多氟烷基芳基醚的合成

位置异构的甲氧基苯酚和苯二酚与六氟丙烯在微量碱催化下反应,得到亲核加成产物。从邻苯二酚和六氟丙烯反应产物中,分离得化合物2～9.这些产物是由碳阴离子13与六氟丙烯加成、消除等反应生成。间苯二酚和对苯二酚仅产生简单的加成产物10及少量加成消除产物Z, E11, 12.各新化合物由^1H NMR, 19F NMR, MS, IR和元素分析加以鉴定,并对化合物4、5的19F NMR进行了讨论。     

一种由多氟碘代烷合成多氟羧酸的新方法

本文报道了一种新的合成多氟羧酸的方法:即在银(I)离子存在下,甲酸钠与多氟烷基碘代烷反应的结果。     

Syntheses of polyfluoroalkyl aryl ether

The reactions of methoxyphenol and dihydroxybenzene with hexafluoropropene were studied. Eight new compounds 2-9 were separated from the reaction mixture of catechol and hexafluoropropene. The formation of these products was explained through nucleophilic attack of the aryloxy anion on hexafluoropropene, followed by elimination and addition (Scheme 1). However, the reaction of resorcinol and hydroquinone with C₃F₄ only gave the simple addition products 10 and addition-elimination products Z, E-11, 12. All new compounds were characterized by ¹H and ¹⁹F NMR, IR, MS and elemental analyses. The ¹⁹F NMR of seven membered ring compounds 4 and 5 were discussed in detail.     

Some properties of polyfluoroalkyl fluosulfates

Conclusions The reaction of polyfluoroalkyl fluosulfates with either SbF₅ or tertiary amines leads to elimination of SO₂F₂ and the formation of fluorocarboxylic acid fluorides. The reaction of 1,2-bis (fluosulfonyloxy)hexafluoropropane with SbF₅ gives pentafluoroethyl fluosulfate.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 8, pp. 1906–1907, August, 1982.     

Hydroxy- and alkoxymethylation of polyfluoroalkyl pyrazoles

A synthetic route to 1-hydroxy- and 1-alkoxymethyl-3-polyfluoroalkylpyrazoles via regioselective N-hydroxy- and alkoxymethylation of N-unsubstituted pyrazoles with paraformaldehyde has been proposed. The alkoxyalkylation of polyfluoroalkylpyrazoles proceeds in aqueous-alcohol medium, whereas hydroxymethylation requires anhydrous conditions.     

Thermochemistry of per- and polyfluoroalkyl substances

The determination of gas phase thermochemical properties of per- and polyfluoroalkyl substances (PFAS) is central to understanding the long-range transport behavior of PFAS in the atmosphere. Prior gas-phase studies have reported the properties of perfluorinated sulfonic acid (PFOS) and perfluorinated octanoic acid (PFOA). Here, this study reports the gas phase enthalpies of formation of short- and long-chain PFAS and their precursor molecules determined using density functional theory (DFT) and ab initio approaches. Two density functionals, two ab initio methods and an empirical method were used to compute enthalpies of formation with the total atomization approach and an isogyric reaction. The performance of the computational methods employed in this work were validated against the experimental enthalpies of linear alkanoic acids and perfluoroalkanes. The gas-phase determinations will be useful for future studies of PFAS in the atmosphere, and the methodological choices will be helpful in the study of other PFAS.     

Synthesis of heterocycles with polyfluoroalkyl substituents from unsaturated compounds containing polyfluoroalkyl groups. (Review)

Methods for the construction of heterocyclic systems containing polyfluoroalkyl substituents from derivatives of ethylene and acetylene are discussed. It is shown that various compounds with polyfluoroalkyl groups can be used as building blocks: α,β-unsaturated carbonyl compounds, their synthetic organosilicon equivalents (silyl-substituted alcohols, silyl ethers of enols), and also sulfones, nitriles, polyfluoroalkenes (in reactions at the double bond), acetylenecarboxylic acids, their esters, and polyfluoroalkynes. __________ Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 3, pp. 323–360, March, 2006.     

Synthesis of di(polyfluoroalkyl) ethers

New procedures for preparing di(polyfluoroalkyl) ethers by reactions of polyfluoropropyl chlorosulfonites with polyfluorinated alcohols were tested.Translated from Zhurnal Prikladnoi Khimii, Vol. 77, No. 9, 2004, pp. 1573–1574.Original Russian Text Copyright © 2004 by Rakhimov, Nalesnaya, Vostrikova.     

Preparation of O-(polyfluoroalkyl) alkylchlorophosphonates and O-(polyfluoroalkyl) aryl chlorophosphates by catalytic phosphorylation of polyfluoroalkanols

Conclusions A new method was developed for the synthesis of O-(polyfluoroalkyl) alkylchlorophosphonates and 0-(polyfluoroalkyl) aryl chlorophosphates, which consists in phosphorylating polyfluoroalkanols with an excess of the dichlorides of the corresponding phosphorus acids in the presence of salts of the Group II metals.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 3, pp. 656–658, March, 1979.     

Addition of polyfluoroalkyl iodides to allyl glycidyl ether

Addition of polyfluoroalkyl iodides to the double bond of allyl glycidyl ether occurred under mild conditions (20–25 °C, MeCN/H₂O, Na₂S₂O₄, NaHCO₃) with retention of the oxirane ring. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 8, pp. 1476–1478, August, 2007.     

N-(polyfluoroalkyl)imidazolium-2-carbodithioates

Chemical properties of carbenes derived from 1-methyl-3-polyfluoroalkylimidazolium salts were studied. These unstable intermediate products reacted with carbon disulfide to give the corresponding imidazolium-2-carbodithioates which were subjected to methylation at the sulfur atom.     

Esterification of polyfluoroalkyl alcohols with tall oil rosin

Acid-catalyzed nonsolvent esterification of 1H,1H,5H-perfluoropentan-1-ol, 1H,1H,7H-perfluoroheptan-1-ol, and 1H,1H,9H-perfluorononan-1-ol with tall oil rosin was studied.