.     

The photochemical addition of 2,2,2-trifluoroethanol to methoxy-substituted stilbenes

The excited-state lifetime of the trans-stilbene chromophore in acetonitrile is prolonged by methoxy substituents in the meta positions. The long-lived singlet excited state of trans-3,5-dimethoxystilbene (trans-2d) is quenched upon the addition of 2,2,2-trifluoroethanol (TFE), and the Markovnikov ether is observed as the major product from steady-state irradiations. The results indicate that the reaction pathway proceeds through a carbocation intermediate.     

A peptide co-solvent under scrutiny: self-aggregation of 2,2,2-trifluoroethanol

Trifluoroethanol (TFE) and its aggregates are studied via supersonic jet FTIR and Raman spectroscopy as well as by quantum chemistry and simple force field approaches. A multi-slit nozzle is introduced to study collisionally excited clusters. Efforts are made to extract harmonic frequencies from experiment for better comparison to theory. Based on deuteration, the OH stretching anharmonicity changes weakly upon dimerization, but increases for trimers. Among the possible dimer conformations, only an all-gauche, homoconfigurational, compact, OH-F connected structure is observed in an extreme case of chiral discrimination. Quantum tunneling assisted pathways for this surprising helicity synchronization are postulated. The oscillator coupling in hydrogen-bonded trimers is analyzed. Trans conformations of TFE start to become important for trimers and probably persist in the liquid state. Simple force fields can be refined to capture some molecular recognition features of TFE dimer, but their limitations are emphasized.     

Chromato-mass-spectrometric identification using partition coefficients in the system of hexane-2,2,2-trifluoroethanol

An additional characteristic of organic compounds, the partition coefficients in the heterophase solvent system n-hexane-2,2,2-trifluoroethanol, is shown to be useful for refining the results of chromatographic and gas chromatography-mass spectrometric identification. This opportunity is the most important for compounds that were not yet characterized by either mass spectra or chromatographic retention indices.     

Kinetic studies on the reactions of some tetrakis(arylisocyanide)cobalt(II) complexes with pyridine in 2,2,2-trifluoroethanol

The interaction of pyridine with four tetrakis(arylisocyanide)cobalt(II) complexes, [Co(CNR)₄(ClO₄)₂] R = 2,6-Me₂C₆H₃ (A), 2,4,6-Me₃C₆H₂ (B), 2,6-Et₂C₆H₃ (C) and 2,6-iPr₂C₆H₃ (D), have been studied in 2,2,2-trifluoroethanol medium. The kinetics of the reactions were investigated over the 293–318 K temperature range. The reaction profile exhibited two distinct processes, proposed to be an initial fast substitution followed by a slow reduction, for each of the reactions. The pseudo first-order rate constants for both processes increased with increasing concentration of pyridine with the reduction processes exhibiting saturation kinetics at high pyridine concentrations. Steric hindrance plays a significant role in the rates of the reactions, as the rates decrease in the order k(A) > k(B) > k(C) > k(D). The activation enthalpies, ΔH^‡, increase from A to D while the activation entropies, ΔS^‡, are relatively similar for the four reactions, indicating similar transition states and hence similar mechanisms. Complex B was first synthesized and characterized in this study.     

Dediazoniation of Arenediazonium Ions. Part XIX. Effect of thiocyanate ion in the reactions of 2,4,6-trimethylbenzenediazonium tetrafluoroborate in 2,2,2-trifluoroethanol

The dediazoniation of 2,4,6-trimethylbenzenediazonium tetrafluoroborate ( 1 ) in 2,2,2-trifluoroethanol (TFE) was studied in the presence of potassium thiocyanate. The effect of added salt on the dediazoniation rate, the N_α-N_β rearrangement (Eqn. 2), the exchange of the ¹⁵N-labelled diazo group with molecular nitrogen (Eqn. 3), and the reaction products was determined. With 0.3_M KSCN a dediazoniation-rate increase of 16.5% was achieved, and the amounts of rearranged and exchanged product were reduced to 88% and 70%, respectively, of the values found in pure TFE. The dediazoniation products formed are ArF ( 3 ), ArOCH₂CF₃ ( 4 ), ArSCN ( 5 ), ArNCS ( 6 ) and traces of 5, 7-dimethylindazole ( 7 ). All the data are in agreement with, and support the previously proposed mechanism (Equ. 1) of heterolytic dediazoniation of arenediazonium salts.     

