375-17-7Relevant academic research and scientific papers
Copper-mediated aerobic fluoroalkylation of arylboronic acids with fluoroalkyl iodides at room temperature
Qi, Qingqing,Shen, Qilong,Lu, Long
supporting information; experimental part, p. 6548 - 6551 (2012/06/04)
A Cu-mediated ligandless aerobic fluoroalkylation of arylboronic acids under mild conditions is described for the first time. The reaction tolerates a wide range of functional groups, allowing for further transformation. Mechanistic studies suggest that [RfCu] is the active Cu species that forms the desired perfluoroalkylarenes and that [RfCu] is generated from [PhCu] by either an oxidative addition/reductive elimination mechanism or nucleophilic substitution via a halogen "ate" intermediate.
Synthesis of 2-(perfluoroalkyl)ethyl potassium sulfates based on perfluorinated Grignard reagents
Paterová, Jana,Skalicky, Martin,Rybá?ková, Markéta,Kví?alová, Magdalena,Cva?ka, Josef,Kví?ala, Jaroslav
experimental part, p. 1338 - 1343 (2011/02/22)
The first example of nucleophilic substitution with perfluoroalkyl Grignard reagents on the sp3 carbon centre is described. Thus, a series of organometals RF-MgBr, prepared from perfluorinated alkyl iodides RF-I with RF = C4F9, C 6F13, C8F17, C10F 21 and C12F25, reacted with 1,3,2-dioxathiolane-2,2-dioxide to afford the corresponding 2-(perfluoroalkyl) ethyl magnesium sulfates, which were isolated after metathesis to the corresponding potassium salts. In the model reaction, perfluorohexylmagnesium iodide was reacted with methyl triflate yielding polyfluorinated alkane. The attempts to extend the reaction to 1,3,2-dioxathiane-2,2-dioxide were unsuccessful due to its inferior reactivity and only reduced polyfluoroalkane and the product of coupling were detected in the reaction mixture. Polyfluorinated sulfates are easily hydrolyzed with hydrochloric or triflic acid to the corresponding alcohols, which is an alternative to standard transformation of perfluoroalkyl iodides to 2-(perfluoroalkyl)ethanols. Quantum-chemical calculations of the PES of the reaction with both sulfur-containing heterocycles found that the failure of the reaction with 1,3,2-dioxathiane-2,2-dioxide is caused by higher activation energy of the process.
An improved procedure for the synthesis of perfluoroalkylacetylenes
Calleja-Rubio,Crette,Blancou
, p. 361 - 364 (2007/10/03)
A new and easy way to synthesize acetylene compounds is proposed. This synthesis is improved by including in one-pot, three reactions in a single step, with good yields. The reactants are commonly used compounds.
Synthese de 3-perfluoroalkylprop-1-enes RF-CH2-CH=CH2
Rubio,Blancou,Commeyras
, p. 171 - 175 (2007/10/03)
The reactions of perfluoroalkyl iodides with allylbromide or chloride, in the presence of solid potassium hydroxide KOH give 3-perfluoroalkylprop-1-enes RFCH2CH=CH2 in good yields under mild conditions. This reaction represents a synthetically viable and convenient route to such compounds.
Organofluorine compounds and fluorinating agents part 17: Sonochemical-forced preparation of perfluoroalkanals and their use for non-conventional acetalations of carbohydrates 1, 2
Miller, Alexey O.,Peters, Dietmar,Zur, Cornelia,Frank, Michael,Miethchen, Ralf
, p. 33 - 38 (2007/10/03)
The homologous 1-iodo-perfluoroalkanes 1a-1c and α,ω-dibromo-perfluoroalkanes 4a, 4b were carbonylated with DMF in the presence of Al/SnCl2 or Al/PbBr2 under sonication in a short reaction time. The hydrated aldehydes 2a-2c and 5a, 5b respectively were obtained in good yields allowing dehydration to 3a-3c and 6a, 6b. Some of the fluorinated aldehydes were selected as substrates in a Wittig-Horner olefination assisted by ultrasound and in non-conventional acetalations of methyl α-L-rhamnopyranoside (9). Thus, (E)-1-perfluorooctyl-2-phenylsulphonyl-ethene (8) was prepared from 3c and the phosphonate 7 by Wittig-Horner synthesis. Acetalations of 9 were carried out with the aldehydes (3a, 3b, 6a), hydrated aldehydes (2a, 2b), and the aldehyde hemiacetal 12 respectively, in the presence of dicyclohexylcarbodiimide (DCC). In all cases, a selective epimerization was observed at the C-atom 3 of the monosaccharide, i.e. polyfluoroalkylidenated 6-deoxy-α-L-altropyranosides 10, 11, 13, and 14 were obtained.
A novel synthesis of per(poly)fluoroalkyl aldehydes
Hu, Chang-Ming,Tang, Xiao-Qing
, p. 217 - 222 (2007/10/02)
A novel synthesis of per(poly)fluoroalkyl aldehydes in high yield by the reaction of per(poly)fluoroalkyl iodides or bromides with dimethylformamide initiated by a PbBr2(catalyst)/Al bimetal redox system is described.
SYNTHESIS OF PERFLUOROALKYL CARBOXYLIC ACIDS BY REACTION OF PERFLUOROALKYL IODIDES WITH ELECTROGENERATED SUPEROXIDE ION
Amatore, C.
, p. 357 - 379 (2007/10/02)
The electrogenerated superoxide ion O2 is shown to react with perfluoroalkyliodides to afford F-alkyl carboxylic acids.A mechanism is proposed on the basis of the results obtained in preparative experiments and by cyclic voltammetry.
THE FLUORINATION OF BUTANE OVER COBALT TRIFLUORIDE
Burdon, James,Ezmirly, Saleh T.,Huckerby, Thomas N.
, p. 283 - 318 (2007/10/02)
The fluorination of butane over cobalt trifluoride has given a complex mixture of partially fluorinated compounds: 51 of these have been identified, comprising over 99percent of the products.Most were polyfluor-butanes but 1-2percent were polyfluoro-2-methylpropanes.The reaction has no synthetic utility.There was some selectivity in the fluorination: secondary C-H was convertart byed into C-F more easily then primary, and the ease of replacement of a particular H was reduced by geminal vicinal fluorines.A computer model of the fluorination was only partially successful, perhaps because the fluorination proceeded in part by simple F for H replacement and in part via alkenes: the model only allowed for the former.
