Synthesis of Aluminium Isopropoxide with a Gallium Catalyst

By Abromination

Abstract: Aluminium isopropoxide is a useful reagent in organic chemistry, but is

often difficult for the amature to obtain without needing mercury or mercuric
chloride. Mercury can be substituted with gallium metal, which prevents the need
for working with toxic reagents.

Preparation of Dry Isopropanol:

Water-free isopropanol is required for application in the synthesis of aluminium

isopropoxide. Dry isopropanol was prepared by salting out 70 percent isopropanol
and further drying with 3A molecular sieves in accordance to a paper by Lewis
Gilson (1).

Stirring iPrOH with NaOH

A large amount (about 70g) of technical grade sodium chloride was added to
400mL of isopropanol. The mixture was stirred for six hours and vacuum filtered
to remove excess salt. The bottom water layer was removed with a separatory
funnel, leaving what Gilson approximated to be a 91% isopropanol azeotrope. The
isopropanol was then heated, prompting the separation of additional brine. This
brine layer was removed, and an apparatus for fractional distillation was
constructed. The isopropanol boiled over around 80ºC, the expected boiling point
for the azeotrope. 224g of the alcohol was collected, which was further salted out
with sodium hydroxide. Gilson found success by shaking the alcohol with 10% of
its weight of sodium hydroxide; 22.4g sodium hydroxide was added to the
isopropanol with stirring. After an hour, the stirring was stopped and the bottom
water layer was removed. Sodium hydroxide was again added in one gram portions
with heavy stirring until the pellets no longer dissolved* (totalling around 4g). The
bottom layer was removed, and the isopropanol was once again fractionally
distilled, yielding a product with a boiling point of around 83 degrees. To remove
any excess water, activated 3A molecular sieves were added to the alcohol and left
for a week. The isopropanol tested dry after adding a few flakes of anhydrous
copper (II) sulfate and was considered adequate for synthesis.

*It should be noted that adding extra NaOH in this step causes the mixture to form an unworkable,
gel-like mass

Preparation of Aluminium Isopropoxide:

Reagents:
27g aluminium foil
300mL dried isopropanol
2.5g gallium metal

27 grams of shredded aluminium foil was heated with 2.5 grams of gallium. The
mixture was stirred to distribute the liquid gallium across the surface of the
aluminium. Once it had cooled, the aluminium alloy was added to a 500mL round-
bottom flask charged with 300mL dried isopropanol. The flask was equipped with
a dimroth condenser and drying tube and was set up for reflux. The mixture was
heated for approximately 1.5 hours, at which point the corrosion on the surface of
the aluminium became significant. The heating mantle was turned off and the
reaction was allowed to proceed on its own. The corrosion became quite rapid,
notable by the continued boiling of the isopropanol and the effervescence of
hydrogen on the surface of the metal. Although the drip rate from the dimroth was
rapid, the condenser was easily able to handle the vapour.
 Apparatus for alkoxide synthesis

The reaction continued on its own for another two hours, during which most of the
aluminium was consumed. The heating mantle was turned back on and the
isopropoxide mixture was allowed to stir for an additional two hours. Finally, the
mixture was allowed to cool overnight, leaving a solid mass of grey, impure
aluminium isopropoxide
 Solid, Impure Aluminium Isopropoxide

From here, the isopropoxide can either be distilled under reduced pressure or used
as is.