Y. M a c é, B. Raymondeau, C. Pradet, J.-C. Blazejewski, E. Magnier
(75 MHz, CDCl3): δ = 157.3, 149.2, 128.4, 128.2, 126.8, 126.2, δ = –52.8 (s, 3 F), –79.0 (s, 3 F) ppm. 1H NMR (200 MHz, CDCl3):
FULL PAPER
125.9, 125.9, 124.8 (q, J = 335 Hz, SOCF3), 43.5, 30.6 ppm. MS
(EI): m/z = 312 [M+], 243 [M – CF3+]. HRMS: calcd. for
C16H15F3NaO32S 335.0693; found 335.0695 (δ = –0.5 ppm).
δ = 8.32 (d, J = 8.3 Hz, 1 H), 7.97 (m, 1 H), 7.92 (s, 1 H), 7.85 (t,
J = 7.5 Hz, 1 H), 7.75 (d, J = 7.5 Hz, 1 H), 7.70 (d, J = 8.3 Hz, 1
H), 2.78 (s, 3 H), 2.54 (s, 3 H) ppm.
1-Phenoxy-4-[(trifluoromethyl)sulfinyl]benzene (36p) and 1-Phen-
oxy-2-[(trifluoromethyl)sulfinyl]benzene (36o): Diphenyl ether
(0.99 g, 5.8 mmol) gave isomers 36o/36p (20:80; 1.07 g, 3.74 mmol,
64%). 13C NMR (75 MHz, CDCl3): δ = 162.7, 156.2, 155.0, 154.7,
134.7, 130.2, 128.4, 128.1, 127.0, 125.3, 125.3 (q, J = 337 Hz),
125.1, 124.8 (q, J = 335 Hz), 123.6, 120.3, 120.0, 118.3, 116.6 ppm.
MS (EI): m/z = 286 [M+], 217 [M – CF3+]. C13H9F3O2S (286.27):
calcd. C 54.54, H 3.17; found C 54.41, H 3.15. Data for 36p: 19F
NMR (188 MHz, CDCl3): δ = –75.6 (s, 3 F) ppm. 1H NMR
(300 MHz, CDCl3): δ = 7.71 (d, J = 8.5 Hz, 2 H), 7.36 (t, J =
7.5 Hz, 2 H), 7.18 (t, J = 7.5 Hz, 1 H), 7.10 (d, J = 9.0 Hz, 2 H),
7.04 (d, J = 7.5 Hz, 2 H) ppm. Data for 36o: 19F NMR (188 MHz,
2,4-Dimethyl-5-(trifluoromethyl)dibenzo[b,d]thiophenium Trifluoro-
methanesulfonate (18): Compound 13 (0.85 g, 4.7 mmol) 18 gave
(0.7 g, 1.63 mmol, 36%). M.p. 138.6Ϯ0.2 °C. 19F NMR (188 MHz,
CDCl3): δ = –52.8 (s, 3 F), –78.8 (s, 3 F) ppm. 1H NMR (300 MHz,
CDCl3): δ = 8.43 (d, J = 8.0 Hz, 1 H), 8.11 (d, J = 7.7 Hz, 1 H),
7.93 (t, J = 7.6 Hz, 1 H), 7.89 (s, 1 H), 7.73 (t, J = 7.7 Hz, 1 H),
7.37 (s, 1 H), 2.74 (s, 3 H), 2.55 (s, 3 H) ppm. 13C NMR (75 MHz,
CDCl3): δ = 148.9, 142.3, 142.0, 141.0, 136.3, 134.1, 131.9, 130.5,
124.8, 124.3 (q, J = 220 Hz, CF3), 123.5 (q, J = 256 Hz, CF3),
123.5, 122.9, 118.4, 21.9, 20.7 ppm. MS (ESI+): m/z = 281 [M +
H+], 212 [M + H – CF3+]. C16H12F6O3S2 (430.39): calcd. C 44.65,
H, 2.81; found C 44.79, H 3.17.
1
CDCl3): δ = –74.3 (s, 3 F) ppm. H NMR (300 MHz, CDCl3): δ =
2,4,6,8-Tetramethyl-5-(trifluoromethyl)dibenzo[b,d]thiophenium Tri-
fluoromethanesulfonate (19): Compound 14 (0.21 g, 1.0 mmol) gave
19 (0.21 g, 0.46 mmol, 46%). M.p. 170.1Ϯ0.2 °C. 19F NMR
(188 MHz, CDCl3): δ = –52.8 (s, 3 F), –78.9 (s, 3 F) ppm. 1H NMR
(300 MHz, CDCl3): δ = 7.70 (s, 2 H), 7.32 (s, 2 H), 2.77 (s, 6 H),
2.52 (s, 2 H) ppm. 13C NMR (75 MHz, CDCl3): δ = 148.2, 142.7,
140.9, 133.9, 129.3 (q, J = 349 Hz, CF3), 124.9 (q, J = 332 Hz,
CF3), 123.4, 119.7, 21.9, 20.7 ppm. MS (ESI+): m/z = 309 [M +
H+], 240 [M + H – CF3+]. C18H16F6O3S2 (458.44): calcd. C 47.16,
H 3.52; found C 47.31, H 3.81.
