Fluorophenyl derivatives

The benzene derivatives containing the fluorinated sulfone have been prepared either by nucleophilic substitution of the 4-fluorophenyl derivative (e.g. 1) or by starting with the appropriately substituted sodium thiophenoxide and reacting with perfluoroalkyl iodide follow by oxidation with either MCPBA or chromium oxide (12. li.) The biphenyl derivatives have been prepared by palladium catalyzed cross coupling chemistry of the 4-bromophenyl derivative (e.g. 2) with substituted phenyl boronic acid (yields 37-84%) (JLH, .). Compound 16 has been prepared by palladium catalyzed cross coupling of (4-bromophenyl)perfluorohexyl sulfone with vinyl anisole in 37 % yield (JJL). The vinyl sulfones, 7 and 9, have been prepared by condensation of CH3S02Rf (JJL) with the appropriate aldehyde (yields 70,and 73%) following a literature procedure (1 ). Yields were not optimized. 

Parshall (44, 45) has used fluorine-19 nuclear magnetic resonance spectra of the fluorophenyl derivatives of platinum (II), VIII and IX, to study the trans influence of the X ligand. The meta 19F shielding... 

The same conclusion, that the PhsSi group is a good cr-donor, was drawn from F-NMR experiments on fluorophenyl derivatives of Si-Pt compounds (entry 16) additionally, it was concluded that PhsSi attached to Pt was a good 7r-acceptor. A wide range of chemical shifts and coupling constants involving H, P, and Pt nuclei were determined by double-resonance experiments on a large number of Si-Pt derivatives (entry 17). 

The mass spectra of a number of derivatives of 617 have been recorded cation-radicals RPS2 are most abundant. The F nmr spectra of a number of m- or p-fluorophenyl derivatives of 617 have been reported. ... 

Similarly prepared were the corresponding diphenyl. bis[4-methylphenyl], bis[4-bromophenyl]. and fluorophenyl] derivatives ... 

From the F spectra of fluorophenyl derivatives and spectra of phenyl derivatives, one can determine the heteroaromatic groups from the chemical shift values of amino and hydroxy group protons in the H-NMR spectra of aminophenyl and hydroxyphenyl derivatives, one can obtain other a constants for heteroaromatic groups, in particular [Pg.5]

A similar procedure was used for 2-fluorophenyl derivatives.118 High-field NMR instruments allow the use of very diluted solutions for 19F NMR studies. The 19F NMR spectra of 1 x 10-4m solution of a dye in chloroform can be obtained within ca. 10 min of accumulation in a 5-mm tube at 376.5 MHz. Practically no changes of 19F chemical shifts were obtained within the concentration range 1 x 10 2 to 1 x 10 4mol/litre, in contrast to the following case. 

Radical deoxygenation of sec.-alcohols, Barton-McCombie reaction.2" This reaction proceeds more rapidly with xanthates [ R CHOC(S)SCHr than with any of the known phenoxy thiocarbonyl derivatives [R2CHOC(S)OCf,H ]. Of these the unsubstituted phenoxythiocarbonyl derivative is slightly more reactive than the 2,4,6-trichloro- or the p-fluorophenyl derivative. The pentafluorophcnyl derivative, R2CHOC(S)OC6F5, is the slowest of all known derivatives. 

Structure-function relationships were examined for complexes with a variety of related diphosphine ligands.Generally the phenylphosphine complexes are more active than are ethyl, pyridyl or fluorophenyl derivatives. As would be expected when a cationic complex is the active species, the nature of the anion [e.g. Cl , Br or NO3 ) does not substantially affect the potency of the drug. 

Radical deoxygenation of sec.-aJeottai action proceeds more rapidly with xanihan known phenoxy thiocarbonyl derivative [R phenoxythiocarbonyl derivative is shghtlv 1 p-fluorophenyl derivative. The pemaflmmu slowest of all known derivatives. 

T-parameter of X, a better fit was obtained with a combination of Taft inductive and resonance parameters. The effect is more dramatic in tram-FC6H4PtX(PEt3)2 compounds. The shielding parameters of the m-and p-fluorophenyl derivatives permit a more direct evaluation of the electronic interaction between an anionic ligand and the metal (75). In both the titanium and platinum compoimds, the metal atom appears to release electron density to the aromatic ring. 

Silicon, Germanium, Tin, and Lead.—Ihe mass spectra of the tetrakis(penta-fluorophenyl) derivatives (CgFs)4M (M = Si, Ge, Sn, or Pb) have been studied. Rearrangements involving transfer of fluorine to metal, with or without charge, are prevalent. The heavier metal species give simpler spectra, and the bulk of the ion current is carried by fluorocarbon ions for the silicon compound and by metal-containing ions, particularly MF, for the other compounds. ... 

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