´
A. Harsanyi et al. / Journal of Fluorine Chemistry 132 (2011) 1241–1246
1245
tRET: 8.30 min. 1H NMR (CDCl3):
2H, J = 8.6 Hz). 13C NMR (CDCl3): 123.5 (q, JC,F = 21.8 Hz), 129.2 (q,
JC,F = 308.1 Hz), 125.9, 132.8, 137.7. 19F NMR (CDCl3):
(EI+): m/z (%) = 256 (97) [M]+, 187 (95) [MÀCF3]+, 158 (25) [MÀF–
Br]+, 108, (67) [MÀCF3-Br]+, 75 (29) [C6H3]+, 69 (100) [CF3]+, 63 (59)
[C5H3]+, 50 (56) [C4H2]+, 45 (25) [HCS]+.
d
7.50 (d, 2H, J = 8.5 Hz), 7.55 (d,
4.2.13. 2,4,6-Trimethylphenyl trifluoromethyl sulfide (2n)
Yield: 6.94 g (63%) colorless liquid from 7.61 g (50.0 mmol) of
d
À42.7. MS
1n, bp 92–93 8C/20 mmHg, solidifies at ꢀ20 8C. GC assay: 99%, tRET
9.73 min. 1H NMR (CDCl3):
2.28 (s, 3H), 2.52 (s, 6H), 6.98 (s, 2H).
13C NMR (CDCl3):
21.1, 22.0, 120.1 (q, JC,F = 2.2 Hz), 129.6, 141.4,
145.3, 130.2 (q, JC,F = 310.0 Hz). 19F NMR (CDCl3):
:
d
d
d
À41.9. MS (EI+):
m/z (%) = 220 (91) [M]+, 201 (6) [MÀF]+, 151 (100) [MÀCF3]+, 119
(15) [MÀSCF3]+, 105 (40) [MÀH2CSCF3]+, 107 (48) [MÀCSCF3]+, 91
(37) [C7H7]+, 77 (18) [C6H6]+, 69 (12) [CF3]+, 45 (38) [HCS]+, 65 (12)
[C5H5]+, 51 (12) [C4H3]+, 39 (15) [C3H3]+.
4.2.8. 2-Bromophenyl trifluoromethyl sulfide (2h)
Yield: 3.82 g (62%) colorless liquid from 4.54 g (24.0 mmol) of
1h, only steam-distilled. GC assay: 98%, tRET: 8.76 min. 1H NMR
(CDCl3):
d
7.30 (t, 1H, J = 5.9 Hz), 7.36 (t, 1H, J = 6.0 Hz), 7.71 (d, 1H,
126.4 (q,
J = 7.8 Hz), 7.76 (d, 1H, J = 7.6 Hz). 13C NMR (CDCl3):
d
4.2.14. 4-tert-Butyl-2,6-dimethylphenyl trifluoromethyl sulfide (2o,
n. c.)
JC,F = 2.2 Hz), 129.3 (q, JC,F = 308.0 Hz), 128.3, 130.6, 132.1, 133.9,
138.0. 19F NMR (CDCl3):
d
À42.0. MS (EI+): m/z (%) = 256 (70) [M]+,
Yield: 5.38 g (82%) colorless crystals from 4.86 g (25.0 mmol) of
187 (56) [MÀCF3]+, 158 (18) [MÀF–Br]+, 108 (100) [MÀCF3–Br]+,
75 (12) [C6H3]+, 69 (43) [CF3]+, 63 (16) [C5H3]+, 50 (15) [C4H2]+, 45
(6) [HCS]+.
1o, bp 131–133 8C (20 mmHg), mp 34–36 8C. GC assay: 98%, tRET
13.02 min. 1H NMR (CDCl3):
1.33 (s, 9H), 2.59 (s, 6H), 7.21 (s, 2H).
13C NMR (CDCl3):
22.4, 31.1, 34.6, 120.1 (q, JC,F = 2.2 Hz), 125.5,
129.8 (q, JC,F = 307.0 Hz), 144.6, 153.9. 19F NMR (CDCl3):
:
d
d
d
À41.7.
