Darryl D. DesMarteau

Direct synthesis of fluorinated peroxides. V. The preparation of pentafluorosulfurperoxy esters by reactions of pentafluorosulfur hydroperoxide with acyl fluorides

Abstract The reaction of SF 5 OOH with acyl fluorides in the presence of NaF has been investigated and found to yield new peroxy esters of the type RC(O)OOSF 5 . An alternate method of synthesis using SF 5 OOCl and acyl chlorides is discussed and the cesium fluoride catalyzed conversion of two of the esters to RCF(OF)OOSF 5 is described.

The reaction of 2-trifluoromethyl-3,3-difluorooxaziridine with nucleophiles.

Abstract The facile reactions of CF 3 NCF 2 O with a variety of non-fluorinated nucleophiles are discussed. CF 3 NCF 2 O + Nu - → CF 3 N(Nu)C(O)F + F - Reactions with alcohols, carboxylic acids, mercaptans, amines, KSCN, KCN, NaN 3 and NaOCN were carried out. All except NaN 3 and NaOCN were reactive and the expected compounds were isolated in most cases. Subsequent reaction of CF 3 N(Nu)C(O)F with additional nucleophile was observed in many cases forming CF 3 N(Nu)C(O)Nu. With CH 3 CO 2 H, the latter reaction forms CH 3 C(O)F and the novel amine CF 3 N(H)OC(O)CH 6 3 . Ten new compounds are reported with characterization by IR, NMR and physical properties.

Synthesis of pentafluorophenyl esters from acid fluorides and potassium pentafluorophenoxide

Abstract The reaction of potassium pentafluorophenoxide with acid fluorides has been investigated and found to yield pentafluorophenyl esters. The compounds CH 3 C(O)OC 6 F 5 , CF 3 C(O)OC 6 F 5 , CF(O)OC 6 F 5 , CF 3 OOC(O)OC 6 F 5 , and (C 6 F 5 O) 2 CO have been prepared. Physical and spectral data for each compound are reported.

Synthesis of perfluoro-t-butyl esters from acid fluorides and potassium perfluoro-t-butoxide

Abstract Reactions of potassium perfluoro-t-butoxide with acyl fluorides lead to the corresponding perfluoro-t-butyl esters in high yield. The compounds [(CF 3 ) 3 CO] 2 CO, (CF 3 ) 3 COC(O)F, CF 3 C(O)OC(CF 3 ) 3 , CH 3 C(O)OC(CF 3 ) 3 and CF 3 OOC(O)OC(CF 3 ) 3 have been thus obtained and some physical and chemical properties of each are reported.

Further reactions of chlorine(I) and bromine(I) trifluoromethanesulfonate and bromine(I)fluorosulfate

Abstract Substitutive electrophilic dehalogenation reactions of CF3SO2OX (X=Cl,Br) are reported with some covalent inorganic chlorides. These reactions result in the formation of XX′(X,X′Cl,Br) and several new trifluoromethanesulfonate derivatives in excellent yields. Chlorine(I) trifluoromethanesulfonate also oxidatively adds to unsaturated inorganic substrates such as CO, SO2 and SF4 forming new compounds. The reactivity of CF3SO2OCl is rather similar to that of FSO2OBr and some comparisons between the two are given.

The addition of fluorine to perhalogenated compounds containing carbon-nitrogen double bonds

Abstract The reaction of elementary fluorine with ten perhalogenated compounds containing carbon-nitrogen double bonds is reported. The reactions were carried out without added catalysts in a static system. With CF 3 N=CF 2 , (CF 3 ) 2 NCF=NCF 3 , SF 5 N=CF 2 , CF 2 =NCl, CF 3 CF=NCl and CF 2 =NF a simple addition of fluorine to the carbon-nitrogen double bond was observed forming the respective N-fluoroamines in high yield. Two imines, CF 3 CF=NF and (CF=NF) 2 , were unreactive under the same conditions and reactions of CF 3 CF 2 CF=NF and (CF 3 ) 2 C=NF were explosive.

Synthesis of pentafluorophenoxy derivatives of phosphorus in various oxidation states

Abstract The reaction of potassium pentafluorophenoxide with phosphorus halides in a variety of oxidation states has been investigated. The new compounds PCl 2 OC 6 F 5 , PF 2 OC 6 F 5 , OPF 2 OC 6 F 5 , PF 4 OC 6 F 5 and PF 3 (OC 6 F 5 ) 2 result from the reaction of KOC 6 F 5 with PCl 3 , PF 2 Br, OPF 2 Br, and PF 5 . Spectral data and physical properties of the new compounds have been reported.

Some reactions of potassium perfluoro-t-butoxide with strong oxidizing agents

Abstract Several reactions of potassium perfluoro-t-butoxide with strong oxidizing agents have been studied. The new compounds (CF3)3COOSO2F and (CF3)3CONO2 have been prepared by reactions with peroxydisulfuryl difluoride and nitryl fluoride, and their properties are reported. Evidence is also presented for the formation of the novel peroxy salt KOOCF3 in the reaction with bis(fluoroxy)difluoromethane. A mechanism for the reaction of —OF compounds with KOC(CF3)3 is proposed.

Synthesis of trifluoromethanesulfonate esters by reaction of alkyl chlorides with chlorine (I) and bromine (II) trifluoromethanesulfonate

Abstract The synthesis of the first trifluoromethanesulfonate esters of the type CF 3 SO 3 (CH 2 ) n O 3 SCF 3 (n=1,2,3) are reported. The new compounds are prepared from Cl(CH 2 ) n Cl by substitutive electrophilic dehalogenation reactions with CF 3 SO 2 OX (x=Cl,Br). The extension of this reaction to HCCl 3 results in HC(O 3 SCF 3 ) 3 but the compound is unstable at 22°.

Some novel oxime ethers. The synthesis of 1,1-difluoro-2-alkoxymethanimines

Abstract The syntheses of four novel 1,1-difluoro-2-alkoxymethanimines, RONCF 2 , are reported. The oxime ethers are prepared in excellent yield by dehydrofluorination of the amines, RON(H)CF 3 (RCF 3 , (CF 3 ) 2 CF, CH 3 , (CH 3 ) 3 C) with KF. These oxime ethers are thermally stable at 24°C and are characterized by IR, NMR, and physical properties. The two perfluoro compounds undergo dimerization to give CF 3 N(OR)CFNOR in the presence of CsF at room temperature.