The Journal of Organic Chemistry
Page 6 of 11
– 7.33 (m, 4H), 6.77 – 6.76 (m, 1H), 6.25 – 6.20 (m, 2H), 3.52
1H), 6.75 (m, 1H), 6.60 – 6.58 (m, 1H), 6.20 – 6.19 (m, 1H),
(s, 3H); 13C{1H} NMR (150 MHz, Chloroform-d) δ 146.6,
132.2, 128.3, 128.0, 126.5, 126.0, 122.6, 120.2, 119.80 (q, J =
257.8 Hz), 109.6, 107.2, 33.9; 19F NMR (400 MHz, Chloro-
form-d) δ 107.6; HRMS (ESI) m/z calcd for C12H10F3NO
[M+H]+: 242.0787, found 242.0778.
4.01 (s, 3H); 13C{1H} NMR (150 MHz, Chloroform-d) δ 152.8,
1
2
3
4
5
6
7
8
148.6, 136.3, 132.4, 126.5, 121.6, 120.3, 110.8, 107.8, 36.9.
2-(1-Methyl-1H-pyrrol-2-yl)pyrazine (3ra).26 Yellow oil
(21.3 mg, 67%); Rf = 0.4 (PE/EA=50/1); LC-MS (ESI) [M+1]+
160.0; 1H NMR (400 MHz, Chloroform-d) δ 8.83 (m, 1H), 8.44
(m, 1H), 8.28 – 8.27 (m, 1H), 6.80 – 6.79 (m, 1H), 6.73 – 6.71
(m, 1H), 6.22 – 6.20 (m, 1H), 3.99 (s, 3H); 13C{1H} NMR (150
MHz, Chloroform-d) δ 148.6, 142.9, 142.8, 140.2, 128.9, 127.9,
111.9, 108.3, 37.2.
1-Methyl-2-(m-tolyl)-1H-pyrrole (3ka).22 White solid (25.7
mg, 75%); Rf = 0.4 (PE/EA=200/1); LC-MS (ESI) [M+1]+
1
172.1; H NMR (400 MHz, Chloroform-d) δ 7.35 – 7.31 (m,
1H), 7.27 – 7.24 (m, 2H), 7.17 – 7.15 (m, 1H), 6.75 (m, 1H),
6.26 – 6.24 (m, 2H), 3.70 (s, 3H), 2.43 (s, 3H); 13C{1H} NMR
(150 MHz, Chloroform-d) δ 137.9, 134.7, 133.3, 129.4, 128.2,
127.5, 125.7, 123.5, 108.5, 107.7, 35.0, 21.5.
9
2-(1-Methyl-1H-pyrrol-2-yl)quinolone (3sa).27 Yellow solid
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
(19.2 mg, 46%); Rf = 0.4 (PE/EA=50/1); LC-MS (ESI) [M+1]+
1
209.1; H NMR (400 MHz, Chloroform-d) δ 8.08 – 8.06 (m,
1-Methyl-2-(3-(trifluoromethoxy)phenyl)-1H-pyrrole (3la).
Yellow oil (41.0 mg, 85%); Rf = 0.4 (PE/EA=100/1); LC-MS
(ESI) [M+1]+ 242.1; 1H NMR (400 MHz, Chloroform-d) δ 7.44
– 7.39 (m, 1H), 7.35 – 7.33 (m, 1H), 7.26 (s, 1H), 7.16 – 7.14
(m, 1H), 6.75 – 6.74 (m, 1H), 6.28 (d, J = 1.9 Hz, 1H), 6.22 (d,
J = 2.6 Hz, 1H), 3.68 (s, 3H); 13C{1H} NMR (150 MHz, Chlo-
roform-d) δ 149.3, 135.3, 133.0, 129.7, 126.7, 124.5, 120.9,
120.5 (q, J = 256.8 Hz), 118.9, 109.5, 108.1, 35.1; 19F NMR
(400 MHz, Chloroform-d) δ 107.1; HRMS (ESI) m/z calcd for
C12H10F3NO [M+H]+: 242.0787, found 242.0777.
2H), 7.77 – 7.66 (m, 3H), 7.49 – 7.45 (m, 1H), 6.83 – 6.81 (m,
2H), 6.26 – 6.25 (m, 1H), 4.22 (s, 3H); 13C{1H} NMR (150
MHz, Chloroform-d) δ 151.1, 146.5, 134.9, 131.1, 128.4, 127.9,
126.7, 126.4, 125.0, 124.5, 119.1, 111.4, 106.8, 36.6.
