The Journal of Organic Chemistry
Article
cm−1; mp 63−64 °C; HRMS (EI, m/z): calcd. for C10H8F5O2 [M −
2JC−FB = 22.8 Hz) ppm; 19F NMR (282 MHz, chloroform-d): δ
−81.58 (s, 3F), −122.06 (dd, JAB = 276.1, 7.3 Hz, 1F), −129.71 (dd,
JAB = 276.3, 16.3 Hz, 1F) ppm; ATR−FTIR (KBr) ν: 3346, 1595,
1209, 1180, 1128, 1078, 1032, 831, 791, 742, 534, 469, 430, 405
cm−1; mp 42−44 °C; HRMS (EI, m/z): calcd. for C9H5BrF5O [M −
H]−, 302.9444; found: 302.9445.
H]−, 255.0444; found, 255.0447.
2,2,3,3,3-Pentafluoro-1-(p-tolyl)propan-1-ol (2b). Followed by
the general procedure, it was purified by column chromatography on
silica gel (n-hexane/ethyl acetate = 95/5) to give 2b (40.3 mg, 84%
yield) as colorless oil. 1H NMR (300 MHz, chloroform-d): δ 7.34 (d,
J = 7.8 Hz, 2H), 7.22 (d, J = 7.8 Hz, 2H), 5.16−5.00 (m, 1H), 2.50
1-(3-Bromophenyl)-2,2,3,3,3-pentafluoropropan-1-ol (2g). Fol-
lowed by the general procedure, it was purified by column
chromatography on silica gel (n-hexane/ethyl acetate = 95/5) to
(d, J = 4.6 Hz, 1H), 2.38 (s, 3H) ppm; 13C {1H} NMR (126 MHz,
1
chloroform-d): δ 139.7, 130.9, 129.3, 127.7, 119.1 (C−F, JC−F
=
2
2
1
1
287.0, JC−FA = 36.3, JC−FB = 35.3 Hz), 113.0 (C−F, JC−FA = 260.6,
give 2g (53.7 mg, 88% yield) as colorless oil. H NMR (300 MHz,
2
2
2
1JC−FB = 254.7, JC−F = 35.7 Hz), 71.9 (C−F, JC−FA = 27.9, JC−FB
22.4 Hz), 21.2 ppm; 19F NMR (282 MHz, chloroform-d): δ −81.75
(s, 3F), −122.44 (dd, JAB = 275.4, 7.5 Hz, 1F), −129.91 (dd, JAB
=
chloroform-d): δ 7.55 (s, 1H), 7.48 (d, J = 7.9 Hz, 1H), 7.31 (d, J =
7.7 Hz, 1H), 7.25−7.15 (m, 1H), 5.02 (dd, J = 16.4, 7.0 Hz, 1H), 2.57
(s, 1H) ppm; 13C {1H} NMR (126 MHz, chloroform-d): δ 135.9,
132.8, 130.9, 130.1, 126.5, 122.6, 122.8−115.1 (m), 112.7 (C−F,
=
275.3, 16.7 Hz, 1F) ppm; ATR−FTIR (neat) ν: 3435, 3035, 2929,
1618, 1516, 1363, 1211, 1132, 1032, 791, 733, 534, 488, 438 cm−1;
HRMS (EI, m/z): calcd. for C10H8F5O [M − H]−, 239.0495; found,
239.0495.
1JC−FA = 261.1, 1JC−FB = 255.3, 2JC−F = 36.0 Hz) 71.3 (C−F, 2JC−FA
=
28.1, 2JC−FB = 22.8 Hz) ppm; 19F NMR (282 MHz, chloroform-d): δ
−81.62 (s, 3F), −121.73 (dd, JAB = 276.7, 6.9 Hz, 1F), −129.86 (dd,
JAB = 276.6, 16.5 Hz, 1F) ppm; ATR−FTIR (neat) ν: 3435, 3068,
2925, 1699, 1572, 1475, 1360, 1209, 1188, 1132, 1038, 870, 820, 775,
735, 675, 627, 484, 447 cm−1; HRMS (EI, m/z): calcd. for
C9H5BrF5O [M − H]−, 302.9444; found, 302.9443.
