9
8.4, 7.6 Hz, 2H), 7.09 (d, J = 8.4 Hz, 1H), 6.92 (d, J = 7.6 Hz,
2H), 6.79 (t, J = 7.6 Hz, 1H), 6.28 (dd, J = 16.0, 2.4 Hz, 2H),
5.61 (s, 1H), 3.77 (s, 3H), 3.41 (s, 2H); 13C NMR (101 MHz,
CDCl3) δ 151.80, 145.46, 142.05, 129.19, 123.53, 121.36,
119.26, 115.75, 107.04, 99.77, 55.57; HRMS (ESI) m/z calcd for
C13H15N2O+ (M+H)+ 215.11789, found 215.11726; IR (cm-1):
3405, 2361, 2343, 1621, 1455, 1048, 880.
143.12, 130.23, 129.32, 121.01, 118.34, 108.37, 108.14,
ACCEPTED MANUSCRIPT
104.10; HRMS (ESI) m/z calcd for C12H12ClN2 (M+H)+
219.06835, found 219.06804; IR (cm-1): 3413, 2277, 2360, 2342,
1582, 1489, 1154, 785, 694.
+
4.29. N1-(p-tolyl)benzene-1,3-diamine (5c)
Follow general procedure A, using 3-bromonitrobenzene 2f
(55.5 mg, 0.275 mmol, 1.1 eq.) and p-toluidine 1b (26.8 mg, 0.25
mmol, 1.0 eq.) as starting material, purification by flash
chromatography on silica gel using petroleum ether : ethyl
acetate = 3 : 1. 5c was obtained as yellow solid (26.8 mg, isolated
4.25. 2-fluoro-N1-phenylbenzene-1,4-diamine (4b)
Follow
general
procedure
A,
using
4-bromo-3-
fluoronitrobenzene 2c (60.5 mg, 0.275 mmol, 1.1 eq.) as starting
material, purification by flash chromatography on silica gel using
petroleum ether : ethyl acetate = 3 : 1. 4b was obtained as gray
solid (28.8 mg, isolated yield 57%); Melting point (oC): 86.2-
87.4; 1H NMR (400 MHz, CDCl3) δ 7.20 (t, J = 7.6 Hz, 2H), 7.11
(t, J = 8.4 Hz, 1H), 6.83 (dd, J = 11.6, 7.2 Hz, 3H), 6.48 (d, J =
12.0 Hz, 1H), 6.42 (d, J = 8.4 Hz, 1H), 5.32 (s, 1H), 3.61 (s, 2H);
13C NMR (101 MHz, CDCl3) δ 156.46 (d, J = 241 Hz), 145.27,
143.26 (d, J = 10 Hz), 129.27, 124.70 (d, J = 3 Hz), 121.19 (d, J
= 13 Hz), 119.57, 115.28, 110.94 (d, J = 3 Hz), 103.28 (d, J = 23
Hz); 19F NMR (376 MHz, CDCl3) δ -126.28; HRMS (ESI) m/z
yield 54%); Melting point (oC): 86.5-88.1; H NMR (400 MHz,
1
CDCl3) δ 7.08 (d, J = 8.0 Hz, 2H), 7.04ꢁ6.98 (m, 3H), 6.40
(ddd, J = 1.2, 2.4, 3.2 Hz, 1H), 6.36 (t, J = 2.0 Hz, 1H), 6.22
(ddd, J = 0.8, 2.0, 2.8 Hz, 1H), 5.51 (s, 1H), 3.32 (s, 2H), 2.30 (s,
3H); 13C NMR (101 MHz, CDCl3) δ 147.49, 145.22, 140.24,
130.97, 130.19, 129.82, 119.44, 107.57, 107.48, 103.13, 20.72;
HRMS (ESI) m/z calcd for C13H15N2 (M+H)+ 199.1152, found
+
199.1155.
