General Trick: Here is an excellent organic extraction solvent: 3:1 CHCl 3/ isopropanol. This mixture sometimes has the ability to pull aqueous-soluble organics out of the aqueous phase when CH 2Cl, EtOAc, Et 2O, etc. don't work. (submitted by Bill Spencer, AMRI).
If convenient, remove solvent before workup to avoid losing polar products. If product is very nonpolar, partition between hexanes and water and carry out aqueous extraction. On small scale, you can dilute with a lot of the extraction solvent, and washed several times. Acetonitrile will partition into the aqueous layer.
Miscible with both water and organic solvents, alcohols do not cooperate during the typical aqueous workup. Remove the solvent by rotoevaporation first.
If diluted sufficiently with extraction solvent, and washed several times, they will partition into the aqueous layer. However, sometimes product goes along with them, and sometimes emulsions form. It is safer to remove THF by rotoevaporation before workup if practical, especially for large scale procedures. Dioxane is high boiling, usually making rotoevaporation impractical
Sometimes workups of reactions in benzene will lead to emulsion formation. If this is the case, the solvent should be either removed by rotoevaporation before workup, or diluted well with the extraction solvent before washing with water.