Organometallics
Article
1.73 (m, 2H), 1.32 (s, 14H), 0.92 (t, J = 6.43 Hz, 3H). 13C NMR
(500 MHz, CDCl3, 300 K), δ (ppm): 146.29, 127.73, 126.30, 114.78,
110.37, 33.31, 32.02, 29.65, 29.57, 29.42, 29.21, 28.89, 28.55, 22.81,
14.24.
4-(Decylthio)benzonitrile (CD25). Silica gel column chromatog-
raphy having eluent as n-hexane and ethyl acetate of 10:1 (v/v).
White solid. Yield: 256.1 mg, 93% (Ni B-1); 247.9 mg, 90% (Pd B-1).
ESI-MS m/z [M + H]+ = 276.0078 (calculated for C17H25NS,
276.0043). 1H NMR (500 MHz, CDCl3, 300 K): δ (ppm): 7.51 (d, J
= 8.41 Hz, 2H), 7.28 (d, J = 8.41 Hz, 2H), 2.96 (t, J = 7.40 Hz, 2H),
1.66−1.72 (m, 2H), 1.41−1.47 (m, 2H), 1.261 (b, 12H), 0.88 (t, J =
6.91 Hz, 3H). 13C NMR (500 MHz, CDCl3, 300 K), δ (ppm):
145.48, 132.32, 126.82, 119.09, 108.06, 32.07, 32.01, 29.64, 29.59,
29.41, 29.24, 29.00, 28.71, 22.80, 14.23.
1.42−1.39 (m, 2H) 1.28, (s, 12H), 0.90 (t, J = 6.89 Hz, 3H). 13C
NMR (500 MHz, CDCl3, 300 K), δ (ppm): 135.21, 133.20, 128.86,
127.46, 39.07, 32.01, 29.65, 29.62, 29.51, 29.42, 29.26, 28.54, 22.79,
14.21. NMR data are consistent with the reported literature.62
2-(tert-Butylthio)thiazole (CD32). Silica gel column chromatog-
raphy having eluent as n-hexane and ethyl acetate of 10:1 (v/v).
Colorless oil. Yield: 162.8 mg, 94% (Ni B-1); 152.4 mg, 88% (Pd B-
1). ESI-MS m/z [M + H]+ = 174.0193 (calculated for C7H11NS2,
174.0094). 1H NMR (500 MHz, CDCl3, 300 K): δ (ppm): 7.78 (d, J
= 3.40 Hz, 1H), 7.31 (d, J = 3.43 Hz, 1H), 1.38(s, 9H). 13C NMR
(500 MHz, CDCl3, 300 K), δ (ppm): 160.39, 143.99, 122.72, 49.42,
30.94.
2-(Hexylthio)thiazole (CD33). Silica gel column chromatography
having eluent as n-hexane and ethyl acetate of 10:1 (v/v). Colorless
oil. Yield: 195.3 mg, 97% (Ni B-1); 189.2 mg, 94% (Pd B-1). ESI-MS
3-(tert-Butylthio)thiophene (CD26). Silica gel column chromatog-
raphy having eluent as n-hexane and ethyl acetate of 30:1 (v/v).
Colorless oil. Yield: 165.4 mg, 96% (Ni B-1); 163.6 mg, 95% (Pd B-
1). ESI-MS m/z [M + H]+ = 173.0032 (calculated for C8H12S2,
1
m/z [M + H]+ = 202.0241 (calculated for C9H15NS2, 202.0176). H
NMR (500 MHz, CDCl3, 300 K): δ (ppm): 7.63 (d, J = 3.36 Hz,
1H), 7.18 (d, J = 3.38 Hz, 1H), 3.19 (t, J = 7.30 Hz, 2H), 1.72−1.75
(m, 2H), 1.41−1.44 (m, 2H), 1.29 (b, 4H), 0.87 (t, J = 6.84 Hz, 3H).
13C NMR (500 MHz, CDCl3, 300 K), δ (ppm): 165.51, 142.79,
118.65, 34.72, 31.36, 29.29, 28.51, 22.59, 14.07.
2-(Decylthio)thiazole (CD34). Silica gel column chromatography
having eluent as n-hexane and ethyl acetate of 10:1 (v/v). Colorless
oil. Yield: 242.0 mg, 94% (Ni B-1); 234.2 mg, 91% (Pd B-1). ESI-MS
m/z [M + H]+ = 258.0075 (calculated for C13H23NS2, 258.0034). 1H
NMR (500 MHz, CDCl3, 300 K): δ (ppm): 7.63 (d, J = 3.35 Hz,1H),
7.17 (d, J = 3.37 Hz, 1H), 3.18 (t, J = 7.37 Hz, 2H), 1.76−1.70 (m,
2H), 1.43−1.39 (m, 2H), 1.24 (s, 12H), 0.86 (t, J = 6.87 Hz, 3H).
