Rate and product studies in the solvolyses of N,N-dimethylsulfamoyl and 2-propanesulfonyl chlorides.
Contrary to earlier suggestions of an S(N)1 pathway for solvolyses of N,N-dimethylsulfamoyl chloride (1), an extended Grunwald-Winstein equation treatment of the specific rates of solvolysis in 32 solvents shows an appreciable sensitivity towards changes in both solvent nucleophilicity and solvent ionizing power. The actual values are very similar to those obtained in earlier studies of the solvolyses of sulfonyl and phosphoryl chlorides, solvolyses which are believed to proceed by an S(N)2 pathway. The observation of similar selectivities in aqueous-alcohol solvents further supports this assignment. In a recent report, an addition-elimination (association-dissociation) pathway was proposed for solvolyses of 2-propanesulfonyl chloride (2). A severe multicollinearity problem has been removed by the addition of several specific rates of solvolysis in fluoroalcohol-containing solvents. The new analyses using the extended Grunwald-Winstein equation lead to sensitivities similar to those for and the previously studied related compounds, and these solvolyses are also best described as following an S(N)2 pathway.
Kevill
Dennis N
DN
Department of Chemistry and Biochemistry, Northern Illinois University, DeKalb, Illinois 60115-2862, USA.
Park
Byoung-Chun
BC
Park
Kyoung-Ho
KH
D'Souza
Malcolm J
MJ
Yaakoubd
Lamia
L
Mlynarski
Stacey L
SL
Kyong
Jin Burm
JB
D007700:Kinetics; D015394:Molecular Structure; D012996:Solutions / Q000737:chemistry*; D013441:Sulfinic Acids / Q000737:chemistry*; D013449:Sulfonamides / Q000737:chemistry*; D013696:Temperature
C521727:2-propanesulfonyl chloride; C521726:N,N-dimethylsulfamoyl chloride; D012996:Solutions; D013441:Sulfinic Acids; D013449:Sulfonamides