Thermodynamic analysis of partially folded states of myoglobin in presence of 2,2,2-trifluoroethanol

The thermal denaturation of myoglobin was studied in the presence of 2,2,2-trifluoroethanol (TFE) at various pH values using differential scanning calorimetry and UV–visible spectroscopy. The most obvious effect of TFE was lowering the transition temperature up to 1.5 mol · kg⁻¹, beyond which no thermal transitions were observed. The protein conformation was analysed by fluorescence and circular dichroism measurements. Quantitative binding of ANS to the TFE induced molten globule state of myoglobin was studied by using isothermal titration calorimetry. The results enable quantitative estimation of the binding strength of ANS with the molten globule state of myoglobin along with the enthalpic and entropic contributions to the binding process. The results suggest occurrence of common structural features of the molten globule states of proteins offering two types of binding sites to ANS molecules which are a widely used fluorescence probe to characterise partially folded states of proteins.     

Conformation of 2,2,2-trifluoroethanol and the solvation structure of its 2-fluoropyridine clusters

The conformation of 2,2,2-trifluoroethanol (TFE) in the 2-fluoropyridine-(TFE)(m)-(H(2)O)(n) clusters in a supersonic jet has been investigated with fluorescence-detected infrared spectroscopy and quantum chemical calculations. It is common to the observed clusters that they form chain structures containing the weak interaction of the pyridyl CH with the fluorine or oxygen atom in the terminal TFE. The detectable conformation of TFE is gauche only even in the case of the existence of the strong base such as 2-fluoropyridine. This result is explained by the change in hyperconjugation among several dominant orbitals. The preference of the terminal TFE in the mixed clusters with TFE and water solvents is observed, which is ascribed to the stronger cooperative effect of TFE than water.     

Nitro-substituted stilbeneboronate pinacol esters and their fluoro-adducts. Fluoride ion induced polarity enhancement of arylboronate esters

A series of stilbeneboronate pinacol cyclic esters, containing none to three nitro groups, have been synthesized by various olefination reactions and characterized by X-ray single-crystal structure analysis. A stilbeneboronate ester bearing electron-acceptor groups experiences transition to a push-pull pi-electron system upon complexation with one fluoride ion at the boron atom. The UV-vis absorption maxima of the presented nitro-substituted stilbeneboronate esters are red-shifted upon addition of fluoride ions, indicating this binding event. The enhancement of the polarity of the investigated compounds and the changes in the electronic system were investigated by UV-vis absorption spectroscopy and solvatochromism. Additionally, studies were performed by natural bond orbital (NBO) analysis and RI-CC2 calculations of the vertical excitation energies. The synergism of fluoride ion complexation and solvation upon the UV-vis band shift is interpreted in terms of linear solvation energy relationships (LSERs) using the Kamlet-Taft solvent parameter set. It is found that the UV-vis absorption of the fluoro-boronates is strongly dependent on the solvents hydrogen-bond donating ability.     

A thallium-205 NMR study of thallium acetate ion association in 2,2,2-trifluoroethanol and dimethylsulfoxide

The association of thallium acetate ion in 2,2,2-trifluoroethanol and dimethyl-sulfoxide has been investigated by thallium-205 NMR spectroscopy. Analysis of the association constants as a function of temperature indicates that in trifluoroethanol the association enthalpy and entropy are, respectively, 1.6 kcal-mol^–1 and 19.3 cal-mol^–1-K^–1 and in dimethylsulfoxide they are-0.99 kcal-mol^–1 and 18.0 cal-mol^–1-K^–1. Examination of the temperature dependence of the chemical shift of the ion-pair reveals that in dimethylsulfoxide the ion-pair exists as a contact species, while in trifluoroethanol the solvent-separated ion-pair is more likely.