The Journal of Organic Chemistry
Article
127.6, 125.9 (q, J = 277.7 Hz), 122.5, 68.4, 43.0 (q, J = 27.0 Hz). MS
(EI): m/z 268 (M+). HRMS (EI-TOF): m/z [M]+ calcd for
C9H8BrF3O 267.9711, found 267.9731.
CDCl3): δ 159.9, 134.7, 127.2, 126.1 (q, J = 275.0 Hz), 114.4, 68.6,
55.6, 43.0 (q, J = 26.7 Hz). MS (ESI): m/z 221 (M + H)+. HRMS
(ESI-TOF): m/z [M + H]+ calcd for C10H12F3O2 221.0789, found
221.0794.
Data for 1-(4-Bromophenyl)-3,3,3-trifluoropropan-1-one (4d).7c
Light yellow solid. Rf(10% ethyl acetate/hexane) = 0.41, 24% yield (25
Data for 3,3,3-Trifluoro-1-(4-methoxyphenyl)propan-1-one
(4h).7c Colorless oil. Rf(10% ethyl acetate/hexane) = 0.32, 10% yield
1
mg). H NMR (500 MHz, CDCl3): δ 7.81 (d, J = 8.2 Hz, 2H), 7.67
1
(d, J = 8.2 Hz, 2H), 3.77 (q, J = 9.9 Hz, 2H). 19F NMR (470 MHz,
CDCl3): δ −62.01 (t, J = 9.7 Hz, 3F). 13C NMR (125 MHz, CDCl3):
δ 189.0, 134.7, 132.6, 130.0, 129.9, 124.0 (q, J = 278.0 Hz), 42.3 (q, J =
28.4 Hz). MS (ESI): m/z 289 (M + Na)+. HRMS (ESI-TOF): m/z
[M + Na]+ calcd for C9H6BrF3ONa 288.9446, found 288.9439.
Data for 3,3,3-Trifluoro-1-(4-(trifluoromethyl)phenyl)propan-1-ol
(3e).7c Colorless oil. Rf(10% ethyl acetate/hexane) = 0.37, 48% yield
(9 mg). H NMR (500 MHz, CDCl3): δ 7.94−7.91 (m, 2H), 6.99−
6.96 (m, 2H), 3.89 (s, 3H), 3.74 (q, J = 10.1 Hz, 2H). 19F NMR (470
MHz, CDCl3): δ −61.98 (t, J = 10.0 Hz, 3F). 13C NMR (125 MHz,
CDCl3): δ 188.3, 164.6, 132.2, 131.0, 124.3 (q, J = 277.1 Hz), 114.3,
55.8, 42.0 (q, J = 28.0 Hz). MS (ESI): m/z 241 (M + Na)+. HRMS
(ESI-TOF): m/z [M + Na]+ calcd for C10H9F3O2Na 241.0447, found
241.0438.
(49 mg). H NMR (500 MHz, CDCl3): δ 7.66 (d, J = 8.1 Hz, 2H),
Data for 1-(2-Chlorophenyl)-3,3,3-trifluoropropan-1-ol (3i).7c
Light yellow oil. Rf(10% ethyl acetate/hexane) = 0.35, 60% yield
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7.52 (d, J = 8.1 Hz, 2H), 5.17 (m, 1H), 2.69−2.58 (m, 1H), 2.52−2.42
(m, 1H), 2.31 (d, J = 3.3 Hz, 1H). 19F NMR (470 MHz, CDCl3): δ
−62.56 (s, 3F), −63.59 (t, J = 10.4 Hz, 3F). 13C NMR (125 MHz,
CDCl3): δ 146.3, 130.8 (q, J = 32.6 Hz), 126.3, 126.0 (q, J = 3.7 Hz),
125.9 (q, J = 276.3 Hz), 124.2 (q, J = 271.3 Hz), 68.5, 43.1 (q, J = 27.1
Hz). MS (EI): m/z 258 (M+). HRMS (EI-TOF): m/z [M]+ calcd for
C10H8F6O 258.0479, found 258.0459.
