Y. Carcenac et al. / Journal of Fluorine Chemistry 126 (2005) 1347–1355
1353
2.0–2.2 (m, 4H), 6.34 (br, 1H); 13C NMR (75 MHz, CDCl3)
4.1.3.7. 1-Pentafluoroethyl-4-methylcyclohexene
(4g). 62% yield; colorless oil; 19F NMR (188 MHz, CDCl3)
d ꢀ84.4 (s, 3F), ꢀ116.1 (d, 1F, 2JF–F = 265 Hz), ꢀ119.1 (d,
1F, 2JF–F = 265 Hz); 1H NMR (200 MHz, CDCl3) d 0.99 (d,
d 21.3, 21.5 (C4, C5), 21.9 (q, 3JC–F = 1.1 Hz, C6), 24.3 (C3),
1
124.0 (q, JC–F = 272 Hz, CF3), 128.1 (q, JC–F = 29.7 Hz,
2
3
C1), 130.3 (q, JC–F = 6.0 Hz, C2); IR (neat) 3031, 2920,
2878, 1680 cmꢀ1
.
3H, JH–H = 6.1 Hz), 1.2–2.2 (m, 7H), 6.32 (s, 1H); 13C
3
NMR (50 MHz, CDCl3) d 21.3 (CH3), 22.6 (C6), 27.3 (C4),
1
29.9 (C5), 33.2 (C3), 113.4 (tq, JC–F = 252 Hz, JC–
2
4.1.3.2. 1-Trifluoromethyl-4-methylcyclohexene (4b). 77%
yield; colorless oil; 19F NMR (282 MHz, CDCl3) d ꢀ69.7 (s,
1
F = 37.6 Hz, CF2), 119.3 (qt, JC–F = 287 Hz, JC–
2
3
2
F = 39.4 Hz, CF3), 126.8 (t, JC–F = 21.3 Hz, C1), 133.0
CF3); 1H NMR (300 MHz, CDCl3) d 0.92 (d, 3H, JH–
3
H = 6.2 Hz), 1.3 (m, 1H), 1.7–2.3 (m, 6H), 6.23 (s, 1H); 13
NMR (75 MHz, CDCl3) d 21.1 (CH3), 21.9 (C6), 27.4 (C5),
C
(q, JC–F = 8.9 Hz, C2); IR (neat) 2950, 2873, 1670 cmꢀ1
.
1
29.5 (C3), 32.6 (C4), 124.0 (q, JC–F = 271 Hz, CF3), 127.9
4.1.3.8. 1-Pentafluoroethyl-4-isopropylcyclohexene
(4h). 79% yield; colorless oil; 19F NMR (282 MHz, CDCl3)
d ꢀ84.4 (s, 3F), ꢀ115.8 (d, 1F, 2JF–F = 264 Hz), ꢀ119.2 (d,
1F, 2JF–F = 264 Hz); 1H NMR (300 MHz, CDCl3) d 0.91 (d,
2
3
(q, JC–F = 29.7 Hz, C1), 129.7 (q, JC–F = 5.7 Hz, C2); IR
(neat) 3032, 2919, 2878, 1680 cmꢀ1; MS (CI CH4) m/z 164
(23), 149 (36), 95 (100).
3
3
3H, JH–H = 6.8 Hz), 0.93 (d, 3H, JH–H = 6.8 Hz), 1.2–1.4
(m, 2H), 1,53 (m, 1H), 1.8–2.3 (m, 5H), 6.35 (s, 1H); 13C
NMR (75 MHz, CDCl3) d 19.4 (CH3), 19.7 (CH3), 23.4 (C6),
4.1.3.3. 1-Trifluoromethyl-4-ethylcyclohexene (4c). 57%
yield; colorless oil; 19F NMR (282 MHz, CDCl3) d ꢀ69.9
1
3
1
(s, CF3); H NMR (300 MHz, CDCl3) d 0.95 (d, 3H, JH–
H = 7.4 Hz), 1.2–2.3 (m, 9H), 6.32 (s, 1H); 13C NMR
(75 MHz, CDCl3) d 11.3 (CH3), 22.1 (C6), 27.5, 28.7, 30.7
25.4 (C3), 28.6 (C5), 32.0 (CH), 39.1 (C4), 113.4 (tq, JC–
2
1
F = 252 Hz, JC–F = 37.7 Hz, CF2), 119.4 (qt, JC–
F = 287 Hz, 2JC–F = 39.7 Hz, CF3), 127.0 (t, 2JC–
1
3
(C3, C5, CH2), 34.4 (C4), 124.2 (q, JC–F = 271 Hz, CF3),
F = 21.5 Hz, C1), 133.4 (q, JC–F = 8.5 Hz, C2); IR (neat)
128.2 (q, 2JC–F = 29.7 Hz,C1), 129.9 (q, 3JC–F = 5.7 Hz, C2);
IR (neat) 2955, 2920, 2863, 1680 cmꢀ1; MS (CI CH4) m/z
178 (18), 163 (33), 149 (68), 109 (100).
2960, 2868, 1665 cmꢀ1; MS (CI CH4) m/z 243 (34), 223
(100), 203 (86). Anal. Calcd. for C11H15F5: C, 54.5; H, 6.2.
Found: C, 54.6; H, 6.2.
