4
Tetrahedron
ACCEPTED MANUSCRIPT
4.2.5. 1-(2-bromo-1-phenylvinyl)-4-(trifluoro-
100 MHz) δ 146.80, 140.71, 139.00, 138.04, 136.48, 133.17,
methyl)benzene (6e)
133.09, 132.92, 132.86, 129.76, 129.03, 128.45, 128.28, 128.22,
1
128.17, 128.06, 128.03, 127.84, 127.73, 127.58, 127.40, 127.01,
126.43, 126.37, 126.19, 125.24, 105.60, 105.49; HRMS (EI): m/z
calcd for C18H13Br: 308.0201; found: 308.0207.
White solid; 62 mg, yield 95%; Z/E isomer ratio: 3:2; H
NMR (CDCl3, 400 MHz) δ 7.68 (s, 0.6H), 7.66 (s, 0.6H), 7.56 (s,
0.4H), 7.54 (s, 0.4H), 7.44-7.41 (m, 2.4H), 7.33-7.28 (m, 3.4H),
7.22-7.09 (m, 1.2H), 6.87 (s, 0.4H), 6.84 (s, 0.6H); 13C NMR
(CDCl3, 100 MHz) δ 145.73, 144.09, 142.73, 139.93, 138.30,
130.11, 129.56, 128.61, 128.47, 128.44, 128.35, 127.86, 127.52,
125.43, 125.39, 125.30, 125.27, 107.32, 106.28; HRMS (EI): m/z
calcd for C15H10F3Br: 325.9918; found: 325.9929.
4.2.11. 4,4'-(2-bromoethene-1,1-diyl)bis(methyl-
benzene) (6k)
White solid; 54 mg, yield 95%; 1H NMR (CDCl3, 400 MHz)
δ 7.19 (s, 4H), 7.09 (s, 4H), 6.68 (s, 1H), 2.38 (s, 3H), 2.32 (s,
3H); 13C NMR (CDCl3, 100 MHz) δ 146.6, 138.2, 138.0, 137.7,
136.2, 129.6, 129.7, 128.9, 127.6, 103.9, 21.4, 21.2; HRMS (EI):
m/z calcd for C16H15Br: 286.0357; found: 286.0364.
4.2.6. 1-(2-bromo-1-phenylvinyl)-3-chlorobenzene
(6f)
1
Colorless oil; 54 mg, yield 93%; Z/E isomer ratio: 1:1; H
4.2.12. 4,4'-(2-bromoethene-1,1-diyl)bis(fluoro-
NMR (CDCl3, 400 MHz) δ 7.41-7.17 (m, 8.5H), 7.08 (d, J = 7.6
Hz, 0.5H), 6.79 (s, 0.5H), 6.79 (s, 0.5H); 13C NMR (CDCl3, 100
MHz) δ 145.66, 145.64, 142.43, 140.78, 140.04, 138.37, 134.40,
134.14, 129.65, 129.62, 129.56, 128.55, 128.37, 128.36, 128.24,
128.15, 127.92, 127.62, 127.52, 125.77, 112.49, 106.49, 106.03;
EI-MS (m/z, %): 169 (M+, 55.27), 178 (100), 292 (42.34), 213
(40.21); HRMS (EI): m/z calcd for C15H10ClBr: 291.9666; found:
291.9660.
benzene) (6l)
White solid; 58 mg, yield 98%; 1H NMR (CDCl3, 400 MHz) δ
7.30-7.26 (m, 2H), 7.17 (m, 2H), 7.09 (m, 2H), 6.99 (m, 2H),
6.71 (s, 1H); 13C NMR (100 MHz, CDCl3) δ 163.92, 163.60,
161.45, 161.14, 144.87, 136.71, 134.68, 131.52, 131.44, 129.33,
129.25, 115.56, 115.47, 115.35, 115.25, 105.16; GC-MS(EI)
(m/z, %): 294 (M+); HRMS (EI): m/z calcd for C14H9F2Br:
293.9856; found: 293.9861.
