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

Abstract

The solvolysis rate constants of 5-nitro-2-furoyl chloride (5-NO2 ( , 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.

Kinetic Study on Solvolysis of 2‐Methylfuran‐3‐carbonyl Chloride in Binary Solvent Mixtures

“…In ethanol at 0 o C, the rate constant for solvolysis of 1 ( k = 3.26 × 10 −5 s −1 ) is much smaller than that reported previously for solvolysis of 5‐nitro‐2‐furoyl chloride ( 2 , k = 7.42 × 10 −3 s −1 ) under identical conditions. This can be explained by the fact that 1 has an electron‐donating methyl group at position 2 while 2 has an electron‐withdrawing NO 2 group at position 5.…”

“…The rate constant increases in the order acetone < ethanol < methanol < 2,2,2‐trifluoroethanol (TFE) < 1,1,1,3,3,3‐hexafluoro‐2‐propanol (HFIP) and with increasing the water content in the binary solvents (except in HFIP). The increasing rate constant with the water content is typical for solvolysis reactions which proceed through a polar TS …”