´
´
J. Vaclavık et al. / Journal of Fluorine Chemistry 169 (2015) 24–31
29
(s, CArH), 126.3 (s, CAr), 129.4 (s, CArH), 130.9 (s, CArH), 136.0 (s,
1.22–1.43 (m, 7H, 3 Â CH2, CHaHb), 1.57–1.68 (m, 2H, CH2), 1.71–
1.83 (m, 1H, CHaHb), 2.17 (br s, 1H, OH), 4.19–4.34 (m, 1H, CH),
7.62–7.72 (m, 2H, CArH), 7.79–7.89 (m, 1H, CArH), 8.01–8.09 (m, 2H,
C
ArH), 160.3 (s, CAr); 19F {1H} NMR (CDCl3):
d
À124.6 (d, 1F,
2JFF = 280.0, CFaFb), À113.4 (d, 1F, 2JFF = 280.0, CFaFb), À111.5 (d, 1F,
2JFF = 255.5, CFaFb), À110.7 (d, 1F, JFF = 255.5, CFaFb); FTIR (film):
C
ArH); 13C NMR (CDCl3):
28.6 (s, CH2), 31.6 (s, CH2), 70.4 (dd, 2JCF = 27.5, 23.2, CH), 129.5 (s,
d 14.0 (s, CH3), 22.6 (s, CH2), 25.1 (s, CH2),
2
n
max 3527, 3451, 2841, 1613, 1584, 1515, 1450, 1358, 1315, 1255,
1169, 1076, 1068, 1031, 999, 846, 758, 685, 634, 597, 534 cmÀ1
;
C
ArH), 131.0 (s, CArH), 132.3 (s, CArH), 136.2 (s, CArH); 19F {1H} NMR
MS (EI): m/z (%) = 378 (2) [M]+, 207 (11), 149 (23), 137 (100), 77
(29); HRMS (ESIÀ): calcd for C16H13F4O3S [MÀOH]À 361.0522,
found 361.0532.
(CDCl3):
d
À125.9 (dd, 1F, 2JFF = 278.5, 3JFF = 6.0, CFaFb), À115.9 (dd,
1F, 2JFF = 278.5, 3JFF = 2.8 Hz), À112.5 (dd, 1F, 2JFF = 254.2, 3JFF = 6.0,
CFaFb), À110.6 (d, 1F, 2JFF = 254.2, 3JFF = 2.8 Hz, CFaFb); FTIR (film):
n
max 3536, 3070, 2958, 2931, 1860, 1584, 1468, 1359, 1315, 1176,
4.2.3.5. 2,2,3,3-Tetrafluoro-1-(naphthalen-1-yl)-3-(phenylsulfonyl)-
1095, 1076, 1024, 757, 685, 597, 538 cmÀ1; MS (EI): m/z (%) 356 (1)
[M]+, 256 (19), 195 (18), 141 (100), 115 (37), 97 (41), 77 (96), 55
(37); HRMS (CI+): calcd for C15H21F4O3S [M+H]+ 357.1148, found
357.1156.
propan-1-ol (5e).
4.2.3.8. 1,1,2,2-Tetrafluoro-5-phenyl-1-(phenylsulfonyl)pentan-3-ol
Yield: 150 mg (40%, GCMS purity 95%), yellow oil; Rf 0.10
(5h).