1-([1,1′-Biphenyl]-4-yl)-2,2,3,3,3-pentafluoropropan-1-ol (2c).
Followed by the general procedure, it was purified by column
chromatography on silica gel (n-hexane/ethyl acetate = 95/5) to give
2c (54.4 mg, 90% yield) as a white solid. 1H NMR (300 MHz,
chloroform-d): δ 7.69−7.34 (m, 9H), 5.25−5.11 (m, 1H), 2.57 (d, J =
4.7 Hz, 1H) ppm; 13C {1H} NMR (126 MHz, chloroform-d): δ 142.6,
140.2, 132.7, 128.9, 128.2, 127.7, 127.4, 127.2, 122.9−115.3 (m),
1-(2-Bromophenyl)-2,2,3,3,3-pentafluoropropan-1-ol (2h). Fol-
lowed by the general procedure, it was purified by column
chromatography on silica gel (n-hexane/ethyl acetate = 95/5) to
1
1
2
1
113.0 (C−F, JC−FA = 261.0, JC−FB = 255.1, JC−F = 35.7 Hz), 71.8
give 2h (51.9 mg, 85% yield) as colorless oil. H NMR (300 MHz,
(C−F, JC−FA = 28.2, JC−FB = 22.6 Hz) ppm; 19F NMR (282 MHz,
chloroform-d): δ −81.67 (s, 3F), −122.08 (dd, JAB = 275.6, 7.3 Hz,
1F), −129.87 (dd, JAB = 275.8, 16.7 Hz, 1F) ppm; ATR−FTIR (KBr)
ν: 3442, 1209, 1182, 1132, 1034, 754, 698, 465 cm−1; mp 101−102
°C; HRMS (EI, m/z): calcd. for C15H10F5O [M − H]−, 301.0652;
found, 301.0651.
2
2
chloroform-d): δ 7.67 (d, J = 7.8 Hz, 1H), 7.60 (d, J = 8.0 Hz, 1H),
7.40 (td, J = 7.6, 1.3 Hz, 1H), 7.27 (td, J = 7.7, 1.7 Hz, 1H), 5.78 (dt,
J = 18.2, 4.9 Hz, 1H), 2.63 (d, J = 4.8 Hz, 1H) ppm; 13C {1H} NMR
(126 MHz, chloroform-d): δ 133.7, 133.0, 131.0, 129.8 (C−F, 3JC−F
=
1
2
1.8 Hz), 127.8, 124.0, 119.0 (C−F, JC−F = 287.0, JC−FA = 36.6,
1
1
2
2JC−FB = 34.9 Hz), 112.9 (C−F, JC−FA = 262.4, JC−FB = 256.0, JC−F
= 36.3 Hz), 69.8 (C−F, JC−FA = 28.6, JC−FB = 21.1 Hz) ppm; 19F
NMR (282 MHz, chloroform-d): δ −82.37 (s, 3F), −121.23 (dd, JAB
= 277.5, 4.6 Hz, 1F), −131.08 (dd, JAB = 277.6, 18.1 Hz, 1F) ppm;
ATR−FTIR (neat) ν: 3435, 1705, 1593, 1572, 1475, 1441, 1369,
1213, 1132, 1026, 827, 758, 673, 619, 536, 431 cm−1; HRMS (EI, m/
z): calcd. for C9H5BrF5O [M − H]−, 302.9444; found, 302.9443.
