4
Xie et al. Sci China Chem March (2015) Vol.58 No.3
Table 3 Selective hydrogenation of o-CNB to o-CAN over mono-
Table 5 Selective hydrogenation of o-INB to o-IAN over mono-
dispersed Pt NPs with ammonia a)
dispersed Pt NPs with sodium bicarbonate a)
Sel. (%)
Sel. (%)
Entry
X
Additive
Conv. (%)
Entry
X
Additive
Conv. (%)
5
3
5
3
1
2
3
4
5
Cl
Cl
Cl
Cl
Cl
NH3·H2O
NH3·H2O
NH3·H2O
NH3·H2O
NH3·H2O
100
100
100
100
100
99.0
99.6
99.9
99.8
99.9
n.d. b)
n.d.
n.d.
0.1
1
2
3
4
5
I
I
I
I
I
NaHCO3
NaHCO3
NaHCO3
NaHCO3
NaHCO3
100
100
100
100
100
80.4
89.6
80.5
67.3
68.0
11.1
10.5
2.8
27.3
6.3
0.1
a) Reaction conditions: o-CNB, 158 mg; catalysts, 2 mg; ammonia, 30
L; methanol (solvent), 2 mL; hydrogen pressure, 0.1 MPa, 50 °C, 8 h; b)
n.d.=not detected.
a) Reaction conditions: o-INB, 249 mg; catalysts, 2 mg; sodium bicar-
bonate, 84 mg; methanol (solvent), 2 mL; hydrogen pressure, 0.1 MPa,
50 °C, 8 h.
genated of ortho-halogenated nitrobenzene with higher
selectivity and activity under mild reaction conditions than
the conventional metal catalysts. The nanocatalysts were
very stable and recyclable after separation from the reaction
system. The results described here show that the Pt nano-
catalysts are promising catalysts for industrial applications.
Table 4 Selective hydrogenation of o-BNB to o-BAN over mono-
dispersed Pt NPs with sodium bicarbonate a)
Sel. (%)
Entry
X
Additive
Conv. (%)
5
3
1
2
3
4
5
Br
Br
Br
Br
Br
NaHCO3
NaHCO3
NaHCO3
NaHCO3
NaHCO3
100
100
100
100
100
86.6
94.3
95.5
94.1
94.9
1.9
0.6
3.2
4.8
4.6
Supporting information
The supporting information is available online at chem.scichina.com and
link.springer.com/journal/11426. The supporting materials are published as
submitted, without typesetting or editing. The responsibility for scientific
accuracy and content remains entirely with the authors.
a) Reaction conditions: o-BNB, 202 mg; catalysts, 2 mg; sodiumbicar-
bonate, 84 mg; methanol (solvent), 2 mL; hydrogen pressure, 0.1 MPa,
50 °C, 8 h.
o-BNB is converted and selectively afforded the target
o-bromoaniline with yield in 86.6% (Entry 1). After the
reaction was finished, the Pt nanocatalysts were collected
and tested for another round of hydrogenation of o-BNB.
After the Pt NP catalysts were recycled 5 times, we did not
observed an obvious decline of conversion and selectivity
toward the generation of fluoroaniline (Entries 2–5).
Finally, we chose iodo-nitrobenzene as the substrate to
test the catalytic ability of Pt nanocatalysts for the genera-
tion of iodoaniline. In Table 5, Which shows the results of
the hydrogenation of o-INB treated by NaHCO3, 100% of
o-INB is converted and selectively affords the target
o-iodoaniline with a yield of 80.4% (Table 5, Entry 1). Af-
ter the reaction was finished, the Pt NP catalysts were col-
lected and tested for another round of hydrogenation of
o-INB. After the Pt nanocatalysts had been recycled 5 times,
we did not observe an obvious decline of conversion and
selectivity toward the generation of fluoroaniline (Entries 2,
3). However, we did find a severe decrease of efficiency of
the catalyst for the generation of IAN. The final yield was
about 68.0%.
This work was financially supported by the National Natural Science
Foundation of China (21373006, 51402203), the Natural Science Founda-
tion of Jiangsu Province for Young Scholars (BK20140326), the Natural
Science Foundation of Jiangsu Higher Education Institutions
(14KJB430021) and the Priority Academic Program Development of
Jiangsu Higher Education Institutions.
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We report a novel nanocatalyst based on Pt NPs for hydro-