(EtOAc:hexane, 10:90); 1H NMR (CDCl3):
d
3.46 (br s, 1H, OH),
6.32 (d, 1H, J = 20.8, CH), 7.42–7.65 (m, 5H, CArH), 7.69–7.77 (m, 1H,
C
ArH), 7.82–7.91 (m, 3H, CArH), 7.98–8.10 (m, 3H, CArH); 13C NMR
2
1
(CDCl3):
d 67.7 (dd, JCF = 30.0, 21.7, CH), 115.8 (ddt, JCF = 259.0,
2JFF = 26.5, JFF = 25.4, CF2), 116.7 (ddt, JCF = 301.5, JFF = 32.2,
2JFF = 35.0, CF2), 123.1 (s, CArH), 125.1 (s, CArH), 125.7 (s, CArH),
126.7 (s, CArH), 126.8 (s, CArH), 129.5 (s, CArH), 129.9 (s, CArH), 129.9
(s, CArH), 130.1 (s, CAr), 130.9 (s, CArH), 131.4 (s, CAr), 132.2 (s, CAr),
2
1
2
Yield: 479 mg (51%, GCMS purity 98%), yellow oil; Rf 0.24
(EtOAc:hexane, 1:5); 1H NMR (CDCl3):
d 1.93–2.13 (m, 2H, CH2),
2.74 (m, 2H, CH2), 2.98 (m, 1H, CH), 4.27 (m, 1H, OH), 7.20–7.34 (m,
5H, CArH), 7.64 (2H, m-CArH-SO2), 7.81 (1H, p-CArH-SO2), 8.00 (d,
133.5 (s, CAr), 136.2 (s, CArH); 19F {1H} NMR (CDCl3):
d
À125.3 (dd,
1F, JFF = 280.8, 5.86, CFaFb), À112.0 (ddd, 1F, 2JFF = 253.0, 3JFF = 7.6,
2H, JHH = 7.7, o-CArH-SO2); 13C NMR (CDCl3):
d
30.2 (CH2), 31.1
3
2.7, CFaFb), À110.8 (dd, 1F, JFF = 280.8, JFF = 2.7, CFaFb), À110.6
(CH2), 69.5 (dd, JCF = 27.6, 23.3, CH), 112.9–119.5 (m, CF2CF2),
126.2 (s, CArH), 128.5 (s, CArH), 128.6 (s, CArH), 129.6 (s, m-CArH-
SO2), 131.0 (s, o-CArH-SO2), 132.1 (s, CAr), 136.2 (s, p-CArH-SO2),
2
3
2
(dd, 1F, 2JFF = 253.0, 3JFF = 2.7, CFaFb); FTIR (film):
nmax 3536, 3066,
1624, 1598, 1583, 1514, 1450, 1356, 1315, 1163, 1122, 1075, 1061,
999, 816, 757, 596, 537 cmÀ1; MS (EI): m/z (%) 398 (8) [M]+, 281
(23), 207 (100), 157 (85), 129 (40), 77 (21); HRMS (CI+): calcd for
140.7 (s, CAr-SO2); 19F {1H} NMR (CDCl3):
d
À125.6 (dddd, 1F,
2JFF = 278.9, JHF = 19.3, JFF = 6.6, 3.3, CFaFb), À115.8 (dm, 1F,
3
3
C
19H15O3F4S [M+H]+ 399.0678, found 399.0670.
2JFF = 278.9, CFaFb), À112.6 (ddd, 1F, JFF = 254.5, JFF = 6.6, 2.8,
2
3
CFaFb), À110.8 (dd, 1F, JFF = 254.6, JFF = 3.3, CFaFb); MS (EI): m/z
(%) 376 (9) [M]+, 215 (23), 197 (100), 91 (69), 77 (43); HRMS (CI+):
calcd for C17H17O3SF4 [M+H]+ 377.0835, found 377.0838.
2
3
4.2.3.6. 2,2,3,3-Tetrafluoro-1-(naphthalen-2-yl)-3-(phenylsulfonyl)-
propan-1-ol (5f).
4.2.3.9. 1,1,1,3,3,4,4-Heptafluoro-2-phenyl-4-(phenylsulfonyl)butan-
2-ol (5i).