2,2,3,3,3-Pentafluoro-1-(4-iodophenyl)propan-1-ol (2i). Followed
by the general procedure, it was purified by column chromatography
on silica gel (n-hexane/ethyl acetate = 95/5) to give 2i (63.4 mg, 90%
yield) as a white solid. 1H NMR (300 MHz, chloroform-d): δ 7.76 (d,
J = 8.4 Hz, 2H), 7.20 (d, J = 8.1 Hz, 2H), 5.08 (dd, J = 16.2, 7.3 Hz,
1H), 2.61 (s, 1H) ppm; 13C {1H} NMR (126 MHz, chloroform-d): δ
2
2
2,2,3,3,3-Pentafluoro-1-(naphthalen-2-yl)propan-1-ol (2d). Fol-
lowed by the general procedure, it was purified by column
chromatography on silica gel (n-hexane/ethyl acetate = 95/5) to
1
give 2d (50.8 mg, 92% yield) as a white solid. H NMR (300 MHz,
chloroform-d): δ 8.00−7.82 (m, 4H), 7.62−7.47 (m, 3H), 5.38−5.22
(m, 1H), 2.55 (d, J = 5.0 Hz, 1H) ppm; 13C {1H} NMR (126 MHz,
chloroform-d): δ 133.8, 132.8, 131.2, 128.5, 128.2, 127.8, 127.8,
1
2
2
127.0, 126.6, 124.6, 119.1 (C−F, JC−F = 287.0, JC−FA = 36.2, JC−FB
= 35.1 Hz), 113.1 (C−F, 1JC−FA = 261.0, 1JC−FB = 255.0, 2JC−F = 35.8
2
2
Hz), 72.2 (C−F, JC−FA = 28.0, JC−FB = 22.6 Hz) ppm; 19F NMR
(282 MHz, chloroform-d): δ −81.69 (s, 3F), −122.01 (dd, JAB
=
275.9, 7.4 Hz, 1F), −129.47 (dd, JAB = 275.9, 16.7 Hz, 1F) ppm;
ATR−FTIR (KBr) ν: 3448, 1188, 1120, 1041, 802, 742, 721, 482,
444, 416, 403 cm−1; mp 83−84 °C; HRMS (EI, m/z): calcd. for
C13H8F5O [M − H]−, 275.0495; found, 275.0493.
1
2
2
137.8, 133.4, 129.7, 121.2 (C−F, JC−F = 285.0, JC−FA = 35.0, JC−FB
= 35.0 Hz), 112.7 (C−F, 1JC−FA = 261.0, 1JC−FB = 255.3, 2JC−F = 36.0
Hz), 95.8, 71.5 (C−F, JC−FA = 28.0, JC−FB = 22.7 Hz) ppm; 19F
NMR (282 MHz, chloroform-d): δ −81.62 (s, 3F), −122.17 (dd, JAB
= 276.4, 7.3 H, 1F), −129.79 (dd, JAB = 276.2, 16.2 Hz, 1F) ppm;
ATR−FTIR (KBr) ν: 3446, 1595, 1483, 1325, 1207, 1134, 1034, 829,
789, 739, 656, 534, 486, 465 cm−1; mp 53−54 °C; HRMS (EI, m/z):
calcd. for C9H5F5IO [M − H]−, 350.9305; found, 350.9303.
