Direct fluorination of organic compounds: Fluorocarbons for specialized applications

4,4-Bis(methoxymethyl)-2,6-dioxaheptane, 5,5-bis(ethoxymethyl)-3,7-dioxanonane, 6,6-bis(propyloxymethyl)-4,8-dioxaundecane, 7,7-bis(2-methoxyethoxymethyl)-2,5,9,12-tetraoxatridecane, 7,7-bis(butyloxymethyl)-5,9-dioxatridecane, and 8,8-bis(pentyloxymethyl)-6,10-dioxapentadecane were synthesized by the phase transfer catalyzed reaction of pentaerythritol with the appropriate alkyl sulfate or alkyl halide. 7-methyl-7-(2-methoxyethoxymethyl)-2,5,9,12-tetraoxatridecane, 7-methyl-7(butyloxymethyl)-5,9-dioxatridecane, and 8-methyl-8(pentyloxymethyl)-6,10-pentadecane were likewise synthesized by the phase transfer catalyzed reaction of 1,1,1-tris(hydroxymethyl) ethane with the appropriate alkyl halide. 4,4,8,8-Tetrakis(methoxymethyl)-2,6,10-trioxaundecane was also prepared via the phase transfer catalyzed methylation of dipentaerythritol.; Each of these hydrocarbon ethers was converted to its perfluoro analogue by direct fluorination. Compounds were isolated and characterized.; The application of the direct fluorination technique has yielded new branched fluorocarbon compounds unattainable by other fluorination methods.; The synthesis of the first perfluoro cryptand compounds, perfluoro-4,7,13,16,21,24-hexaoxa-1,10-diazabicyclo (8,8,8) hexacosane, and perfluoro-1,10-diaza-4,7,13,16-tetraoxacyclooctadecane is described. Extensive characterization by various mass spectrometric techniques is also discussed.; The direct fluorination synthesis of several perfluoro alkyl orthocarbonates is also described. The fluorination of tetramethyl orthocarbonate and tetraethyl orthocarbonate produced perfluoro tetramethyl orthocarbonate and perfluoro tetraethyl orthocarbonate, respectively, in high yield.; The synthesis of hexafluoroacetone by direct fluorination is explored and the results rationalized in light of the results of past attempts at synthesis by the direct combination of acetone and fluorine.; A method for synthesizing the following materials with the perovskite structure was developed: KNiF{dollar}sb3{dollar}, KNi{dollar}sb{lcub}0.8{rcub}{dollar}Cu{dollar}sb{lcub}0.2{rcub}{dollar}F{dollar}sb3{dollar}, KNi{dollar}sb{lcub}0.6{rcub}{dollar}Cu{dollar}sb{lcub}0.4{rcub}{dollar}F{dollar}sb3{dollar}, KNi{dollar}sb{lcub}0.4{rcub}{dollar}Cu{dollar}sb{lcub}0.6{rcub}{dollar}F{dollar}sb3{dollar}, KNi{dollar}sb{lcub}0.2{rcub}{dollar}Cu{dollar}sb{lcub}0.8{rcub}{dollar}F{dollar}sb3{dollar}, and KCuF{dollar}sb3{dollar}. The following layered perovskite materials were similarly prepared: K{dollar}sb2{dollar}NiF{dollar}sb4{dollar}, K{dollar}sb2{dollar}Ni{dollar}sb{lcub}0.8{rcub}{dollar}Cu{dollar}sb{lcub}0.2{rcub}{dollar}F{dollar}sb4{dollar}, K{dollar}sb2{dollar}Ni{dollar}sb{lcub}0.6{rcub}{dollar}Cu{dollar}sb{lcub}0.4{rcub}{dollar}F{dollar}sb4{dollar}, K{dollar}sb2{dollar}Ni{dollar}sb{lcub}0.4{rcub}{dollar}Cu{dollar}sb{lcub}0.6{rcub}{dollar}F{dollar}sb4{dollar}, K{dollar}sb2{dollar}Ni{dollar}sb{lcub}0.2{rcub}{dollar}Cu{dollar}sb{lcub}0.8{rcub}{dollar}F{dollar}sb4{dollar}, and K{dollar}sb2{dollar}CuF{dollar}sb4{dollar}. Their structure and electrical properties were investigated.; The interaction of elemental fluorine with the porphyrin 5,10,15,20-tetrakis (pentafluorophenyl) 21H, 23H-porphine iron(III) chloride is discussed. Also described is the direct fluorination of 5,5,10,10,15,15,20,20-tetramethyltetraoxaporphyringogen. (Abstract shortened with permission of author.)...