Fluorine-containing carbonyls

According to Klimov (Ref 2) the tetrafluoride is resistant to deton. However, because of its high reactivity, very sensitive explns result from contact with flammable materials such as acet, polyethylene, wool, paper, sawdust, Al foil, ferric carbonyl, lubricants or styrene Refs 1) J.H. Holloway, Noble-Gas Chemistry , Methuen, London (1968), 95 ff 2) BD. Klimov et al, Explosion Hazard During Work With Fluorine Containing Xenon Compounds , Zh Prikl Khim (Leningrad) 42 (12), 2822-24 (1969) CA 72, 85784 (1970) 3) T.C. 

The mechanism of the reaction between a hydrocarbon organolithium compound and a carbonyl compound is well-documented [69] and has been suggested earlier for fluorine-containing compounds [32, 68, 70] More recent studies on the mechanism have resulted m a better understanding ol this reaction [71] (equation 37)... 

Although the early reactions of perfluoroahphatic and aromatic lithium compounds with various carbonyl compounds gave low yields and mixtures of prod ucts, the current understanding of experimental conditions makes this reaction an attractive means of preparing a variety of fluorine-containing compounds... 

Product formation and yields in the Baylis-Hillman reaction also depend on a balance between the reactivities of the carbonyl and olefin partners as was shown, for example, for reactions of fluorine-containing carbonyl compounds [13]. 

The Evans-aldol method using a boron enolate derived from chiral iV-acyloxazolidinone reacted with aldehydes to give syn-aldols via attack exclusively on the re face of the double bond of the enolate (Equation (177)). Unexpected and unusual si face attack was resulted in the reaction with fluorine-containing carbonyl compounds such as trifluoro acetaldehyde (Equation (178)).680 681... 

Carboxylic esters, usually methyl or ethyl esters, can be converted into trifluoromethyl compounds by reaction with sulfur tetrafluoride in the presence of an excess of hydrogen fluoride. In comparison to carboxylic acids more vigorous conditions are needed." Substitution of the ester group carbonyl oxygen is observed with fluoroalkyP or phenyl esters " of polyfluorocarboxylic acids, fluorine-containing a-oxo esters,fluorine-containing a- and j -hydroxy esters, " and furancarboxylic esters. ... 

Carbonyl difluoride is formed frequently during the oxidation of many fluorine-containing halocarbons. The "simplest" fluorocarbon, CFj (prepared from the decomposition of trifluoromethyl fluorophosphoranes), when generated at 100 C in the presence of Oj, gives COFj [1299]. 

The asymmetrical, fluorine-containing carbonyl halides, COXF (X = Cl, Br or I) were first prepared and examined by Kwasnik at I.G. Leverkusen (a part of I.G. Farbenindustrie) during World War II. This work was later disclosed by RUdorff [1751], and by Fischer [656a] in the enemy-property confiscation reports, known as the FIAT Reviews of German Science. 

With world regulatory pressures on the use of chlorinated compounds increasing, the synthesis of fluorine-containing hydrocarbons from oxygen-containing substrates has received much attention in recent years. Reacting simple molecules such as formaldehyde and carbonyl fluoride over an activated carbon catalyst [90] gives an 86% yield of HFC-32 (eq 25). 

Fluorine-Containing Heterocycles. Part II. Synthesis of Perfluoroalkyl Heterocycles from Carbonyl Compounds... 

These reactions indicate that the 0-, N-, and S-nucleophiles attack the C(l) carbonyl carbon, although in the case of N-nucleophiles the attack may be preceded by formation of a salt with fluorine-containing /1-ketoesters. 

Fluorinated homoallylic alcohols are readily prepared from fluorine-containing carbonyl compounds or the allylic halides. ... 

Fluorine atoms alpha to a carbonyl group oppose the normal polarization of the carbonyl, which contains a positive charge on the carbon and a negative charge... 

The EGB derived from 2-pyrrolidone promotes (Eq. 27) [18, 19]. The trifluoromethylation of the formation of trihalomethyl anions from trihalo- carbonyl compounds is remarkably useful for the methane and their addition to carbonyl compounds synthesis of fluorine containing compounds. 

A similar study has not been carried out for fluorine-containing radicals due in part to the very great complexity of the esr spectra (31) and the difficulty of obtaining ENDOR spectra from fluorine-containing radicals. However some similarity must exist between the radiation decay mechanism of protonated radicals and that for fluorinated radicals as a number of the decay and formation processes in both instances involve the carbonyl proton in acids and the N-H proton in amides. Thus it is important to briefly review the radiation decay processes observed for the irradiated carboxylic acids and acetate crystals which do not contain fluorines. 

Fluorine-Containing Carbonyls, Thiocarbonyls, Selenocarbonyls and Tellurocarbonyls... 

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