V.M. Timoshenko et al. / Journal of Fluorine Chemistry 131 (2010) 172–183
181
J = 281.0 Hz, CF3), 126.69 (q, J = 283.0 Hz, CF3), 126.95, 127.00,
127.02, 127.10, 128.52, 128.65 (CH–Ar of both isomers), 144.66 (C–
Ar), 145.71* (C–Ar). GC/MS (m/e): 332 (M+, 2%), 227 (M+–C8H9,
14%), 194 (M+–C8H10S, 89%), 105 (C8H9+, 100%). Anal. Calcd for
2.38 (d, J = 8.1 Hz, 1H-7), 2.40* (d, J = 9.0 Hz, 1H-7), 3.24* (m, H-4),
3.54 (m, H-4), 4.16 (m, H-1 of both isomers), 4.34* (q, J = 7.1 Hz,
CH–CH3), 4.46 (q, J = 7.1 Hz, CH–CH3), 5.84* (m, H-6), 5.94 (m, H-
6), 6.33* (tdd, J = 53.4, 6.5, 5.1 Hz, HCF2), 6.47 (tdd, J = 53.4, 8.1,
3.0 Hz, HCF2), 6.45 (m, H-5 of both isomers), 7.21–7.36 (m, H–Ar of
C16H19F3S2: C, 57.81; H, 5.76; S, 19.29. Found: C, 57.82; H, 5.77; S,
19.25.
both isomers). 13C NMR (CDCl3):
d 24.59* (CH3), 24.62 (CH3),
47.60* (t, J = 2.3 Hz, C-1), 47.65 (C-1), 51.65* (C-7), 52.07 (C-7),
54.05* (t, J = 1.5 Hz, C-4), 54.90 (C-4), 55.05* (C–Me), 55.43 (t,
J = 2.0 Hz, C–Me), 72.51* (dd, J = 21.3, 18.0 Hz, C-3), 73.14 (t,
J = 19.0 Hz, C-3), 109.60 (tt, J = 252.0, 32.5 Hz, HCF2), 109.72* (tt,
J = 253.0, 33.0 Hz, HCF2), 114.5–121.0 (m, CF2 of both isomers),
126.94, 127.19, 127.33, 127.37. 128.75, 128.76 (CH–Ar of both
isomers), 132.09 (C-6), 132.23* (C-6), 138.99* (t, J = 2.5 Hz, C-5),
139.19 (t, J = 2.0 Hz, C-5), 144.10 (C–Ar), 144.83* (C–Ar). GC/MS
(m/e): 282 (M+–C5H6, 4%), 105 (C8H9+, 100%). Anal. Calcd for
4.4.7. 4,5-Dimethyl-2-[(1-phenylethyl)thio]-2-(1,1,2,2-
tetrafluoroethyl)-3,6-dihydro-2H-thiopyran (5g)
Colourless oil, yield 98%, mixture of isomers in the ratio 46:54
from HPLC, solvent MeCN:H2O (85:15), tr 8.5 (minor) and 9.3
(major) min. 19F NMR (CDCl3):
d
ꢀ117.30* (1F, AB, J = 266.0 Hz,
CF2), ꢀ119.68 (1F, AB, J = 266.0 Hz, CF2), ꢀ121.10 (1F of both
isomers, AB, J = 266.0 Hz), ꢀ133.46 (1F, AB d, J = 299.0, 53.1 Hz,
HCF2), ꢀ134.50* (1F, AB d, J = 299.0, 53.1 Hz, HCF2), ꢀ135.78* (1F,
AB d, J = 299.0, 53.1 Hz, HCF2), ꢀ136.38 (1F, AB d, J = 299.0, 53.1 Hz,
C
16H16F4S2: C, 55.15; H, 4.63; S, 18.41. Found: C, 55.18; H, 4.68; S,
HCF2). 1H NMR (CDCl3):
d
1.32 (s, CH3), 1.57* (d, J = 7.2 Hz, CH3CH),
18.25.
1.63 (d, J = 7.2 Hz, CH3CH), 1.64 (s br, CH3 of both isomers), 1.72* (s,
CH3), 2.09* (1H, AB, J = 18.0 Hz, H-30), 2.15 (1H, AB, J = 19.0 Hz, H-
30), 2.60–2.94 (m, H-30 of both isomers + 3H-60), 3.49 (1H, AB,
J = 16.2 Hz, H-60), 4.24 (2 q, J = 7.2 Hz, CH–CH3 of both isomers),
6.14* (1H, tdd, J = 53.1, 7.6, 4.4 Hz, HCF2), 6.47 (1H, tdd, J = 53.1, 7.2,
4.5 Hz, HCF2), 7.26 (m, C6H5 of both isomers). GC/MS (m/e): 364
(M+, 2%), 259 (M+–C8H9, 10%), 226 (M+–C8H10S), 211 (100%), 105
(C8H9+, 85%). Anal. Calcd for C17H20F4S2: C, 56.02; H, 5.53; S, 17.60.
