4
Journal of Chemical Research 00(0)
2g: 95% yield; H NMR (400MHz, CDCl ): δ=3.62 (s,
1
was stirred for 2h at room temperature. After reaction, the
mixture was dissolved in dichloromethane and was washed 2H), 6.54 (d, J=8.0Hz, 2H), 7.07 (d, J=8.0Hz, 2H);
3
1
3
C
with 0.5M H SO and 0.5M NaHCO ; the organic phase NMR (100MHz, CDCl ): δ=116.30 (s, 2CH), 123.01 (s,
2
4
3
3
was evaporated in vacuo to yield PdNPs.
C), 129.14 (s, 2CH), 145.12 (s, C).
1
2
h: 94% yield; H NMR (400MHz, CDCl ): δ=3.62 (s,
3
1
3
2
H), 6.50-6.52 (m, 2H), 7.19-7.21 (m, 1H); C NMR
General procedure for hydrogenation of
various nitroaromatic compounds and the
recycling experiment
(
100MHz, CDCl ): δ=110.11 (s, C), 116.79 (s, 2CH),
3
1
32.03 (s, 2CH), 145.56 (s, C).
1
2
i: 93% yield; H NMR (400MHz, CDCl ): δ=4.18 (s,
3
To a Schlenk tube was added nitroarene 1 (2mmol) and 2H), 6.87 (d, J=8.0Hz, 1H), 7.48-7.63 (m, 4H), 7.90 (d,
1
3
PdNPs (10mg). The tube was purged with H for 5min by J=8.0Hz, 1H), 8.00 (s, 1H); C NMR (100MHz, CDCl ):
2
3
hydrogen generator, and H O (2mL)/glycerol (2mL) was δ=109.87 (s, CH), 119.07 (s, CH), 121.11 (s, CH), 123.85
2
added under H . The reaction mixture was stirred at room (s, C), 125.04 (s, CH), 126.09 (s, CH), 126.63 (s, CH),
2
temperature and the reaction progress was monitored by gas 128.77 (s, CH), 134.62 (s, C), 142.42 (s, C).
1
chromatography (GC). Upon completion, the mixture was fil-
2j: 95% yield; H NMR (400MHz, CDCl ): δ=2.35 (s,
3
1
3
tered free of PdNPs. H O (10mL) was added to the mixture 6H), 3.58 (s, 2H), 6.40 (s, 2H), 6.54 (s, 1H); C NMR
2
and extracted with acetic ether (3×20mL). The combined (100MHz, CDCl ): δ=21.46 (s, 2CH ), 113.28 (s, 2CH),
3
3
organic layers were dried (anhyd MgSO ) and concentrated. 120.55 (s, CH), 139.05 (s, 2C), 146.62 (s, C).
4
1
The residue was subjected to flash column chromatography
2k: 93% yield; H NMR (400MHz, CDCl ): δ=2.48 (s,
3
on silica gel (petroleum ether/acetic ether) to afford the cor- 6H), 3.79 (s, 2H), 7.02 (t, J=8.0Hz, 1H), 7.30 (d, J=8.0Hz,
13
responding compound 2.
2H); C NMR (100MHz, CDCl ): δ=17.86 (s, 2CH ), 118.24
3 3
To study the recyclability of PdNPs, the hydrogenation (s, CH), 121.90 (s, 2C), 128.61 (s, 2CH), 143.20 (s, C).
1
of 1f was conducted under the same conditions as described
2l: 90% yield; H NMR (400MHz, CDCl ): δ=3.36 (s,
3
1
3
above. After reaction, the catalyst was separated through 4H), 6.67-6.73 (m, 4H); C NMR (100MHz, CDCl3):
centrifugation, and then the catalyst was washed with δ=116.77 (s, 2CH), 120.30 (s, 2CH), 134.78 (s, C).
1
EtOH, and reused in a next run under the same conditions.
2m: 92% yield; H NMR (400MHz, CDCl ): δ=3.33 (s,
3
1
3
The catalytic cycle efficiency was compared by isolated 4H), 6.56 (d, J=1.2Hz, 4H); C NMR (100MHz, CDCl ):
3
yield. All products were identified by comparison of their δ=116.73 (s, 4CH ), 138.60 (s, 2C).
3
1
spectroscopic data with literature data. Analytical data for
2n: 91% yield; H NMR (400MHz, CDCl ): δ=1.91 (s,
3
the products are given as follows:
3H), 3.52 (s, 4H), 6.15 (d, J=8.0Hz, 2H), 8.81 (t, J=4.0Hz,
1
13
2
a: 97% yield; H NMR (400MHz, CDCl ): δ=3.53 (s, 1H); C NMR (100MHz, CDCl ): δ=10.26 (s, CH ), 106.72
3
3
3
2
H), 6.58-6.60 (m, 2H), 6.72 (t, J=8.0Hz, 1H), 7.11 (t, (s, 2CH), 107.37 (s, C), 126.83 (s, CH), 145.33 (s, C).