2
2
1-(4-Chlorophenyl)-2,2,3,3,3-pentafluoropropan-1-ol (2e). Fol-
lowed by the general procedure, it was purified by column
chromatography on silica gel (n-hexane/ethyl acetate = 95/5) to
1
give 2e (43.8 mg, 84% yield) as a white solid. H NMR (300 MHz,
chloroform-d): δ 7.48−7.33 (m, 4H), 5.20−5.04 (m, 1H), 2.57 (d, J =
5.0 Hz, 1H) ppm; 13C {1H} NMR (126 MHz, chloroform-d): δ 135.7,
2,2,3,3,3-Pentafluoro-1-(4-fluorophenyl)propan-1-ol (2j). Fol-
lowed by the general procedure, it was purified by column
chromatography on silica gel (n-hexane/ethyl acetate = 95/5) to
give 2j (37.1 mg, 76% yield, 99% 19F NMR yield) as colorless oil. 1H
NMR (300 MHz, chloroform-d): δ 7.52−7.38 (m, 2H), 7.17−7.05
(m, 2H), 5.20−5.05 (m, 1H), 2.58 (d, J = 4.8 Hz, 1H) ppm; 13C {1H}
1
2
2
132.2, 129.2, 128.9, 118.9 (C−F, JC−F = 286.8, JC−FA = 36.3, JC−FB
= 35.1 Hz), 112.8 (C−F, 1JC−FA = 260.8, 1JC−FB = 255.3, 2JC−F = 36.0
2
2
Hz), 71.4 (C−F, JC−FA = 28.0, JC−FB = 22.9 Hz) ppm; 19F NMR
(282 MHz, chloroform-d): δ −81.59 (s, 3F), −122.22 (dd, JAB
=
276.4, 7.4 Hz, 1F), −129.64 (dd, JAB = 276.3, 16.0 Hz, 1F) ppm;
ATR−FTIR (KBr) ν: 3348, 2952, 1601, 1496, 1365, 1209, 1176,
1130, 1095, 1032, 833, 795, 744, 685 cm−1; mp 42−43 °C; HRMS
(EI, m/z): calcd. for C9H5ClF5O [M − H]−, 258.9949; found,
258.9942.
1
NMR (126 MHz, chloroform-d): δ 163.4 (C−F, JC−F = 248.9 Hz),
129.7 (C−F, 3JC−F = 8.4 Hz), 115.6 (C−F, 2JC−F = 21.8 Hz), 122.6−
1
1
2
115.2 (m), 112.8 (C−F, JC−FA = 260.6, JC−FB = 254.7, JC−F = 35.9
Hz), 71.3 (C−F, JC−FA = 27.9, JC−FB = 22.7 Hz) ppm; 19F NMR
(282 MHz, chloroform-d): δ −81.66 (s, 3F), −111.85−−112.10 (m,
1F), −122.52 (dd, JAB = 275.9, 7.5 Hz, 1F), −129.79 (dd, JAB = 275.9,
16.2 Hz, 1F) ppm; ATR−FTIR (neat) ν: 3429, 2929, 1608, 1514,
1329, 1209, 1104, 1034, 850, 802, 737, 571, 444 cm−1; HRMS (EI,
m/z): calcd. for C9H5F6O [M − H]−, 243.0245, found, 243.0241.
2,2,3,3,3-Pentafluoro-1-(4-(trifluoromethoxy)phenyl)propan-1-ol
(2k). Followed by the general procedure, it was purified by column
chromatography on silica gel (n-hexane/ethyl acetate = 95/5) to give
2
2
1-(4-Bromophenyl)-2,2,3,3,3-pentafluoropropan-1-ol (2f). Fol-
lowed by the general procedure, it was purified by column
chromatography on silica gel (n-hexane/ethyl acetate = 95/5) to
1
give 2f (54.9 mg, 90% yield) as a white solid. H NMR (300 MHz,
chloroform-d): δ 7.56 (d, J = 8.5 Hz, 2H), 7.34 (d, J = 8.1 Hz, 2H),
5.17−5.03 (m, 1H), 2.51 (d, J = 5.0 Hz, 1H) ppm; 13C {1H} NMR
(126 MHz, chloroform-d): δ 132.7, 131.8, 129.4, 124.0, 118.9 (C−F,
1JC−F = 286.9, 2JC−FA = 36.1, 2JC−FB = 35.0 Hz), 112.7 (C−F, 1JC−FA
=
1
2
2
1
260.9, JC−FB = 255.1, JC−F = 35.9 Hz), 71.4 (C−F, JC−FA = 28.0,
2k (42.2 mg, 68% yield, 98% 19F NMR yield) as colorless oil. H
5888
J. Org. Chem. 2021, 86, 5883−5893