ACCEPTED MANUSCRIPT
Tetrahedron
5
4
.3.3. o-Aminotoluene (2c). General procedure was followed
4.3.13. 4-Chloroaniline (2m). General procedure was followed
(
(
3
eluted with petroleum ether/EtOAc=10:1), light yellow liquid
(eluted with petroleum ether/EtOAc=10:1), white crystalline
1
o
1
101.7 mg, 94%). H NMR (600 MHz, DMSO-d ) δ 1.99 (s, 3H),
solid (118.6 mg, 90%), mp: 71.3-72.0 C; H NMR (600 MHz,
CDCl ) δ 3.63 (br, N-H), 6.60 (d, J=8.6 Hz, 2H), 7.09 (d, J=8.7
6
.34 (br, N-H), 6.42 (dd, J=7.9,1.9 Hz, 1H), 6.61(s,1H), 6.86(d, J
3
1
3
13
=
7.9 Hz, 1H); C NMR (151 MHz, DMSO-d
6
) δ 19.99, 117.60,
3
Hz, 2H); C NMR (151 MHz, CDCl ) δ 118.88 (2C), 125.76
1
21.30, 124.98, 129.60 , 133.09, 147.16.
(2C), 131.76(2C),147.59.
4
.3.4. m-Aminotoluene (2d). General procedure was followed
4.3.14. 4-Chloro-2-methylaniline (2n). General procedure was
(
eluted with petroleum ether/EtOAc=10:1), light yellow liquid
followed (eluted with petroleum ether/EtOAc=10:1), brown
1
1
(
98.3 mg, 92%); H NMR (600 MHz, CDCl
3
) δ 2.28 (s, 3H),
liquid (129.7 mg, 92%); H NMR (600 MHz, CDCl
3
) δ 2.18(s,
1
3
3
.47(br, N-H), 6.60 (d, J=7.4 Hz, 1H), 6.54-6.48(m, 2H),7.06 (d,
3H), 3.48 (br, N-H), 6.75-6.65 (m, 2H), 7.10 (s, 1H); C NMR
1
3
J=7.7 Hz, 1H); C NMR (151 MHz, CDCl ) δ 24.09, 114.93,
(151 MHz, CDCl ) δ 19.98, 117.58, 121.27, 124.96, 129.60,
3
3
1
18.59, 122.12, 131.80 , 141.75, 148.96.
133.08, 147.18.
4
.3.5. p-Methoxyaniline (2e). General procedure was followed
4.3.15. 4-Bromoaniline (2o). General procedure was followed
(
eluted with petroleum ether/EtOAc=10:1), white solid (120.3
(eluted with petroleum ether/EtOAc=10:1), colorless crystalline
o
1
o
1
mg, 98%), mp: 57.0 -57.4 C; H NMR (600 MHz, CDCl ) δ 3.37
(
2
solid (45.9 mg, 54%), mp: 59.0-60.5 C; H NMR (600 MHz,
CDCl ) δ 3.51 (br, N-H), 6.56 (d, J=8.6 Hz, 2H), 7.24 (d, J=9.5
3
br, N-H) 3.75 (s, 3H), 6.65 (d, J=8.8 Hz, 2H), 6.75 (d, J=8.7 Hz,
3
13
13
H); C NMR (151 MHz, CDCl
3
) δ 55.72, 114.77 (2C), 116.42
Hz,2H); C NMR (151 MHz, CDCl
3
) δ 110.18, 116.70 (2C),
(
2C), 139.90, 152.76.
131.98 (2C), 145.39.
4
.3.6. 4-Aminophenol (2f). General procedure was followed
4.3.16. 1, 2-Diaminobenzene (2p). General procedure was
(
eluted with petroleum ether/EtOAc=10:1), red solid (106 mg,
followed (eluted with petroleum ether/EtOAc = 1:1), colorless
o
1
o
1
9
4
8
1
8%)); mp: 186.2 -187.3 C; H NMR (600 MHz, DMSO-d
6
) δ
crystalline solid (69.8 mg, 89%), mp: 100.0-102.3 C; H NMR
13
.83 (br, N-H), 5.92 (d, J=6.4 Hz, 1H), 5.99(s, 2H), 6.75 (s, 1H),
3
(600 MHz, CDCl ) δ 3.37 (br, N-H), 6.63-6.82 (m, 4H); C
13
.79(s, 1H); C NMR (101 MHz, DMSO-d ) δ 115.80 (2C),
NMR (151 MHz, CDCl ) δ 116.74(2C), 120.28 (2C), 134.76
6
3
16.05 (2C), 141.05, 148.74.
(2C).
4
.3.7. 3-Aminophenol (2g). General procedure was followed
4.3.17. 1, 4-Diaminobenzene (2q). General procedure was
(
Eluted with petroleum ether/EtOAc=10:1), white solid (106.9
followed (eluted with petroleum ether/EtOAc=1:1), brown
o
1
o
1
mg, 98%), mp: 120.0 -121.4 C; H NMR (600 MHz, DMSO-d
δ 4.83 (br, N-H), 5.92 (d, J=6.4 Hz, 1H), 5.99(s, 1H), 6.76 (t,
6
)
crystalline solid (70.3 mg, 90%), mp: 142.0-144.5 C; H NMR
13
(600 MHz, CDCl
3
) δ 3.31 (br. N-H), 6.57 (s, 4H); C NMR (151
1
3
MHz, CDCl ) δ 116.71(4C), 138.58 (2C).
