Page 5 of 9
The Journal of Organic Chemistry
4,4'-bis(trifluoromethyl)-1,1'-biphenyl (10)22 Yield: 209.0
mg, 72% (X = I); 145.1 mg, 50% (X = Br). H NMR (400 MHz,
CDCl3) : 7.77-7.71 (m, 8H). 13C{1H} NMR (101 MHz, CDCl3)
: 143.4, 130.5 (q, J = 32.7 Hz), 127.8, 126.1 (q, J = 3.7 Hz),
124.1 (q, J = 272.0 Hz). 19F NMR (377 MHz, CDCl3) : -62.56.
GC-MS: rt = 7.16 min, m/z = 290. Column chromatography:
SiO2, n-Pentane 100%.
CDCl3) : 7.59 (d, J = 7.1 Hz, 4H), 7.44 (t, J = 7.6 Hz, 4H), 7.34
(t, J = 7.4 Hz, 2H). 13C{1H} NMR (101 MHz, CDCl3) : 141.4,
128.9, 127.43, 127.35. GC-MS: rt = 7.17 min, m/z = 154.
Column chromatography: SiO2, n-Pentane 100%.
1
1
2
3
4
5
6
7
8
4,4'-dimethyl-1,1'-biphenyl (2).22 Yield: 154.9 mg, 85% (X =
Br). 1H NMR (400 MHz, CDCl3) : 7.56 (d, J = 8.1, 4H), 7.31
(d, J=8.1, 4H), 2.46 (s, 6H). 13C{1H} NMR (101 MHz, CDCl3)
: 138.4, 136.9, 129.6, 127.0, 21.3. GC-MS: rt = 8.36 min, m/z
= 182. Column chromatography: SiO2, n-Pentane 100%.
3,3'-bis(trifluoromethyl)-1,1'-biphenyl (11)22 Yield: 232.2
mg, 80% (X = I); 203.1 mg, 70% (X = Br). 1H NMR (400 MHz,
CDCl3) : 7.85 (d, J = 0.5 Hz, 2H), 7.79 (d, J = 7.7 Hz, 2H),
7.68 (d, J = 7.8 Hz, 2H), 6.61 (t, J = 7.7 Hz, 2H). 13C{1H} NMR
(101 MHz, CDCl3) : 140.8, 131.7 (q, J = 32.4 Hz), 130.7,
129.7, 124.9 (q, J = 3.7 Hz), 124.23 (q, J = 272.4 Hz), 124.20
(q, J = 3.8 Hz). 19F NMR (377 MHz, CDCl3) : -62.68. GC-MS:
rt = 6.94 min, m/z = 290. Column chromatography: SiO2, n-
Pentane 100%.
9
3,3'-dimethyl-1,1'-biphenyl (3).22 Yield: 164.0 mg, 90% (X =
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
1
Br). H NMR (400 MHz, CDCl3) : 7.46-7.44 (m, 4H), 7.37 (t,
J = 7.5, 2H), 7.21 (t, J = 7.5, 2H), 2.47 (s, 6H). 13C{1H} NMR
(101 MHz, CDCl3) : 141.5, 138.4, 128.8, 128.14, 128.08,
124.5, 21.7. GC-MS: rt = 8.24 min, m/z = 182. Column
chromatography: SiO2, n-Pentane 100%.
2,2'-dimethyl-1,1'-biphenyl (4).22 Yield: 127.6 mg, 70% (X =
2,2'-bis(trifluoromethyl)-1,1'-biphenyl (12)22 Yield: 145.1
1
Br). H NMR (400 MHz, CDCl3) : 7.28 – 7.19 (m, 6H), 7.10
mg, 50% (X = I); 87.1 mg, 30% (X = Br); 185.7 mg, 64% (X =
(d, J = 6.8 Hz, 2H), 2.06 (s, 6H). 13C{1H} NMR (101 MHz,
CDCl3) : 141.8, 136.0, 130.0, 129.5, 127.3, 125.7, 20.0. GC-
MS: rt = 7.36 min, m/z = 182. Column chromatography: SiO2,
n-Pentane 100%.
