- Alkali metal trifluoroacetates for the nucleophilic trifluoromethylation of fullerenes
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Fullerene C60 readily reacts with potassium and cesium trifluoroacetates yielding C60(CF3)–M+ salts, and subsequent acid hydrolysis gives ortho-C60(CF3)H. The reaction rate and the probability of the alternative reaction pathways strongly depend on the particular metal cation. Thus, the reactivity increases in the order Li 2- rather than CF3-functionalization of the fullerene, in good accordance with the hard/soft acids and bases theory. The nucleophilic trifluoromethylation is found to be applicable to other pristine fullerenes like C70 as well as to fullerene derivatives like p7mp-C70(CF3)10. It enables selective preparation of low trifluoromethylated fullerenes via regioselective consecutive trifluoromethylation under accurately controlled solution-phase conditions.
- Bogdanov, Viktor P.,Dmitrieva, Veronika A.,Ioutsi, Vitaliy A.,Belov, Nikita M.,Goryunkov, Alexey A.
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Read Online
- Convenient synthesis of perfluoroalkyltrifluoroborates
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Perfluoroalkyltrimethoxyborates were converted into the corresponding perfluoroalkyltrifluoroborates in high yield by the action of potassium bifluoride in acidic media, i.e. in hydrochloric acid (37%), glacial acetic acid, and trifluoroacetic acid as wel
- Sprenger, Jan A.P.,Kerpen, Christoph,Ignat'ev, Nikolai,Finze, Maik
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- Recyclable Trifluoromethylation Reagents from Fluoroform
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We present a strategy to rationally prepare CF3- transfer reagents at ambient temperature from HCF3. We demonstrate that a highly reactive CF3- adduct can be synthesized from alkali metal hydride, HCF3, and borazine Lewis acids in quantitative yield at room temperature. These nucleophilic reagents transfer CF3- to substrates without additional chemical activation, and after CF3 transfer, the free borazine is quantitatively regenerated. These features enable syntheses of popular nucleophilic, radical, and electrophilic trifluoromethylation reagents with complete recycling of the borazine Lewis acid.
- Geri, Jacob B.,Szymczak, Nathaniel K.
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supporting information
p. 9811 - 9814
(2017/08/03)
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- COMPLEXES FOR NUCLEOPHILIC, RADICAL, AND ELECTROPHILIC POLYFLUOROALKYLATION
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Disclosed herein are borazine complexes and use of the same in perfluoroalkylation reactions.
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Paragraph 00155; 00156
(2018/04/11)
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- TEMPO mediated oxidation of fluorinated alcohols to carboxylic acids
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Fluorinated carboxylic acids (3a-f) have been prepared in good yield by oxidizing the corresponding alcohols (2a-f) in the presence of TEMPO (1) as catalyst, using oxidants like bleach and oxygen.
- Ignatowska, Jolanta,Shyshkov, Oleg,Zipplies, Tilman,Hintzer, Klaus,R?schenthaler, Gerd-Volker
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experimental part
p. 35 - 40
(2012/09/21)
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- METHODS OF PREPARING FLUORINATED CARBOXYLIC ACIDS AND THEIR SALTS
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A method for preparing fluorinated carboxylic acids and theirs salts is described comprising subjecting a fluorinated alcohol of the general formula (A): A-CH2-OH to at least one first and at least one second oxidizing agent to produce a highly fluorinated carboxylic acid or their salts of the general formula (B): A-COO M+, wherein M+ represents a cation and wherein A in formulas (A) and (B) is the same and A represents the residue: Rf-[0]p-CX"Y"-[0]m-CX'Y'-[0]n-CXY- wherein Rf represents a fluorinated alkyl residue which may or may not contain one or more catenary oxygen atoms, p, m and n are independently from each other either 1 or O, X, X', X", Y, Y' and Y" are independently from each other H, F, CF3, or C2F5 with the proviso that not all of X, X', X", Y, Y' and Y' ' are H; or A represents the residue: R-CFX- wherein X and R are independently selected from a hydrogen, a halogen, or an alkyl, alkenyl, cycloalkyl, or aryl residue, which may or may not contain one or more fluorine atoms and which may or may not contain one or more catenary oxygen atoms; wherein said at least one first oxidizing agent is a compound that can be converted, by action of the second oxidizing agent, into a reactive species capable of oxidizing the fluorinated alcohol.
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Page/Page column 40
(2011/05/06)
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- Production of carboxylic acid halides and carboxylate salts
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A process for preparing carboxylic acid halides and carboxylate salts by reacting metal or "onium" halides with carboxylic anhydrides, which process is very suitable for working-up anhydrous, spent catalyst preparations. The resulting carboxylic acid halide or carboxylate salt can be used as an acylating reagent or alkylating reagent, and metal halide or "onium" halide liberated during this can be reacted anew with carboxylic anhydride and regenerated, thereby making it possible to effect a hydrolysis-free alkylation or acylation without forming salt-type waste products. If the mixture of carboxylic acid halide and carboxylate salt is allowed to react with an alcohol, preferably in situ, the resulting ester can be isolated without hydrolysis.
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- Perfluoro-organochalcogenyl acids in high oxidation states
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Keywords: Perfluoro-organochalcogenyl acids; High oxidation states; Sulphur; Selenium; Tellurium; Single-crystal X-ray diffraction study
- Haas, A.,Herkt, S.
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p. 165 - 166
(2007/10/02)
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