Organic & Biomolecular Chemistry
Paper
solutions also contained at least a 10-fold excess of the nucleo-
phile, relative to the electrophile. For the studies of the SN2
reaction, the electrophile 5 was included in the stock solution
with ca. 0.5 mL aliquots being transferred to 5 mm NMR tubes
which were kept at −196 °C prior to conducting the kinetic
3 F. Endres and S. Z. El Abedin, Acc. Chem. Res., 2007, 40,
1106–1113.
4 A. Maia, Mini-Rev. Org. Chem., 2011, 8, 178–185.
5 K. N. Marsh, A. Deev, A. Wu, E. Tran and A. Klamt, Korean
J. Chem. Eng., 2002, 19, 357–362.
studies. For the S
N
Ar reaction, an approximately 10-fold excess
6 N. Kaur, Synth. Commun., 2018, 48, 473–495.
7 J. P. Hallett and T. Welton, Chem. Rev., 2011, 111, 3508–
3576.
8 G. Huddleston, D. Jonathan and R. Rogers, Chem.
Commun., 1998, 1765–1766.
of triethylamine, relative to the electrophile 6, was also
included in the stock solution and the required amount of the
electrophile 6 was added to a 5 mm NMR tube instead of to
the stock solution. A 0.5 mL aliquot of the stock solution was
added to the prepared NMR tube containing the electrophile 6
and was thoroughly mixed prior to undertaking the kinetic
9 A. Berthod, M. J. Ruiz-Ángel and S. Carda-Broch,
J. Chromatogr. A, 2018, 1559, 2–16.
studies. The bimolecular rate constants for both processes 10 D. R. MacFarlane, M. Forsyth, P. C. Howlett, M. Kar,
were determined by division of the observed pseudo-first order
rate constant, obtained by fitting a linear equation to the
natural log of the area under the respective NMR signals dis-
S. Passerini, J. M. Pringle, H. Ohno, M. Watanabe, F. Yan,
W. Zheng, S. Zhang and J. Zhang, Nat. Rev. Mater., 2016, 1,
15005.
cussed above with time using LINEST in Microsoft Excel, by 11 I. Osada, H. de Vries, B. Scrosati and S. Passerini, Angew.
the concentration of the nucleophile. Chem., Int. Ed., 2016, 55, 500–513.
The temperature dependent kinetic studies were under- 12 Q. Yang, Z. Zhang, X.-G. Sun, Y.-S. Hu, H. Xing and S. Dai,
taken in an analogous manner to those kinetic studies Chem. Soc. Rev., 2018, 47, 2020–2064.
described above at select solvent compositions discussed in 13 R. A. Sheldon, Green Chem., 2005, 7, 267–278.
the main text. Four temperatures were selected across a range 14 M. Amde, J.-F. Liu and L. Pang, Environ. Sci. Technol., 2015,
of 30 °C for both substitution reactions. These rate constants
were fit to the bimolecular form of the Eyring equation using 15 K. S. Egorova, E. G. Gordeev and V. P. Ananikov, Chem.
49, 12611–12627.
4
6
the LINEST function in Microsoft Excel to determine the acti-
vation parameters.
Rev., 2017, 117, 7132–7189.
16 M. Freemantle, Chem. Eng. News, 1998, 76, 32–37.
Additional details pertaining to the exact stock solution 17 M. T. Clough, C. R. Crick, J. Gräsvik, P. A. Hunt,
compositions (including masses, concentrations of reagents
and the mole fractions of salt), temperatures, rate constants,
rate equations can be found in the ESI.†
H. Niedermeyer, T. Welton and O. P. Whitaker, Chem. Sci.,
2015, 6, 1101–1114.
18 I. Newington, J. M. Perez-Arlandis and T. Welton, Org. Lett.,
2
007, 9, 5247–5250.
9 C. Austen Angell, Y. Ansari and Z. Zhao, Faraday Discuss.,
012, 154, 9–27.
0 K. Yoshida, M. Nakamura, Y. Kazue, N. Tachikawa,
S. Tsuzuki, S. Seki, K. Dokko and M. Watanabe, J. Am.
Chem. Soc., 2011, 133, 13121–13129.
1
2
2
Conflicts of interest
There are no conflicts to declare.
21 K. Ueno, K. Yoshida, M. Tsuchiya, N. Tachikawa, K. Dokko
and M. Watanabe, J. Phys. Chem. B, 2012, 116, 11323–
Acknowledgements
11331.
JBH acknowledges financial support from the Australian 22 W. Shinoda, Y. Hatanaka, M. Hirakawa, S. Okazaki,
Research Council Discovery Project Funding Scheme (Project
DP180103682). KSSM and AG acknowledge the support of the
S. Tsuzuki, K. Ueno and M. Watanabe, J. Chem. Phys., 2018,
148, 193809.
Australian government through the receipt of Research 23 D. A. Dolan, D. A. Sherman, R. Atkin and G. G. Warr,
Training Programme Stipends. KSSM thanks the Faculty of
ChemPhysChem, 2016, 17, 3096–3101.
Science at the University of New South Wales for a Science PhD 24 D. J. Eyckens, B. Demir, T. R. Walsh, T. Welton and
Writing Scholarship. The authors would like to acknowledge
the NMR Facility as well as the BSMF within the Mark
L. C. Henderson, Phys. Chem. Chem. Phys., 2016, 18, 13153–
13157.
Wainwright Analytical Centre at the University of New South 25 L. Crowhurst, R. Falcone, N. L. Lancaster, V. Llopis-Mestre
Wales for support with NMR and mass spectroscopy.
and T. Welton, J. Org. Chem., 2006, 71, 8847–8853.
2
6 A. Gilbert, R. S. Haines and J. B. Harper, in Elsevier
Reference Modules in Chemistry, Molecular Sciences and
Chemical Engineering, ed. J. Reedijk, Elsevier, Waltham,
Notes and references
MA,
409542.414212-X.
C. Chiappe and D. Pieraccini, J. Phys. Org. Chem., 2005, 18, 27 R. R. Hawker, R. S. Haines and J. B. Harper, Adv. Phys. Org.
75–297. Chem., 2018, 52, 49–85.
2018,
DOI:
10.1016/B1978-1010-1012-409547-
1
2
T. Welton, Chem. Rev., 1999, 99, 2071–2083.
2
This journal is © The Royal Society of Chemistry 2019
Org. Biomol. Chem., 2019, 17, 9243–9250 | 9249