SUPPORTING INFORMATION
Oxidation of anti-tubercular drug Isoniazid by lipopathic oxidant,
Cetyltrimethylammonium dichromate: A mechanistic study
Sarita Garnayak and Sabita Patel*
Department of Chemistry, NIT, Rourkela, India-769008
E–mail: sabita_patel@yahoo.com
TABLE OF CONTENTS
Page no
Figure SI1.
Plot of H‡ versus S‡ in the oxidation reaction of isoniazid with
2
CTADC in presence of acetic acid for a series of solvents.
Figure SI2.
Plot of 103kobs versus π∗ in the oxidation reaction of isoniazid with
2
CTADC at 298 K.
Figure SI3.
Plot of 103kobs versus dielectric constant (ε) in the oxidation reaction of
3
isoniazid with CTADC at 298 K.
Figure SI4.
Plot of 103kobs versus Dipole moment (μ) in the oxidation reaction of
3
isoniazid with CTADC at 298 K.
Figure SI5.
Plot of 103kobs versus A and B of the solvents in the oxidation reaction
3
of isoniazid with CTADC at 298 K.
Table SI1.
Observed rate constants for the oxidation of isoniazid by CTADC in
various organic solvents in presence of acetic acid at 298K.
1
4
40000
y = 314x + 89,837
R² = 1
H‡ in J mol-1
30000
20000
10000
0
-300
-250
-200
S‡ in J
K-1
-150
-100
mol-1
Figure SI1: Plot of H‡ versus S‡ for the oxidation reaction of isoniazid with CTADC in
presence of acetic acid for a series of solvents.
10
103 kobs in s-1
8
6
4
2
0
0.4
0.6
0.8
1
1.2
*
Figure SI2: Plot of 103kobs versus π∗ of the solvents in the oxidation reaction of isoniazid
with CTADC at 298 K.
2
10
103 kobs in s-1
8
6
4
2
0
0
20
40
dielectric constant
60
Figure SI3: Plot of 103kobs versus dielectric constant (ε) of the solvents in the oxidation
reaction of isoniazid with CTADC at 298 K.
10
103 kobs in s-1
8
6
4
2
0
0
1
2
3
dipole moment
4
5
Figure SI4: Plot of 103kobs versus Dipole moment (μ) of the solvents in the oxidation
reaction of isoniazid with CTADC at 298 K.
10
A
B
103 kobs in s-1
8
6
4
2
0
0
0.2
0.4
0.6
0.8
1
1.2
A or B
Figure SI5: Plot of 103kobs versus A and B of the solvents in the oxidation reaction of
isoniazid with CTADC at 298 K.
3
TABLE SI 1. Observed rate constants for the oxidation of isoniazid by CTADC in various
organic solvents in presence of acetic acid at 298K.a
Sl. No.
a
103 kobs s-1
Solvents
1
Toluene
2.63 ± 0.09
2
Benzene
2.37 ± 0.09
3
Chloroform
4.82 ± 0.17
4
Dichloromethane
5.74 ± 0.23
5
Dioxane
4.78 ± 0.20
6
Nitrobenzene
3.86 ± 0.14
7
Tetrahydrofuran
7.23 ± 0.29
8
Acetonitrile
5.08 ± 0.18
9
Ethyl acetate
7.89 ± 0.32
10
Acetone
5.70 ± 0.22
11
Dimethylsulfoxide
1.75 ± 0.05
12
N,N-Dimethylformamide
3.72 ± 0.13
[Isoniazid] = 1.1 x 10-3M, [CTADC]= 2.18 x 10-4 M, [Acetic acid]=0.79M
4