13C NMR (500 MHz, CDCl3, 300 K), δ (ppm): 165.49, 142.77,
118.61, 34.69, 31.96, 29.59, 29.54, 29.37, 29.31, 29.17, 28.82, 22.75,
14.17.
1
173.0077). H NMR (500 MHz, CDCl3, 300 K): δ (ppm): 7.43(d,
1H), 7.31 (m, 1H), 7.10 (d, 1H), 1.31 (s, 9H). 13C NMR (500 MHz,
CDCl3, 300 K), δ (ppm): 134.51, 131.98, 129.22, 125.30, 45.96,
31.05.
3-(Hexylthio)thiophene (CD27). Silica gel column chromatogra-
phy having eluent as n-hexane and ethyl acetate of 30:1 (v/v).
Colorless oil. Yield: 196.3 mg, 98% (Ni B-1); 182.3 mg, 91% (Pd B-
1). ESI-MS m/z [M + H]+ = 201.0032 (calculated for C10H16S2,
201.0077). 1H NMR (500 MHz, CDCl3, 300 K): δ (ppm): 7.30 (dd, J
= 7.96 Hz, J = 4.96 Hz, 1H), 7.10 (d, J = 7.95 Hz, 1H), 7.01 (d, J =
4.95 Hz, 1H), 2.84 (t, J = 7.62 Hz, 2H), 1.57−1.61 (m, 2H), 1.37−
1.40 (m, 2H), 1.26−1.31 (m, 4H), 0.87−0.90 (m, 3H). 13C NMR
(500 MHz, CDCl3, 300 K), δ (ppm): 132.49, 129.78, 126.09, 122.99,
35.47, 31.49, 29.50, 28.51, 22.69, 14.12. NMR data are consistent with
the reported literature.60
3-(Decylthio)thiophene (CD28). Silica gel column chromatogra-
phy having eluent as n-hexane and ethyl acetate of 30:1 (v/v).
Colorless oil. Yield: 253.9 mg, 99% (Ni B-1); 238.5 mg, 93% (Pd B-
1). ESI-MS m/z [M + H]+ = 257.0068 (calculated for C14H24S2,
257.0057). 1H NMR (500 MHz, CDCl3, 300 K): δ (ppm): 7.31 (d, J
= 2.89 Hz, 1H), 7.12 (d, J = 2.69 Hz, 1H), 7.02 (d, J = 4.92 Hz, 1H),
2.85 (t, J = 7.28 Hz, 2H), 1.64−1.61 (m, 2H), 1.29 (s, 14H), 0.90 (t, J
= 6.82 Hz, 3H). 13C NMR (500 MHz, CDCl3, 300 K), δ (ppm):
132.51, 129.73, 126.03, 122.90, 35.43, 32.00, 29.65, 29.62, 29.51,
29.41, 29.28, 28.82, 22.79, 14.21. NMR data are consistent with the
reported literature.61
2-(tert-Butylthio)thiophene (CD29). Silica gel column chromatog-
raphy having eluent as n-hexane and ethyl acetate of 30:1 (v/v).
Colorless oil. Yield: 167.1 mg, 97% (Ni B-1); 155.0 mg, 90% (Pd B-
1). ESI-MS m/z [M + H]+ = 173.0029 (calculated for C8H12S2,
173.0077). 1H NMR (500 MHz, CDCl3, 300 K): δ (ppm): 7.41 (d, J
= 5.37 Hz, 1H), 7.14 (d, J = 3.50 Hz, 1H), 7.02−7.04 (dd, J = 5.36
Hz, J = Hz, 3.49, 1H), 1.31 (s, 9H). 13C NMR (500 MHz, CDCl3,
300 K), δ (ppm): 137.02, 132.02, 130.83, 127.60, 46.84, 30.67.
2-(Hexylthio)thiophene (CD30). Silica gel column chromatogra-
phy having eluent as n-hexane and ethyl acetate of 30:1 (v/v).
Colorless oil. Yield: 196.3 mg, 98% (Ni B-1); 192.3 mg, 96% (Pd B-
1). ESI-MS m/z [M + H]+ = 201.0051 (calculated for C10H16S2,
201.0077). 1H NMR (500 MHz, CDCl3, 300 K): δ (ppm): 7.30 (dd, J
= 5.35, 1.10 Hz, 1H), 7.11 (dd, J = 3.55, 1.10 Hz, 1H), 6.97 (dd, J =
5.25, 3.62 Hz, 1H), 2.80 (t, J = 7.07 Hz, 2H), 1.65−1.56 (m, 2H),
1.44−1.38 (m, 2H) 1.33−1.28 (m, 4H), 0.91 (t, J = 6.99 Hz, 3H). 13C
NMR (500 MHz, CDCl3, 300 K), δ (ppm): 135.16, 133.21, 128.87,
127.47, 39.05, 31.44, 29.45, 28.19, 22.62, 14.10. NMR data are
consistent with the reported literature.60
1-(5-(tert-Butylthio)thiophen-2-yl)ethan-1-one (CD35). Silica gel
column chromatography having eluent as n-hexane and ethyl acetate
of 10:1 (v/v). Light brown solid. Yield: 207.9 mg, 97% (Ni B-1);
199.3 mg, 93% (Pd B-1). ESI-MS m/z [M + H]+ = 215.0066
1
(calculated for C10H14OS2, 215.0079). H NMR (500 MHz, CDCl3,
300 K): δ (ppm): 7.59 (d, J = 3.77 Hz, 1H), 7.13 (d, J = 3.78 Hz,
1H), 2.52 (s, 3H), 1.34 (s, 9H). 13C NMR (500 MHz, CDCl3, 300
K), δ (ppm): 190.18, 147.96, 142.41, 137.25, 132.30, 48.22, 30.85,
26.79.