4.1.3.4. 1-Trifluoromethyl-4-isopropylcyclohexene
(4d). 72% yield; colorless oil; 19F NMR (282 MHz, CDCl3)
d ꢀ69.9 (s, CF3); 1H NMR (300 MHz, CDCl3) d 0.93 (d, 3H,
4.1.4. Reduction of perfluoroalkylated alkenes: general
procedure
In a Schlenck tube PtO2 (5% mol) in ether (10 mL) was
sonicated under hydrogen 30 min prior to the addition of a
solution of alkene (2 mmol) in ether (10 mL). The mixture
was hydrogenated at room temperature for 6 h, under
ultrasound. The solution was then filtered and concentrated.
All the alkenes were purified by flash chromatography
eluted with pentane (Rf ꢃ 0.9). It was not possible to
separate the mixture of diastereoisomers.
3
3JH–H = 6.7 Hz), 0.95 (d, 3H, JH–H = 6.7 Hz), 1.2–2.3 (m,
8H), 6.34 (s, 1H); 13C NMR (75 MHz, CDCl3) d 19.4 (CH3),
19.7 (CH3), 22.8 (C6), 25.1 (C3), 28.0 (C5), 32.0 (CH), 39.2
1
(C4), 124.2 (q, JC–F = 271 Hz, CF3), 128.2 (q, JC–
2
3
F = 29.7 Hz, C1), 130.3 (q, JC–F = 5.7 Hz, C2).
4.1.3.5. 1-Trifluoromethyl-4-phenylcyclohexene (4e). 87%
yield; Rf: 0.7. White solid; mp 42–43 8C; 19F NMR
1
(282 MHz, CDCl3) d ꢀ69.8 (s, CF3); H NMR (300 MHz,
4.1.4.1. Trifluoromethyl-cyclohexane (401-75-2)
(7a). 97% yield; colorless oil; spectral data: 19F NMR
CDCl3) d 1.5–2.5 (m, 6H), 2.84 (m, 1H), 6.46 (s, 1H), 7.1–7.4
(m 5H); 13C NMR (75 MHz, CDCl3) d 22.7 (C6), 28.7 (C3),
3
1
(282 MHz, CDCl3) d ꢀ74.6 (d, JF–H = 8.9 Hz, CF3); H
NMR (300 MHz, CDCl3) d 1.1–1.4 (m, 5H), 1.6–2.0 (m,
6H); 13C NMR (75 MHz, CDCl3) d 25.0 (C3), 25.1 (q, 3JC–
1
32.3 (C5), 39.1 (C4), 124.0 (q, JC–F = 272 Hz, CF3), 126.5
2
(C4 ), 126.8 (C2 ), 128.1 (q, JC–F = 30.0 Hz, C1), 128.6 (C3 ),
0
0
0
3
130.0 (q, JC–F = 5.6 Hz, C2); IR (KBr) 3063, 3021, 2924,
2
F = 2.5 Hz, C2), 25.6 (C4), 42.0 (q, JC–F = 26.3 Hz, C1),
1
127.8 (q, JC–F = 278 Hz, CF3).
1675, 785, 692 cmꢀ1; MS (EI) m/z 226 (27), 104 (100). Anal.
Calcd. for C13H13F3: C, 69.0; H, 5.8. Found: C, 69.0; H, 5.9.
4.1.4.2. 1-Trifluoromethyl-4-methylcyclohexane (13127-
02-1) [27] (7b). 64% yield; mixture (60/40) of cis and
trans isomers; colorless oil; spectral data for major isomer:
4.1.3.6. 1-Trifluoromethyl-4-tertbutylcyclohexene
(4f). 81% yield; colorless oil; 19F NMR (282 MHz, CDCl3)
d ꢀ69.8 (s, CF3); 1H NMR (300 MHz, CDCl3) d 0.92 (s, 9H),
1.2–2.3 (m, 7H), 6.36 (s, 1H); 13C NMR (75 MHz, CDCl3) d
23.0 (C3), 23.4 (C6), 26.0 (C5), 27.0 (3CH3), 32.1 (C(CH3)3),
3
19F NMR (282 MHz, CDCl3) d ꢀ72.8 (d, JF–H = 8.9 Hz,
3
CF3); 1H NMR (300 MHz, CDCl3) d 0.83 (d, 3H, JH–
H = 6.4 Hz), 1.1–2.0 (m, 10H); 13C NMR (75 MHz, CDCl3)
1
2
3
d 18.2 (Me), 20.3 (q, JC–F = 2.3 Hz, C2), 27.5 (C4), 30.2
43.2 (C3), 124.1 (q, JC–F = 272 Hz, CF3), 128.0 (q, JC–
3
F = 29.7 Hz, C1), 130.7 (q, JC–F = 5.9 Hz, C2); IR (neat)
2965, 2858, 1680 cmꢀ1; MS (CI CH4) m/z 206 (7), 191 (15),
149 (100), 135 (62). Anal. Calcd. for C11H17F3: C, 64.1; H,
8.3. Found: C, 63.9; H, 8.2.
2
1
(C3), 40.8 (q, JC–F = 26.3 Hz, C1), 128.1 (q, JC–
F = 279 Hz, CF3); spectral data for minor isomer: 19F
NMR (282 MHz, CDCl3) d ꢀ74.3 (d, 3JF–H = 8.9 Hz, CF3);
1H NMR (300 MHz, CDCl3) d 0.89 (d, 3H, 3JH–H = 7.2 Hz),