Page 7 of 11
The Journal of Organic Chemistry
10.8, 3F); HRMS (ESI-TOF) Calcd for C14H18BrF3NO2S+
([M+H]+) 400.0188. Found 400.0189.
7.29-7.39 (m, 3H), 7.49 (ddd, J = 1.4, 7.5, 7.5 Hz, 1H), 7.98
(dd, J = 1.3, 7.9 Hz, 1H); 13C{1H} NMR (100 MHz, CDCl3) δ
= 140.0, 138.1, 135.3, 133.3, 133.0, 130.8, 130.4, 127.4, 127.1,
126.7, 126.4, 126.3, 126.1 (q, 1J(C–F) = 277.2 Hz), 53.1 (q, 4J(C–F)
= 1.7 Hz), 47.4, 42.4 (q, 2J(C–F) = 26.6 Hz), 36.5 (q, 3J(C–F) = 1.4
1
2
3
4
5
6
7
8
2k',
5-bromo-1-(ethylsulfonyl)-3,6-dimethyl-3-(2,2,2-
trifluoroethyl)indoline, colorless oil. 1H NMR (400 MHz,
CDCl3) δ = 1.43 (t, J = 7.4 Hz, 3H), 1.45 (d, J = 0.6 Hz, 3H),
2.37 (s, 3H), 2.41-2.59 (m, 2H), 3.14 (q, J = 7.4 Hz, 2H), 3.81
(d, J = 10.5 Hz, 1H), 4.04 (d, J = 10.5 Hz, 1H), 7.257 (s, 1H),
7.265 (s, 1H); 13C{1H} NMR (100 MHz, CDCl3) δ = 140.2,
138.7, 136.5, 126.7, 125.9 (q, 1J(C–F) = 276.9 Hz), 118.4, 115.4,
62.1 (q, 4J(C–F) = 2.1 Hz), 44.5, 42.7 (q, 2J(C–F) = 27.1 Hz), 40.8
4
Hz), 24.3 (q, J(C–F) = 1.3 Hz), 20.9; 19F NMR (376 MHz,
CDCl3) δ = -59.50 (t, J(H–F) = 11.3, 3F); HRMS (ESI-TOF)
Calcd for C19H21F3NO2S+ ([M+H]+) 384.1240. Found
384.1253.
4c,
4,6-dimethyl-2-(o-tolylsulfonyl)-4-(2,2,2-
9
3
4
(q, J(C–F) = 1.7 Hz), 25.9 (q, J(C–F) = 1.4 Hz), 23.4, 7.7; 19F
NMR (376 MHz, CDCl3) δ = -60.31 (t, J(H–F) = 11.2, 3F);
HRMS (ESI-TOF) Calcd for C14H18BrF3NO2S+ ([M+H]+)
400.0188. Found 400.0189.
trifluoroethyl)-1,2,3,4-tetrahydroisoquinoline, colorless oil. 1H
NMR (400 MHz, CDCl3) δ = 1.39 (d, J = 0.6 Hz, 3H), 2.31 (s,
3H), 2.35-2.51 (m, 2H), 2.66 (s, 3H), 3.00 (d, J = 12.5 Hz,
1H), 3.61 (d, J = 12.4 Hz, 1H), 4.24 (d, J = 14.8 Hz, 1H), 4.50
(d, J = 14.8 Hz, 1H), 6.94 (d, J = 7.9 Hz, 1H), 7.01 (dd, J =
0.8, 7.9 Hz, 1H), 7.09 (s, 1H), 7.31-7.37 (m, 2H), 7.48 (ddd, J
= 1.2, 7.5, 7.5 Hz, 1H), 7.97 (dd, J = 1.1, 8.0 Hz, 1H); 13C{1H}
NMR (100 MHz, CDCl3) δ = 140.0, 138.1, 137.1, 135.4, 133.2,
133.0, 130.4, 128.0, 127.7, 126.7, 126.6, 126.3, 126.1 (q, 1J(C–F)
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
2l,
5-bromo-3,4-dimethyl-1-(methylsulfonyl)-3-(2,2,2-
trifluoroethyl)indoline, colorless oil. 1H NMR (400 MHz,
CDCl3) δ = 1.59 (d, J = 0.8 Hz, 3H), 2.42 (s, 3H), 2.60 (q, J(H–
F) = 11.0 Hz, 2H), 2.92 (s, 3H), 3.64 (d, J = 10.6 Hz, 1H), 4.10
(d, J = 10.6 Hz, 1H), 7.18 (d, J = 8.6 Hz, 1H), 7.46 (d, J = 8.6
Hz, 1H); 13C{1H} NMR (100 MHz, CDCl3) δ = 140.7, 135.2,
4
2
= 277.3 Hz), 53.1 (q, J(C–F) = 1.7 Hz), 47.3, 42.4 (q, J(C–F)
=
3
4
1
26.5 Hz), 36.4 (q, J(C–F) = 1.4 Hz), 24.3 (q, J(C–F) = 1.1 Hz),
134.7, 133.2, 125.9 (q, J(C–F) = 277.1 Hz), 120.9, 112.4, 61.7
21.3, 20.9; 19F NMR (376 MHz, CDCl3) δ = -59.48 (t, J(H–F)
=
3
(q, 4J(C–F) = 2.2 Hz), 42.2 (q, J(C–F) = 1.7 Hz), 41.1 (q, 2J(C–F)
=
11.4, 3F); HRMS (ESI-TOF) Calcd for C20H23F3NO2S+
([M+H]+) 398.1396. Found 398.1394.
