NONCATALYTIC AND AUTOCATALYTIC RATE CONSTANTS
1753
–
1
Here, A is the optical density at 2260 cm , and
RNCO] is the concentration of 1, M. In the calibration
8. Samuilov, A.Ya., Kamalov, T.A., Balabanova, F.B.,
Samuilov, Ya.D., and Konovalov, A.I., Russ. J. Org.
Chem., 2012, vol. 48, p. 158. doi 10.1134/
S1070428012020029
[
experiments, the concentration of 1 was varied from
×10 to 3×10 M. The kinetic measurements were
performed under pseudo-first-order conditions. The
initial concentration of isocyanate 1 was 1 ×10 ‒
–
2
–2
1
9
. Samuilov, A.Ya., Balabanova, F.B., Kamalov, T.A.,
Samuilov, Ya.D., and Konovalov, A.I., Russ. J. Org.
Chem., 2010, vol. 46, p. 1452. doi 10.1134/
S1070428010100027
–
2
–
2
3
×10 M, and of butan-1-ol (2), 0.1‒0.6 M. The
reaction temperature was maintained with an accuracy
of ±0.1°C using a U-2 thermostat (Germany). Samples
of the reaction mixture were withdrawn and analyzed
by IR spectroscopy to determine the concentration of
1
0. Samuilov, A.Ya., Balabanova, F.B., Samuilov, Ya.D.,
and Konovalov, A.I., Russ. J. Gen. Chem., 2015,
vol. 85, p. 1808. doi 10.1134/S1070363215080034
11. Samuilov, A.Ya., Zenitova, L.A., Samuilov, Ya.D., and
isocyanate 1. The effective rate constants k were
Konovalov, A.I., Russ. J. Org. Chem., 2008, vol. 44,
ef
calculated by Eq. (12) from the slopes of the straight
p. 1316. doi 10.1134/S107042800809011X
lines in the coordinates ln([RNCO] /[RNCO])—τ.
12. Samuilov, A.Ya., Zenitova, L.A., Samuilov, Ya.D., and
Konovalov, A.I., Russ. J. Org. Chem., 2009, vol. 45,
p. 68. doi 10.1134/S1070428009010096
0
Each run was repeated 2‒4 times, and average values
of the rate constants were calculated from the obtained
data with an accuracy of ±5%. The rate constants of
the noncatalytic (k ) and autocatalytic paths (K k )
1
3. Samuilov, A.Ya., Balabanova, F.B., Samuilov, Ya.D.,
and Konovalov, A.I., Russ. J. Org. Chem., 2012, vol. 48,
p. 164. doi 10.1134/S1070428012020030
1
eq
2
were calculated from the dependences of the effective
rate constant on the initial concentration of alcohol 2
using Eq. (13). In all kinetic and calibration experi-
ments, the same cell with NaCl windows and a cell
path length of 0.422 mm was used.
1
1
1
1
1
1
2
4. Robertson, W.G.P. and Stutchburu, J.E., J. Chem. Soc.,
1
964, p. 4000.
5. Draye, A.-C., Tarasov, D.N., and Tondeur, J.-J., React.
Kinet. Catal. Lett., 1999, vol. 66, p. 199.
6. Draye, A.-C. and Tondeur, J.-J., React. Kinet. Catal.
Lett., 1999, vol. 66, p. 319.
7. Dyer, E., Taylor, H.A., Mason, S.J., and Samson, J.,
J. Am. Chem. Soc., 1949, vol. 71, p. 4106.
8. Ephraim, S., Woodward, H.A., and Mesrobian, R.B.,
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RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 54 No. 12 2018