4.30. N1-(4-methoxyphenyl)benzene-1,3-diamine(5d)
+
calcd for C12H12FN2 (M+H)+ 203.09790, found 203.09776; IR
Follow general procedure A, using 3-bromonitrobenzene 2f
(55.5 mg, 0.275 mmol, 1.1 eq.) and 4-methoxyaniline 1d (31.1
mg, 0.25 mmol, 1.0 eq.) as starting material, purification by flash
chromatography on silica gel using petroleum ether : ethyl
acetate = 3 : 1. 5d was obtained as yellow solid (27.8 mg,
isolated yield 52%); Melting point (oC): 67.3-69.0; 1H NMR (400
MHz, CDCl3) δ 7.09 ꢁ 7.03 (m, 2H), 6.99 (t, J = 8.0 Hz, 1H),
6.88 ꢁ 6.82 (m, 2H), 6.31 (ddd, J = 0.8, 2.0, 2.8 Hz, 1H), 6.24
(t, J = 2.4 Hz, 1H), 6.18 (dd, J = 8.0, 1.6 Hz, 1H), 5.35 (s, 1H),
3.79 (s, 3H), 3.25 (s, 2H); 13C NMR (101 MHz, CDCl3) δ 155.31,
147.52, 146.46, 135.69, 130.20, 122.70, 114.61, 106.82, 106.51,
101.99, 55.59; HRMS (ESI) m/z calcd for C13H15N2O+ (M+H)+
215.1101, found 215.1106.
(cm-1): 3362, 3046, 2360, 2342, 1594, 1490, 1268, 817, 743.
4.26. 2-methyl-N1-phenylbenzene-1,4-diamine (4c)
Follow general procedure A, using 2-bromo-5-nitrotoluene 2d
(59.4 mg, 0.275 mmol, 1.1 eq.) as starting material, purification
by flash chromatography on silica gel using petroleum ether :
ethyl acetate = 3 : 1. 4c was obtained as liquid (37.6 mg, isolated
1
yield 76%); H NMR (400 MHz, CDCl3) δ 7.15 (dd, J = 8.4, 7.2
Hz, 2H), 7.00 (d, J = 8.0 Hz, 1H), 6.73 (t, J = 7.2 Hz, 1H), 6.65
(dd, J = 8.8, 1.2 Hz, 2H), 6.58 (d, J = 2.4 Hz, 1H), 6.51 (dd, J =
8.0, 2.4 Hz, 1H), 5.12 (s, 1H), 3.53 (s, 2H), 2.14 (s, 3H); 13C
NMR (101 MHz, CDCl3) δ 146.95, 143.45, 134.78, 131.59,
129.24, 126.31, 118.25, 117.60, 114.29, 113.62, 18.05; HRMS
4.31. N1-(4-(trifluoromethyl)phenyl)benzene-1,3-diamine (5e)
+
(ESI) m/z calcd for C13H15N2 (M+H)+ 199.12297, found
199.12285; IR (cm-1): 3424, 2360, 2342, 1626, 1505, 1299, 741.
Follow general procedure A, using 3-bromonitrobenzene 2f
(55.5 mg, 0.275 mmol, 1.1 eq.) and 4-(trifluoromethyl)aniline 1i
(31.3 μL, 0.25 mmol, 1.0 eq.) as starting material, purification
by flash chromatography on silica gel using petroleum ether :
ethyl acetate = 3 : 1. 5e was obtained as white solid (31.5 mg,
isolated yield 50%); 1H NMR (400 MHz, CDCl3) δ 7.45 (d, J =
8.4 Hz, 2H), 7.10 (t, J = 7.6 Hz, 1H), 7.04 (d, J = 8.4 Hz, 2H),
6.56 ꢁ 6.50 (m, 1H), 6.48 (t, J = 2.4 Hz, 1H), 6.38 (ddd, J =
8.0, 2.0, 0.8 Hz, 1H), 5.83 (s, 1H), 3.64 (s, 2H); 13C NMR (101
MHz, CDCl3) δ 147.64, 146.76, 142.32, 130.40, 126.63 (q, J =
4 Hz), 124.67 (q, J = 269 Hz), 121.52 (q, J = 32 Hz), 115.71,
110.25, 109.87, 106.21; 19F NMR (376 MHz, CDCl3) δ -61.44;
HRMS (ESI) m/z calcd for C13H12F3N2+ (M+H)+ 253.0869, found
253.0806.