1-Methyl-2-(thiophen-2-yl)-1H-pyrrole (3ta).28 Yellow oil
(20.9 mg, 64%); Rf = 0.4 (PE/EA=200/1); LC-MS (ESI) [M+1]+
164.0; 1H NMR (400 MHz, Chloroform-d) δ 7.25 (m, 1H), 7.07
– 7.05 (m, 1H), 7.03 – 7.01 (m, 1H), 6.71 – 6.70 (m, 1H), 6.33
– 6.32 (m, 1H), 6.17 – 6.15 (m, 1H), 3.72 (s, 3H); 13C{1H} NMR
(150 MHz, Chloroform-d) δ 135.0, 127.3, 127.1, 124.9, 124.5,
123.9, 110.0, 107.9, 35.2.
2-(2,4-Dimethylphenyl)-1-methyl-1H-pyrrole (3ma). Yellow
oil (27.4 mg, 74%); Rf = 0.4 (PE/EA=100/1); LC-MS (ESI)
[M+1]+ 186.1; 1H NMR (400 MHz, Chloroform-d) δ 7.19 – 7.15
(m, 2H), 7.08 (m, 1H), 6.75 – 6.74 (m, 1H), 6.25 (dd, J = 3.6,
1.9 Hz, 1H), 6.10 (d, J = 3.5 Hz, 1H), 3.44 (s, 3H), 2.41 (s, 3H),
2.21 (s, 3H); 13C{1H} NMR (150 MHz, Chloroform-d) δ 137.0,
136.6, 132.3, 130.1, 129.7, 129.2, 125.1, 120.5, 107.4, 106.2,
33.0, 20.1, 18.9; HRMS (ESI) m/z calcd for C13H15N [M+H]+:
186.1277, found 186.1278.
2-(3,5-Dimethylphenyl)-1-methyl-1H-pyrrole (3na).23 Color-
less oil (28.2 mg, 76%); Rf = 0.4 (PE/EA=200/1); LC-MS (ESI)
[M+1]+ 186.1; 1H NMR (400 MHz, Chloroform-d) δ 7.05 (s,
2H), 6.98 (s, 1H), 6.72 (m, 1H), 6.22 (m, 2H), 3.68 (s, 3H), 2.38
(s, 6H); 13C{1H} NMR (150 MHz, Chloroform-d) δ 137.2,
134.2, 132.7, 127.9, 125.9, 122.8, 107.8, 107.0, 34.4, 20.8.
1-Methyl-2-(naphthalen-2-yl)-1H-pyrrole (3oa).24 White
solid (31.1 mg, 75%; using 2-bromonaphthalene as the sub-
strate, yield=45%); Rf = 0.4 (PE/EA=200/1); LC-MS (ESI)
[M+1]+ 208.1; 1H NMR (400 MHz, Chloroform-d) δ 7.89 – 7.85
(m, 4H), 7.59 – 7.57 (m, 1H), 7.52 – 7.49 (m, 2H), 6.79 (m, 1H),
6.37 – 6.36 (m, 1H), 6.28 – 6.27 (m, 1H), 3.76 (s, 3H); 13C{1H}
NMR (150 MHz, Chloroform-d) δ 134.6, 133.4, 132.2, 130.8,
127.9, 127.9, 127.7, 127.1, 126.9, 126.3, 125.8, 123.9, 109.2,
108.0, 35.2.
1,1'-Biphenyl (3ab).29 White solid (23.4 mg, 76%); Rf = 0.5
1
(PE/EA=200/1); H NMR (400 MHz, Chloroform-d) δ 7.65 –
7.62 (m, 4H), 7.50 – 7.46 (m, 4H), 7.40 – 7.36 (m, 2H); 13C{1H}
NMR (150 MHz, Chloroform-d) δ 141.3, 128.8, 127.3, 127.12.
2,5-Dimethoxy-1,1'-biphenyl (3ac).30 White solid (32.1 mg,
1
75%); Rf = 0.4 (PE/EA=100/1); H NMR (400 MHz, Chloro-
form-d) δ 7.55 – 7.52 (m, 2H), 7.44 – 7.40 (m, 2H), 7.36 – 7.33
(m, 1H), 6.94 – 6.91 (m, 2H), 6.88 – 6.84 (m, 1H), 3.81 (s, 3H),
3.76 (s, 3H); 13C{1H} NMR (150 MHz, Chloroform-d) δ 153.8,
150.8, 138.4, 131.8, 129.5, 128.0, 127.1, 116.8, 113.2, 112.8,
56.4, 55.8.
