The effects of solvent-solute interactions on the stereochemical course of the high-energy chlorine-38 for chlorine substitution process in diastereomeric dichloroalkanes in the condensed phase

Abstract

It is clear that more work, both structural and theoretical, is needed to resolve the questions still surrounding the substituent-cyclopropane interaction. One attack is to compare structures of identical substitution where B is fixed at 0 and 9 0 ' . Such studies are currently in progress. Tables I I and V, which list the structure amplitudes for each structure (19 pages). Ordering information is given on any current masthead page. Supplementary Material Available:

Liquid Phase Hot Atom Chemistry: At Crossroads

“…Since MACHULLA and STÖCKLIN [26] already studied retention and inversion yields for 38 Cl-for-Cl exchange in d, I-and meso-1,2-dichloro-1,2-difluoroethane (DCDFE) as a function of system density, ACHE, RACK et al [33] studied the effects of various solvents on the stereochemical course of this exchange. The experimental results were quite similar to those previously observed by Wu and ACHE [32] and discussed above. If this is the case and consistent with the MACHUL-LA and STÖCKLIN study with DCDFE [26], then the results would provide first evidence for the fact that the excited intermediate resulting from the 328 Cl-for-Cl substitution is not preferentially formed by back side attack leading to an inverted product.…”

“…Therefore, according to the model, Waiden inversion as a displacement event is viewed as unlikely. However, WU and ACHE [32] found no general conformational effect for various diasteromeric dichloroalkanes. They suggested that the stereochemical course of the substitution process is controlled by solvent properties, specifically the dielectric constant, which in turn is responsible for the magnitude of individual interactions between reactants and solvents.…”

Formation of Dichlorobenzenes 38Cl by Recoil in Systems with Chiorobenzene

“…Such effects have also been reported in hot-atom chemistry but little is still known, particularly of the influence of the solvent in connection with its type and amount present in a reaction [3,[24][25][26][27][28].…”

Chemical Kinetics and Hot Atom Chemistry — Present Status and Future Perspectives

“…These findings contrast with previous stereochemical studies in which observations of retention of configuration accompanying recoil tritiumfor-hydrogen (T-for-H) atomic substitution [10][11][12][13][14][15]have been interpreted within the context of a 3-center direct, or "impact" [3,4], reaction model. 2 Although evidence has also been available for many years supporting the occurrence of inverting hot T-for-H and Cl-for-Cl reaction modes [16][17][18][19][20][21][22][23][24][25][26][27], the significance of the available gas phase results has often been challenged.…”