J.-Y. Yang et al. / Journal of Fluorine Chemistry 186 (2016) 45–51
49
CDCl3):
d
ppm ꢂ62.92 (s, 3F). 13C NMR (100.7 MHz, CDCl3):
d
ppm
4.4.10. 2-(Trifluoromethyl)naphthalene (2p)
165.4, 132.9, 131.5, 131.1 (q, J = 32.9 Hz), 129.4 (q, J = 3.8 Hz), 129.1,
126.6 (q, J = 4.0 Hz), 123.8 (q, J = 272.6 Hz), 61.6, 14.3. MS (EI): m/z
218 (M+). HRMS: Calculated for C13H7F3O (M+): 218.0555; Found
[M]+, 218.0558.
Compound 2p was prepared following the general procedure in
60% yield, starting from mesityl(naphthalen-2-yl)iodonium tetra-
fluoroborate (230.0 mg, 0.5 mmol) prepared by procedure B. 1H
NMR (300 MHz, CDCl3):
3H), 7.67–7.56 (m, 3H). 19F NMR (376 MHz, CDCl3):
(s, 3F). 13C NMR (100.7 MHz, CDCl3):
ppm 134.6, 132.2, 129.0,
d
ppm 8.19–8.14 (m, 1H), 8.00-7.89 (m,
d
ppm ꢂ62.26
4.4.5. Ethyl 4-(trifluoromethyl)benzoate (2h)
d
Compound 2h was prepared following the general procedure in
72% yield, starting from [4-(ethoxycarbonyl)phenyl](mesityl)iodo-
nium trifluoromethanesulfonate (272.2 mg, 0.5 mmol) prepared by
128.8, 128.1, 127.9, 127.7 (q, J = 32.4 Hz), 127.2, 125.7 (q, J = 4.5 Hz),
124.4 (q, J = 272.5 Hz), 121.4 (q, J = 3.4 Hz). MS (EI): m/z 196 (M+).
HRMS: Calculated for C11H7F3 (M+): 196.0500; Found, 196.0504.
procedure A. 1H NMR (300 MHz, CDCl3):
d ppm 8.15 (d, J = 7.8 Hz,
2H), 7.69 (d, J = 7.8 Hz, 2H), 4.41 (q, J = 7.1 Hz, 2H), 1.41 (t, J = 7.1 Hz,
4.4.11. 1-Methyl-4-(trifluoromethyl)naphthalene (2q)
3H). 19F NMR (376 MHz, CDCl3):
(100.7 MHz, CDCl3):
d
ppm ꢂ63.16 (s, 3F). 13C NMR
Compound 2q was prepared following the general procedure in
57% yield, starting from mesityl(4-methylnaphthalen-1-yl)iodo-
nium tetrafluoroborate (237.0 mg, 0.5 mmol) prepared by
d
ppm 165.5, 134.4 (q, J = 32.6 Hz), 133.8, 130.1,
125.5 (q, J = 3.8 Hz), 123.8 (q, J = 273.3 Hz), 61.7, 14.4. MS (EI): m/z
218 (M+). HRMS: Calculated for C10H9F3O2 (M+): 218.0555; Found,
218.0550.
procedure B. 1H NMR (300 MHz, CDCl3):
d
ppm 8.30–8.27 (m,
1H), 8.11–8.08 (m, 1H), 7.79 (d, J = 7.5 Hz, 1H), 7.67–7.63 (m, 2H),
7.34 (d, J = 7.5 Hz, 1H), 2.74 (s, 3H). 19F NMR (376 MHz, CDCl3):
d
4.4.6. 1-[4-(Trifluoromethyl)phenyl]ethanone (2i)
ppm ꢂ59.25 (s, 3F). 13C NMR (100.7 MHz, CDCl3):
d ppm 139.7,
Compound 2i was prepared following the general procedure in
64% yield, starting from (4-acetylphenyl)(mesityl)iodonium tri-
fluoromethanesulfonate (257.2 mg, 0.5 mmol) prepared by proce-
133.2, 129.2, 127.3, 126.5, 125.2 (q, J = 273.3 Hz), 125.1, 124.9, 124.9,
124.6 (q, J = 6.0 Hz),124.5 (q, J = 30.1 Hz),19.8. MS (EI): m/z 210 (M+).