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(54 mg). H NMR (500 MHz, CDCl3): δ 7.56−7.54 (m, 1H), 7.29−
7.24 (m, 2H), 7.20−7.17 (m, 1H), 5.43 (dt, J = 9.3 Hz, 3.0 Hz, 1H),
2.54−2.34 (m, 2H), 2.27 (d, J = 3.8 Hz, 1H). 19F NMR (470 MHz,
CDCl3): δ −63.88 (t, J = 10.6 Hz, 3F). 13C NMR (125 MHz, CDCl3):
δ 139.8, 131.5, 129.9, 129.5, 127.6, 127.2, 126.1 (q, J = 277.8 Hz),
65.7, 41.5 (q, J = 27.3 Hz). MS (ESI): m/z 225 (M + H)+. HRMS
(ESI-TOF): m/z [M + H]+ calcd for C9H9ClF3O 225.0294, found
225.0288.
Data for 3,3,3-Trifluoro-1-(4-(trifluoromethyl)phenyl)propan-1-
one (4e).7c White solid. Rf(10% ethyl acetate/hexane) = 0.44, 22%
1
yield (22 mg). H NMR (500 MHz, CDCl3): δ 8.06 (d, J = 8.6 Hz,
Data for 3,3,3-Trifluoro-1-o-tolylpropan-1-ol (3j). Colorless oil.
2H), 7.80 (d, J = 8.7 Hz, 2H), 3.84 (q, J = 9.9 Hz, 2H). 19F NMR (470
MHz, CDCl3): δ −62.06 (t, J = 9.7 Hz, 3F), −63.38 (s, 3F). 13C NMR
(125 MHz, CDCl3): δ 189.1, 138.5, 135.7 (d, J = 32.7 Hz), 129.0,
126.3 (q, J = 3.7 Hz), 123.9 (q, J = 276.3 Hz), 123.6 (q, J = 271.3 Hz),
42.7 (q, J = 28.7 Hz). MS (EI): m/z 256 (M+). HRMS (EI-TOF): m/z
[M]+ calcd for C10H6F6O 256.0323, found 256.0364.
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Rf(10% ethyl acetate/hexane) = 0.34, 44% yield (36 mg). H NMR
(500 MHz, CDCl3): δ 7.51 (d, J = 7.6 Hz, 1H), 7.29−7.22 (m, 2H),
7.18 (d, J = 7.4 Hz, 1H), 5.35−5.33 (m, 1H), 2.65−2.54 (m, 1H),
2.49−2.38 (m, 1H), 2.36 (s, 3H), 2.12 (s, 1H). 19F NMR (470 MHz,
CDCl3): δ −64.15 (t, J = 10.6 Hz, 3F). 13C NMR (125 MHz, CDCl3):
δ 140.7, 134.3, 131.0, 128.3, 126.9, 126.3 (q, J = 276.3 Hz), 125.3,
65.4, 42.1 (q, J = 26.9 Hz), 19.0. MS (ESI): m/z 227 (M + Na)+.
HRMS (ESI-TOF): m/z [M + Na]+ calcd for C10H11F3ONa 227.0654,
found 227.0641.
Data for 3,3,3-Trifluoro-1-(4-nitrophenyl)propan-1-ol (3f).7c Light
yellow solid. Rf(20% ethyl acetate/hexane) = 0.35, 59% yield (55 mg).
1H NMR (500 MHz, CDCl3): δ 8.21 (d, J = 8.8 Hz, 2H), 7.58 (d, J =
8.8 Hz, 2H), 0.5.24−5.20 (m, 1H), 2.68−2.57 (m, 1H), 2.51 (s, 1H),
2.50−2.42 (m, 1H). 19F NMR (470 MHz, CDCl3): δ −63.59 (t, J =
10.5 Hz, 3F). 13C NMR (125 MHz, CDCl3): δ 149.4, 147.9, 126.8,
125.7 (q, J = 275.0 Hz), 124.2, 68.1, 43.0 (q, J = 27.2 Hz). MS (EI):
m/z 235 (M+). HRMS (EI-TOF): m/z [M]+ calcd for C9H8F3NO3
235.0456, found 235.0420.
