Reaction mechanism studies of solvolytic displacement of chloride from phosphorus and sulfur

ORGN 519

Dennis N. Kevill, dkevill@niu.edu1, Han Joong Koh2, Suk Jin Kang2, Malcolm J. D'Souza, dsouzama@wesley.edu3, Stacey Mlynarski, stacey.mlynarski@students.wesley.edu3, and Lamia Yaakoubd, lamia.yaakoubd@gmail.com3. (1) Department of Chemistry & Biochemistry, Northern Illinois University, DeKalb, IL 60115, (2) Department of Science Education, Jeonju National University, Jeonju, 560-757, South Korea, (3) Department of Chemistry, Wesley College, 120 N State Street, Dover, DE 19901
We are applying the extended Grunwald-Winstein equation to solvolytic displacements at phosphorus and sulfur.

log(k/ko) = lN + mY + c

In the above equation, k and ko are the first order rate coefficients for solvolysis in a given solvent and in 80% ethanol, l is the sensitivity to changes in solvent nucleophilicity (N), m is the sensitivity to changes in solvent ionizing power (Y), and c is a constant (residual) term. Studies of solvolysis of phosphorochloridates, (RO)2POCl and [(CH3)2N]2POCl, have been extended to cyclic phosphorochloridates, with five-and six-membered rings. Both kinetic and product studies are performed. We also report on kinetic studies of the solvolyses of phosphinyl chlorides and chlorophosphines. Solvolyses at sulfur have involved both alkane- and arene- sulfonyl chlorides. Recent studies include α-toluenesulfonyl chloride solvolyses. [This project was supported in part by NIH NCRR INBRE grant number; 2P20 RR016472-06]

 

Physical Organic Chemistry, Metal-Mediated Reactions, Asymmetric Reactions and Syntheses
8:00 PM-10:00 PM, Tuesday, August 21, 2007 BCEC -- Exhibit Hall - B2, Poster

Division of Organic Chemistry

The 234th ACS National Meeting, Boston, MA, August 19-23, 2007