76248-62-9

Basic information

• Product Name: 3,3,3',3'-Tetrakis(trifluoromethyl)-1,1'-spiro[1H,3H-2,1-benzoxaphosphole]-1-hydroxide
• Synonyms: 3,3,3',3'-Tetrakis(trifluoromethyl)-1,1'-spiro[1H,3H-2,1-benzoxaphosphole]-1-hydroxide
• CAS NO: 76248-62-9
• Molecular Weight: 532.222
• Mol File: 76248-62-9.mol

Chemical Properties

• CAS DataBase Reference: 3,3,3',3'-Tetrakis(trifluoromethyl)-1,1'-spiro[1H,3H-2,1-benzoxaphosphole]-1-hydroxide(CAS DataBase Reference)
• NIST Chemistry Reference: 3,3,3',3'-Tetrakis(trifluoromethyl)-1,1'-spiro[1H,3H-2,1-benzoxaphosphole]-1-hydroxide(76248-62-9)
• EPA Substance Registry System: 3,3,3',3'-Tetrakis(trifluoromethyl)-1,1'-spiro[1H,3H-2,1-benzoxaphosphole]-1-hydroxide(76248-62-9)

Safety Data

• Hazardous Substances Data: 76248-62-9(Hazardous Substances Data)

Upstream product

• 77121-88-1 (S)-3,3,3',3'-tetrakis(trifluoromethyl)-1,1'-spirobi<3H,2,1λ⁵-benzoxaphosphole> 
• 1439-07-2 trans-Stilbene oxide 
• 1689-71-0 cis-1,2-diphenyloxirane 
• 100-52-7 benzaldehyde 
• 476315-26-1 [TBPY-5-12/11]-1-phenylmethyl-3,3,3',3'-tetrakis(trifluoromethyl)-1,1'-spirobi[3H,2,1,λ⁵-benzoxaphosphole] 
• 508231-25-2 1-(2-oxo-1,2-diphenylethyl)-3,3,3',3'-tetrakis(trifluoromethyl)-1,1'-spirobi[3H,2,1λ⁵-benzoxaphosphole] 
• 2272-55-1 ethyl trans-3-phenyl-1-oxirane-2-carboxylate 

Relevant articles and documents

Novel results obtained by freezing berry pseudorotation of phosphoranes (10-P-5)

By freezing Berry pseudorotation of spirophosphoranes with recourse to the rigidity of the Martin bidentate ligand, we successfully prepared configurationally stable enantiomeric pairs of optically active phosphoranes, and could isolate anti-apicophilic C-apical O-equatorial (O-cis) phosphoranes. The effect of σ* P-O orbital of the O-cis phosphorane was investigated both experimentally and theoretically, O-cis phosphoranes were revealed to be much more electrophilic at the phosphorus atom than O-trans isomers by experimental studies. The acidity of the α-proton of an O-cis benzylphosphorane was found to be higher than that of the corresponding O-trans isomer. By the reaction of the α-carbanion of an O-cis benzylphosphorane with PhCHO, we succeeded in the first isolation and full structural characterization of a 12-P-6 phosphate bearing an oxaphosphetane ring, the intermediate in the Wittig type reaction using a 10-P-5 phosphorane.

Stereospecific stilbene formation from β-hydroxy-α,β-diphenylethylphosphoranes. Mechanistic proposals based upon stereochemistry

All four diastereomers of β-hydroxy-α,β-diphenylethylspirophosphoranes bearing two Martin ligands were prepared from a P-H (equatorial) spirophosphorane. Treatment of these phosphoranes with t-BuOK or t-BuONa at low temperature (ca. -40°C) led to the formation of stilbene with complete stereospecificity. In half of the cases the reaction proceeded quantitatively, whereas the other half gave rise to retro-aldol reaction with the formation of varying amounts of benzaldehyde and benzylphosphorane. A kinetic examination revealed that of the four the quantitatively proceeding reaction that gives cis-stilbene was the fastest. Based on the experimental observations, a mechanistic rationale for the previously reported Wittig-type reaction of exceptionally high Z-selectivity using an ethoxycarbonylmethylspirophosphorane is presented.

The stereospecific olefin formation reaction of 10-P-5 β-hydroxy- α,β-diphenylethylphosphoranes

Deprotonation of P-H spirophosphorane 4 bearing Martin ligands with n- BuLi followed by reaction with trans-stilbene oxide gave a pair of anti-β- hydroxy-α,β-diphenylethylspirophosphoranes 5-Sp*R*S* and 5-Sp*S*R*, whereas treatment with cis-stilbene oxide yielded syn-β-hydroxy-α,β- diphenylethylspirophosphoranes 5-Sp*S*S*. The remaining diastereomer 5- Sp*R*R* was obtained selectively by α-benzoylation of benzyl- spirophosphorane 3 followed by reduction with LiBH4. Deprotonation of the diastereomers with t-BuOK or t-BuONa lead to the stereospecific formation of stilbenes. The anti diastereomers gave cis-stilbene (Z:E=99:1) and the syn diastereomers furnished trans-stilbene (Z:E=1:99).