Reactions of perfluoroalkylacetones with nucleophilic reagents

Kurykin, M. A.; Vol'pin, I. M.; Герман, Л. С.

doi:10.1016/s0022-1139(96)03451-3

Cited by 25 publications

(9 citation statements)

References 2 publications

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“…The resulting soluble structure will eventually decompose, but not evolve into higher molecular weight species. Indeed, base-promoted dehydrofluorination of 2,2-dihydroperfluoroalkanoic acids, esters, and amides (which can stabilize a negative charge proximate to a −CF 2 R group) is known and supports this mechanism. For electron-rich systems (e.g., isoDH-4T ), the oxidation process generates a radical cation, which can undergo coupling with neutral molecules to produce dimers and, subsequently, larger oligomers and polymers via well-known electropolymerization pathways (Scheme ) .…”

Section: Resultsmentioning

confidence: 90%

Building Blocks for N-Type Molecular and Polymeric Electronics. Perfluoroalkyl- versus Alkyl-Functionalized Oligothiophenes (nTs; n = 2−6). Systematic Synthesis, Spectroscopy, Electrochemistry, and Solid-State Organization

et al. 2004

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The synthesis, comparative physicochemical properties, and solid-state structures of five oligothiophene (nT) series differing in substituent nature and attachment, regiochemistry, and oligothiophene core length (n) are described. These five series include the following 25 compounds: (i) alpha,omega-diperfluorohexyl-nTs 1 (DFH-nTs, n = 2-6), (ii) beta,beta'-diperfluorohexyl-nTs 2 (isoDFH-nTs, n = 2-6), (iii) alpha,omega-dihexyl-nTs 3 (DH-nTs, n = 2-6), (iv) beta,beta'-dihexyl-nTs 4 (isoDH-nTs, n = 2-6), and (v) unsubstituted oligothiophenes 5 (alphanTs, n = 2-6). All new compounds were characterized by elemental analysis, mass spectrometry, and multinuclear NMR spectroscopy. To probe and address quantitatively how the chemistry and regiochemistry of conjugated core substitution affects molecular and solid-state properties, the entire 1-5 series was investigated by differential scanning calorimetry, thermogravimetric analysis, and optical absorption and emission spectroscopies. Single-crystal X-ray diffraction data for several fluorocarbon-substituted oligomers are also presented and compared. The combined analysis of these data indicates that fluorocarbon-substituted nT molecules strongly interact in the condensed state, with unit cell level phase separation between the aromatic core and fluorocarbon chains. Surprisingly, despite these strong intermolecular interactions, high solid-state fluorescence efficiencies are exhibited by the fluorinated derivatives. Insight into the solution molecular geometries and conformational behavior are obtained from analysis of optical and variable-temperature NMR spectra. Finally, cyclic voltammetry data offer a reliable picture of frontier MO energies, which, in combination with DFT computations, provide key information on relationships between oligothiophene substituent effects and electronic response properties.

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Section: Resultsmentioning

confidence: 90%

Building Blocks for N-Type Molecular and Polymeric Electronics. Perfluoroalkyl- versus Alkyl-Functionalized Oligothiophenes (nTs; n = 2−6). Systematic Synthesis, Spectroscopy, Electrochemistry, and Solid-State Organization

et al. 2004

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“…Comparable replacement reactions are known for a number of perfluoroalkylated heterocyclic compounds and anilines [8][9][10]. Even substitution of b-fluorine atoms can occur provided the starting material allows a sequence a,b-elimination/Michael addition as found for a-perfluoroalkylated acetic acid derivatives or ketones [11,12]. By contrast neither phenyl-perfluorohexyl-nor benzyl-perfluorohexyl-thioether yielded orthoesters on treatment with methanolic methanolate solution.…”

Section: Resultsmentioning

confidence: 99%

Organofluorine compounds and fluorinating agents

Schwäbisch

Hein

Miethchen

2004

Journal of Fluorine Chemistry

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“…We report the characterization and formulation of fluorinated β-diketonate PFHA and its metal complexes. The use of PFHA has been described previously for a handful of synthetic procedures, − but its use as a potential imaging agent has not been explored. The Fe-PFHA complex has several advantages over previously reported iron complexes for 19 F MRI; , it is readily prepared at multigram scales using a single synthetic step, and it has a single, well-defined structure.…”

Section: Discussionmentioning

confidence: 99%

β-Diketonate-Iron(III) Complex: A Versatile Fluorine-19 MRI Signal Enhancement Agent

Wang

Adams

et al. 2019

ACS Appl. Bio Mater.

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Fluorine-19 magnetic resonance imaging (MRI) has gained considerable momentum as a promising imaging modality for in vivo tracking of cellular therapies and as a diagnostic for inflammatory disease. To further the utility of this technique, we increase imaging probe sensitivity by merging paramagnetic metal chelates with aqueous perfluorocarbon (PFC) nanoemulsions. We prepared a highly fluorinated ferric tris(β-diketonate) chelate (MW = 1265.2 g/mol) at gram scale. This iron chelate is soluble in multiple PFC oils used for MRI and readily reduces the 19 F longitudinal relaxation time (T 1 ) to <100 ms with modest line broadening and displays superior properties for 19 F MRI applications. The sensitivity enhancement by Fe(III) laden PFC nanoemulsion was confirmed in MRI phantom studies, where reduced T 1 speeds data acquisition thereby increasing the 19 F image sensitivity per time via signal averaging. Additionally, 19 F relaxivity of nanoemulsions incorporating other metal ions, including Gd, Er, Ho, Dy, Mn, Cr, and Ni, were evaluated. Highmoment lanthanide ions, such as Gd(III), display severe line broadening, but other ions [e.g., Ho(III)] induce pseudocontact chemical shifts (up to 0.5 ppm) of 19 F in nanoemulsion, which makes them potentially useful for multichromatic 19 F imaging. Formulated nanoemulsions have a shelf life >200 days. Free β-diketonate or its iron complex in formed PFC nanoemulsion did not induce cytotoxicity in intracellularly labeled macrophages. Overall, ferric tris(β-diketonate) chelate provides a scalable approach for boosting sensitivity of PFC-based 19 F MRI probes. More generally, it can functionalize PFC oil, whose chemical modification remains challenging.

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Reactions of perfluoroalkylacetones with nucleophilic reagents

Cited by 25 publications

References 2 publications

Building Blocks for N-Type Molecular and Polymeric Electronics. Perfluoroalkyl- versus Alkyl-Functionalized Oligothiophenes (nTs; n = 2−6). Systematic Synthesis, Spectroscopy, Electrochemistry, and Solid-State Organization

Building Blocks for N-Type Molecular and Polymeric Electronics. Perfluoroalkyl- versus Alkyl-Functionalized Oligothiophenes (nTs; n = 2−6). Systematic Synthesis, Spectroscopy, Electrochemistry, and Solid-State Organization

Organofluorine compounds and fluorinating agents

β-Diketonate-Iron(III) Complex: A Versatile Fluorine-19 MRI Signal Enhancement Agent

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