8.00 (dd, J = 7.8, 1.5 Hz, 1 H), 7.44 (t, J = 7.4 Hz, 1 H), 7.36 (t, J
= 7.5 Hz, 2 H), 7.25 (t, J = 7.4 Hz, 1 H), 7.18 (t, J = 7.4 Hz, 1 H),
7.04 (d, J = 7.5 Hz, 2 H), 6.81 (dd, J = 8.3, 0.8 Hz, 1 H) ppm.
General Procedure for the Preparation of Sulfonium Salts: Under an
atmosphere of argon, a round-bottomed flask was charged with
pure potassium trifluoromethanesulfinate (0.5 g, 3 mmol) dried un-
der high vacuum and trifluoromethanesulfonic anhydride (1 mL,
6 mmol). After stirring for 5 min, the substrate (3 mmol) was
added, and the resulting mixture was stirred at room temperature.
After consumption of the starting material (monitored by TLC),
the reaction mixture was filtered, diluted with CH2Cl2 (10 mL),
washed with brine (10 mL) and then a solution of NaHCO3
(10 mL), dried with MgSO4 and concentrated under reduced pres-
sure. The residue was purified by column chromatography on silica
gel (dichloromethane/methanol, 95:5)to give a slightly off-white
powder.
2,4-Dimethyl-7-nitro-5-(trifluoromethyl)dibenzo[b,d]thiophenium Tri-
fluoromethanesulfonate (20): Compound 15 (0.1 g, 0.44 mmol) gave
20 (0.06 g, 0.11 mmol, 27%). M.p. 146.0Ϯ0.2 °C. 19F NMR
(188 MHz, CDCl3): δ = –52.0 (s, 3 F), –79.5 (s, 3 F) ppm. 1H NMR
(300 MHz, CDCl3): δ = 9.18 (s, 1 H), 8.74 (d, J = 8.3 Hz, 1 H),
8.28 (d, J = 8.9 Hz, 1 H), 7.91 (s, 1 H), 7.50 (s, 1 H), 2.80 (s, 3 H),
2.60 (s, 3 H) ppm. 13C NMR (75 MHz, CDCl3): δ = 149.2, 149.1,
147.2, 140.7, 139.9, 135.2, 131.0, 125.7, 125.3, 124.9, 124.8, 123.8
(q, J = 332 Hz, CF3), 121.7, 120.3 (q, J = 319 Hz, CF3), 20.4,
19.2 ppm. MS (ESI+): m/z = 326 [M + H+], 257 [M + H – CF3+].
HRMS: calcd. for C15H1119F3NO232S 326.0472; found 326.0463 (δ
= 3.0 ppm).
5-(Trifluoromethyl)dibenzo[b,d]thiophenium Trifluoromethanesulfon-
ate (9): 1,1Ј-Biphenyl (0.5 g, 3.24 mmol) gave 9 (0.15 g, 0.37 mmol,
12%). M.p. 133Ϯ0.2 °C. 19F NMR (188 MHz, CDCl3): δ = –53.7
1
(s, 3 F), –79.0 (s, 3 F) ppm. H NMR (200 MHz, CDCl3): δ = 8.43
(d, J = 7.9 Hz, 2 H), 8.16 (d, J = 8.1 Hz, 2 H), 8.00 (t, J = 7.7 Hz,
2 H), 7.80 (t, J = 7.6 Hz, 2 H) ppm. 13C NMR (50 MHz, CDCl3):
δ = 141.8, 136.0, 131.7, 129.2, 124.8, 124.0, 120.3 (q, J = 318 Hz,
CF3) ppm. MS (CI): m/z = 253 [M + H+], 184 [M + H – CF3+].