26.6 Hz), 34.7, 25.0 (q, J(C–F) = 1.3 Hz), 19.1; 19F NMR (376
MHz, CDCl3) δ = -60.28 (t, J(H–F) = 10.8, 3F); HRMS (ESI-
TOF) Calcd for C13H16BrF3NO2S+ ([M+H]+) 386.0032.
Found 386.0031.
4
4d,
6-chloro-4-methyl-2-(o-tolylsulfonyl)-4-(2,2,2-
trifluoroethyl)-1,2,3,4-tetrahydroisoquinoline, colorless oil. 1H
NMR (400 MHz, CDCl3) δ = 1.40 (d, J = 0.6 Hz, 3H), 2.31-
2.54 (m, 2H), 2.66 (s, 3H), 3.00 (d, J = 12.6 Hz, 1H), 3.62 (d,
J = 12.6 Hz, 1H), 4.24 (d, J = 15.2 Hz, 1H), 4.51 (d, J = 15.2
Hz, 1H), 7.01 (d, J = 8.3 Hz, 1H), 7.18 (dd, J = 2.1, 8.3 Hz,
1H), 7.28 (d, J = 2.0 Hz, 1H), 7.33-7.39 (m, 2H), 7.50 (ddd, J
= 1.3, 7.5, 7.5 Hz, 1H), 7.97 (dd, J = 1.1, 7.9 Hz, 1H); 13C{1H}
NMR (100 MHz, CDCl3) δ = 142.0, 138.1, 135.2, 133.4, 133.2,
133.0, 130.4, 129.3, 128.1, 127.5, 126.6, 126.4, 125.9 (q, 1J(C–F)
2l',
5-bromo-3,6-dimethyl-1-(methylsulfonyl)-3-(2,2,2-
trifluoroethyl)indoline, colorless oil. 1H NMR (400 MHz,
CDCl3) δ = 1.46 (s, 3H), 2.39 (s, 3H), 2.42-2.60 (m, 2H),
2.93 (s, 3H), 3.76 (d, J = 10.5 Hz, 1H), 3.97 (d, J = 10.5 Hz,
1H), 7.28 (s, 1H), 7.31 (s, 1H); 13C{1H} NMR (100 MHz,
CDCl3) δ = 139.9, 138.9, 136.7, 126.9, 125.9 (q, 1J(C–F) = 277.0
4
2
Hz), 118.9, 115.5, 62.1 (q, J(C–F) = 2.0 Hz), 42.6 (q, J(C–F)
=
3
4
27.1 Hz), 40.8 (q, J(C–F) = 1.7 Hz), 34.9, 25.9 (q, J(C–F) = 1.4
4
2
Hz), 23.4; 19F NMR (376 MHz, CDCl3) δ = -60.27 (t, J(H–F)
=
= 277.2 Hz), 52.8 (q, J(C–F) = 1.7 Hz), 47.1, 42.8 (q, J(C–F)
=
3
4
11.2, 3F); HRMS (ESI-TOF) Calcd for C13H16BrF3NO2S+
([M+H]+) 386.0032. Found 386.0030.
26.8 Hz), 36.7 (q, J(C–F) = 1.4 Hz), 24.3 (q, J(C–F) = 1.2 Hz),
20.9; 19F NMR (376 MHz, CDCl3) δ = -59.45 (t, J(H–F) = 11.6,
3F); HRMS (ESI-TOF) Calcd for C19H20ClF3NO2S+
([M+H]+) 418.0850. Found 418.0832.
