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Methylenetriphenylphosphorane

Methylenetriphenylphosphorane is an organophosphorus compound with the formula Ph<sub>3</sub>PCH<sub>2</sub>. 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 methyltriphenylphosphonium bromide by its deprotonation using a strong base like butyllithium:

Ph<sub>3</sub>PCH<sub>3</sub>Br + BuLi → Ph<sub>3</sub>PCH<sub>2</sub> + LiBr + BuH

The phosphorane is generally not isolated, instead it is used in situ. The estimated pK<sub>a</sub> of this carbon acid is near 15. Potassium tert-butoxide has been used in place of butyl lithium. Sodium amide has also been used a base.

Methylenetriphenylphosphorane is used to replace oxygen centres in aldehydes and ketones with a methylene group, i.e., a methylenation:

R<sub>2</sub>CO + Ph<sub>3</sub>PCH<sub>2</sub> → R<sub>2</sub>C=CH<sub>2</sub> + Ph<sub>3</sub>PO

The phosphorus-containing product is triphenylphosphine oxide.

Structure

Crystallographic characterization of the colourless ylide reveals that the phosphorus atom is approximately tetrahedral. The PCH<sub>2</sub> centre is planar and the P=CH<sub>2</sub> distance is 1.661 Å, which is much shorter than the P-Ph distances (1.823 Å). The compound is usually described as a combination of two resonance structures:

Ph<sub>3</sub>P<sup>+</sup>CH<sub>2</sub><sup>−</sup> ↔ Ph<sub>3</sub>P=CH<sub>2</sub>

Uses

Methylenetriphenylphosphorane has become a standard tool for synthetic organic chemists.

Related reagents

References