Perfluoroalkyl calcium derivatives: reactions with carbonyl compounds

Santini, G.; Blanc, Maurice; Riess, Jean G.

doi:10.1039/c39750000678

Cited by 19 publications

(5 citation statements)

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“…Trifluoroacetaldehyde (fluoral), in its hemiketal form (16), reacted with N-benzyl piperazine (17) giving piperazino hemiaminal (18) [83]. This is a stable compound which, after silylation, gave the corresponding Osilylated hemiaminal (19) which is able to trifluoromethylate nonenolizable carbonyl compounds (20) into trifluoromethyl carbinols (21) [83] (Scheme 26).…”

Section: Methods Using Hemiaminals Of Fluoralmentioning

confidence: 97%

“…10 h at -20°C. No reaction was observed in more basic solvents such as triethylamine, ethylenediamine, or tetramethylethylenediamine, which are known to form complexes with R F I [18]. Ishikawa and co-workers studied the introduction of perfluoroalkyl group to an organic molecule with perfluoroorganometallic compounds [19], and reported a trifluoromethylation of carbonyl compounds with trifluoromethyl iodide by ultrasonically dispersed zinc in N,N-dimethyl formamide (DMF) [20].…”

Section: Methods Using the Trifluoromethyl Halides In The Presence Ofmentioning

confidence: 99%

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Trifluoromethylation of Carbonyl Compounds

Boechat¹,

Bastos

2010

COS

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Section: Methods Using Hemiaminals Of Fluoralmentioning

confidence: 97%

Section: Methods Using the Trifluoromethyl Halides In The Presence Ofmentioning

confidence: 99%

Trifluoromethylation of Carbonyl Compounds

Boechat¹,

Bastos

2010

COS

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“…Hexafluoro-2-methyl-2-propanol (>97%) was prepared as described in ref from reaction of hexafluoroacetone with methyllithium. 2-Perfluorobutyl-2-propanol (>97%) and 2-perfluorohexyl-2-propanol (>97%) were prepared from perfluorobutyl iodide and perfluorohexyl iodide, respectively, by reaction with methyllithium and acetone . All materials were used as received, without further purification.…”

Section: Methodsmentioning

confidence: 99%

Phase Behavior and Microemulsion Formation in Compressible Perfluorinated Monomer Oil and Water Mixtures

Dobreva-Veleva¹,

Kaler²,

Schubert³

et al. 1999

Langmuir

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The phase behavior of mixtures of water, hexafluoropropylene (HFP), ammonium perfluorooctanoate (C8), fluorinated alcohol, and ammonium chloride is reported as a function of temperature, pressure, electrolyte concentration, and hydrophobicity of the surfactant blend. The addition of a short-chain alcohol, hexafluoro-2-methyl-2-propanol, to the water−HFP−C8 mixture promotes formation of microemulsion phases. Replacing the weak amphiphile with a medium-chain alcohol, for example, 2-perfluorobutyl-2-propanol or 2-perfluorohexyl-2-propanol, produces large liquid crystalline regions. Microemulsion formulations containing the fluorinated olefin in a near-critical state along with water, fluorinated surfactant, fluorinated alcohol, and salt follow the generic patterns of phase behavior common for conventional liquid mixtures as a function of experimental variables. Pressure has a strong effect on the phase behavior when one of the components is compressible.

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“…Other examples of thermally stable (perfluoroalkyl)metal (Ca, 48 Mn, 49 Ag, 49 and Sn 50 ) species are known.…”

Section: R-trifluoromethylmentioning

confidence: 99%

“…Thermal stability of perfluoroalkyl agents (R F -M) depends on the kind of metal present (M). Intuitively, a large degree of covalency of carbon−metal bonds (M is a less electropositive element) and a low degree of orbital overlap of carbon−metal with carbon−fluorine bonds (M is a heavier or higher period element) increase the thermal stability of R F -M. Other examples of thermally stable (perfluoroalkyl)metal (Ca, Mn, Ag, and Sn) species are known.…”

Section: Introductionmentioning

confidence: 99%

α-Trifluoromethylated Carbanion Synthons

2008

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Trifluomethylated organic compounds often have properties that make them suitable for diverse applications, including materials science, agrochemistry, and pharmaceutical industry. But of all the therapeutic drugs currently available, about 10% of them have a partially fluorinated moiety. Thus, a great deal of attention is being paid to the development of reliable methodologies for trifluoromethylation. Introduction of a trifluoromethyl group into the target molecules mostly relies on either trifluoromethylating reagents or trifluoromethylated synthetic blocks. The chemistry of trifluoromethyl carbanions, nucleophilic trifluoromethylating agents such as the Ruppert-Prakash reagent, and organometallic species has been intensively developed for their important synthetic applications. But the chemistry of beta,beta,beta-trifluoroethyl carbanions (alpha-trifluoromethyl carbanions) and organometallic species has remained undeveloped despite their potential usefulness in organic synthesis. The issue needs to be addressed. This Account outlines successful alkylations and useful synthetic applications of alpha-trifluoromethyl carbanions, such as alpha-substituted beta,beta,beta-trifluoroethyl, alpha-trifluoromethylethenyl, trifluoroacetimidoyl, alpha-trifluoromethyloxiranyl, and related alpha-trifluoromethylated carbanions. The strong electron-withdrawing effect of the alpha-trifluoromethyl group may stabilize the carbanion species electronically. But alpha-trifluoromethyl carbanions and their corresponding organometallic species mostly release fluoride spontaneously to produce difluoroalkenes. This notorious decomposition of alpha-trifluoromethylated carbanions and anionoids has hindered the development of these species for organic synthesis. A well-designed device for the generation, stabilization, and acceleration for alkylation of the alpha-trifluoromethylated carbanions is needed for their synthetic application, as well as stabilization by the electron-withdrawing alpha-substituent. The reported alpha-substituted alpha-trifluoromethyl carbanions can be roughly categorized into three classes based on their structures. The first category, A, is pi-conjugation-stabilized carbanions, which are stabilized by ester, nitro, sulfone, carbonyl, or phenyl groups. alpha-Substituents of these carbanions can delocalize the negative charges on their pi-system with large sigma R electron-withdrawing effects; this prevents accumulation of negative charge on the fluorine atoms. The second category, B, consists of carbanions with sp(3) orbitals either of highly halogenated carbanionsexamples include pentafluoroethyl(trimethyl)fluorosilicate, pentafluoroethyllithium, and alpha,alpha-dichloro-beta,beta,beta-trifluoroethylzinc speciesor of cyclic structures such as oxiranyl- and aziridinyllithiums. Both of these carbanions are also stabilized since they reduce molecular orbital (MO) overlapping of the carbanion orbital to C-F bond orbitals. The third category, C, has carbanions with their anion center at the sp(2) orbital, such as alpha...

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Perfluoroalkyl calcium derivatives: reactions with carbonyl compounds

Cited by 19 publications

References 0 publications

Trifluoromethylation of Carbonyl Compounds

Trifluoromethylation of Carbonyl Compounds

Phase Behavior and Microemulsion Formation in Compressible Perfluorinated Monomer Oil and Water Mixtures

α-Trifluoromethylated Carbanion Synthons

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