4.2.9. 2-(Trifluoromethylthio)aniline (2i)
Yield: 3.62 g (75%) colorless liquid from 3.13 g (25.0 mmol) of
1i, bp 112–114 8C (20 mmHg). GC assay: 98%, tRET: 8.52 min. 1H
MS (EI+): m/z (%) = 262 (63) [M]+, 247 (100) [MÀCH3]+, 219 (33)
[MÀC3H7]+, 207 (11) [MÀC4H7]+, 178 (29) [247-CF3]+, 163 (18)
[178-CH3]+, 161 (12) [MÀSCF3]+, 146 (46) [247-SCF3]+, 131 (29)
[146-CH3]+, 91 (26) [C7H7]+, 77 (14) [C6H6]+, 69 (15) [CF3]+, 57 (20)
[C4H9]+, 41 (38) [C3H5]+. HRMS (TOF, EI+): calculated for C13H17F3S:
262.1003; found: 262.0996.
NMR (CDCl3):
1.5 Hz), 7.45 (d, 1H, J = 7.6 Hz). 13C NMR (CDCl3):
JC,F = 2.2 Hz), 115.6, 118.6, 129.5 (q, JC,F = 306.6 Hz), 133.0, 139.1,
150.3. 19F NMR (CDCl3):
d
4.44 (s, 2H), 6.73 (m, 2H), 7.24 (td, 1H, J = 8.1 and
d
106.1 (q,
d
À42.8. MS (EI+): m/z (%) = 194 (18)
[M+H]+, 193 (100) [M]+, 173 (10) [MÀHF]+, 154 (33) [MÀHFCN]+,
124 (98) [MÀCF3]+, 97 (30) [MÀCF3–HCN]+, 91 (12) [C7H7]+, 80 (91)
[MÀCSCF3]+, 69 (32) [CF3]+, 65 (15) [C5H5]+, 53 (31) [C3H3N]+, 45
(18) [HCS]+, 39 (25) [C3H3]+.
4.2.15. n-Octyl trifluoromethyl sulfide (2p)
Yield: 1.18 g (22%) colorless liquid from 3.66 g (25.0 mmol) of
1p, bp 114–115 8C (20 mmHg). GC assay: 97%, tRET: 7.76 min. 1H
NMR (CDCl3):
J = 6.5 Hz), 1.68 (m, 2H), 2.87 (t, 2H, J = 6.5 Hz). 13C NMR (CDCl3):
14.0, 22.6, 28.5, 28.9, 29.4, 31.75, 29.9 (q, JC,F = 2.2 Hz), 131.3 (q,
JC,F = 305.0 Hz). 19F NMR (CDCl3):
d 0.88 (t, 3H, J = 6.6 Hz), 1.28 (s, 9H), 1.37 (t, 2H,
d
4.2.10. Methyl (2-trifluoromethythio)benzoate (2j)
Yield: 2.60 g (44%) colorless liquid from 4.21 g (25.0 mmol) of
1j, bp 119–121 8C (20 mmHg). GC assay: 99%, tRET: 10.93 min. 1H
d
À41.4. MS (EI+): m/z (%) = 214
[M+ not observed], 157 (17) [MÀC4H9]+, 145 (92) [MÀCF3]+, 129
(15) [MÀC6H13]+, 115 (42) [MÀC7H15]+, 69 (89) [CF3]+, 84 (34), 83
(47), 71 (42), 70 (69), 57 (70), 56 (100), 55 (75), 43 (73), 41 (62), 29
(64), 27 (60) [aliphatic marker ions].
NMR (CDCl3):
J = 7.5 Hz), 7.73 (d, 1H, J = 8.0 Hz), 7.91 (d, 1H, J = 7.8 Hz). 13C NMR
(CDCl3): 52.5, 128.2 (q, JC,F = 2.2 Hz), 128.7, 129.5 (q,
d 3.93 (s, 1H), 7.42 (t, 1H, J = 7.6 Hz), 7.52 (d, 1H,
d
JC,F = 308.0 Hz), 130.9, 132.4, 132.6, 132.7 (q, JC,F = 2.2 Hz), 166.6.
19F NMR (CDCl3):
d
À41.4. MS (EI+): m/z (%) = 236 (22) [M]+, 205
4.3. Inhibition experiments
(39) [MÀOCH3]+, 177 (6) [MÀCOOCH3]+, 167 (100) [MÀCF3]+, 152
(22) [MÀCF3–CH3]+, 136 (22) [MÀCF3–OCH3]+, 69 (20) [CF3]+, 63
(9) [C5H3]+, 50 (9) [C4H2]+, 45 (5) [HCS]+.
