It would be better even to distill any acetone (even dry) before synthesis over
P2O5 B2O3 or CaCl2 to remove any water and impurities.
Drying of Acetone. Acetone has been dried with a wide
spectrum of desiccants.8 Thus, alumina, calcium chloride,
phosphorus pentoxide, and 4A molecular sieves,16 as well as
calcium and (anhydrous) cupric sulfate, have all been used.
Since acetone has the lowest dielectric constant of the sol-
vents investigated here, it might be predicted that its drying
should be relatively easy. In fact, in many respects the drying
of acetone proved to be the most difficult case. As with Me2SO,
the root of the difficulty is the acidic a protons, which in this
case compounds the drying problem not only by inflating
apparent water content by exchange process but also by
providing a pathway to self-condensation through enol in-
termediates. This facet of acetone chemistry makes the choice
of a successful desiccant a delicate process. As Table IV shows,
mild siccatives such as calcium sulfate are inept; more potent
desiccants such as molecular sieves exhibit a short initial
drying action but thereafter actually cause disastrous in-
creases in water content by displacement of the condensation
equilibrium. This interpretation was confirmed for molecular
sieves and other basic desiccants such as barium oxide by gas
chromatographic analysis which demonstrated the presence
of mesityl oxide in the dried solvent (see Table IV).
In summary, while both cupric sulfate and 3A molecular
sieves are clearly at least useful preliminary desiccants, the
agent par excellence for acetone is powdered boric anhydride.
Using stirring and sequential drying conditions, this siccation
gave a solvent containing only 18 ppm of water and caused no
detectable condensation. In fact, the true water content is
likely to be lower as even with the premise that drying occurs
considerably faster than other processes, some labeling via the
enol surely occurs on preparation of the standard wet solu-
tion.
In view of the remarkable efficiency of this desiccant for
acetone and acetonitrile,1 it is puzzling that boric anhydride
is not particularly outstanding for other members of this series
(Tables I—III). This finding emphasizes once more the danger
in assuming the existence of any kind of absolute scale in the
efficiency of desiccants for solvent drying.
Source:
https://doi.org/10.1021/jo00414a038