1-(5-(Decylthio)thiophen-2-yl)ethan-1-one (CD36). Silica gel
column chromatography having eluent as n-hexane and ethyl acetate
of 10:1 (v/v). Light brown solid. Yield: 280.5 mg, 94% (Ni B-1);
271.6 mg, 91% (Pd B-1). ESI-MS m/z [M + H]+ = 299.0127
1
(calculated for C16H26OS2, 299.0093). H NMR (500 MHz, CDCl3,
300 K): δ (ppm): 7.52 (d, 1H, J = 3.90 Hz), 6.96 (d, 1H, J = 3.91
Hz), 2.95 (t, 2H, J = 7.38 Hz), 2.50 (s, 3H), 1.64−1.71 (m, 2H),
1.37−1.41 (m, 2H), 1.25 (s, 12H), 0.87 (t, 3H, J = 6.90 Hz). 13C
NMR (500 MHz, CDCl3, 300 K), δ (ppm): 189.73, 148.42, 144.38,
132.97, 129.42, 37.49, 32.00, 29.63, 29.58, 29.40, 29.34, 29.20, 28.71,
26.44, 22.79, 14.22.
5-(Decylthio)-2-methylpyrimidin-4-ol (CD37). Silica gel column
chromatography having eluent as n-hexane and ethyl acetate of 10:1
(v/v). White solid. Yield: 259.8 mg, 92% (Ni B-1); 240.0 mg, 85%
(Pd B-1). ESI-MS m/z [M + H]+ = 283.0015 (calculated for
1
C15H26N2OS, 283.0078). H NMR (500 MHz, CDCl3, 300 K): δ
(ppm): 13.31 (br, 1H), 6.10(s, 1H), 2.94 (t, J = 7.37 Hz, 2H), 2.43 (s,
3H), 1.68−1.71 (m, 2H), 1.41−1.43 (m, 2H), 1.25 (b, 12H), 0.87 (t,
J = 6.85 Hz, 3H). 13C NMR (500 MHz, CDCl3, 300 K), δ (ppm):
171.38, 164.24, 158.11, 104.58, 32.01, 30.66, 29.65, 29.59, 29.41,
29.23, 29.00, 28.77, 22.79, 21.62, 14.22.
4-(Pyridin-4-ylthio)phenol (CD38). Silica gel column chromatog-
raphy having eluent as n-hexane and ethyl acetate of 5:1 (v/v). Light
brown solid. Yield: 203.1 mg, 92% (Ni B-1); 174.8 mg, 86% (Pd B-
1). ESI-MS m/z [M + H]+ = 204.0067 (calculated for C11H9NOS,
2-(Decylthio)thiophene (CD31). Silica gel column chromatogra-
phy having eluent as n-hexane and ethyl acetate of 30:1 (v/v).
Colorless oil. Yield: 238.5 mg, 93% (Ni B-1); 233.3 mg, 91% (Pd B-
1). ESI-MS m/z [M + H]+ = 257.0093 (calculated for C14H24S2,
257.0057). 1H NMR (500 MHz, CDCl3, 300 K): δ (ppm): 7.32 (dd, J
= 5.33, 0.86 Hz, 1H), 7.11 (dd, J = 3.45, 0.91 Hz, 1H), 6.96 (dd, J =
5.30, 3.55 Hz, 1H), 2.80 (t, J = 7.37 Hz, 2H), 1.65−1.59 (m, 2H),
1
204.0024). H NMR (500 MHz, CDCl3, 300 K): δ (ppm): 8.38 (br,
2H), 7.35 (t, J = 8.03 Hz, 2H), 7.17 (d, J = 7.43 Hz, 1H), 7.02 (d, J =
7.63 Hz, 2H), 6.76 (d, J = 6.11 Hz, 2H). 13C NMR (500 MHz,
CDCl3, 300 K), δ (ppm): 165.00, 154.14, 151.40, 130.34, 125.59,
120.95, 112.34.
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Organometallics XXXX, XXX, XXX−XXX