4.3.1. Reaction of PhSNa and CF3I in the presence of PhNO2
This experiment was performed according to the typical
procedure, but nitrobenzene (50 mmol and 2.5 mmol) was added
to the reaction mixture, and the reaction flask was covered with
aluminium foil to protect it from direct light. Yield of 2a: 76 and
77%, GC assay: 97 and 98%, respectively.
4.2.11. 2-Naphthyl trifluoromethyl sulfide (2l)
Yield: 2.68 g (47%) colorless liquid from 4.01 g (25.0 mmol) of
1l, only steam-distilled. GC assay: 99%, tRET: 13.39 min. 1H NMR
(CDCl3):
3H, J = 8.8 Hz), 8.16 (s, 1H). 13C NMR (CDCl3):
JC,F = 2.2 Hz), 129.8 (q, JC,F = 308.1 Hz), 126.9, 127.7, 127.9, 128.2,
129.2, 131.7, 133.4, 133.9, 136.9. 19F NMR (CDCl3):
(EI+): m/z (%) = 228 (92) [M]+, 189 (12) [MÀC3H3]+, 159 (89)
[MÀCF3]+, 127 (10) [MÀSCF3]+, 115 (100) [MÀCSCF3]+, 89 (18)
[C7H5]+, 69 (27) [CF3]+, 63 (18) [C5H3]+, 50 (12) [C4H2]+.
d
7.53 (m, 2H, J = 5.0 Hz), 7.63 (d, 1H, J = 8.5 Hz), 7.82 (d,
d
121.5 (q,
4.3.2. Reaction of PhSNa and CF3I in the presence of 4-
CH3C6H4CH55CH2
d
À42.4. MS
Thiophenol (2.75 g, 25 mmol) was reacted with NaH and CF3I in
the presence of 4-methylstyrene (8.85 g, 75 mmol, bp: 63–65 8C/
17 mmHg) as described in the typical procedure. Steam distillation
and ether extraction allowed to recover pure 4-methylstyrene as a
colorless liquid (7.08 g, 80% recovery, analyzed by GC and NMR),
but no PhSCF3 (2a) was detected in the distillate. The residue was
acidified with 5% aq-HCl and extracted with ether. The organic
layer was separated, washed with water and dried (Na2SO4). The
evaporation of the ether extract gave a yellow oil (2.20 g, 80%
recovery), which was a 30:70% mixture of PhSH and Ph2S2 (GC).
4.2.12. 2-Trifluoromethylthio-5,6,7,8-tetrahydronaphthalene
(2m, n. c.)
Yield: 1.45 g (25%) colorless liquid from 4.11 g (25.0 mmol) of
1m, only steam-distilled. GC assay: 96%, tRET: 13.20 min. 1H NMR
(CDCl3):
J = 8.5 Hz), 7.34 (s, 2H). 13C NMR (CDCl3):
120.5 (q, JC,F = 2.2 Hz), 129.7 (q, JC,F = 308.0 Hz), 130.2, 133.2, 137.0,
138.7, 140.5. 19F NMR (CDCl3):
d
1.79 (quintett, 4H, J = 3.0 Hz), 2.77 (s, 4H), 7.08 (d, 1H,
d
22.7, 22.8, 29.1, 29.2,
4.4. Preparation of stock solutions of CF3I
d
À43.1. MS (EI+): m/z (%) = 232 (75)
[M]+, 213 (5) [MÀF]+, 204 (22) [MÀC2H4]+, 191 (9) [MÀC3H5]+, 163
(8) [MÀCF3]+, 135 (19) [MÀC2H4CF3]+, 131 (100), [MÀSCF3]+, 130
(31) [MÀHSCF3]+, 115 (24) [C9H7]+, 91 (38) [C7H7]+, 77 (8) [C6H5]+,
69 (9) [CF3]+, 65 (7) [C5H5]+, 51 (7) [C4H3]+, 39 (6) [C3H3]+. HRMS
(TOF, EI+): calculated for C11H11F3S: 232.0534; found: 232.0540.
To a pre-weighed 100 ml one necked round bottom flask
equipped with a magnetic stirrer bar (also weighed) DMSO is
measured by weight (44.72 g). A balloon is filled with approxi-
mately 25 g of CF3I, sealed and fixed to the neck of the flask. The
seal is opened and the DMSO is stirred in a cold water bath for