First post, I know but I found this little gem and was wondering if anyone had tried it on unsubstituted benzaldehydes?
Quote
Check this out!!
(Rated as: excellent)
To a three-necked 3000ml rb flask with a stir bar add 166g (1mol) 2,5-dimethoxybenzaldehyde, 15g Aliquat 336, 159g (1.3mol, 139.5ml) methyl 2-chloropropionate, 500ml toluene and 200ml MeOH .With a cold water bath the temperature is brought down to 10-15 deg C. 60g solid NaOH is added in portions of 2-4g over two hours while not allowing the temperature to rise over 15 deg C.
Do not get to brave while adding the hydroxide because the temperature can rise very quick, and you do not want to mop up the haloester from the floor and ceiling – trust me.
When about about 30g NaOH has been added the solution becomes very thick from some precipitate but this will gradually dissolve again. If it becomes too thick to be properly stirred add some more MeOH.
When all NaOH has been added allow the solution to stir for another two hours at room temp.
Then add a pre-made solution of 100g NaOH in 450ml MeOH dropwise during 2 hours while keeping the temperature at 20-30 deg C. Keep it stirring at room temp for another 4 hours and the let it stand over night. The next day the solution will be very thick from precipitated crystals. Add 500ml water and the crystals will dissolve. Separate the two layers and extract the organic layer with another 500ml water. The toluene layer can now be discarged.
To the combined aqueous extracts conc HCl is added until pH 2.5-3 is reached. This will cause a yellow oil to fall out. Allow the acid solution to stir for one hour at room temp, add solid NaCl (enough to saturate the solution) and 500ml toluene and stir for 10 minutes.
Separate the layers and extract the aqueous phase once more with 250ml toluene. Wash the combined toluene phases once with saturated NaHCO3 solution, dry with MgSO4 and remove the toluene by distillation. This leaves 2,5-dimethoxyphenylacetone as a yellow oil.
Yield: 152g (0.78mol) 2,5-dimethoxyphenylacetone


