BULLETIN OF THE
Article
Aminolysis of Phenyl Y-Substituted Phenyl Carbonates
KOREAN CHEMICAL SOCIETY
nature from a primary or a secondary amine to a tertiary amine
causes a change in the reaction mechanism (i.e., from a step-
wise mechanism to a concerted mechanism).
(c) T. H. Lowry, K. S. Richardson, Mechanism and Theory in
Organic Chemistry, 3rd ed., Harper Collins Publishers,
New York, 1987, Chapter 8.5.
2
. Reviews: (a) E. A. Castro, Pure Appl. Chem 2009, 81, 685;
(
(
b) E. A. Castro, J. Sulfur Chem. 2007, 28, 401;
c) E. A. Castro, Chem. Rev. 1999, 99, 3505; (d) W. P. Jencks,
Experimental
Chem. Rev. 1985, 85, 511.
Materials. Phenyl Y-substituted phenyl carbonates (7a–7l)
were prepared from reactions of phenyl chloroformate with
the respective Y-substituted phenol under the presence of
3
. (a) E. A. Castro, M. E. Aliaga, M. Gazitua, P. Pavez, J. G. Santos,
J. Phys. Org. Chem 2014, 27, 265; (b) P. Pavez, D. Millan,
J. I. Morales, E. A. Castro, J. Org. Chem. 2013, 78, 9670;
(c) R. Aguayo, F. Arias, A. Canete, C. Zuniga, E. A. Castro,
P. Pavez, J. G. Santos, Int. J. Chem. Kinetics 2013, 45, 202;
(d) E. A. Castro, D. Ugarte, M. F. Rojas, P. Pavez,
J. G. Santos, Int. J. Chem. Kinetics 2011, 43, 708;
10
triethylamine in anhydrous ether as reported previously.
The crude product was purified by column chromatography
silica gel, methylene chloride/n-hexane 50/50). DBU and
(
other chemicals were of the highest quality available. Doubly
glass distilled water was further boiled and cooled under nitro-
gen just before use. Due to low solubility of the substrates in
(
e) E. Castro, M. Aliaga, P. R. Campodonico, M. Cepeda,
R. Contreras, J. G. Santos, J. Org. Chem. 2009, 74, 9173.
. (a)H. K. Oh, J. Y. Oh, D. D. Sung, I. Lee, J. Org. Chem. 2005, 70,
4
5
purewater, aqueousDMSO(80mol%H O/20mol%DMSO)
2
5
624; (b) H. K. Oh, Y. C. Jin, D. D. Sung, I. Lee, Org. Biomol.
Chem. 2005, 3, 1240; (c) I. Lee, D. D. Sung, Curr. Org. Chem.
004, 8, 557.
. (a) J. F. Kirsch, A. Kline, J. Am. Chem. Soc. 1969, 91, 1841;
b) T. H. Fife, L. Chauffe, J. Org. Chem. 2000, 65, 3579;
was used as the reaction medium.
Kinetics. The kinetic study was performed with a UV–Vis
spectrophotometer for slow reactions (e.g., t1/2 ≥ 10 s) or
with a stopped-flow spectrophotometer for fast reactions
2
(
(
e.g., t1/2 < 10 s) equipped with a constant temperature circu-
(c) W. J. Spillane, C. Brack, J. Chem. Soc., Perkin Trans. 2
1998, 2381.
lating bath. The reactions were followed by monitoring
appearance of the leaving Y-substituted phenoxide ion. All
the reactions were carried out under pseudo-first-order condi-
tions in which the DBU concentrations were at least 20 times
greater than the substrate concentration.
6. (a)I. H. Um, J. Y. Han, Y. H. Shin, J. Org. Chem. 2009, 74, 3073;
b) I. H. Um, K. Akhtar, Y. H. Shin, J. Y. Han, J. Org. Chem.
007, 72, 3823.
(
2
7
. (a) I. H. Um, K. H. Kim, H. R. Park, M. Fujio, Y. Tsuno, J. Org.