1
3
1
J=8.0Hz, 2H); C NMR (100MHz, CDCl ): δ=115.26 (s,
2o: 95% yield; H NMR (400MHz, DMSO): δ=4.36 (s,
2H), 6.44-6.53 (m, 4H), 8.44 (s, 1H); C NMR (100MHz,
3
1
3
2
CH), 118.59 (s, CH), 129.45 (s, 2CH), 146.68 (s, C).
1
2
b: 97% yield; H NMR (400MHz, CDCl ): δ=2.20 (d, DMSO): δ=115.93 (s, 2CH), 116.11 (s, 2CH), 140.97 (s,
3
J=8.0Hz, 3H), 3.44 (s, 2H), 6.51-6.54 (m, 2H), 6.90-6.93 (m, C), 148.82 (s, C).
13
1
2
H); C NMR (100MHz, CDCl ): δ=20.59 (s, CH ), 115.38
2p: 89% yield; H NMR (400 MHz, CDCl ): δ = 6.08
3
3
3
(
s, 2CH), 127.74 (s, C), 129.88 (s, 2CH), 144.08 (s, C).
(s, 2H), 6.53-6.65 (m, 2H), 7.19 (t, J = 8.0 Hz, 1H), 7.36
1
13
2
c: 97% yield; H NMR (400MHz, CDCl ): δ=3.76 (s, (d, J = 8.0 Hz, 1H), 9.75 (s, 1H); C NMR (100 MHz,
3
2
H), 6.82-6.84 (m, 2H), 7.39 (d, J=8.0Hz, 1H), 7.51-7.55 CDCl ): δ = 116.07 (s, CH), 116.34 (s, CH), 118.80 (s,
3
1
3
(
m, 4H), 7.67 (d, J=4.0Hz, 2H); C NMR (100MHz, C), 135.25 (s, CH), 135.76 (s, CH), 150.01 (s, C), 194.15
CDCl ): δ=115.52 (s, 2CH), 126.38 (s, CH), 126.51 (s, (s, CH).
3
1
2
1
CH), 128.10 (s, 2CH), 128.81 (s, 2CH), 131.57 (s, C),
2q: 83% yield; H NMR (400MHz, CDCl ): δ=2.89 (s,
3
41.28 (s, C), 146.04 (s, C).
1H), 3.71 (s, 2H), 6.45 (d, J=8.0Hz, 2H), 7.19 (d, J=8.0Hz,
1
13
2
d: 94% yield; H NMR (400MHz, CDCl ): δ=3.42 (s, 2H); C NMR (100MHz, CDCl ): δ=75.17 (s, CH), 84.61
3
3
2
H), 3.71 (s, 3H), 6.61 (d, J=8.0Hz, 2H), 6.72-6.74 (m, 2H); (s, C), 111.16 (s, C), 114.67 (s, 2CH), 133.50 (s, 2CH),
13
C NMR (100MHz, CDCl ): δ=55.74 (s, CH ), 114.83 (s, 147.20 (s, C).
3
3
1
2CH), 116.43 (s, 2CH), 140.08 (s, C), 152.75 (s, C).
2r: 80% yield; H NMR (400MHz, CDCl ): δ=4.90 (s,
NMR (376MHz, CDCl3): 2H), 6.77 (d, J=8.0Hz, 1H), 6.99 (d, J=8.0Hz, 1H), 7.18
3
1
9
2
e: 97% yield;
F
1
δ=−61.11ppm; H NMR (400MHz, CDCl ): δ=3.92 (s, (t, J=6.0Hz, 2H), 7.89 (d, J=8.0Hz, 1H), 8.62 (t, J=2.0Hz,
2
3
1
3
13
H), 6.66 (d, J=8.0Hz, 2H), 7.38 (d, J=8.0Hz, 2H);
C
1H); C NMR (100MHz, CDCl ): δ=110.06 (s, CH),
3
NMR (100MHz, CDCl ): δ=114.19 (s, 2CH), 124.89 (d, 116.01 (s, CH), 121.37 (s, CH), 127.43 (s, CH), 128.88 (s,
3
J =270.0Hz, C), 126.70 (d, J =11.2Hz, C), 126.71 (d, C), 136.01 (s, CH), 138.45 (s, C), 144.05 (s, C), 147.45 (s,
CF
CF
J =3.7Hz, 2CH), 149.43 (s, C).
CH).
2s: 85% yield; H NMR (400MHz, CDCl ): δ=4.48 (s,
CF
1
1
2
f: 95% yield; H NMR (400MHz, CDCl ): δ=3.52 (s,
3
3
1
3
2
H), 6.54 (dd, J=4.0, 4.0Hz, 2H), 6.82 (d, J=8.0Hz, 2H); 2H), 6.62-6.68 (m, 2H), 7.22-7.27 (m, 2H); C NMR
1
3
C NMR (100MHz, CDCl ): δ=115.68 (d, J =22.7Hz, (100MHz, CDCl ): δ=95.67 (s, C), 115.33 (s, CH), 117.85
3
CF
3
2
CH), 116.13 (d, J =7.3Hz, 2CH), 142.69 (d, J =2.2Hz, (s, CH), 117.91 (s, C), 132.33 (s, CH), 134.11 (s, CH),
CF CF
C), 156.38 (d, J =235.0Hz, C).
150.00 (s, C).
CF