Methylenetriphenylphosphorane
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IUPAC name
Methylene(triphenyl)phosphorane
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Identifiers | |
3D model (JSmol)
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PubChem CID
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CompTox Dashboard (EPA)
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Properties | |
C19H17P | |
Appearance | yellow solid |
Density | 1.19 g/cm3 |
decompose | |
Solubility | THF |
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
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Methylenetriphenylphosphorane is an organophosphorus compound with the formula Ph3PCH2. It is the parent member of the phosphorus ylides, popularly known as Wittig reagents. It is a highly polar, highly basic species.
Preparation and use
Methylenetriphenylphosphorane is prepared from triphenylphosphine and methyl bromide followed by deprotonation of the resulting phosphonium salt using a strong base like butyllithium:[1]
- Ph3PCH3Br + BuLi → Ph3PCH2 + LiBr + BuH
The compound is generally not isolated, instead it is used in situ.
Methylenetriphenylphosphorane is used to replace oxygen centres in aldehydes and ketones with a methylene group:
- R2CO + Ph3PCH2 → R2C=CH2 + Ph3PO
The phosphorus-containing product is triphenylphosphine oxide.
Structure
Crystallographic characterization of the colourless ylide reveals that the phosphorus atom is approximately tetrahedral. The PCH2 centre is planar and the P=CH2 distance is 1.661 Å, which is much shorter than the P-Ph distances (1.823 Å).[2] The compound is usually described as a combination of two resonance structures:
- Ph3P+CH2− ↔ Ph3P=CH2
References
- ^ Georg Wittig U. Schoellkopf (1960). "Methylenecyclohexane". Organic Syntheses. 40: 66. doi:10.15227/orgsyn.040.0066; Collected Volumes, vol. 5, 1973, p. 751.
- ^ Bart, J. C. J. "Structure of the non-stabilized phosphonium ylid methylenetriphenylphosphorane". Journal of the Chemical Society B. 1969: 350–365. doi:10.1039/J29690000350.