Data for 3-(3,3,3-Trifluoro-1-hydroxypropyl)benzaldehyde (3k).
Colorless oil. Rf(25% ethyl acetate/hexane) = 0.30, 41% yield (36 mg).
1H NMR (500 MHz, CDCl3): δ 10.05 (s, 1H), 7.93 (s, 1H), 7.86 (d, J
= 7.6 Hz, 1H), 7.69 (d, J = 8.7 Hz, 1H), 7.58 (t, J = 7.6 Hz, 1H), 5.21
(d, J = 8.9 Hz, 1H), 2.72−2.61 (m, 1H), 2.56−2.45 (m, 1H), 2.32 (d, J
= 2.8 Hz, 1H). 19F NMR (470 MHz, CDCl3): δ −63.65 (t, J = 10.3
Hz, 3F). 13C NMR (125 MHz, CDCl3): δ 192.3, 143.7, 137.0, 132.0,
130.1, 129.8, 126.8, 125.9 (q, J = 275.0 Hz), 68.4 (q, J = 3.0 Hz), 43.1
(q, J = 27.2 Hz). MS (ESI): m/z 219 (M + H)+. HRMS (ESI-TOF):
m/z [M + H]+ calcd for C10H10F3O2 219.0627, found 219.0608.
Data for 3-(3,3,3-Trifluoropropanoyl)benzaldehyde (4k).7c Color-
Data for 3,3,3-Trifluoro-1-(4-nitrophenyl)propan-1-one (4f).7c
Light yellow solid. Rf(10% ethyl acetate/hexane) = 0.40, 20% yield
1
(18 mg). H NMR (500 MHz, CDCl3): δ 8.38−8.36 (m, 2H), 8.13−
8.11 (m, 2H), 3.87 (q, J = 9.7 Hz, 2H). 19F NMR (470 MHz, CDCl3):
δ −61.97 (t, J = 9.8 Hz, 3F). 13C NMR (125 MHz, CDCl3): δ 188.6,
151.1, 140.1, 129.7, 124.4, 123.8 (q, J = 274.3 Hz), 42.9 (q, J = 29.0
Hz). MS (EI): m/z 233 (M+). HRMS (EI-TOF): m/z [M]+ calcd for
C9H6F3NO3 233.0300, found 233.0287.
1
less oil. Rf(25% ethyl acetate/hexane) = 0.33, 16% yield (14 mg). H
NMR (500 MHz, CDCl3): δ 10.12 (s, 1H), 8.42 (t, J = 1.7 Hz, 1H),
8.23 (dt, J = 7.8 Hz, 1.3 Hz, 1H), 8.16 (dt, J = 7.6 Hz, 1.3 Hz, 1H),
7.73 (t, J = 7.7 Hz, 1H), 3.87 (q, J = 9.8 Hz, 2H). 19F NMR (470
MHz, CDCl3): δ −61.99 (t, J = 9.7 Hz, 3F). 13C NMR (125 MHz,
CDCl3): δ 191.2, 189.0, 137.1, 136.7, 135.0, 133.9, 130.2, 129.4, 124.0
(q, J = 277.1 Hz), 42.5 (q, J = 28.6 Hz). MS (ESI): m/z 239 (M +
Na)+. HRMS (ESI-TOF): m/z [M + Na]+ calcd for C10H7F3O2Na
239.0290, found 239.0275.
Data for 3,3,3-Trifluoro-1-(3-nitrophenyl)propan-1-ol (3l). Yellow
oil. Rf(25% ethyl acetate/hexane) = 0.38, 63% yield (59 mg). 1H NMR
(500 MHz, CDCl3): δ 8.28 (t, J = 1.8 Hz, 1H), 8.19 (ddd, J = 8.2 Hz,
2.2 Hz, 1.0 Hz, 1H), 7.75 (d, J = 7.7 Hz, 1H), 7.58 (t, J = 7.9 Hz, 1H),
5.25−5.22 (m, 1H), 2.72−2.61 (m, 1H), 2.56−2.46 (m, 2H). 19F
NMR (470 MHz, CDCl3): δ −63.58 (t, J = 10.5 Hz, 3F). 13C NMR
(125 MHz, CDCl3): δ 148.7, 144.5, 132.0, 130.1, 125.8 (q, J = 277.3
Hz), 123.5, 121.0, 68.1, 43.1 (q, J = 27.2 Hz). MS (ESI): m/z 236 (M
+ H)+. HRMS (ESI-TOF): m/z [M + H]+ calcd for C9H9F3NO3
236.0529, found 236.0517.
