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3.9. Synthesis of (Z)-1-chloro-1,2-difluoro-2-(4-methoxyphenyl)
ethene (7)
3.11. Synthesis of (Z)-1-chloro-1,2-difluoro-2-(4-
fluorophenyl)ethene (9)
Similar to the procedure described in Section 3.6. 4-Iodoanisole
(1.17 g, 5 mmol), DMF (2 mL), Pd(PPh3)4 (0.3 g, 0.25 mmol), and 1
(9.8 mL, 6 mmol, 0.61 M) were stirred for 5 h at 85 8C. Hexane and
ethyl acetate (3:1) was used as an eluent to isolate 7 as a colorless
liquid (0.88 g, 4.3 mmol, 86% isolated yield, Rf = 0.35, purity by 1H
NMR = 97%); 1H NMR (CDCl3): 7.49 (broad d, 3JHH = 8.7 Hz, 2H), 6.93
(broad d, 3JHH = 8.6 Hz, 2H), 3.83 (s, 3H); 13C NMR (CDCl3): 145.3 (dd,
1JCF = 234.3 Hz, 2JCF = 43.8 Hz), 137.5 (dd, 1JCF = 290.4 Hz,
Similar to the procedure described in Section 3.6. 1-Fluoro-4-
iodobenzene (1.11 g, 5 mmol), DMF (2 mL), Pd(PPh3)4 (0.3 g,
0.25 mmol), and 1 (9.5 mL, 6 mmol, 0.63 M) gave after silica gel
chromatographic isolation
9 as a colorless liquid (0.88 g,
4.55 mmol, 91% isolated yield, Rf = 0.7, purity by 1H NMR = 98%);
1H NMR (CDCl3): 7.56 (ddd, 3JHH = 9.2 Hz, 4JHF = 5.3 Hz,
4JHF = 3.0 Hz, 2H), 7.13 (ddd, 3JHH = 9.0 Hz, 3JHF = 8.6 Hz,
5JHF = 2.2 Hz, 2H); 13C NMR (CDCl3): 144.6 (dd, JCF = 235.1 Hz,
1
2
3
2JCF = 60.3 Hz), 120.8 (dd, JCF = 24.8 Hz, JCF = 6.6 Hz), 126.8 (dd,
2JCF = 43.2 Hz), 138.6 (ddd, 1JCF = 292.0 Hz, 2JCF = 59.2 Hz,
4
4
3JCF = 7.6 Hz, JCF = 5.9 Hz), 114.1 (d, JCF = 2.16 Hz), 160.3 (d,
5JCF = 2.5 Hz), 55.3 (s); 19F NMR (CDCl3): ꢀ121.4 (d, 3JFF = 126.6 Hz,
1F), ꢀ147.5 (d, 3JFF = 126.5 Hz, 1F); GC–MS, m/z (relative intensity):
206 (M++2, 35), 204 (M+, 100); HRMS: C9H7OF235Cl (calculated:
204.0153; found: 204.0154).
2
3
4
5JCF = 2.2 Hz), 124.4 (ddd, JCF = 24.4 Hz, JCF = 6.7 Hz, JCF = 3.3),
3
3,4
2
127.3 (dt, JCF = 8.2 Hz,
J
CF
= 6.5 Hz), 115.9 (dd, JCF = 21.9 Hz,
4JCF = 1.8 Hz), 163.0 (dd, JCF = 250.7 Hz, JCF = 2.7 Hz); 19F NMR
1
5
3
3
(CDCl3): ꢀ119.3 (d, JFF = 127.2 Hz, 1F), ꢀ147.6 (d, JFF = 127.2 Hz,
1F), ꢀ110.7 (m, 1F); GC–MS, m/z (relative intensity): 194 (M++2,
49), 192 (M+, 76), 157 (100), 137 (61); HRMS: C8H4F335Cl
(calculated: 191.9954; found: 191.9955).
3.12. Synthesis of (Z)-1-chloro-1,2-difluoro-2-(3-
trifluoromethylphenyl)ethene (10)
A minor amount (2%) of byproduct, (1Z,3E)-1-chloro-1,2,3,4-
tetrafluoro-4-(4-methoxyphenyl)butadiene was detected by 19F
3
5
NMR (CDCl3): ꢀ108.0 (ddd, JF(1,2) = 132.6 Hz, JF(1,4) = 26.9 Hz,
3
3
4JF(1,3) = 13.4 Hz, 1F), ꢀ153.7 (ddd, JF(2,1) = 132.2 Hz, JF(2,3)
=
4
3
35.9 Hz, JF(2,4) = 12.2 Hz, 1F), ꢀ163.0 (ddd, JF(3,4) = 130.0 Hz,
3JF(3,2) = 35.9 Hz,
4JF(3,1) = 13.2 Hz,
1F),
ꢀ139.6
(ddd,
3JF(4,3) = 131.4 Hz, 5JF(4,1) = 27.2 Hz, 4JF(4,2) = 11.9 Hz, 1F).