Found: C, 56.05; H, 5.56; S, 17.50.
4.4.11. 4,5-Dimethyl-2-trifluoromethyl-2-{[(1S)-exo-1,7,7-
trimethylbicyclo[2.2.1]hept-2-yl]thio}-3,6-dihydro-2H-thiopyran
(5k)
Pale-yellow oil, yield 98%, mixture of isomers in the ratio 41:59
from HPLC, solvent MeOH:H2O (87:13), tr 36.0 (major) and 37.6
(minor) min. 19F NMR (CDCl3):
1H NMR (CDCl3):
d
ꢀ74.08 (s, CF3), ꢀ74.34* (s, CF3).
d
0.82 (s, CH3 of both isomers), 0.84* (s, CH3),
0.90* (s, CH3), 0.97 (s, CH3), 0.99 (s, CH3), 1.11–1.43 (m, CH2 of both
isomers), 1.61–1.77 (m, CH2 + 2CH3 of both isomers), 1.93–1.99 (m,
CH2 of both isomers), 2.15–2.24 (m, H-30 of both isomers), 2.73–
2.90 (m, H-30 + H-60 of both isomers), 3.00–3.05 (m, 2H-60 of both
4.4.8. 2-[(1-Phenylethyl)thio]-2-trifluoromethyl-3,6-dihydro-2H-
thiopyran (5h)
Pale-yellow oil, yield 98%, mixture of isomers in the ratio 34:66
from HPLC, solvent MeCN:H2O (75:25), tr 24.6 (minor) and 26.2
isomers), 3.33 (dd, J = 15.2, 14.8, H-2 of both isomers). GC/MS (m/
e): 364 (M+, 2%), 194 (M+–C10H18S, 100%), 179 (80%), 137 (C10H17
,
+
(major) min. 19F NMR (CDCl3):
1H NMR (CDCl3):
d
ꢀ74.15 (s, CF3), ꢀ74.94* (s, CF3).
81%). Anal. Calcd for C18H27F3S2: C, 59.31; H, 7.47; S, 17.59. Found:
C, 59.35; H, 7.49; S, 17.36.
d
1.62 (d, J = 7.2 Hz, CH3), 1.67* (d, J = 7.2 Hz, CH3),
2.29 (m, H-30 of both isomers), 2.64–2.91 (m, H-30 of both isomer
+2H-60 of major isomer), 3.10 (dm, J = 16.6 Hz, H-60), 3.51 (dm,
J = 16.6 Hz, H-60), 4.32 (q, J = 7.2 Hz, CH–CH3), 4.34* (q, J = 7.2 Hz,
CH–CH3), 5.47 (m, H-4), 5.67* (m, H-4), 5.80 (m, H-4 of both
isomer), 7.28 (m, C6H5 of both isomers). GC/MS (m/e): 304 (M+, 2%).
Anal. Calcd for C14H15F3S2: C, 55.24; H, 4.97; S, 21.07. Found: C,
55.26; H, 4.99; S, 20.90.
4.4.12. 4,5-Dimethyl-2-(1,1,2,2-tetrafluoroethyl)-2-{[(1S)-exo-1,7,7-
trimethylbicyclo[2.2.1]hept-2-yl]thio}-3,6-dihydro-2H-thiopyran (5l)
Colourless oil, yield 85%. Rf 0.33 (hexane), mixture of isomers in
the ratio 40:60 from HPLC, solvent MeOH:H2O (87:13), tr 27.0
(major) and 28.2 (minor) min. 19F NMR (CDCl3):
d
ꢀ118.67* (1F,
AB, J = 263.5 Hz, CF2), ꢀ119.82 (1F, AB, J = 259.0 Hz, CF2), ꢀ121.49
(2F, AB of both isomers), ꢀ132.47 (1F, ddm, J = 297.0, 54.0 Hz,
HCF2), ꢀ133.42* (1F, ddm, J = 297.0, 54.0 Hz, HCF2), ꢀ136.69* (1F,
ddm, J = 297.0, 54.0 Hz, HCF2), ꢀ137.55 (1F, ddm, J = 297.0,
4.4.9. 3-[(1-Phenylethyl)thio]-3-trifluoromethyl-2-
thiabicyclo[2.2.1]hept-5-ene (5i)
Pale-yellow oil, yield 90%. Rf 0.40–0.45 (hexane:CH2Cl2, 5:1),
54.0 Hz, HCF2). 1H NMR (CDCl3):
d 0.82* (s, CH3), 0.84 (s, CH3),
mixture of four isomers. Data for two main isomers are given. 19
F
0.88* (s, CH3), 0.90 (s, CH3), 0.94 (s, CH3), 0.95* (s, CH3), 1.09–1.37
