Chin-Fa Lee et al.
ringe. The alkyl thiol (1.0 mmol) was then added by syringe, and the vial
sealed with a cap containing a PTFE septum and the reaction vessel was
heated at 1358C in an oil bath. After stirring at this temperature for 48 h,
the heterogeneous mixture was cooled to room temperature and diluted
with ethyl acetate (20 mL). The resulting solution was directly filtered
through a pad of Celite then washed with ethyl acetate (20 mL) and con-
centrated under reduced pressure to give the crude material, which was
then purified by column chromatography (SiO2, hexane or hexane/
EtOAc 9:1) to yield 5.
29.2, 29.3, 29.5, 29.6, 29.6, 29.6, 31.9, 35.8, 55.2, 114.4, 126.9, 132.8,
158.6 ppm.
Hexyl 3-methylphenyl sulfide 5 f (Table 4, entry 6)
Following the general procedure for Table 4, 1-hexanethiol (0.141 mL,
1.0 mmol), 3-iodotoluene (0.156 mL, 1.2 mmol), and L3 (36.0 mg,
0.2 mmol) in toluene. The crude product was then purified by column
chromatography (SiO2, hexane) to provide 5 f as a colorless oil (175 mg,
84% yield). 1H NMR (400 MHz, CDCl3): d=0.85–0.89 (m, 3H), 1.27–
1.33 (m, 4H), 1.37–1.44 (m, 2H), 1.58–1.66 (m, 2H), 2.29 (s, 3H), 2.86–
2.91 (m, 2H), 6.92–6.95 (m, 1H), 7.08–7.16 ppm (m, 3H); 13C NMR
(400 MHz, CDCl3): d=14.0, 21.2, 22.5, 28.5, 29.0, 31.3, 33.4, 125.6, 126.4,
128.5, 129.3, 136.7, 138.4 ppm. HREI-MS calcd. for C13H20S: 208.1285,
found: 208.1279.
Dodecyl 4-methylphenyl sulfide 5a (Table 4, entry 1)[4a]
Following the general procedure for Table 4, using 1-dodecanethiol
(0.240 mL, 1.0 mmol), 4-iodotoluene (261 mg, 1.2 mmol), and L3
(36.0 mg, 0.2 mmol) in toluene. The crude product was purified by
column chromatography (SiO2, hexane) to provide 5a as a colorless oil
(237 mg, 81% yield). 1H NMR (400 MHz, CDCl3): d=0.88 (t, J=6.8 Hz,
3H), 1.25–1.31 (m, 16H), 1.37–1.40 (m, 2H), 1.56–1.62 (m, 2H), 2.28 (s,
3H), 2.84 (t, J=7.4 Hz, 2H), 7.05 (d, J=8.0 Hz, 2H), 7.22 ppm (d, J=
8.4 Hz, 2H); 13C NMR (100 MHz, CDCl3): d=14.1, 20.9, 22.6, 28.8, 29.1,
29.2, 29.3, 29.5, 29.6, 29.6, 29.6, 31.9, 34.2, 129.5, 129.6, 133.2, 135.5 ppm.
Hexyl 2-methylphenyl sulfide 5g (Table 4, entry 7)
Following the general procedure for Table 4, using 1-hexanethiol
(0.141 mL, 1.0 mmol), 2-iodotoluene (0.156 mL, 1.2 mmol), and L3
(36.0 mg, 0.2 mmol) in toluene. The crude product was then purified by
column chromatography (SiO2, hexane) to provide 5g as a colorless oil
1
(162 mg, 78% yield). H NMR (400 MHz, CDCl3): d=0.85–0.90 (m, 3H),
Dodecyl 3-methylphenyl sulfide 5b (Table 4, entry 2)
1.26–1.32 (m, 4H), 1.39–1.46 (m, 2H), 1.61–1.69 (m, 2H), 2.33 (s, 3H),
2.82–2.89 (m, 2H), 7.02–7.06 (m, 1H), 7.11–7.14 (m, 2H), 7.18–7.23 ppm
(m, 1H); 13C NMR (400 MHz, CDCl3): d=14.0, 20.2, 22.5, 28.6, 28.9,
31.4, 32.6, 125.1, 126.2, 127.0, 129.9, 136.4, 136.9 ppm. HREI-MS calcd.
for C13H20S: 208.1285, found: 208.1278.