4.2.13. 4,4'-(2-bromoethene-1,1-diyl)bis(chloro-
benzene) (6m)
4.2.7. 4-(2-bromo-1-phenylvinyl)-1,2-dimethyl-
benzene (6g)
White solid; 62 mg, yield 96%; 1H NMR (CDCl3, 400 MHz)
δ 7.38 (d, J = 8.6 Hz, 2H), 7.2-7.22 (m, 4H), 7.12 (d, J = 8.6 Hz,
2H), 6.77 (s, 1H); 13C NMR (100 MHz, CDCl3) δ 144.69, 138.74,
136.93, 134.35, 134.16, 131.04, 128.81, 128.73, 128.65, 106.14;
HRMS (EI): m/z calcd for C14H9Cl2Br: 325.9265; found:
325.9268.
1
Colorless oil; 55 mg, yield 96%; Z/E isomer ratio: 1:1; H
NMR (CDCl3, 400 MHz) δ 7.41-7.34 (m, 1.5H), 7.32-7.25 (m,
2.5H), 7.19-7.23 (m, 1H), 7.16 (d, J = 8.2 Hz, 0.5H), 7.03-7.06
(m, 1.5H), 6.98 (s, 0.5H), 6.94-6.90 (m, 0.5H), 6.71 (d, J = 1.0
Hz, 1H), 2.29 (s, 1.5H), 2.26 (s, 1.5H), 2.23 (s, 1.5H), 2.21 (s,
1.5H); 13C NMR (CDCl3, 100 MHz) δ 146.87, 146.78, 141.00,
139.26, 138.34, 136.73, 136.58, 136.48, 136.39, 130.62, 129.63,
129.42, 128.71, 128.66, 128.32, 128.25, 128.12, 127.96, 127.81,
127.64, 127.11, 125.12, 104.63, 104.16, 19.78, 19.75, 19.65,
19.48; HRMS (EI): m/z calcd for C16H15Br: 286.0357; found:
286.0362.
4.2.14. 4,4'-(2-bromoethene-1,1-diyl)bis((trifluoro-
methyl)benzene) (6n)
White solid; 70.9 mg, yield 90%; 1H NMR (400 MHz,
CDCl3) δ 7.69 (d, J = 8.1 Hz, 2H), 7.58 (d, J = 7.9 Hz, 2H), 7.43
(d, J = 7.9 Hz, 2H), 7.30 (d, J = 8.1 Hz, 2H), 6.96 (s, 1H); 13C
NMR (100 MHz, CDCl3) δ 144.64, 143.27, 141.93, 130.61,
130.29, 130.06, 127.80, 125.65, 125.62, 125.55, 125.51, 122.55,
108.52; HRMS (EI): m/z calcd for C16H9F6Br: 393.9792; found:
393.9795.
4.2.8. 1-(2-bromo-1-phenylvinyl)-2-methylbenzene
(6h)
1
Colorless oil; 51 mg, yield 94%; Z/E isomer ratio: 4:1; H
NMR (CDCl3, 400 MHz) δ 7.29-7.18 (m, 8H), 7.12-7.15 (m,
1H), 6.92 (s, 0.8H), 6.46 (s, 0.2H), 2.13 (s, 2.4H), 2.03 (s, 0.6H);
13C NMR (CDCl3, 100 MHz) δ146.45, 146.19, 141.08, 139.08,
138.77, 138.34, 136.33, 135.99, 130.52, 130.27, 130.06, 129.34,
129.24, 128.60, 128.21, 128.05, 127.94, 127.90, 126.50, 125.89,
125.79, 106.55, 105.43, 20.19, 19.42; HRMS (EI): m/z calcd for
C15H13Br: 272.0201; found: 272.0194.