Data for 3,3,3-trifluoro-1-p-tolylpropan-1-ol (3g).7c Colorless oil.
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Rf(10% ethyl acetate/hexane) = 0.36, 36% yield (29 mg). H NMR
(500 MHz, CDCl3): δ 7.27−7.25 (m, 2H), 7.20−7.18 (m, 2H), 5.07−
5.04 (m, 1H), 2.69−2.57 (m, 1H), 2.45−2.39 (m, 1H), 2.36 (s, 3H),
2.05 (s, 1H). 19F NMR (470 MHz, CDCl3): δ −63.77 (t, J = 9.9 Hz,
3F). 13C NMR (125 MHz, CDCl3): δ 139.6, 138.5, 129.7, 126.1 (q, J =
277.0 Hz), 125.8, 68.9 (q, J = 3.0 Hz), 43.0 (q, J = 26.8 Hz), 21.3. MS
(EI): m/z 204 (M+). HRMS (EI-TOF): m/z [M]+ calcd for
C10H11F3O 204.0762, found 204.0750.
Data for 3,3,3-Trifluoro-1-p-tolylpropan-1-one (4g).7c White
1
solid. Rf(10% ethyl acetate/hexane) = 0.45, 17% yield (14 mg). H
NMR (500 MHz, CDCl3): δ 7.84 (d, J = 8.3 Hz, 2H), 7.31 (d, J = 8.0
Hz, 2H), 3.77 (q, J = 10.1 Hz, 2H), 2.44 (s, 3H). 19F NMR (470 MHz,
CDCl3): δ −62.03 (t, J = 10.0 Hz, 3F). 13C NMR (125 MHz, CDCl3):
δ 189.5, 145.5, 133.7, 129.8, 128.7, 124.3 (q, J = 277.0 Hz), 42.2 (q, J =
28.2 Hz), 21.9. MS (ESI): m/z 225 (M + Na)+. HRMS (ESI-TOF):
m/z [M + Na]+ calcd for C10H9F3ONa 225.0498, found 225.0470.
Data for 3,3,3-Trifluoro-1-(4-methoxyphenyl)propan-1-ol (3h).7c
Colorless oil. Rf(15% ethyl acetate/hexane) = 0.30, 32% yield (28 mg).
1H NMR (500 MHz, CDCl3): δ 7.32−7.29 (m, 2H), 6.93−6.90 (m,
2H), 5.05 (dt, J = 7.4 Hz, 3.4 Hz, 1H), 3.82 (s, 3H), 2.70−2.59 (m,
1H), 2.49−2.39 (m, 1H), 2.06 (d, J = 3.1 Hz, 1H). 19F NMR (470
MHz, CDCl3): δ −63.75 (t, J = 10.4 Hz, 3F). 13C NMR (125 MHz,
Data for 3,3,3-Trifluoro-1-m-tolylpropan-1-ol (3m). Colorless oil.
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Rf(10% ethyl acetate/hexane) = 0.35, 44% yield (36 mg). H NMR
(500 MHz, CDCl3): δ 7.19 (t, J = 7.6 Hz, 1H), 7.10 (s, 1H), 7.07 (t, J
= 7.6 Hz, 1H), 4.96−4.93 (m, 1H), 2.59−2.48 (m, 1H), 2.41−2.30 (m,
1H), 2.29 (s, 3H), 2.10 (s, 1H). 19F NMR (470 MHz, CDCl3): δ
−63.80 (t, J = 10.6 Hz, 3F). 13C NMR (125 MHz, CDCl3): δ 142.5,
138.8, 129.3, 128.9, 126.5, 126.1 (q, J = 276.3 Hz), 122.9, 0.69.1, 43.0
G
J. Org. Chem. XXXX, XXX, XXX−XXX