TY - JOUR
T1 - The molecularity of the Newman-Kwart rearrangement
AU - Burns, Matthew
AU - Lloyd-Jones, Guy C.
AU - Moseley, Jonathan D.
AU - Renny, Joseph S.
PY - 2010/10/1
Y1 - 2010/10/1
N2 - It was recently reported that the venerable Newman-Kwart rearrangement (1→2) proceeds via mixed first- and second-order kinetics. Prior to this, the rearrangement had been considered to proceed exclusively via an intramolecular O
Ar→S
Ar migration. A new bimolecular pathway, possibly involving an 8-membered cyclic transition state, was proposed to account for reaction rates that increased disproportionately with substrate concentration under microwave heating conditions. We report a reanalysis of the kinetics and molecularity of the rearrangement of N,N-dimethyl O-(p-nitrophenyl)thiocarbamate 1a in N,N-dimethylacetamide solvent. Using HPLC, isotopic labeling (
2H,
18O,
34S), and ESI-ICRMS methods, we show that there is no evidence for a bimolecular pathway en route to 2a, with near-perfect exponential decay in 1a at concentrations ranging from 0.11 to 4.70 M. Instead, it is demonstrated that under the microwave heating conditions, a delayed negative feedback signal to the microwave power balancing loop results in oscillatory reaction overheating. Due to higher tan δ in the solute, the amplitude of this oscillation increases with the concentration of 1a, and this phenomenon best accounts for the kinetic behavior previously misinterpreted as being mixed 'irst- and second-order in nature. © 2010 American Chemical Society.
AB - It was recently reported that the venerable Newman-Kwart rearrangement (1→2) proceeds via mixed first- and second-order kinetics. Prior to this, the rearrangement had been considered to proceed exclusively via an intramolecular O
Ar→S
Ar migration. A new bimolecular pathway, possibly involving an 8-membered cyclic transition state, was proposed to account for reaction rates that increased disproportionately with substrate concentration under microwave heating conditions. We report a reanalysis of the kinetics and molecularity of the rearrangement of N,N-dimethyl O-(p-nitrophenyl)thiocarbamate 1a in N,N-dimethylacetamide solvent. Using HPLC, isotopic labeling (
2H,
18O,
34S), and ESI-ICRMS methods, we show that there is no evidence for a bimolecular pathway en route to 2a, with near-perfect exponential decay in 1a at concentrations ranging from 0.11 to 4.70 M. Instead, it is demonstrated that under the microwave heating conditions, a delayed negative feedback signal to the microwave power balancing loop results in oscillatory reaction overheating. Due to higher tan δ in the solute, the amplitude of this oscillation increases with the concentration of 1a, and this phenomenon best accounts for the kinetic behavior previously misinterpreted as being mixed 'irst- and second-order in nature. © 2010 American Chemical Society.
UR - http://www.scopus.com/inward/record.url?scp=77957172606&partnerID=8YFLogxK
U2 - 10.1021/jo1014382
DO - 10.1021/jo1014382
M3 - Article (Academic Journal)
C2 - 20812755
SN - 0022-3263
VL - 75
SP - 6347
EP - 6353
JO - Journal of Organic Chemistry
JF - Journal of Organic Chemistry
IS - 19
ER -