Chem. 2004, 69, 3937;(b) I. H. Um, S. E. Jeon, J. A. Seok, Chem.
Eur. J. 2006, 12, 1237.
. (a) I. H. Um, S. J. Hwang, S. R. Yoon, S. E. Jeon, S. K. Bae,
J. Org. Chem. 2008, 73, 7671; (b) I. H. Um, J. A. Seok,
H. T. Kim, S. K. Bae, J. Org. Chem. 2003, 68, 7742;
Typically, the reaction was initiated by adding 5 μL of a
.02 M solution of the substrate in acetonitrile to a 10-mm
0
8
quartz UV cell containing 2.50 mL of the thermostated reac-
tion mixture made up of solvent and aliquot of the DBU stock
solution. All the solutions were transferred by gas-tight syr-
inges. Generally, the DBU concentration was varied over
(
c)I. H. Um, S. E. Lee, H. J. Kwon, J. Org. Chem. 2002, 67, 8999.
9. (a) I. H. Um, A. R. Bea, J. Org. Chem. 2012, 77, 5781;
(b) I. H. Um, A. R. Bae, T. I. Um, J. Org. Chem. 2014, 79, 1206.
10. (a) J. S. Kang, Y. J. Song, I. H. Um, Bull. Korean Chem. Soc.
−3
the range (20–100) × 10 M, while the substrate concentra-
−
5
tion was 2 × 10 M. Pseudo-first-order rate constants (kobsd
)
2
013, 34, 2023; (b) Y. J. Song, M. Y. Kim, I. H. Um, Bull.
were calculated from the equation, ln (A∞ – A ) = –k ꢁt +
t
obsd
Korean Chem. Soc. 2013, 34, 1722.
C. The plots of ln (A – A ) vs. time were linear over approx-
∞
t
1
1
1
1. I. Kaljurand, A. Kütt, L. Sooväli, T. Rodima, V. Mäemets,
I. Leito, I. A. Koppel, J. Org. Chem. 2005, 70, 1019.
2. J. G. Smith, Organic Chemistry, 3rd ed., McGraw Hill, Singa-
pore, 2011, p. 286.
3. (a) J. H. Moon, M. Y. Kim, S. Y. Han, I. H. Um, Bull. Korean
Chem. Soc. 2015, 36, 1563; (b) H. J. Hong, A. R. Bae,
I. H. Um, Bull. Korean Chem. Soc. 2013, 34, 2251;
(c) S. I. Kim, H. J. Cho, I. H. Um, Bull. Korean Chem. Soc.
2014, 35, 177.
imately 90% of the total reaction. Usually, five different DBU
concentrations were employed to obtain the second-order rate
constants (k ) from the slope of linear plots of k
vs. [DBU].
N
obsd
Product Analysis. Y-Substituted phenoxide ion was liber-
ated quantitatively and identified as one of the products by
comparison of the UV–Vis spectra after completion of the
reaction with the authentic sample under the same reaction
conditions.
1
4. (a) Y. Tsuno, M. Fujio, Adv. Phys. Org. Chem. 1999, 32, 267;
Acknowledgments. This research was supported by a grant
from 2014 Research Development Program funded by Ansan
Green Environment Center (14-2-10-16).
(
(
b) Y. Tsuno, M. Fujio, Chem. Soc. Rev. 1996, 25, 129;
c) Y. Yukawa, Y. Tsuno, Bull. Chem. Soc. Jpn. 1959, 32, 965.
1
5. (a) M. M. R. Badal, M. Zhang, S. Kobayashi, M. Mishima, Bull.
Chem. Soc. Jpn. 2013, 86, 856; (b) M. Zhang, M. M. R. Badal,
I. A. Koppel, M. Mishima, Bull. Chem. Soc. Jpn. 2013, 86, 813;
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Bull. Korean Chem. Soc. 2016, Vol. 37, 77–81
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www.bkcs.wiley-vch.de
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