4.27. N1-phenylbenzene-1,3-diamine (5a)
Follow general procedure A, using 3-bromonitrobenzene 2f
(55.5 mg, 0.275 mmol, 1.1 eq.) and aniline 1a (23.3 μL, 0.25
mmol, 1.0 eq.) as starting material, purification by flash
chromatography on silica gel using petroleum ether : ethyl
acetate = 3 : 1. 5a was obtained as gray solid (25.4 mg, isolated
1
yield 55%); Melting point (oC): 60.5-61.7; H NMR (400 MHz,
CDCl3) δ 7.28 – 7.22 (m, 2H), 7.04 (dd, J = 16.0, 7.6 Hz, 3H),
6.92 (t, J = 7.2 Hz, 1H), 6.46 (ddd, J = 0.8, 2.4, 2.8 Hz, 1H), 6.41
(t, J = 2.4 Hz, 1H), 6.26 (dd, J = 8.0, 1.6 Hz, 1H), 5.60 (s, 1H),
3.55 (s, 2H); 13C NMR (101 MHz, CDCl3) δ 147.52, 144.36,
143.08, 130.22, 129.30, 121.01, 118.33, 108.37, 108.11, 104.03;
+
HRMS (ESI) m/z calcd for C12H13N2 (M+H)+ 185.10732, found
Follow general procedure A, using LiOt-Bu (70.0 mg, 0.875
185.10721; IR (cm-1): 3415, 3379, 2360, 2342, 1588, 1494, 1152,
762, 691.
mmol, 3.5 eq.) as base for 6a, 6b, 6c, 6d.
4.32. N1-phenylbenzene-1,2-diamine(6a)
4.28. 5-chloro-N1-phenylbenzene-1,3-diamine (5b)
Follow general procedure A, using 2-bromo nitrobenzene 2h
(55.5 mg, 0.275 mmol, 1.1 eq.) and aniline 1a (23.3 ꢀL, 0.25
mmol, 1.0 eq.) as starting material, purification by flash
chromatography on silica gel using petroleum ether : ethyl
acetate = 4 : 1. 6a was obtained as white solid (17.9 mg, isolated
Follow general procedure A, using 1-bromo-3-chloro-5-
nitrobenzene 2g (147.8 mg, 0.25 mmol, 2.5 eq.) and aniline 1a
(23.3 ꢀL, 0.25 mmol, 1.0 eq.) as starting material, purification by
flash chromatography on silica gel using petroleum ether : ethyl
acetate = 2 : 1. 5b was obtained as gray solid (30.0 mg, isolated
1
yield 39%); Melting point (oC): 77.2-80.5; H NMR (400 MHz,
1
yield 55%); Melting point (oC): 57.6-60.4; H NMR (400 MHz,
CDCl3) δ 7.23 ꢁ 7.17 (m, 2H), 7.12 (dd, J = 7.6, 1.6 Hz, 1H),
7.04 ꢁ 6.98 (m, 1H), 6.84 ꢁ 6.78 (m, 2H), 6.78 ꢁ 6.72 (m,
3H), 5.16 (s, 1H), 3.48 (s, 2H); 13C NMR (101 MHz, CDCl3) δ
144.31, 140.92, 128.28, 127.49, 124.69, 123.86, 118.27, 118.11,
CDCl3) δ 7.25 (t, J = 8.0 Hz, 1H), 7.04 (dd, J = 14.4, 7.2 Hz,
3H), 6.91 (t, J = 7.2 Hz, 1H), 6.45 (dd, J = 8.0, 2.0 Hz, 1H), 6.39
(t, J = 2.0 Hz, 1H), 6.25 (dd, J = 7.6, 1.6 Hz, 1H), 5.61 (s, 1H),
3.46 (s, 2H); 13C NMR (101 MHz, CDCl3) δ 147.56, 144.38,