34973-56-3Relevant academic research and scientific papers
Thermolysis of Highly Congested Tri-tert-alkylmethanes. Rearrangement of a 3-Noradamantylmethyl Radical
Lomas, John S.
, p. 519 - 528 (2007/10/02)
Activation energies for C-Ad fission in the thermolysis of di-1-adamantyl-tert-alkylmethanes and 1-adamantyl-di-1-bicyclooctylmethane, AdR1R2CH, in toluene are best correlated with the strain energy difference (MMP2 force field) between the methane and the corresponding radical, R1R2C radical H; difficulties were encountered in the application of MM3 to certain of these trialkylmethanes.Normally, the major thermolysis product is the di-tert-alkylmethane, R1R2CH2, but when a 3-noradamantly group is present (1d) the initially formed radical ring opens to give 1,2'-biadamantyl in amounts which depend on the temperature and the solvent (normal or octadeuteriated).This rearrangement is readily explained by MMP2 calculations.Since the cross-product yield is low (less than 3percent, even in deuteriated solvent at the highest temperature) the thermodynamic parameters for the hydrogen transfer and ring opening reactions of the 1-adamantyl-3-noradamantylmethyl radical can be compared directly.Both the activation enthalpy and entropy are much greater for ring opening than for hydrogen abstraction from the solvent.Isotope effects on hydrogen abstraction are high and satisfy certain criteria for tunnelling, as do data on the analogous reaction of Ad2C radical H.A more sophisticated treatment of the product composition for 1d thermolysis, using kinetic simulation, leads to essentially the same conclusions as the simpler treatment.
PHOTOSTIMULATED REACTIONS OF 1-IODOADAMANTANE AND IODOBENZENE WITH THIOLATE, SELENATE, AND TELLURATE IONS
Palacios, Sara M.,Alonso, Ruben A.,Rossi, Roberto A.
, p. 4147 - 4156 (2007/10/02)
The photostimulated reaction of 1-iodoadamantane (1-IAd) with benzenethiolate ion gave the substitution product 1-adamantylphenylsulfide.With benzeneselenate ion (PhSe-) it gave three products: diphenylselenide, 1-adamantylphenylselenide and di(1-adamantyl) selenide.With benzenetellurate ions it gave the substitution product 1-adamantylphenyltelluride and diphenyltelluride, the latter is ascribed to the photodecomposition of the nucleophile.The photostimulated reaction of 1-IAd with 1-naphtaleneselenate ion only gave the substitution product without scrambling of products.The photostimulated reaction of PhI with 1-adamantaneselenate ion gave the same three products as the reaction of 1-IAd and PhSe- ion, but with different ratios of products.The reaction with 1-adamantanetellurate ion gave mainly diphenyltelluride, together with the substitution product 1-adamantylphenyltelluride.The relationship of the fragmentation rates of Ad-Z and Ph-Z bonds in radical anions of structure (1-AdZPh). were studied, and kfAdZ/kfPhZ, being Z=S is 3.7, Z=Se is 9.5 and Z=Te is 13.These results suggest that in the photostimulated reactions the products obtained depend on the energy levels of the antibonding ?* MO and the ?* MO of the C-Z(Z=S, Se and Te) bonds of the radical anion intermediate.The fragmentation rates of the radical anion intermediates depend on the energy levels of the MO'S involved.
PHOTOCHEMISTRY OF PHENYLADAMANTYL KETONE IN HOMOGENEOUS ORGANIC AND IN MICELLAR SOLUTION.
Turro, Nicholas J.,Tung, Chen-Ho
, p. 4321 - 4322 (2007/10/02)
The photolysis of 1-phenyladamantyl ketone in benzene and in micellar solution has been investigated and compared.