4a,
4-methyl-2-(phenylsulfonyl)-4-(2,2,2-trifluoroethyl)-
1,2,3,4-tetrahydroisoquinoline, white solid: mp 133-134 °C.
1H NMR (400 MHz, CDCl3) δ = 1.47 (d, J = 1.0 Hz, 3H),
2.46-2.71 (m, 2H), 2.79 (d, J = 12.0 Hz, 1H), 3.62 (d, J = 12.0
Hz, 1H), 4.03 (d, J = 14.8 Hz, 1H), 4.46 (d, J = 14.8 Hz, 1H),
7.01-7.04 (m, 1H), 7.16-7.24 (m, 2H), 7.31 (d, J = 7.6 Hz,
1H), 7.56-7.66 (m, 3H), 7.86-7.89 (m, 2H); 13C{1H} NMR
(100 MHz, CDCl3) δ = 139.8, 135.8, 133.1, 130.5, 129.3,
127.8, 127.4, 127.1, 126.5, 126.4, 126.3 (q, 1J(C–F) = 277.1 Hz),
53.6 (q, 4J(C–F) = 1.6 Hz), 48.3, 42.7 (q, 2J(C–F) = 26.6 Hz), 36.5
6,
5-bromo-1-(methylsulfonyl)-3-(2,2,2-
1
trifluoroethyl)indoline, white solid: mp 100-101 °C. H NMR
(400 MHz, CDCl3) δ = 2.31-2.45 (m, 1H), 2.56-2.69 (m, 1H),
2.91 (s, 3H), 3.67-3.74 (m, 1H), 3.77 (dd, J = 7.6, 10.5 Hz,
1H), 4.20 (dd, J = 9.1, 9.9 Hz, 1H), 7.31 (d, J = 8.6 Hz, 1H),
7.33 (s, 1H), 7.39 (ddd, J = 0.5, 1.9, 8.6 Hz, 1H); 13C{1H}
NMR (100 MHz, CDCl3) δ = 140.9, 134.1, 132.2, 127.7, 125.9
1
4
(q, J(C–F) = 275.8 Hz), 116.6, 115.3, 56.1 (q, J(C–F) = 1.4 Hz),
38.3 (q, J(C–F) = 28.3 Hz), 35.1, 34.5 (q, J(C–F) = 2.8 Hz); 19F
NMR (376 MHz, CDCl3) δ = -64.64 (t, J(H–F) = 10.5, 3F);
HRMS (ESI-TOF) Calcd for C11H12BrF3NO2S+ ([M+H]+)
357.9719. Found 357.9722.
2
3
3
4
(q, J(C–F) = 1.4 Hz), 24.5 (q, J(C–F) = 1.2 Hz); 19F NMR (376
MHz, CDCl3) δ = -59.21 (t, J(H–F) = 11.6, 3F); HRMS (ESI-
TOF) Calcd for C18H19F3NO2S+ ([M+H]+) 370.1083. Found
370.1086.
7, (3,3,3-trifluoroprop-1-ene-1,1-diyl)dibenzene, colorless
4b,
4-methyl-2-(o-tolylsulfonyl)-4-(2,2,2-trifluoroethyl)-
1
oil. H NMR (400 MHz, CDCl3) δ = 6.13 (q, J(H–F) = 8.2 Hz,
1,2,3,4-tetrahydroisoquinoline, white solid: mp 127-128 °C.
1H NMR (400 MHz, CDCl3) δ = 1.41 (d, J = 1.1 Hz, 3H),
2.33-2.55 (m, 2H), 2.67 (s, 3H), 3.02 (d, J = 12.5 Hz, 1H),
3.63 (dd, J = 0.9, 12.5 Hz, 1H), 4.29 (d, J = 15.1 Hz, 1H), 4.56
(d, J = 15.0 Hz, 1H), 7.05-7.07 (m, 1H), 7.18-7.25 (m, 2H),
1H), 7.23-7.26 (m, 4H), 7.30-7.41 (m, 6H); 13C{1H} NMR
(100 MHz, CDCl3) δ = 152.5 (q, 3J(C–F) = 5.6 Hz), 140.1, 137.3,
4
129.4, 129.1 (q, J(C–F) = 1.8 Hz), 128.48, 128.47, 128.03,
1
2
127.96, 123.1 (q, J(C–F) = 269.0 Hz), 115.4 (q, J(C–F) = 33.6
7
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