Accession Number:

ADA151567

Title:

Thermolysis of 4-Methyl-4-(1-propenyl)malonyl Peroxide: Mechanistic Limits to Chemiluminescence Efficiency.

Descriptive Note:

Technical rept.,

Corporate Author:

ILLINOIS UNIV AT URBANA DEPT OF CHEMISTRY

Personal Author(s):

• Porter,J. E.
• Schuster,G. B.

Report Date:

1985-02-28

Pagination or Media Count:

24.0

Abstract:

The preparation and thermal chemistry of 4-methyl-4-1-propenylmalonyl peroxide 3 is described. Thermolysis in acetonitrile at 84 C gives 2,4-dimethylbut-2-ene-4-olide in 45 yield and oligomeric ester derived from an intermediate alpha-lactone in 55 yield. The reaction of 3 can be catalyzed by aromatic hydrocarbons such as perylene. Under these conditions weak chemiluminescence results. The mechanism for light generation is identified as chemically initiated electron-exchange luminescence CIEEL. Application of the CIEEL mechanism to 3 reveals an important limitation to light generation by this path. Originator-supplied keywords include Chemiluminescence, Malonyl peroxide, Electron transfer.

Descriptors:

• *PYROLYSIS
• *PEROXIDES
• *CHEMILUMINESCENCE
• METHYL RADICALS
• ELECTRON TRANSFER
• PROPYL RADICALS

Subject Categories:

• Physical Chemistry

Distribution Statement:

APPROVED FOR PUBLIC RELEASE