Similar to the procedure described in Section 3.6. 3-Iodoben-
zotrifluoride (1.36 g, 5 mmol), DMF (2 mL), Pd(PPh3)4 (0.3 g,
0.25 mmol), and 1 (9.8 mL, 6 mmol, 0.61 M) gave after silica gel
3.10. Synthesis of (Z)-1-chloro-1,2-difluoro-2-(3-methoxyphenyl)
ethene (8)
chromatographic isolation 10 as
a colorless liquid (1.07 g,
4.4 mmol, 88% isolated yield, Rf = 0.65, purity by 1H
NMR = 98%); 1H NMR (CDCl3): 7.82 (broad s, 1H), 7.74 (broad d,
0
3JHH = 7.9 Hz, 1H), 7.56 (broad t, 3,3 JHH = 7.9 Hz, 1H), 7.64 (broad d,
3JHH = 7.9 Hz, 1H); 13C NMR (CDCl3): 144.2(dd, JCF = 235.6 Hz,
1
1
2
2JCF = 43.1 Hz), 140.0 (dd, JCF = 294.1 Hz, JCF = 58.5 Hz), 129.1
(dd, 2JCF = 24.3 Hz, 3JCF = 6.7 Hz), 122.0 (qd, 3JCF = 5.8 Hz,
3JCF = 3.2 Hz), 131.5 (qd, 2JCF = 32.9 Hz, 4JCF = 2.4 Hz), 126.1 (broad
3
4
3
q, JCF = 2.1 Hz), 129.4 (d, JCF = 2.0 Hz), 128.1 (dd, JCF = 7.0 Hz,
4JCF = 6.3 Hz), 123.7 (q, 1JCF = 272.6 Hz); 19F NMR (CDCl3): ꢀ116.1
(d, 3JFF = 127.1 Hz, 1F), ꢀ149.0 (d, 3JFF = 126.7 Hz, 1F), ꢀ63.5(s, 3F);
GC–MS, m/z (relative intensity): 244 (M++2, 10), 242 (M+, 42), 69
(100); HRMS: C9H4F535Cl (calculated: 241.9922; found:
241.9912).
Similar to the procedure described in Section 3.6. 3-Iodoanisole
(0.6 mL, 1.17 g, 5 mmol), DMF (2 mL), Pd(PPh3)4 (0.3 g, 0.25 mmol),
and 1 (9.5 mL, 6 mmol, 0.63 M) were stirred for 5 h at 85 8C. Hexane
andethyl acetate (3:1)wasused asan eluent toisolate8as a colorless
liquid (1.0 g, 4.9 mmol, 97% isolated yield, Rf = 0.35, purity by 1H
NMR = 99%); 1H NMR (CDCl3): 7.15 (dd, 4JHH = 2.4 Hz, 5JHH = 2.0 Hz,
3
6
7
1H), 6.99 (ddd, JHH = 8.3 Hz, JHF = 2.6 Hz, JHF = 0.9 Hz, 1H), 7.40
(broad t, 3JHH = 8.0 Hz, 1H), 7.22 (dm, 3JHH = 7.9 Hz, 1H), 3.88 (s, 3H);
3.13. Synthesis of (Z)-1-chloro-1,2-difluoro-2-(2-thienyl)ethene (11)
1
2
13C NMR (CDCl3): 145.1 (dd, JCF = 235.3 Hz, JCF = 43.0 Hz), 139.0
1
2
2
(dd, JCF = 293.0 Hz, JCF = 59.5 Hz), 129.4 (dd, JCF = 24.0 Hz,
3JCF = 6.7 Hz), 117.7 (dd, JCF = 9.1 Hz, JCF = 6.7 Hz), 159.7 (d,
3
4
4JCF = 2.1 Hz), 115.3 (d, JCF = 1.5 Hz), 129.8 (d, JCF = 1.4 Hz), 110.6
5
4
(dd, 3JCF = 7.8 Hz, 4JCF = 7.1 Hz), 55.3 (s); 19F NMR (CDCl3): ꢀ117.6 (d,
3JFF = 126.5 Hz, 1F), ꢀ147.6 (d, JFF = 126.5 Hz, 1F); GC–MS, m/z
3
(relativeintensity):206(M++2, 23), 204(M+, 100), 161 (39), 125(45);
HRMS: C9H7OF235Cl (calculated: 204.0153; found: 204.0152).
Similar to the procedure described in Section 3.6. 2-Iodothio-
phene (0.63 g, 3 mmol), DMF (1.5 mL), Pd(PPh3)4 (0.17 g,