HRMS: Calculated for C12H9F3 (M+): 210.0656; Found, 210.0651.
dure A. 1H NMR (300 MHz, CDCl3):
d ppm 7.83 (d, J = 8.7 Hz, 2H),
7.66 (d, J = 8.7 Hz, 2H), 2.57 (s, 3H). 19F NMR (376 MHz, CDCl3):
d
4.4.12. 9,9-Dimethyl-3-(trifluoromethyl)-9H-fluorene (2r)
ppm ꢂ63.14 (s, 3F). 13C NMR (100.7 MHz, CDCl3):
d
ppm 197.0,
Compound 2r was prepared following the general procedure in
56% yield, starting from (9,9-dimethyl-9H-fluoren-2-yl)(mesityl)
iodonium tetrafluoroborate (263.1 mg, 0.5 mmol) prepared by
139.7, 134.4 (q, J = 32.7 Hz), 128.6, 125.7 (q, J = 3.9 Hz), 123.6 (q,
J = 272.7 Hz), 26.7. MS (EI): m/z 188 (M+). HRMS: Calculated for
C9H7F3O (M+): 188.0449; Found, 188.0447.
procedure B. 1H NMR (300 MHz, CDCl3):
d
ppm 7.82-7.73 (m, 2H),
7.68 (d, J = 0.8 Hz, 1H), 7.62 (dd, J = 7.6 Hz, J = 0.8 Hz, 1H), 7.50-7.48
4.4.7. 1-[3-(Trifluoromethyl)phenyl]ethanone (2j)
(m,1H), 7.41-7.39 (m, 2H),1.53 (s, 6H). 19F NMR (376 MHz, CDCl3):
d
Compound 2j was prepared following the general procedure in
54% yield, starting from (3-acetylphenyl)(mesityl)iodonium tri-
fluoromethanesulfonate (257.2 mg, 0.5 mmol) prepared by proce-
ppm ꢂ61.62 (s, 3F). 13C NMR (100.7 MHz, CDCl3):
d ppm 154.3,
154.1, 142.9, 137.9, 129.3 (q, J = 32.0 Hz), 128.6, 127.4, 124.8 (q,
J = 272.5 Hz), 124.5 (q, J = 3.6 Hz), 123.0, 120.9, 120.2, 119.8 (q,
J = 3.8 Hz), 47.2, 27.1. MS (EI): m/z 262 (M+). HRMS: Calculated for
dure A. 1H NMR (300 MHz, CDCl3):
d ppm 8.16 (s, 1H), 8.09 (d,
J = 8.0 Hz, 1H), 7.76 (d, J = 8.0 Hz, 1H), 7.57 (t, J = 7.8 Hz, 1H), 2.60 (s,
C
13H7F3O (M+): 262.0969; Found, 262.0974.
3H). 19F NMR (376 MHz, CDCl3):
(100.7 MHz, CDCl3):
d
ppm ꢂ62.95 (s, 3F). 13C NMR
d
ppm 196.1, 137.7, 131.5, 131.3 (q, J = 33.0 Hz),
4.4.13. 4-(Pentyloxy)-40-(trifluoromethyl)-1,10-biphenyl (2s)
129.5 (q, J = 3.6 Hz),129.4,125.1 (q, J = 3.2 Hz),123.8 (q, J = 273.0 Hz),
26.5. MS (EI): m/z 188 (M+). HRMS: Calculated for C13H7F3O (M+):
188.0449; Found, 188.0448.
