Acetic Anhydride (Wittcoff, H., Reuben, B., Plotkin, J.

Industrial Organic Chemicals, Third

Edition. Wiley & Sons. Inc)

Acetic anhydride is made by tree processes. In one, acetic acid (or acetone, but that is
uneconomical) is pyrolyzed to ketene, which in turn reacts with acetic acid. The
pyrolysis takes place at 700-800C in presence of triethyl phosphate at a very low
residence time of 0.2 0.5 second. Molar yields are 85 - 89 %.

The second procedure involves the in situ production of peracetic acid form
acetaldehyde, which in turn reacts with more acetaldehyde to yield the anhydride.
This process is probably not in use. Ethyl acetate may be used as a solvent, the
reaction is catalyzed by a mixture of cobalt and copper acetates. The molar yield
anhydride is abut 75 %.

Eastman Chemical working with Halcon have development a novel process involving
the carbonilation of methyl acetate with a catalyst comprising rhodium chloride and
chromium hexacarbonyl, Cr(CO)6, in acetic acid solvent. In one reaction described in a
patent, -picoline is a catalyst modifier and methyl iodine is a promoter. The
hydrogen/carbon monoxide ratio is important, since increase in the hydrogen content
provides a corresponding increase in the production of ethylidene diacetate. This
compound is the basis for a proposed process for vinyl acetate but is undesirable if
high selectivity to the anhydride is desired. Since this reaction is novel, the possible
mechanism is of interest. Only the rhodium is show as the catalyst. In the first steps,
acetyl iodide is formed. Reaction of this product with acetate ion yields acetic
anhydride.

Acetic anhydrides main use is in the production of cellulose acetate. Other uses are
small and include the formation of various esters such acetylsalicylic acid (aspirin)
and acetylated amides of which N-acetyl-p-aminophenol (acetaminophen or
paracetamol) is a prime example.

Ketene, the intermediate in one acetic anhydride process, is a powerfully lachrymatory
gas with a choking smell. It is a invariably used in situ. Apart from its role in acetic
anhydride production, it can be dimerized over trimethyl phosphate to diketene.
Ammonia is added to inhibit the back reaction. Diketene reacts with methanol and
ethanol to give methyl and ethyl acetoacetates.