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In some instances, 2 was isolated, with melting points in agreement
with that measured5 earlier and with an excellent elemental analysis
(C, H, N). When the 0.03 M stock solution in acetonitrile was prepared
by redissolving the isolated solid, the observed kinetics were in
excellent agreement with those obtained without intermediate isolation
of the substrate. In a typical isolation, p‑nitrobenzoyl chloride (9.2 g)
was reacted with silver p‑toluenesulfonate (13.9 g) in acetonitrile
(40 mL) to give on workup5 (2 8.5 g, 61%), m.p. 166–167 °C (lit.5
167–169 °C). Anal. calcd for C14H11NO6S: C, 52.33; H, 3.45; N 4.36;
found: C, 52.21; H, 3.38; N, 4.33% (PerkinElmer 2400 CHN elemental
analyser).
The progress of the reaction was followed by following the
conductivity changes as p‑toluenesulfonic acid was produced, as
previously described.9 Details of the conductivity apparatus and
the computer procedure for calculation of the specific rates have
previously been reported.49,50
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Since the variation of specific rates of solvolysis of 2 in aqueous
acetone mixtures was considerably reduced from what had been
observed for various acyl chlorides and chloroformate esters, we
repeated the measurements, with new preparations of the mixed
solvents and substrate. Excellent agreement was observed between
the two sets of measurements. The multiple regression analyses were
performed using commercially available statistical packages.
22 F.L. Schadt, T.W. Bentley and P.v.R. Schleyer, J. Am. Chem. Soc., 1976, 98,
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23 W.J. Moore, Physical chemistry, 2nd edn, Prentice‑Hall, Englewood
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29 T.W. Bentley, G.E. Carter and H.C. Harris, J. Chem. Soc., Perkin Trans. 2,
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30 D.N. Kevill and M.J. D’Souza, J. Org. Chem., 2004, 69, 7044.
31 R. Hirata, N.Z. Kiyan and J. Miller, Quim. Nova, 1997, 20, 238.
32 D.N. Kevill and M.J. D’Souza, J. Phys. Org. Chem., 2002, 15, 881.
33 T.W. Bentley and H.C. Harris, J. Chem. Soc., Perkin Trans. 2, 1986, 619.
34 M.J. D’Souza, Z.H. Ryu, B.‑C. Park and D.N. Kevill, Can. J. Chem., 2008,
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35 D.N. Kevill, F. Koyoshi and M.J. D’Souza, Int. J. Mol. Sci., 2007, 8, 346.
36 D.N. Kevill and B. Miller, J. Org. Chem., 2002, 67, 7399.
37 H.J. Koh and D.N. Kevill, Phosphorus, Sulfur, Silicon, Relat. Elem., 2010,
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38 D.N. Kevill, K.‑H. Park and H.J. Koh, J. Phys. Org. Chem., 2011, 24, 378.
39 M. Halmann, Phosphorus, Sulfur, 1988, 40, 251.
40 H. Weiner and R.A. Sneen, J. Am. Chem. Soc., 1965, 87, 287.
41 T.W. Bentley and K. Roberts, J. Org. Chem., 1985, 50, 4821.
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7927.
This research was supported by the donors of the American
Chemical Society Petroleum Research Fund (PRF# 38163‑
AC4). Z.H.R. thanks Dong‑Eui University for support of
this work during the 2005 research year. We thank Professor
Malcolm J. D’Souza (Wesley College, Dover, Delaware,
USA) for helpful discussions and assistance with the multiple
correlation analyses.
Electronic Supplementary Information
Tables S1 and S2 available through stl.publisher.ingentaconnect.
com/content/stl/jcr/supp‑data give the specific rates used in the
Eyring equation calculations (Table 2) which are additional to
those reported in Table 1.
Received 14 March 2014; accepted 6 May 2014
Paper 1402524 doi: 10.3184/174751914X14018022669011
Published online: 12 July 2014
44 Z.H. Ryu, G.T. Lim and T.W. Bentley, Bull. Korean Chem. Soc., 2003, 24,
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Soc., 1988, 32, 85.
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