129804-48-4Relevant articles and documents
Kinetic and Equilibrium Studies of ?-Adduct Formation and Nucleophilic Substitution in the Reactions of Hydroxide Ions with 2,4,6-Trinitrophenyl Sulfides and Ethers
Chamberlin, Rachel,Crampton, Michael R.,Knight, Roland L.
, p. 2986 - 2998 (2007/10/02)
Kinetic and equlibrium data are reported for reaction of hydroxide ions in 20/80 DMSO/water (v/v) with a series of 4'-substituted phenyl 2,4,6-trinitrophenyl sulfides, 1, and with ethyl thiopicrate, 2, ethyl picrate, 3, phenyl picrate, 4, and 1,3,5-trinitrobenzene, 5.In each case a rapid reaction is observed involving reversible hydroxide addition at an unsubstituted ring-position.In the case of 1-4 this is followed by slower, irreversible attack at the 1-position leading to the formation of picric acid.The Hammett ρ value for equilibrium addition of hydroxide to the 3-position of 1 is 0.98, and the ρ value for rate constants for attack at the 1-position is 0.62.The results are discussed in terms of the electronic and steric effects of the 1-substituents.Comparison of 1-5 indicates that changing from an OR to SR group introduces additional steric crowding.However for the reactions studied changing from R = Et to R = Ph has little steric consequence.