1
H). H NMR (400 MHz, CDCl3) : 7.76 (dd, J = 7.6, 1.5 Hz,
2H), 7.54 (dd, J = 7.5, 1.5 Hz 4H), 7.31 (d, J = 7.5 Hz, 2H).
13C{1H} NMR (101 MHz, CDCl3) : 137.7, 131.7, 130.8, 129.0
(q, J = 30.1 Hz), 128.3, 126.2 (m), 124.1 (q, J = 274.2 Hz). 19
F
4,4'-dimethoxy-1,1'-biphenyl (5)23 Yield: 171.4 mg, 80% (X =
Br). 1H NMR (400 MHz, CDCl3) : 7.49 (d, J = 8.8 Hz, 4H),
6.98 (d, J = 8.8 Hz, 4H), 3.86 (s, 6H). 13C{1H} NMR (101 MHz,
CDCl3) : 158.9, 133.7, 127.9, 114.4, 55.5. GC-MS: rt = 9.77
NMR (377 MHz, CDCl3) : -58.12. GC-MS: rt = 7.16 min, m/z
= 290. Column chromatography: SiO2, petrolium ether 100%.
2,2'-bipyridine (13)25 Yield: 93.7 mg, 60% (X = Br). 1H NMR
(400 MHz, CDCl3) : 8.69 (d, J = 4.4 Hz, 2H), 8.40 (d, J = 8.0
Hz, 2H), 7.81 (ddd, J = 7.9, 2.8, 1.4 Hz, 2H), 7.30 (ddd, J = 7.4,
4.8, 1.2 Hz, 2H). 13C{1H} NMR (101 MHz, CDCl3) : 156.3,
149.3, 137.1, 123.9, 121.2. GC-MS: rt = 7.51 min, m/z = 156.
Column chromatography: Al2O3, n-pentane/EtOAc 80/20.
min, m/z
= 214. Column chromatography: SiO2, n-
Pentane/DCM 50/50.
3,3'-dimethoxy-1,1'-biphenyl (6)24 Yield: 203.5 mg, 95% (X =
Br). 1H NMR (400 MHz, CDCl3) : 7.40 (t, J = 7.9 Hz, 2H),
7.23 (d, J = 7.9 Hz, 2H), 7.18 (t, J = 2.4 Hz, 2H), 6.95 (dd, J =
8.2, 2.4 Hz, 2H), 3.90 (s, 6H). 13C{1H} NMR (101 MHz,
CDCl3) : 160.1, 142.8, 129.9, 119.8, 113.1, 112.9, 55.4. GC-
MS: rt = 9.61 min, m/z = 214. HRMS (ESI+) m/z: [M+H]+
Calcd. for C14H15O2 215.1072; Found : 215.1074. Column
chromatography: SiO2, n-Pentane/DCM 50/50.
1
1,1'-biisoquinoline (14)26 Yield: 199.9 mg, 78% (X = I). H
NMR (400 MHz, CDCl3) : 8.72 (d, J = 5.7 Hz, 2H), 7.93 (d, J
= 8.3 Hz, 2H), 7.80 (d, J = 5.7 Hz, 2H), 7.76 (dd, J = 8.5, 0.5
Hz, 2H), 7.69 (ddd, J = 8.3, 6.8, 1.1 Hz, 2H), 7.47 (ddd, J = 8.3,
6.8, 1.2 Hz, 2H). 13C{1H} NMR (101 MHz, CDCl3) : 158.3,
142.1, 136.9, 130.4, 127.9, 127.6, 127.3, 127.0, 121.1. GC-MS:
rt = 12.22 min, m/z = 256. Column chromatography: Al2O3,
petrolium ether/EtOAc 70/30.
