The Journal of Organic Chemistry
Article
7.4 Hz, 2H) 1.13 (t, J = 7.4 Hz, 2H); 13C NMR (100 MHz, D2O) δ
42.0, 39.9, 37.9, 34.7, 25.3, 25.0, 13.8, 8.1; HRMS (ESI-TOF) m/z
[M]+ Calc for C8H18ClS2 213.0535, found 213.0528.
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NMR Kinetic Runs. All kinetic runs were performed in the
following manner. Compound 1 was weighed into a 4 mL vial. Into a
separate 4 mL vial was placed the D2O and acetone-d6. This solvent
vial was tared, the internal standard (methylene chloride or p-xylene)
was added, and the mass was recorded. Final solvent volumes were 600
μL (v/v). To start the run, the solvent was pipetted all at once into the
vial containing 1, agitated 5−6 times, and then placed into an NMR
tube, which was then immediately placed into the magnet. The kinetics
macro was run after locking the instrument. Approximately 2−3 min
were consumed on average before the t = 0 point was collected.
GC−MS Kinetic Runs. All GC−MS kinetic runs to follow the
35Cl/37Cl ratios in 1 were performed in the following manner.
Compound 1 was placed into a 4 mL vial. Into a separate 4 mL vial
was weighed the Na35Cl, which was then dissolved in the appropriate
amount of H2O and acetone. Final solvent volumes were 3 mL (v/v).
The run was started by adding all of the solvent at once to the vial
containing 1, stirring rapidly, and then withdrawing a 100 μL aliquot,
which was added to 900 μL of CH2Cl2 in a GC vial following by
immediate vortexing. This was recorded as t = 0. All subsequent time
points were 100 μL aliquots handled in the same manner. GC−MS
analysis was then performed to measure the 35Cl/37Cl ratio in the
remaining 1.
For all initial rate studies, 1 was placed into an appropriate vial
(either 4 or 40 mL), depending on the concentration to be studied,
and the amount of 1 and internal standard (sulfolane) was added. The
water/acetone mixture was added all at once with rapid stirring, and
then an aliquot for the desired analysis concentration was withdrawn
and added to 1.5 mL of CH2Cl2 in a GC vial, followed by immediate
vortexing. This was recorded as t = 0. All subsequent time points were
prepared in the same fashion. The resulting decays were normalized,
and the rates of decay were compared.
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ASSOCIATED CONTENT
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S
* Supporting Information
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Relat. Elem. 1993, 80, 47−61.
1H and 13C NMR spectra for 1−4, and additional rate data and
plots. This material is available free of charge via the Internet at
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AUTHOR INFORMATION
Corresponding Author
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Notes
The authors declare no competing financial interest.
ACKNOWLEDGMENTS
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The authors would like to thank Dr. Sari Paikoff at the Defense
Threat Reduction Agency-Joint Science and Technology Office
(DTRA-JSTO) for funding this work under contract
(CBCALL12-TAS-2-0130), Dr. David B. Collum at Cornell
University for helpful discussions and insights, and Mr. Dennis
Bevilacqua at the Edgewood Chemical Biological Center for
programming assistance with the Bruker 500.
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