Published October 2012 | Version v1
Journal article

Rate-Product Correlations for the Solvolysis of 5-Nitro-2-Furoyl Chloride

  • 1. Gyeongsang National Univ., Jinju (Korea, Republic of)
  • 2. Jeonju National Univ. of Education, Jeonju (Korea, Republic of)
  • 3. Univ. of Balochistan, Quetta (Pakistan)

Description

The solvolysis rate constants of 5-nitro-2-furoyl chloride (5-NO2(C4H2O)-2-COCl, 1) in 27 different solvents are well correlated with the extended Grunwald-Winstein equation, using the NT solvent nucleophilicity scale and YCl solvent ionizing scale, with sensitivity values of 1.20 ± 0.05 and 0.37 ± 0.02 for l and m, respectively. The activation enthalpies (ΔH≠) were 5.63 to 13.0 kcal·mol-1 and the activation entropies (ΔS≠) were -25.9 to -43.4 cal·mol-1·K-1, which is consistent with the proposed bimolecular reaction mechanism. The solvent kinetic isotope effect (SKIE, kMeOH/kMeOD) of 2.65 was also in accord with the SN2 mechanism and was possibly assisted using a general-base catalysis. The product selectivity (S) for solvolysis of 1 in alcohol/water mixtures was 1.2 to 11, which is also consistent with the proposed bimolecular reaction mechanism

Additional details

Publishing Information

Journal Title
Bulletin of the Korean Chemical Society
Journal Volume
33
Journal Issue
10
Series
23 refs, 4 figs, 4 tabs
Journal Page Range
p. 3293-3297
ISSN
0253-2964

INIS

Country of Publication
Korea, Republic of
Country of Input or Organization
Korea, Republic of
INIS RN
45096370
Subject category
S37: INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY;
Descriptors DEI
CATALYSIS; CHLORIDES; CORRELATIONS; ENTHALPY; EQUATIONS; SOLVENTS; SOLVOLYSIS
Descriptors DEC
CHEMICAL REACTIONS; CHLORINE COMPOUNDS; DECOMPOSITION; HALIDES; HALOGEN COMPOUNDS; PHYSICAL PROPERTIES; THERMODYNAMIC PROPERTIES