反応 #349965

反応方程式

methyl phenylacetate

phosphonate

n-butyllithium

dimethyl methylphosphonate

→

dimethyl 2-oxo-3-phenylpropylphosphonate

収率 29.0%

溶媒

acetic acid

hexane

tetrahydrofuran

反応条件

後処理

1. 1
   その他the reaction temperature less than -70° (20 minutes)
2. 2
   workup.WAITAfter 3.5 hours at -78° the reaction mixture was allowed
3. 3
   その他rotary evaporated to a white gel
4. 4
   抽出the aqueous phase extracted with 100 ml portions of chloroform (3x)
5. 5
   乾燥dried (MgSO4)
6. 6
   濃縮concentrated (water aspirator) to a crude residue
7. 7
   workup.DISTILLATIONdistilled

実験手順

A solution of 6.2 g (50 mmoles) dimethyl methylphosphonate (Aldrich) in 125 ml dry tetrahydrofuran was cooled to -78° in a dry nitrogen atmosphere. To the stirred phosphonate solution was added 21 ml of 2.37 M n-butyllithium in hexane solution (Alfa Inorganics, Inc.) dropwise over a period of 18 minutes at such a rate that the reaction temperature never rose above -65°. After an additional 5 minutes stirring at -78°, 7.5 g (50.0 mmole) methyl phenylacetate was added dropwise at a rate that kept the reaction temperature less than -70° (20 minutes). After 3.5 hours at -78° the reaction mixture was allowed to warm to ambient temperature, neutralized with 6 ml acetic acid and rotary evaporated to a white gel. The gelatonous material was taken up in 75 ml water, the aqueous phase extracted with 100 ml portions of chloroform (3x), the combined organic extracts were backwashed (50 cc H2O), dried (MgSO4), and concentrated (water aspirator) to a crude residue and distilled, b.p. 134°-5° (<0.1 mm) to give 3.5 g (29%) dimethyl 2-oxo-3-phenylpropylphosphonate. (2).

出典