4.2.15. (2-chloroethene-1,1-diyl)dibenzene (7a)
Yellow oil; 41 mg, yield 95%; 1H NMR (CDCl3, 400 MHz) δ
7.41-7.26 (m, 8H), 7.21-7.18 (m, 2H), 6.58 (s, 1H); 13C NMR
(100 MHz, CDCl3) δ 143.84, 140.09, 137.55, 129.83, 128.40,
128.18, 128.04, 127.94, 127.69, 115.85; EI-MS (m/z, %): 214
(M+, 80.78), 178 (100), 179 (90.88), 214 (80.78); HRMS (EI):
m/z calcd for C14H11Cl: 214.0549; found: 214.0545.
4.2.16. 1-(2-chloro-1-phenylvinyl)-4-methoxy-
benzene (7b)
4.2.9. 1-(2-bromo-1-phenylvinyl)-2-fluorobenzene
(6i)
1
Colorless oil; 51 mg, yield 94%; Z/E isomer ratio: 3:1; H
Colorless oil; 45 mg, yield 93%; Z/E isomer ratio: 1:1;1H
NMR (CDCl3, 400 MHz) δ 7.39-7.24 (m, 5.5H), 7.24-7.17 (m,
1.1H), 7.12 (d, J = 8.8 Hz, 1.1H), 6.92 (d, J = 8.8 Hz, 1.1H), 6.82
(m, 1.2H), 6.50 (m, 1H), 3.83 (s, 1.5H), 3.78 (s, 1.5H); 13C NMR
(100 MHz, CDCl3) δ 159.50, 159.15, 143.34, 143.30, 140.50,
137.76, 132.65, 131.21, 129.81, 129.74, 128.84, 128.34, 128.13,
127.99, 127.85, 115.06, 114.16, 113.75, 113.49, 55.26, 55.19;
HRMS (EI): m/z calcd for C14H10Cl2: 244.0655; found: 244.0653.
NMR (CDCl3, 400 MHz) δ 7.38-7.11 (m, 9H), 6.93 (s, 0.75H),
6.80 (s, 0.25H); 13C NMR (CDCl3, 100 MHz) δ 161.01, 160.64,
158.53, 158.17, 141.62, 140.86, 139.21, 138.70, 131.42, 131.38,
131.11, 131.07, 131.04, 130.10, 130.02, 129.75, 129.66, 129.12,
128.56, 128.43, 128.32, 128.24, 128.13, 127.99, 126.84, 126.65,
124.17, 124.09, 124.05, 124.00, 116.18, 116.06, 115.96, 115.84,
108.52, 108.46, 108.09; 19F NMR (376 MHz, CDCl3) δ -113.27,
-113.61; EI-MS (m/z, %): 276 (M+, 74.43), 197 (100), 196
(84.29), 276 (74.43); HRMS (EI): m/z calcd for C14H10FBr:
275.9950; found: 275.9942.
4.2.17. (2-chloro-1-phenylvinyl)-4-methylbenzene
(7c)
4.2.10. 2-(2-bromo-1-phenylvinyl)naphthalene (6j)
1
1
Colorless oil; 44 mg, yield 97%; Z/E isomer ratio: 3:2; H
White solid; 61 mg, yield 99%; Z/E isomer ratio: 3:2; H
NMR (CDCl3, 400 MHz) δ 7.39-7.28 (m, 4H), 7.21 (m, 3H), 7.09
(m, 2H), 6.56 (s, 1H), 2.40 (s, 1.2H), 2.35 (s, 1.8H); 13C NMR
(100 MHz, CDCl3) δ 143.57, 143.51, 140.14, 137.80, 137.80,
NMR (CDCl3, 400 MHz) δ 7.80 (m, 3.8H), 7.63 (s, 0.6H), 7.56-
7.20 (m, 7.6H), 6.90 (s, 0.6H), 6.85 (s, 0.4H); 13C NMR (CDCl3,