The reaction of 2,2,5,5-tetramethyl-3,4-diphenylhexane with D{sub 2}. Stereochemical effects in a high-temperature reaction
- Univ. of Kentucky, Lexington, KY (United States); and others
The thermolysis of 2,2,5,5-tetramethyl-3,4-diphenylhexane was carried out at temperatures above 300 {degrees}C in the absence and presence of D{sub 2}(14 MPa). The presence of D{sub 2} results in a greatly increased yield of the major product, neopentylbenzene. However, at higher concentrations of starting material, up to 50% of the neopentylbenzene formed avoids deuterium incorporation, an outcome believed to result partly from participation of the phenylneopentyl radical in radical disproportionation reactions. The meso-isomer of starting material produces a substantial yield of stilbene in both the absence and presence of D{sub 2}. Under D{sub 2}, 1,2-diphenylethane is produced, and it is believed that stilbene and other alkenes present serve as D atom traps producing radicals which then participate in termination by disproportionation. Remarkably, the d,l-diastereomer gives a different product distribution than the meso-isomer, giving very little stilbene or other products of tertbutyl group loss. However, both systems produce 1-phenyl-2-methyl-2-propene by methyl radical loss form the phenylneopentyl radical. The formation of such alkenes and the path to termination they provide is blamed for the absence of efficient kinetic chains involving D atoms. 1 fig., 6 tabs.
- Sponsoring Organization:
- USDOE
- OSTI ID:
- 469829
- Journal Information:
- Journal of Organic Chemistry, Vol. 60, Issue 14; Other Information: PBD: 14 Jul 1995
- Country of Publication:
- United States
- Language:
- English
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