Following the general procedure for Table 4, using 1-dodecanethiol
(0.240 mL, 1.0 mmol), 3-iodotoluene (0.156 mL, 1.2 mmol), and L4
(67.2 mg, 0.2 mmol) in 1,4-dioxane (1.0 mL). The crude product was then
purified by column chromatography (SiO2, hexane) to provide 3l as a col-
orless oil (228 mg, 78% yield).1H NMR (400 MHz, CDCl3): d=0.88 (t,
J=7.0 Hz, 3H), 1.25–1.30 (m, 16H), 1.37–1.43 (m, 2H), 1.59–1.68 (m,
2H), 2.32 (s, 3H), 2.90 (t, J=7.4 Hz, 2H), 6.96 (d, J=6.8 Hz, 1H), 7.10–
7.25 ppm (m, 3H); 13C NMR (100 MHz, CDCl3): d=14.1, 21.3, 22.7, 28.8,
29.1, 29.1, 29.3, 29.5, 29.6, 29.6, 31.9, 33.5, 125.7, 126.4, 128.6, 129.4, 136.7,
138.5 ppm. HREI-MS calcd. for C19H32S: 292.2225, found: 292.2228.
Hexyl 2,4,6-trimethylphenyl sulfide 5h (Table 4, entry 8)
Following the general procedure for Table 4, using 1-hexanethiol
(0.141 mL, 1.0 mmol), 2-iodo-1,3,5-trimethylbenzene (295 mg, 1.2 mmol),
and L4 (67.2 mg, 0.2 mmol) in 1,4-dioxane (1.0 mL). The crude product
was then purified by column chromatography (SiO2, hexane) to provide
5h as a colorless oil (142 mg, 60% yield). 1H NMR (400 MHz, CDCl3):
d=0.92 (t, J=6.8 Hz, 3H), 1.28–1.44 (m, 6H), 1.53–1.59 (m, 2H), 2.30 (s,
3H), 2.55 (s, 6H), 2.65 (t, J=7.4 Hz, 2H), 6.96 ppm (s, 2H); 13C NMR
(400 MHz, CDCl3): d=14.0, 20.9, 21.9, 22.5, 28.6, 29.9, 31.5, 35.6, 128.8,
130.6, 137.7, 142.8 ppm. HREI-MS calcd. for C15H24S: 236.1598, found:
236.1605.
Dodecyl 2-methylphenyl sulfide 5c (Table 4, entry 3)[20]
Following the general procedure for Table 4, using 1-dodecanethiol
(0.240 mL, 1.0 mmol), 2-iodotoluene (0.156 mL, 1.2 mmol), and L3
(36.0 mg, 0.2 mmol) in toluene. The crude product was then purified by
column chromatography (SiO2, hexane) to provide 5c as a colorless oil
(207 mg, 71% yield). 1H NMR (400 MHz, CDCl3): d=0.91 (t, J=6.8 Hz,
3H), 1.29–1.33 (m, 16H), 1.43–1.47 (m, 2H), 1.64–1.72 (m, 2H), 2.38 (s,
3H), 2.89 (t, J=7.4 Hz, 2H), 7.05–7.09 (m, 1H), 7.13–7.17 (m, 2H), 7.24–
7.27 ppm (m, 1H); 13C NMR (100 MHz, CDCl3): d=14.1, 20.2, 22.7, 29.0,
29.2, 29.3, 29.5, 29.6, 29.6, 29.7, 31.9, 32.7, 32.8, 125.1, 126.2, 127.2, 129.9,
136.4, 137.1 ppm.
Decyl 2,4,6-trimethylphenyl sulfide 5i (Table 4, entry 9)
Following the general procedure for Table 4, using 1-decanethiol
(0.220 mL, 1.0 mmol), 2-iodo-1,3,5-trimethylbenzene (295 mg, 1.2 mmol),
and L4 (67.2 mg, 0.2 mmol) in 1,4-dioxane (1.0 mL). The crude product
was then purified by column chromatography (SiO2, hexane) to provide
5i as a colorless oil (199 mg, 68% yield). 1H NMR (400 MHz, CDCl3):
d=0.93 (t, J=6.8 Hz, 3H), 1.30–1.43 (m, 14H), 1.53–1.60 (m, 2H), 2.31
(s, 3H), 2.55 (s, 6H), 2.65 (t, J=7.4 Hz, 2H), 6.70 ppm (s, 2H); 13C NMR
(400 MHz, CDCl3): d=14.1, 20.9, 21.9, 22.7, 29.0, 29.1, 29.2, 29.3, 29.5,
29.9, 31.9, 35.5, 128.8, 130.6, 137.7, 142.8 ppm. HREI-MS calcd. for
C19H32S: 292.2224, found: 292.2216.
