Synthesis and steric structure of 2-[1-(3-chlorophenyl)-2,2,2-trifluoroethoxy]-3-(trichloromethyl)-6,7-benzo-1,4,2λ5-dioxaphosphepin-5-one 2-oxide

Abstract

The reaction with chloral of 2-[1-(3-chlorophenyl)-2,2,2-trifluoroethoxy]-5,6-benzo-1,3,2-dioxaphosphorinan-4-one containing a chiral fluorinated exocyclic substituent on phosphorus leads to formation of 2-[1-(3-chlorophenyl)-2,2,2-trifluoroethoxy]-3-(trichloromethyl)-6,7-benzo-1,4,2l 5 -dioxaphosphepin-5-one 2-oxide with a high regio-and stereoselectivity. The molecular and supramolecular structure of the isolated diastereomer was established by means of X-ray diffraction.

Tris(1,1,1,3,3,3-hexafluoroisopropyl) phosphate

“…The title compound displays three intramolecular C-H•••O hydrogen interactions, similar to that found in polyfluorinated dioxaphosphepinone oxide derivatives (Gubaidullin et al, 2004). These hydrogen bonds display an S(6) graph-set motif (Bernstein et al, 1995)…”

“…For related literature, see: Allen et al (1987); Dakternieks et al (1978); Gubaidullin et al (2004); Halper & Cohen (2005); Hanes et al (2002); Robinson et al (1971); Smart (2001); Timperley & White (2003); Timperley et al (2000); Bernstein et al (1995); Larson (1970); Prince (1982); Watkin (1994).…”

“…The steric and electronic effects of aliphatic fluoroalkyl groups are still the subject of experimental and theoretical work (Timperley & White, 2003). We report here the X-ray structure of the title compound, (I), which represents one of the very few examples of crystallized polyfluorinated phosphotriester (Hanes et al, 2002;Gubaidullin et al, 2004).…”

Reactions of 2-phenyl-4,4-bis(trifluoromethyl)-4,5-dihydro-1,3,2-benzodioxaphosphepin-5-one with phenanthrenequinone and dibenzoyl

“…They are capable of being involved in cascade reactions with activated carbonyl compounds, Schiff bases, and ylidene derivatives of dicarbonyl compounds. In these reactions, the carbonyl group can participate in one or another step of the cascade process, leading to the formation of 1,3,2-dioxa(oxaza)-and 1,4,2-dioxa-(oxaza)phosphepines, 1,2-oxaphospholanes, and other difficultly accessible compounds [5][6][7][8][9][10][11][12].We recently showed that cyclic phosphorus(III) derivatives having an activated carbonyl group in the γ-position with respect to the phosphorus atom, e.g., 2-phenyl-4,4-bis(trifluoromethyl)-4,5-dihydro-1,3,2-benzodioxaphosphepin-5-one (I), also undergo cascade transformations by the action of trichloroacetaldehyde and hexafluoroacetone. As a result, cage-like propeller phosphorane with a phosphorus-carbon bond (structure II) [13,14] or spiran structure III is formed; in the latter structure, the γ-carbonyl carbon atom becomes a spiro atom [15] (Scheme 1).…”

“…They are capable of being involved in cascade reactions with activated carbonyl compounds, Schiff bases, and ylidene derivatives of dicarbonyl compounds. In these reactions, the carbonyl group can participate in one or another step of the cascade process, leading to the formation of 1,3,2-dioxa(oxaza)-and 1,4,2-dioxa-(oxaza)phosphepines, 1,2-oxaphospholanes, and other difficultly accessible compounds [5][6][7][8][9][10][11][12].…”