@article {3035,
	title = {CRYSTAL STRUCTURE-REACTIVITY CORRELATIONS IN THE SOLID-STATE PHOTOCHEMISTRY OF N-(TERT-BUTYL)SUCCINIMIDE},
	journal = {Canadian Journal of Chemistry-Revue Canadienne De Chimie},
	volume = {72},
	number = {9},
	year = {1994},
	note = {ISI Document Delivery No.: PJ994Times Cited: 5Cited Reference Count: 20},
	month = {Sep},
	pages = {1952-1960},
	type = {Article},
	abstract = {In order to provide experimental evidence on the stereoelectronic requirements for intramolecular hydrogen atom abstraction by carbonyl oxygen, N-(tert-butyl)succinimide, 1, was investigated by the crystal structure - reactivity correlation method. In this method, the success or failure of a given reaction in the crystalline state is correlated with the geometric parameters associated with the process as determined by X-ray crystallography. In the case of N-(tert-butyl)succinimide, the crystal and molecular structure shows that the molecule adopts a conformation in which there are very close contacts (d = 2.17-2.24 Angstrom) between the carbonyl oxygen atoms and certain gamma-hydrogen atoms on the tert-butyl group. In accord with these close contacts, ultraviolet irradiation of N-(tert-butyl)succinimide in the crystalline state leads to transfer of one of the gamma-hydrogen atoms from carbon to oxygen. This produces a 1,4-biradical which closes to form a cyclobutanol, and the cyclobutanol undergoes ring opening to afford the final stable product, tetrahydro-1H-azepine-2,5-dione, 2. The crystal and molecular structure of photoproduct 2 is also reported. In contrast to many solid state transformations, there was no discernable melting of the crystals during reaction, and complete conversions of 1 into 2 could be achieved. The isolated chemical yield of photoproduct 2 from the solid state reaction (79\%) is in fact considerably higher than that reported by Kanaoka and Hatanaka for the corresponding solution phase process (49\%). This permitted the solid state reaction to be followed to 100\% conversion by X-ray powder diffractometry, which showed that the process is a single crystal-to-polycrystalline transformation involving a regular and progressive conversion of 1 into 2 with no obvious diffraction peaks that might be attributable to the intermediate cyclobutanol.},
	keywords = {C-H...O, SYSTEMS},
	isbn = {0008-4042},
	url = {<Go to ISI>://A1994PJ99400010},
	author = {Fu, T. Y. and Scheffer, J. R. and Trotter, J.}
}