2,2'-dimethoxy-1,1'-biphenyl (7)5a Yield: 192.8 mg, 90% (X =
Br); 150.0 mg, 70% (X = H). 1H NMR (400 MHz, CDCl3) :
7.38-7.32 (m, 2H), 7.27 (dd, J = 7.5, 1,7 Hz, 2H), 7.06 – 6.97
(m, 4H), 3.79 (s, 6H). 13C{1H} NMR (101 MHz, CDCl3) :
157.2, 131.6, 128.8, 128.0, 120.5, 111.3, 55.9. GC-MS: rt =
8.67 min, m/z = 214. HRMS (ESI+) m/z: [M+H]+ Calcd. for
1,1':2',1'':2'',1'''-quaterphenyl (15)27 Yield: 291.1 mg, 95%
1
(X = Br). H NMR (400 MHz, CDCl3) : 7.45-7.40 (m, 2H),
7.39-7.31 (m, 4H), 7.20-7.15 (m, 2H), 7.09 (t, J = 7.3 Hz, 2H),
7.01 (t, J = 7.4 Hz, 4H), 6.62 (d, J = 7.2 Hz, 4H). 13C{1H} NMR
(101 MHz, CDCl3) d: 141.2, 141.1, 140.2, 131.9, 130.1, 129.4,
127.63, 127.59, 127.2, 126.1. GC-MS: rt = 11.50 min, m/z =
306. Column chromatography: SiO2, n-Pentane 100%.
C14H15O2 215.1072; Found
:
215.1073. Column
chromatography: SiO2, n-Pentane/DCM 50/50.
4,4'-di-tert-butyl-1,1'-biphenyl (8)24 Yield: 207.8 mg, 78% (X
= Br). 1H NMR (400 MHz, CDCl3) : 7.56 (d, J = 8.4 Hz, 4H),
7.48 (d, J = 8.4 Hz, 4H), 1.39 (s, 18H). 13C{1H} NMR (101
MHz, CDCl3) : 150.1, 138.4, 126.9, 125.8, 34.7, 31.6. GC-MS:
rt = 10.37 min, m/z = 266. Column chromatography: SiO2, n-
Pentane 100%.
1,1'-binaphthalene (16)24 Yield: 234.0 mg, 92% (X = Br). 1H
NMR (400 MHz, CDCl3) : 7.98-7.95 (m, 4H), 7.65-7.57 (m,
2H), 7.52 – 7.47 (m, 4H), 7.41 (d, J = 8.5 Hz, 2H), 7.34-7.28
(m, 2H). 13C{1H} NMR (101 MHz, CDCl3) : 138.7, 133.7,
133.0, 128.3, 128.1, 128.0, 126.8, 126.2, 126.0, 125.6. GC-MS:
rt = 11.41 min, m/z = 254. Column chromatography: SiO2, n-
Pentane 100%.
N4,N4,N4',N4'-tetramethyl-[1,1'-biphenyl]-4,4'-diamine (9)24
Yield: 228.3 mg, 95% (X = Br). 1H NMR (400 MHz, CDCl3)
: 7.49 (d, J = 8.5 Hz, 4H), 6.83 (d, J = 8.5 Hz, 4H), 3.00 (s,
12H). 13C{1H} NMR (101 MHz, CDCl3) : 149.4, 130.0, 127.1,
113.3, 41.0. GC-MS: rt = 11.41 min, m/z = 240. HRMS (ESI+)
m/z: [M+H]+ Calcd. for C16H21N2 241.1705; Found : 241.1703.
Column chromatography: SiO2, n-Pentane/EtOAc 70/30.
1
2,2'-binaphthalene (17)5a Yield: 203.5 mg, 80% (X = Br). H
NMR (400 MHz, CDCl3) : 8.19 (s, 2H), 7.99 – 7.95 (m, 4H),
7.93 – 7.86 (m, 4H), 7.59 – 7.48 (m, 4H). 13C{1H} NMR (101
MHz, CDCl3) : 138.6, 133.9, 132.9, 128.7, 128.4, 127.9,
126.6, 126.3, 126.2, 125.9. GC-MS: rt = 12.78 min, m/z = 254.
Column chromatography: SiO2, n-Pentane 100%.
ACS Paragon Plus Environment