3
J=6.0 Hz, 2H), 8.79 (s, 1H); C NMR (101 MHz, DMSO-d
6
) δ
58.52, 115.15 (2C), 128.76 (2C), 131.08, 145.95. C NMR (101
MHz, DMSO-d ) δ 101.4, 103.7, 105.88, 129.91, 150.28, 158.52.
13
1
4
.3.18. 1, 3-Diaminobenzene (2r). General procedure was
6
followed (eluted with petroleum ether/EtOAc=1:1), yellow solid
o
1
(
71.3 mg, 91%), mp: 113.5-114.2 C; H NMR (600 MHz,
4
.3.8. 4-Aminobenzylalcohol (2h). General procedure was
CDCl ) δ 3.56 (br. N-H), 6.01(s,1H),6.11 (d, J=7.9 Hz, 2H), 6.94
3
followed (eluted with petroleum ether/EtOAc=10:1), white solid
1
3
o
1
(
1
3
m, 1H); C NMR (151 MHz, CDCl ) δ 104.61, 108.600 (2C),
32.86, 150.20 (2C).
(
3
106 mg, 98%), mp: 57.0 -57.4 C; H NMR (600 MHz, CDCl
3
) δ
.60 (br, N-H)), 4.51(s, 2H), 6.65 (d, J=8.2 Hz, 2H), 7.13(d, J=8
1
3
3
Hz, 2H); C NMR (151 MHz, CDCl ) δ 65.17, 115.15 (2C),
1
4.3.19. 2-Aminobiphenyl (2s). General procedure was followed
28.76 (2C), 131.08, 145.95.
(
eluted with petroleum ether/EtOAc=10:1), purple crystalline
o 1
3
solid (71.3 mg, 91%), mp: 46.5 C; H NMR (600 MHz, CDCl )
4
.3.9. 4-Aminobenzonitrile (2i). General procedure was followed.
δ 3.70 (br. N-H), 6.79 (d, J=8.0 Hz, 1H), 6.86 (t, J=7.4 Hz,
(
eluted with petroleum ether/EtOAc=3:1), pale yellow crystalline
o 1
1H), 7.21-7.13 (m, 2H) 7.37 (t, J=6.8 Hz, 1H), 7.51-7.44 (m,
solid (63.8 mg, 80%),mp: 83.4-85.4 C; H NMR (600 MHz,
13
4
3
H); C NMR (151 MHz, CDCl ) δ 101.51, 105.55, 111.52,
CDCl ) δ 4.22 (br, N-H), 6.77 (d, J=8.6 Hz, 2H), 7.39 (s, 2H);
3
13
1
12.95(2C), 124.73(2C), 128.77, 130.67, 139.48,.
3
C NMR (151 MHz, CDCl ) δ 100.07, 114.42 (2C), 120.22,
1
33.78 (2C), 150.49.
4.3.20. 5-Aminoindole (2t). General procedure was followed
(
eluted with petroleum ether/EtOAc=2:1), light brown crystalline
4
.3.10. 4-Aminobenzoic acid methyl ester (2j). General procedure
o 1
solid (152.2 mg, 90%), mp: 130.3 C; H NMR (600 MHz,
CDCl ) δ 3.49 (br, N-H), 6.38 (s, 1H), 6.68 (d, J=8.5 Hz, 1H),
.96 (s, 1H), 7.12-7.26(m, 2H), 8.01 (br, N-H); C NMR (151
MHz, CDCl ) δ 115.64, 118.70, 127.17, 127.67(2C), 128.50(2C),
was followed (eluted with petroleum ether/EtOAc=1:1), white
solid (107.2 mg, 71%), mp: 111.4 -112.4 C; H NMR (600 MHz,
CDCl ) δ 3.84 (s, 3H), 3.98 (br, N-H), 6.63(d, J=8.6 Hz, 2H),
o
1
3
1
3
6
3
1
3
7
1
.84 (d, J=8.6 Hz, 2H); C NMR (151 MHz, CDCl
13.77 (2C), 119.60, 131.58 (2C), 150.87,167.20.
3
) δ 51.63,
3
1
28.76, 129.10, 130.46(2C), 139.50, 143.42.
4
.3.11. 4-Aminobenzamide (2k). General procedure was followed
Supplementary Material
(
Eluted with petroleum ether/EtOAc=1:1), white solid (68.7 mg,
o 1
8
5%), mp: 182.7 -183.4 C. H NMR (600 MHz, DMSO-d
6
) δ
1
13
Supplementary material (copies of H and C NMR spectra for
the products) associated with this article can be found in the
online version, at http://dx.doi.org/****
5
.56 (br, N-H), 6.50(d, J=8.4 Hz, 2H),6.81(br, N-H), 7.56 (d,
1
3
6
J=8.4 Hz, 2H); C NMR (101 MHz, DMSO-d ) δ 112.91 (2C),
1
21.39, 129.58 (2C), 152.12, 168.52.
Acknowledgment
4
.3.12. 4-Aminobenzenesulphonamide (2l). General procedure
was followed (eluted with petroleum ether/EtOAc=1:1), colorless
o
1
We gratefully acknowledge financial assistance from the
National Natural Science Foundation of China (Nos. 21272050,
21371044) and the Program for New Century Excellent Talents
in University of the Chinese Ministry of Education (NCET-11-
crystalline solid (73.3 mg, 90%), mp: 166.1-166.4 C; H NMR
600 MHz, DMSO-d ) δ 5.79 (s, 1H), 6.57 (d, J=8.7 Hz, 1H),
.88 (s, 1H), 7.44 (d, J=8.6 Hz,1H); C NMR (151 MHz,
DMSO-d ) δ 112.86(2C), 127.86 (2C), 130.44,152.34.
(
6
6
1
3
6
0627).