TY - JOUR
AU - Lee, Ikchoon
AB - Kinetic studies were carried out on the reactions of anilines with 2‐cyano‐2‐propyl and 1‐cyanocyclooctyl arenesulfonates in acetonitrile at 50·0°C. The second‐order rate constants for the former are in general greater than those for the latter but the rates of the two become comparable for a strong nucleofuge. The cross‐interaction constants, ρXZ (and βXZ), are considerably smaller (ca −0·04) than those for the primary (ca 0·33) and secondary (ca 0·12) compounds. The negative sign and small magnitude are consistent with a dissociative SN2 mechanism with a loose transition state structure. The ab initio MO theoretical results for Cl− + RCl ClR + Cl− at the MP2 level (MP2/6‐31 + G*//MP2/6‐31 + G*) confirm the looseness of the transition state for the tertiary (R) alkyl compounds. The average r(Cl…Cl) value is 47middot;88 ± 0·03 Å, which is larger than those for the reactions at primary (4·68 ± 0·02 Å) and secondary (4·80 ± 07middot;02 Å) carbon centers. Thus a looser transition state with a smaller magnitude of ρXZ for the tertiary carbon centers has a larger theoretical r(Cl…Cl) value.
TI - Bimolecular nucleophilic displacement at tertiary carbon centers: Aminolyses of 2‐cyano‐2‐propyl and 1‐cyanocyclooctyl arenesulfonates
JF - Journal of Physical Organic Chemistry
DO - 10.1002/(SICI)1099-1395(199610)9:10<683::AID-POC840>3.0.CO;2-K
DA - 1996-10-01
UR - https://www.deepdyve.com/lp/wiley/bimolecular-nucleophilic-displacement-at-tertiary-carbon-centers-y7wLRFvaYL
SP - 683
EP - 688
VL - 9
IS - 10
DP - DeepDyve
ER -