Karady Sandor, Cummins Jordan M, Dannenberg J J, del Rio Emma, Dormer Peter G, Marcune Benjamin F, Reamer Robert A, Sordo Tomas L
Process Research Department, Merck Research Laboratories, Merck and Company, P.O. Box 2000, Rahway, New Jersey 07065, USA.
Org Lett. 2003 Apr 17;5(8):1175-8. doi: 10.1021/ol027301t.
[reaction: see text] Experiments show that free radical hydrogen shift is significant in the Pschorr cyclization of diphenyl ethers (X = O) and thioethers (X = S) and does not take place with sufoxides (X = SO) and sulfones (X = SO(2)). DFT calculations of the product ratios, activation energies, rate constants for H-transfers, and ring-closings at the UB3PW91/6-31G(d,p) level are in excellent agreement with the experimental results reported here and elsewhere in the literature.
[反应：见正文] 实验表明，自由基氢迁移在二苯醚（X = O）和硫醚（X = S）的普朔尔环化反应中很显著，而在亚砜（X = SO）和砜（X = SO₂）中则不会发生。在UB3PW91/6 - 31G(d,p)水平上对产物比例、活化能、氢转移速率常数和环化反应速率常数进行的密度泛函理论（DFT）计算与本文及文献中其他地方报道的实验结果高度吻合。