2,5-Difluoro-1,1'-biphenyl (3ad).31 Colorless oil (25.8 mg,
1
68%); Rf = 0.4 (PE/EA=200/1); H NMR (400 MHz, Chloro-
form-d) δ 7.57 – 7.54 (m, 2H), 7.49 – 7.41 (m, 3H), 7.17 – 7.12
(m, 2H), 7.02 – 7.00 (m, 1H); 13C{1H} NMR (150 MHz, Chlo-
roform-d) δ 158.8 (d, J = 242.3 Hz), 155.8 (d, J = 243.6 Hz),
134.8, 130.4 (dd, J = 16.1, 8.1 Hz), 128.9 (d, J=3.1 Hz), 128.6,
128.2, 117.3 (dd, J=26.0, 8.8 Hz), 116.9 (dd, J = 25.2, 4.5 Hz),
115.15 (dd, J = 23.8, 8.5 Hz).
The mixture of 2-methoxy-1,1'-biphenyl, 3-methoxy-1,1'-bi-
phenyl and 4-methoxy-1,1'-biphenyl (3ae).29 Colorless oil (26.2
1
mg, 71%, o/m/p=4/1.5/1); Rf = 0.4 (PE/EA=200/1); H NMR
(400 MHz, Chloroform-d) δ 7.59 – 7.17 (m, 7H), 7.12 – 6.75
(m, 2H), 3.80 – 3.62 (m, 3H).
3-(1-Methyl-1H-pyrrol-2-yl)-9-phenyl-9H-carbazole (3pa).
White solid (50.3 mg, 78%); Rf = 0.4 (PE/EA=50/1); LC-MS
(ESI) [M+1]+ 323.0; 1H NMR (400 MHz, Chloroform-d) δ 8.22
– 8.20 (m, 2H), 7.66 – 7.64 (m, 4H), 7.51 – 7.47 (m, 5H), 7.36
– 7.34 (m, 1H), 6.81 (d, J = 2.7 Hz, 1H), 6.36 – 6.32 (m, 2H),
3.75 (s, 3H); 13C{1H} NMR (150 MHz, Chloroform-d) δ 140.2,
138.9, 136.5, 134.3, 128.9, 126.5, 126.2, 126.0, 125.1, 124.3,
122.3, 122.2, 121.8, 119.6, 119.3, 119.0, 108.9, 108.5, 107.3,
106.6, 33.9; HRMS (ESI) m/z calcd for C23H18N2 [M+H]+:
323.1543, found 323.1540.
The mixture of 1,1':2',1''-terphenyl, 1,1':3',1''-terphenyl and
1,1':4',1''-terphenyl (3af).32 Yellow oil (23.9 mg, 52%,
o/m/p=9/3/1); Rf = 0.4 (PE/EA=100/1).
The mixture of 1-phenylnaphthalene and 2-phenylnaphtha-
lene (3ag).29 Rf = 0.4 (PE/EA=100/1). Yellow oil (24.5 mg,
60%,1/1.2).
2-Phenylpyrimidine (3ah).33 Colorless oil (17.8 mg, 57%); Rf
1
= 0.4 (PE/EA=50/1); LC-MS (ESI) [M+1]+ 157.0; H NMR
(400 MHz, Chloroform-d) δ 8.81 (d, J = 4.8 Hz, 2H), 8.45 –
8.43 (m, 2H), 7.51 – 7.49 (m, 3H), 7.19 (t, J = 4.8 Hz, 1H);
13C{1H} NMR (150 MHz, Chloroform-d) δ 164.9, 157.4, 137.7,
130.9, 128.7, 128.3, 119.2.
2-(1-Methyl-1H-pyrrol-2-yl)pyridine (3qa).25 Yellow oil
(25.0 mg, 79%); Rf = 0.4 (PE/EA=50/1); LC-MS (ESI) [M+1]+
1
159.0; H NMR (400 MHz, Chloroform-d) δ 8.58 – 8.56 (m,
1H), 7.66 – 7.61 (m, 1H), 7.55 – 7.53 (m, 1H), 7.09 – 7.06 (m,
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