Y. LU ET AL.
cyclodecanol, and cycloundecanol were synthesized by
reduction of the corresponding ketones with NaBH4 in methanol,
and were identified by NMR spectroscopy (Supplemental
Information). 1-Phenylethanol-a-d and 1-phenylethanol-b,b,b-d3
were synthesized by reduction of the acetophenone and
acetophenone-b,b,b-d3 by NaBD4 and NaBH4, respectively.
1-Phenylethanol-O-d was prepared by OH/OD exchange reaction
of the corresponding normal alcohol in D2O/THF catalyzed by DCl
according to the literature procedure.[49] The D-content of the
deuterated 1-phenylethanols was examined by NMR spec-
troscopy and was found to be higher than 98.5%. Other alcohols
were purchased and purified by conventional methods before
use. Acetonitrile was distilled twice (first time over the P2O5
drying agent) under nitrogen atmosphere.
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Kinetic procedures
Stock solution (80 ml of 0.1 M) of PhXnþ in AN was added to an
8 ml AN solution containing a typical alcohol of a certain
concentration in a well sealed 10 ml reaction vial, which was
pre-thermostated in a water bath with temperature maintained
at 60 8C. About 0.3 ml of the reaction aliquots were periodically
taken into sample vials pre-cooled in ice. The samples were then
immediately placed in a freezer (ꢃ ꢀ20 8C) until 6–8 reaction
aliquots within 1–2 half-lives of the reaction had been collected
(the half-life time of the reactions was usually longer than
90 min). The reaction aliquots were analyzed by diluting 80 ml of
them in 1.92 ml AN/H2O (v/v ¼ 3/1) containing 3 M HClO4,[33] and
the corresponding UV spectra at different reaction times, i.e. the
kinetic scans, were obtained. Absorbance (Abs) decreasing with
time (t) at 373 nm due to the consumption of PhXnþ was
recorded. The obtained Abs-t data were fit to the first-order
integrated rate equation, -ln(Abs) ¼ kꢅt þ constant, and the slope
of the linear plot of -ln(Abs) versus t, was taken as the
pseudo-first-order rate constant (kpfo) of the reaction. The linear
plots usually had regression coefficients (R2) >0.996. Each kinetic
run was repeated at least two times and the determination error
was usually within 7%. The second-order rate constant was
calculated by dividing the kpfo by the alcohol concentration, and
was taken as an averaged value if the rate constants were
determined using multiple alcohol concentrations.
Acknowledgements
This work was supported by the Petroleum Research Fund
administrated by the American Chemical Society (ACS-PRF:
GB-44844) and SIUE’s STEP research award.
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