Yield: 559 mg (56%, GCMS purity 96%), off-white solid; mp 106–
110 8C; Rf 0.12 (EtOAc:hexane, 1:5); 1H NMR (CDCl3):
d
3.18 (br s,
3
4
1H, OH), 5.58 (dd, 1H, JHF = 19.8, JH-H = 6.0, CH), 7.47–8.13 (m,
2
12H, CArH); 13C NMR (CDCl3):
d
72.4 (dd, JCF = 28.5, 22.1, CH),
Yield: 86 mg (48%, GCMS purity 95%), white solid; mp 107–109 8C;
112.5–119.5 (m, CF2CF2), 125.1 (s, CArH), 126.4 (s, CArH), 126.7 (s,
Rf 0.12 (EtOAc:hexane, 10:90); 1H NMR (CDCl3):
d
4.50 (br s, 1H,
OH), 7.50–7.58 (m, 3H, CArH), 7.67–7.76 (m, 2H, CAr ), 7.80–7.93
(m, 3H, CAr ), 8.02–8.12 (m, 2H, CAr 115.5–
); 13C NMR (CDCl3):
CArH), 127.7 (s, CArH), 128.0 (s, CArH), 128.2 (s, CArH), 128.3 (s,
d
C
ArH), 129.6 (s, m-CArH-SO2), 131.0 (s, o-CArH-SO2), 131.2 (s, CAr),
d
d
d
132.3 (s, CAr), 132.9 (s, CAr), 133.7 (s, CAr), 136.2 (s, p-CArH-SO2); 19
F
116.0 (m, CF2), 116.1 (tt, JCF = 300.0, JCF = 27.6, CF2), 118.8 (m,
CF3), 121.6 (s, CAr), 126.8 (s, CArH), 128.3 (s, CArH), 129.5 (s, CArH),
129.9 (s, CArH), 131.0 (s, CArH), 132.6 (s, CAr), 136.1 (s, CArH); 19F
1
2
{1H} NMR (CDCl3):
d
À124.4 (ddd, 1F, JFF = 279.8, JHF = 19.8,
2
3
3JFF = 6.4, CFaFb), À112.4 (d, 1F, 2JFF = 279.6, CFaFb), À111.9 (ddd, 1F,
2JFF = 254.0, JFF = 6.6, 2.3, CFaFb), À110.5 (dd, 1F, JFF = 254.0,
3JFF = 1.7, CFaFb); FTIR (film): nmax 3612, 3560, 3067, 1604, 1585,
1577, 1512, 1479, 1450, 1376, 1355, 1314, 1270, 1186, 1168, 1154,
1130, 1126, 1095, 1063, 1024, 999, 964, 952, 881, 861, 625, 596,
557, 520, 478 cmÀ1; MS (EI): m/z (%) 398 (18) [M]+, 157 (100), 129
(58), 77 (18); HRMS (CI+): calcd for C19H14O3SF4 [M]+ 398.0600,
found 398.0596.
NMR (CDCl3):
1F), À108.9 to À107.9 (m, 1F), À107.0 to À106.1 (m, 1F), À74.3 to
À74.1 (m, 3F, CF3); FTIR (film): max 3471, 1584, 1501, 1451, 1361,
1350, 1315, 1188, 1156, 1078, 997, 757, 705, 683, 589, 529 cmÀ1
d
À114.5 to À113.5 (m, 1F), À112.8 to À111.8 (m,
3
2
n
;
MS (EI): m/z (%) 416 (1) [M]+, 347 (16), 175 (100), 141 (44), 105
(62), 77 (96), 51 (23); HRMS (CI+): calcd for C16H12F7O3S [M+H]+
417.0395, found 417.0392.
4.2.3.7. 1,1,2,2-Tetrafluoro-1-(phenylsulfonyl)nonan-3-ol (5g).
4.2.4. Phenyl(1,1,2,2-tetrafluoroethyl)sulfide (PhSCF2CF2H)
NaBH4 (1.13 g, 30.0 mmol) and LiCl (1.27 g, 30.0 mmol) were
suspended in dry DMF (40 mL) in an oven-dried Schenk flask under
Ar. PhSCF2CF2Br (2.89 g, 10.0 mmol) was added dropwise at rt over
a period of 30 min and the mixture was stirred for 30 min. Water
(20 mL) was added slowly, the mixture was extracted with Et2O
(3 Â 20 mL), washed with brine (3 Â 15 mL) and water (2 Â 20 mL).
Solvent was removed under vacuum, affording product (1.34 g,
Yield: 135 mg (51%, GCMS purity > 98%), colorless oil; Rf 0.18
(EtOAc:hexane, 5:95); 1H NMR (CDCl3):
d 0.76–0.98 (m, 3H, CH3),