English (United Kingdom)

https://curated-unify.zendy.io/wp-json/zendy-region/v1/featured_content/oa?rat=en

https://curated-unify.zendy.io/wp-json/zendy-region/v1/highlighted_journal/

Global: Zendy Plus annual

Presents the access of premium content as premium feature

Premium Content

Presents the keyphrase highlighting as premium feature

Keyphrase Highlighting

Presents the summarisation as premium feature

Summarisation

Insights

Presents the pdf analysis as premium feature

PDF Analysis

Presents the zaia usage as premium feature

ZAIA

Global: Zendy Tools annual

Global: Zendy Free Plan

Global: Zendy Tools monthly

Global: Zendy Plus monthly

Second-order rate constants (kN) have been measured spectrophotometrically for reactions of 3,4-dintrophenyl 2-furoate (2) with a series of secondary alicyclic amines in 80 mol % H2O/20 mol % dimethyl sulfoxide (DMSO) at 25.0 o C. The Bronsted-type plot exhibits a downward curvature for the aminolysis of 2, which is similar to that reported for the corresponding reactions of 2,4-dintrophenyl 2-furoate (1). Substrate 2 is less reactive than 1 toward all the amines studied but the reactivity difference becomes smaller as the amine basicity increases. Dissection of the second-order rate constants into the microscopic rate constants has revealed that the reaction of 2 results in a smaller k2/k–1 ratio but slightly larger k1 value than that of 1. Steric hindrance has been suggested to be responsible for the smaller k1 value found for the reactions of 1, since the ortho-substituent of 1 would inhibit the attack of amines (i.e., the k1 process).

Aminolyses of 2,4-Dinitrophenyl and 3,4-Dinitrophenyl 2-Furoates: Effect of ortho-Substituent on Reactivity and Mechanism