(2-(Dodecylthio)phenyl)methanol 5d (Table 4, entry 4)[4d]
Following the general procedure for Table 4, using Cs2CO3 (812 mg,
2.5 mmol), 1-dodecanethiol (0.240 mL, 1.0 mmol), 2-iodobenzyl alcohol
(281 mg, 1.2 mmol), and L3 (36.0 mg, 0.2 mmol) in toluene. The crude
product was then purified by column chromatography (SiO2, hexane/
EtOAc 9:1) to provide 5d as a white solid (205 mg, 82% yield): M.p.:
38–398C (lit.[4d] 38–398C). 1H NMR (400 MHz, CDCl3): d=0.88 (t, J=
7.0 Hz, 3H), 1.25–1.31 (m, 16H), 1.38 (m, 2H), 1.60–1.68 (m, 2H), 2.37
(brs, 1H), 2.91 (t, J=7.4 Hz, 2H), 4.76 (d, J=6.0 Hz, 2H), 7.18–7.28 (m,
2H), 7.34–7.38 ppm (m, 2H); 13C NMR (100 MHz, CDCl3): d=14.1, 22.6,
28.8, 29.1, 29.1, 29.3, 29.4, 29.5, 29.6, 31.9, 33.9, 63.6, 126.1, 128.1, 128.1,
129.2, 135.1, 140.3 ppm.
Hexyl 4-methoxyphenyl sulfide 5j (Table 4, entry 10)[21]
Following the general procedure for Table 4, using 1-hexanethiol
(0.141 mL, 1.0 mmol), 4-iodoanisole (281 mg, 1.2 mmol), and L3
(36.0 mg, 0.2 mmol) in toluene (1.0 mL). The crude product was then pu-
rified by column chromatography (SiO2, hexane) to provide 5j as a color-
less oil (144 mg, 64% yield). 1H NMR (400 MHz, CDCl3): d=0.87 (t, J=
6.4 Hz, 3 H), 1.22–1.34 (m, 4H), 1.36–1.41 (m, 2H), 1.52–1.60 (m, 2H),
2.78–2.82 (m, 2H), 3.77 (s, 3H), 6.81–6.84 (m, 2H), 7.30–7.34 ppm (m,
2H); 13C NMR (400 MHz, CDCl3): d=13.9, 22.5, 28.3, 29.2, 31.3, 35.7,
55.2, 114.4, 126.9, 132.8, 158.6 ppm.
Dodecyl 4-methoxyphenyl sulfide 5e (Table 4, entry 5)[4a]
Following the general procedure for Table 4, using 1-dodecanethiol
(0.240 mL, 1.0 mmol), 4-iodoanisole (281 mg, 1.2 mmol), and L3
(36.0 mg, 0.2 mmol) in toluene. The crude product was then purified by
column chromatography (SiO2, hexane) to provide 5e as a colorless solid
(194 mg, 63% yield): M.p.: 44–458C (lit.[4a] 44–458C). 1H NMR
(400 MHz, CDCl3): d=0.88 (t, J=7.0 Hz, 3H), 1.30–1.39 (m, 18H), 1.53–
1.62 (m, 2H), 2.80 (t, J=7.4 Hz, 2H), 3.78 (s, 3H), 6.81–6.84 (m, 2H),
7.31–7.34 ppm (m, 2H); 13C NMR (400 MHz, CDCl3): d=14.1, 22.7, 28.7,
(2-(Benzylthio)phenyl)methanol 5k (Table 4, entry 11)[22]
Following the general procedure for Table 4, using Cs2CO3 (812 mg,
2.5 mmol), benzyl mercaptan (0.118 mL, 1.0 mmol), 2-iodobenzyl alcohol
(281 mg, 1.2 mmol), and L3 (36.0 mg, 0.2 mmol) in toluene (1.0 mL). The
product was then purified by column chromatography (SiO2, hexane/
EtOAc 9:1) to provide 5k as a colorless oil (147 mg, 64% yield).
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Chem. Asian J. 2013, 00, 0 – 0
ꢁ 2013 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
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