An effective synthetic route to ortho-difluoromethyl arylphosphosphonates: studies on the reactivity of phosphorus- and fluorine-containing functions

A study of the reaction of perfluoroalkyl Grignard reagents with phosphoryl chloride and phenylphosphonic dichloride

“…31 P and 19 F NMR spectra of the acids agree with the literature values. 11,13 31 P NMR monitoring of the reaction of C 2 F 5 MgCl with OvPCl 3 indicates the presence of a pentet at δ 21.8 ppm ( 2 J P-F = 96 Hz), while the 19 F NMR spectrum showed a broad singlet at δ −79.9 and a doublet at δ −121.3 ppm.…”

“…By contrast with these results, Röschenthaler and coworkers report selective monosubstitution in the case of the reaction of ortho-bromodifluoromethyl arylphosphonic dichlorides with C 2 F 5 Li. 19 It should be noted, however, that disubstitution cannot be ruled out, since under the 10% HCl work up employed, hydrolysis of any initially formed bis( perfluoroethyl)-aryl phosphine oxide to the isolated product, perfluoroethyl(aryl)-phosphinic acid, is likely. The procedure described herein constitutes a convenient "one pot" route to mixed perfluoroalkyl ( phenyl) phosphinic acids.…”

“…The relatively nonhazardous nature and the inexpensive reagents makes the procedure an attractive alternative to previously reported syntheses of bis( perfluoroalkyl)phosphinic acids [7][8][9][10][11][12][13][14][15][16] and perfluoroalkyl-(aryl)phosphinic acids. [17][18][19] …”

Diels–Alder Reaction in the Synthesis of Fluorinated (Hetero)Aromatic Compounds

“…Röschenthaler and Tverdomed synthesized a series of alkynyl phosphonates 292 and studied their Diels–Alder reactions , . Among others, the reaction with 2,3‐dimethyl‐buta‐1,3‐diene was used to prepare aromatic phosphonates 294 by sequential [4+2]‐cycloaddition/oxidative aromatization.…”

Bromodifluoromethylation of aromatic Grignard reagents with CF2Br2

“…In addition, we regarded that difluorostilbene 8 (=H) was produced by dimerization of arylfluorocarbene G, which was generated through a-elimination of E accelerated by two fluorine atoms that destabilized the sp 2 -hybridized benzyl carbanion. 15 Since we thought that the key to success in the bromodifluoromethylation would be to enhance the stability of the intermediate E, which could accelerate the carbene insertion step (A-E) and prevent the decomposition (E-G), 16 we then decided to explore the reaction of the arylmetal species A possessing electron-withdrawing groups on the aromatic ring with CF 2 Br 2 .…”