Compound 2s was prepared following the general procedure in
56% yield, starting from mesityl(40-(pentyloxy)-[1,10-biphenyl]-4-
yl)iodonium (286.1 mg, 0.5 mmol) prepared by procedure B. 1H
NMR (300 MHz, CDCl3):
d ppm 7.68-7.63 (m, 4H), 7.52 (d, J = 9.0 Hz,
4.4.8. 4-(Trifluoromethyl)benzonitrile (2k)
2H), 6.99 (d, J = 9.0 Hz, 2H), 4.00 (t, J = 6.4 Hz, 2H), 1.86-1.79 (m, 2H),
Compound 2k was prepared following the general procedure in
62% yield, starting from (4-cyanophenyl)(mesityl)iodonium tri-
fluoromethanesulfonate (248.6 mg, 0.5 mmol) prepared by proce-
1.49-1.34 (m, 4H), 0.95 (t, J = 7.0 Hz, 3H). 19F NMR (376 MHz, CDCl3):
d
ppm ꢂ62.35 (s, 3F). 13C NMR (100.7 MHz, CDCl3):
d ppm 159.6,
144.6, 132.1, 128.8 (q, J = 32.5 Hz), 128.5, 127.0, 125.8 (q, J = 3.7 Hz),
124.6 (q, J = 271.8 Hz),115.2, 68.3, 29.1, 28.4, 22.6,14.2. IR (thin film)
dure A. 1H NMR (300 MHz, CDCl3):
d
ppm 7.83 (d, J = 6.3 Hz, 2H),
7.76 (d, J = 6.3 Hz, 2H). 19F NMR (376 MHz, CDCl3):
ppm ꢂ63.55 (s,
3F).13C NMR (100.7 MHz, CDCl3):
ppm 134.7 (q, J = 33.5 Hz),132.8,
d
n
2959, 2938, 2874, 1606, 150, 1326, 1275, 1169, 1124, 1072, 909,
825, 734 cmꢂ1. MS (EI): m/z 308 (M+). HRMS: Calculated for
C
18H19F3O (M+): 308.1388; Found, 308.1385.
d
126.3 (q, J = 3.6 Hz), 123.2 (q, J = 273.1 Hz), 117.6, 116.2. MS (EI): m/z
171 (M+). HRMS: Calculated for C8H4F3N (M+): 171.0296; Found,
171.0298.
4.4.14. (8R,9S,13S,14S)-13-Methyl-3-(trifluoromethyl)-
7,8,9,11,12,13,15,16-octahydro-6H-cyclopenta[a]phenanthren-17
(14H)-one (2t)
4.4.9. 2-Chloro-4-(trifluoromethyl)phenyl acetate (2m)
Compound 2mwas prepared following the general procedure in
60% yield, starting from (3-chloro-4-(methoxycarbonyl)phenyl)
Compound 2t was prepared following the general procedure in
41% yield, starting from mesityl((8R,9S,13S,14S)-13-methyl-17-
oxo-7,8,9,11,12,13,14,15,16,17-decahydro-6H-cyclopenta[a]phe-
nanthren-3-yl)iodonium tetrafluoroborate (293.1 mg, 0.5 mmol)
(mesityl)iodonium
0.5 mmol) prepared by procedure A. 1H NMR (300 MHz, CDCl3):
ppm8.11(d,J = 1.6 Hz,1H), 7.67(dd,J = 8.4 Hz,J = 1.4 Hz,1H),7.59(d,
J = 8.0 Hz,1H), 3.97 (s, 3H).19F NMR (376 MHz, CDCl3):
ppm ꢂ62.89
(s, 3F).13C NMR (100.7 MHz, CDCl3):
ppm 164.9,137.9,132.0,130.8,
trifluoromethanesulfonate
(282.4 mg,
d
prepared by procedure B. 1H NMR (300 MHz, CDCl3):
d ppm 7.39
d
(m, 2H), 7.35 (s,1H), 2.98-2.94 (m, 2H), 2.55-2.42 (m, 2H), 2.36-2.31
d
(m, 1H), 2.20-1.98 (m, 4H), 1.67-1.45 (m, 6H), 0.91 (s, 3H). 19F NMR
129.5(q,J = 33.8 Hz),129.2(q,J = 3.6 Hz),128.7(q,J = 3.9 Hz),123.4(q,
J = 272.6 Hz), 52.9. MS (EI): m/z 238 (M+). HRMS: Calculated for
C9H6ClF3O2 (M+): 238.0008; Found, 238.0003.
(376 MHz, CDCl3):
CDCl3):
d
ppm ꢂ62.38 (s, 3F). 13C NMR (100.7 MHz,
d
ppm 143.9, 137.4, 128.2 (q, J = 32.2 Hz), 125.9, 125.9 (q,
J = 3.8 Hz), 125.8, 124.5 (q, J = 273.3 Hz), 122.6 (q, J = 3.6 Hz), 50.6,
48.0, 44.6, 37.9, 35.9, 31.6, 29.4, 26.3, 25.7, 21.7, 13.9. MS (EI): m/z
322 (M+). HRMS: Calculated for C19H21F3O (M+): 322.1545; Found,
322.1548.