Bis(4Ј-nitro-1,1Ј-biphenyl-4-yl)(trifluoromethyl)sulfonium Trifluoro-
methanesulfonate (29): Compound 25 (0.58 g, 2.9 mmol) gave
(0.28 g, 0.43 mmol, 30%). M.p. 100.4Ϯ0.2 °C. 19F NMR
(188 MHz, CDCl3): δ = –50.3 (s, 3 F), –78.9 (s, 3 F) ppm. 1H NMR
(300 MHz, CDCl3): δ = 8.29 (m, 8 H), 8.00 (m, 4 H), 7.73 (m, 4
H) ppm. 13C NMR (50 MHz, CDCl3): δ = 148.6, 147.5, 143.5,
133.6, 130.9, 129.6 (q, J = 301.0 Hz, CF3), 128.6, 126.2 (q, J =
298.0 Hz, CF3), 124.6, 116.8 ppm. MS (ESI+): m/z = 497 [M +
H+], 428 [M + H – CF3+]. HRMS: calcd. for C25H1619F3N2O432S
497.0782; found 497.0783 (δ = –0.1 ppm).
1,1Ј-Biphenyl-4-yl Trifluoromethyl Sulfide (11): 1,1Ј-Biphenyl (0.5 g,
3.24 mmol) gave 11 (0.39 g, 1.54 mmol, 47%). M.p. 40.7Ϯ0.2 °C.
19F NMR (188 MHz, CDCl3): δ = –43.2 (s, 3 F) ppm. 1H NMR
(200 MHz, CDCl3): δ = 7.82–7.58 (m, 6 H), 7.56–7.37 (m, 3 H)
ppm. 13C NMR (50 MHz, CDCl3): δ = 143.8, 139.6, 136.6, 129.6
(q, J = 308 Hz, SCF3), 128.9, 128.1, 127.2, 123.0 ppm. MS (CI):
m/z = 255 [M + H+]. C13H9F3S (254.27): calcd. C 61.41, H 3.57;
found C 61.13, H 3.46.
Bis(4-benzylphenyl)(trifluoromethyl)sulfonium Trifluoromethanesul-
fonate (30): Compound 26 (0.98 g, 5.8 mmol) gave 30 (0.83 g,
1.43 mmol, 48%). 19F NMR (188 MHz, CDCl3): δ = –51.3 (s, 3 F),
2,8-Dimethyl-5-(trifluoromethyl)dibenzo[b,d]thiophenium Trifluoro-
methanesulfonate (16) and 2,6-Dimethyl-5-(trifluoromethyl)dibenzo-
[b,d]thiophenium Trifluoromethanesulfonate (17): 3,3Ј-Dimethyl-
1,1Ј-biphenyl (2.12 g, 11.66 mmol) gave isomers 16/17 (70:30;
0.76 g, 1.77 mmol, 15%). M.p. 135.6Ϯ0.2 °C. 13C NMR (50 MHz,
CD2Cl2): δ = 148.4, 141.4, 136.2, 132.8, 132.6, 129.4, 129.3, 125.5
(q, J = 224.0 Hz, CF3), 125.0, 124.9, 122.0, 119.4 (q, J = 225.0 Hz,
CF3), 118.4, 21.4, 20.2 ppm. MS (ESI+): m/z = 281 [M+], 212 [M –
CF3+]. C16H12F6O3S2 (430.39): calcd. C 44.65, H 2.81, found C
45.03, H 3.22. Data for 16:[12b] 19F NMR (188 MHz, CDCl3): δ =
1
–78.9 (s, 3 F) ppm. H NMR (300 MHz, CDCl3): δ = 8.00 (d, J =
8.5 Hz, 4 H), 7.51 (d, J = 8.5 Hz, 4 H), 7.29–7.18 (m, 6 H), 7.09 (d,
J = 8.2 Hz, 4 H), 4.03 (s, 4 H) ppm. 13C NMR (75 MHz, CDCl3): δ
= 152.1, 138.1, 133.0, 132.6, 129.1, 129.0, 128.8 (q, J = 336.0 Hz,
CF3), 127.1, 126.2 (q, J = 324.0 Hz, CF3), 114.2, 41.8 ppm. MS
(ESI+): m/z = 435 [M + H+], 366 [M + H – CF3+]. C28H22F6O3S2
(584.59): calcd. C 57.53, H 3.79; found C 57.22, H 3.57.
1
–54.8 (s, 3 F), –79.0 (s, 3 F) ppm. H NMR (200 MHz, CDCl3): δ
Bis[4-(1-methyl-1-phenylethyl)phenyl](trifluoromethyl)sulfonium Tri-
fluoromethanesulfonate (31): Compound 27 (0.57 g, 2.9 mmol) gave
31 (0.45 g, 0.71 mmol, 48%). M.p. 173Ϯ0.2 °C. 19F NMR
= 8.26 (d, J = 8.1 Hz, 2 H), 8.01 (s, 2 H), 7.55 (d, J = 8.1 Hz, 2
H), 2.60 (s, 6 H) ppm. Data for 17: 19F NMR (188 MHz, CDCl3):
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Eur. J. Org. Chem. 2009, 1390–1397