tert-Butyl peroxyacetate

Chemical Properties

clear solution

Uses

Allows the direct copper catalyzed acetoxylation of β-lactams at the 4-position.

Uses

It is used to initiate polymerization, and inorganic syntheses.

Uses

Polymerization initiator for vinyl monomers, manufacture of polyethylene and polystyrene.

General Description

tert-Butyl peroxyacetate is sensitive to heat. Storage of tert-Butyl peroxyacetate must be done so with stringent temperature control measures. It's explosion hazard is also mitigated by mixing the peroxide with an inert solid.

Reactivity Profile

tert-Butyl peroxyacetate explodes with great violence when rapidly heated to a critical temperature; pure form is shock sensitive and detonable [Bretherick 1979 p. 602]. Upon contact with organic matter, t-butyl peroxyacetate can ignite or give rise to an explosion [Haz. Chem. Data 1973 p. 77].

Hazard

Flammable, dangerous fire risk. Oxidizer.

Health Hazard

Mild skin and eye irritant. Its toxicity is low,both via inhalation and ingestion routes.
LD₅₀ value, oral (rats): 675 mg/kg.

Fire Hazard

The pure compound is highly reactive and oxidizing, and sensitive to heat and shock.
A 75% solution in benzene or mineral spirits is the maximum assay that is sold commercially. Its benzene solution at this concentration is reactive, oxidizing, and flammable. The flash point varies depending on the solvent; the autoignition temperature not reported; the self-accelerating decomposition temperature is 93°C (199.4°F).
t-Butyl peroxyacetate forms an explosive mixture with air, explosive range not reported. It can ignite or explode when in contact with combustible organic compounds. Fire-extinguishing agent: water from a sprinkler from an explosion-resistant location; keep the containers cool.

Flammability and Explosibility

Flammable

Safety Profile

Moderately toxic by ingestion. Mildly toxic by inhalation. Moderate skin and eye irritant. A shockand heat-sensitive explosive. Dangerous fire hazard when exposed to heat, flame, reducing agents. To fight fire, use dry chemical, alcohol foam, spray and mist. When heated to decomposition it emits acrid smoke and fumes. See also PEROXIDES, ORGANIC; and ESTERS

storage

Store in a cool and well-ventilated placeisolated from other chemicals; protect fromphysical damage. It is shipped in glass andearthenware containers not exceeding 7 lb,inside a wooden or fiberboard box.

Purification Methods

Wash the ester with NaHCO3 from a *benzene solution, then redistil to remove *benzene [Kochi J Am Chem Soc 84 774 1962]. Handle with adequate protection due to possible EXPLOSIVE nature. [Beilstein 2 IV 391.]

Toxics Screening Level

The initial threshold screening level (ITSL) for t-butyl peroxyacetate is 0.06 μg/m3 based on an annual averaging time.

References

[1] J. Wenzel, Sunggyu Lee. “Tert-butyl peroxyacetate initiated semibatch polymerization of 1,1-difluoroethylene in supercritical carbon dioxide.” Polymer Engineering and Science 16 1 (2016): 435–440.
[2] V. A. Donchak, R. S. Yur'ev, S. A. Voronov. “New synthesis of tert-butyl peroxycarboxylates.” Russian Journal of Organic Chemistry 42 4 (2006): 487–490.