67727-67-7

Upstream product

• 2062-98-8 perfluoro(2-propoxypropionyl) fluoride 
• 591-51-5 phenyllithium 
• 71-43-2 benzene 
• 109-72-8 n-butyllithium 
• 626-39-1 1,3,5-trisbromobenzene 
• 76145-88-5 2'-perfluoropropoxy-2-perfluoropropoxyperfluoropropanoic acid ethyl ester 

Relevant academic research and scientific papers

Regiospecific synthesis of aromatic compounds via organometallic intermediates. Part 6. 1,3,5-perfluoroalkylether benzenes

1,2,3-Tribromobenzene can undergo a mono lithium-halogen exchange reaction to yield 3,5-Br2C6H3Li which can subsequently react with a perfluoroalkylether ester, RfORfC(O)OC2H5, yielding the aryl ketone 3,5-Br2C6H3C(O)RfORf.A classical SF4/HF reaction of this ketone yields the perfluoroalkylether benzene, 3,5-Br2C6H3CF2RfORf.This process can be repeated stepwise until all bromines are substituted, yielding the final product 1,3,5-C6H3(CF2RfORf)3.The RfORf was chosen as C3F7O2CF(CF3).Other perfluoroalkyl- and perfluoroalkyl-ether esters or other electrophiles can be chosen to react with the various organolithium intermediates. - Keywords: Regiospecific synthesis; Perfluoroalkylether benzenes; Mass spectrometry; IR spectroscopy

SURFACE ACTIVE SUBSTANCES CONTAINING AN OLIGO(HEXAFLUOROPROPENE OXIDE) CHAIN AS A HYDROPHOBIC AND OLEOPHOBIC MOIETY

Oil soluble surface active substances, (HFPO)n-Ar, where Ar is an aryl group and (HFPO)n is an oligo(hexafluoropropene oxide) group, n = 2 - 5, were prepared and tested for their surface activities in toluene or m-xylene.Addition of a small amount of (HFPO)4-6-Ar (0.2 - 0.5 wtpercent) was found to decrease remarkably the surface tension of these solvents (down to 12 - 14 dyncm-1 at 20 deg C).Water soluble surfactans (HFPO)n-Ar'SO3Na, where Ar' is an arylene group, were also prepared by sulfonation of (HFPO)n-Ar.Some of these subtances (n = 4 - 6) decreased the surface tension of water down to 16 dyncm-1 at 20 deg C in the concentration of 10-4 - 10-5 molel-1.

FLUORO-KETONES. V REACTIONS OF ALKYL AND ARYLLITHIUM COMPOUNDS WITH PERFLUOROALKYLETHER ESTERS

n-Butyllithium and a variety of aryllithium compounds have been shown to react with a perfluoroalkylether ester (RfORfCO2R) at -78 deg C to produce perfluoroalkylether ketones.In the absence of competing reactions, which may be due to additional reactive groups on the ester, high yields of ketones can be prepared.Steric hindrance adjacent to the carbonyl group has an important effect on rates of reactions.Low reaction temperature (-78 deg C) is an important factor when secondary esters are used.At higher reaction temperatures (> -30 deg C), the secondary esters produce decreased yields of ketone due to the instability of the intermediate lithium salt of the hemiketal which decomposes to an aryl ester and a perfluorinated olefin.

FLUORO-KETONES IV. SYNTHESIS OF PHENYLPERFLUOROALKYL KETONES - MECHANISM OF REACTION BETWEEN PHENYLLITHIUM AND FLUOROESTERS

Although fluorine containing ketones (RfC(O)Rf and RfC(O)R, Rf = perfluoroalkyl) have been prepared from the reaction between organolithium reagents and perfluoroalkyl esters, the reaction has not found general applicability.Variable yields of ketones and co-production of secondary and tertiary alcohol by-products have in most instances been experienced.We have examined in more detail the factors e.g., temperature, mode of addition and perfluoroalkyl ester structure which influence ketone product and by-products formation.By controlling experimental conditions excellent yields of C6H5C(O)Rf compounds can be attained.A lithium salt of a hemiketal (II) has been isolated and shown to be the active intermediate in the production of the ketone.The stability of the salt and its potential reaction with the solvent dictates the type of reaction products.Low temperature favors stability of the lithium salt of the hemiketal whereby high yields of ketones are produced on hydrolysis.