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Regioselective Mononitration of Aromatic Compounds
Regioselective Mononitration of Aromatic Compounds
SO
3
), 2.03 (m, 2H, CH
2
CH
2
CH
2
), 1.56 (m, 6H, CH
2
CH
2
CH
3
),
1.27 (m, 6H, CH
2
CH
3
), 0.84 (t, 9H, J = 7.5 Hz, CH
3
).
13
C NMR
(300 MHz, D
2
O): d ppm 58.49, 50.66, 48.42, 23.93, 20.36, 19.16,
14.46. MS (m/z): 405.29 (M
+
), 406.28, 404.28 (100).
4.2.4. N,N,N-Trimethyl-N-butanesulfonic acid ammonium hydrogen
sulfate [TMBSA][HSO
4
]
1
HNMR (300 MHz, D
2
O): d ppm3.24 (t, J = 8.4 Hz, 2H, NCH
2
CH
3
), 3.07 (t, J = 8.4 Hz, 2H, NCH
2
C
3
H
6
SO
3
), 2.82 (t, J = 7.2 Hz,
2H, CH
2
SO
3
), 1.68 (m, 4H, C
2
H
4
CH
2
SO
3
), 1.11 (m, J = 7.2 Hz,
9H, CH
3
).
13
C NMR (D
2
O,): d ppm56.21, 52.85, 50.32, 21.50, 20.20,
6.90. MS (m/z): 335.35 (M
+
), 208.36 (100).
4.3. UVvis acidity evaluation
Dichloromethane solutions of these TSILs were prepared from
dried CH
2
Cl
2
and TSILs that have been treated under vacuum at
80 8C for 6 h. All the spectra were recorded with a UVvis
spectrophotometer.
4.4. Typical nitration procedure
Weighed amounts of aromatic compound, 68% nitric acid, and
TSIL were charged successively into a ask with a reex condenser
(Scheme 1). The nitration reaction was typically allowed to
proceed for a length of time with vigorous stirring and heating at
the desired temperature (monitored by GC). After the reaction, the
system became biphasic once the stirring was discontinued. The
Table 6
Reuse of [TBPSA][HSO
4
] in the nitration of chlorobenzene
a
Runs Yield (%)
b
Product isomers (%)
c
para/ortho
d
ortho meta para
Fresh 65 22.2 0.3 77.5 3.5
1 46 24.1 0.7 75.2 3.1
2 52 23.6 0.7 75.7 3.2
3 65 22.2 0.3 77.5 3.5
4 53 23.4 0.4 76.2 3.1
5 55 23.2 0.6 76.2 3.3
a
Reaction conditions: 20 mmol chlorobenzy, 60 mmol 68% nitric acid, TSILs
0.4 mmol, 10 h.
b
Based on crude product.
c
By quantitative GC analysis and qualitative GC/MS.
d
Ratio of para/ortho calculated from original GC data.
D. Fang et al. / Applied Catalysis A: General 345 (2008) 158163 162
organic phase contained the expected product, that was isolated by
simple decantation from the aqueous system, washed with water,
and then analyzed by GC or HPLC. The TSIL could be recovered by
steam distillation.
Acknowledgment
This work was nancially supported by the Chinese Commis-
sion of Science, Technology & Industry for National Defense.
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