(m, CH2 of both isomers), 1.62–1.76 (m, CH2 of both isomers), 1.70
(s, CH3 of both isomers), 1.76 (s, CH3 of both isomers), 1.93–2.02
(m, CH2 of both isomers), 2.12 (1H, d, J = 17.7 Hz, H-30), 2.18* (1H,
d, J = 17.7 Hz, H-30), 2.78–2.87 (m, H-30 + H-60 of both isomers),
2.99–3.04 (m, H-2 of both isomers), 3.32* (1H, d, J = 14.7 Hz, H-60),
3.37 (1H, d, J = 14.7 Hz, H-60), 6.52* (1H, tdd, J = 54.0, 8.4, 3.5 Hz,
NMR (CDCl3):
d
ꢀ63.95 (s, CF3), ꢀ65.71* (s, CF3). 1H NMR (CDCl3):
d
1.58 (d, J = 7.1 Hz, CH3), 1.68 (d, J = 9.5 Hz, 1H-7), 1.71* (d,
J = 7.1 Hz, CH3), 1.83* (d, J = 9.5 Hz, 1H-7), 2.36 (d, J = 9.5 Hz, 1H-
7), 2.37* (d, J = 9.5 Hz, 1H-7), 3.03 (m, H-4), 3.52* (m, H-4), 4.13 (m,
H-1), 4.19* (m, H-1), 4.39 (q, J = 7.1 Hz, CH–CH3), 4.47* (q,
J = 7.1 Hz, CH–CH3), 5.77 (m, H-6), 5.94* (m, H-6), 6.42 (dd,
J = 5.3, 2.8 Hz, H-5), 6.52* (dd, J = 5.0, 2.8 Hz, H-5), 7.21–7.41 (m, H–
HCF2), 6.57 (1H, tdd, J = 54.0, 8.3, 3.4 Hz, HCF2). 13C NMR (CDCl3):
d
Ar of both isomers). GC/MS (m/e): 250 (M+–C5H6, 2%), 105 (C8H9
,
14.37 (CH3), 14.75* (CH3), 19.20* (CH3), 19.32 (CH3), 19.74 (CH3),
19.86* (CH3), 20.31 (CH3), 20.40* (CH3), 20.98 (CH3), 21.00* (CH3),
27.45 (C-5), 27.51* (C-5), 29.24* (C-60), 29.42 (C-60), 36.86 (m, C-60
of both isomers), 38.45 (C-6), 38.69* (C-6), 42.88* (m, C-30), 44.15
(C-30), 46.21* (C-4), 46.32 (C-4), 47.38* (C-7), 47.39 (C-7), 50.54
(C-1), 50.59* (C-1), 52.95* (q, J = 1.0 Hz, C-2), 53.19 (q, J = 1.5 Hz,
C-2), 60.49* (t, J = 22.0 Hz, C-20), 60.61 (t, J = 21.0 Hz, C-20), 109.43
(tdd, J = 253.0, 32.0, 30.2, Hz, HCF2), 109.62* (tdd, J = 253.0, 33.0,
30.0 Hz, HCF2), 117.13* (tm, J = 261.0 Hz, CF2), 117.16 (tm,
J = 261.0 Hz, CF2), 122.51, 122.57, 123.71, 124.13 (C-40,50 of both
+
100%). Anal. Calcd for C15H15F3S2: C, 56.94; H, 4.78; S, 20.27.
Found: C, 56.99; H, 4.82; S, 20.01.
4.4.10. 3-[(1-Phenylethyl)thio]-3-(1,1,2,2-tetrafluoroethyl)-2-
thiabicyclo[2.2.1]hept-5-ene (5j)
Pale-yellow oil, yield 85%. Rf 0.40–0.45 (hexane:CH2Cl2, 5:1),
mixture of four isomers. Data for two main isomers are given. 19
F
NMR (CDCl3):
d
ꢀ105.56 (1F, AB, J = 263.0 Hz, CF2), ꢀ106.23* (1F,
AB, J = 263.0 Hz, CF2), ꢀ114.46* (1F, AB, J = 263.0 Hz, CF2), ꢀ116.09
(1F, AB, J = 263.0 Hz, CF2), ꢀ136.41 (1F, d AB, J = 299.5, 53.4 Hz,
HCF2), ꢀ137.28* (2F, dm, J = 53.4 Hz, HCF2), ꢀ139.04 (1F, d AB,
isomers). GC/MS (m/e): 396 (M+, 2%), 227 (M+–C10H17S, 73%), 226
(M+–C10H18S, 100%), 137 (C10H17
, 60%). Anal. Calcd for
+
J = 299.5, 53.4 Hz, HCF2). 1H NMR (CDCl3):
d
1.56–1.65 (m, 1H-7 of
C
19H28F4S2: C, 57.55; H, 7.12; S, 16.17. Found: C, 57.56; H, 7.13;
both isomers), 1.63* (d, J = 7.1 Hz, CH3), 1.70 (d, J = 7.1 Hz, CH3),
S, 16.02.