H. Firouzabadi et al. / Tetrahedron 65 (2009) 5293–5301
5299
CDCl3)
d
: 140.6, 118.5, 114.4, 39.2, 26.1, 20.3, 18.4; IR (neat):
n
14.2; IR (neat):
66.63; H, 7.99; S, 12.71. Found: C, 66.67; H, 7.95; S, 12.77.
n
(cmꢂ1)¼1732 (C]O). Anal. Calcd for C14H20O2S: C,
(cmꢂ1)¼2249 (CN),1647 (C]C). Anal. Calcd for C7H11NS: C, 59.53; H,
7.85; N, 9.92; S, 22.70. Found: C, 59.55; H, 7.81; N, 9.86; S, 22.78.
4.2.31. 4-((4-Nitrophenyl)methylsulfanyl)butan-2-one29 (31)
4.2.24. Butyl 3-(2-methylallylthio)propanoate (24)
Colourless oil; 1H NMR (250 MHz, CDCl3)
d: 8.09 (d, J¼8.5 Hz,
Colourless oil; 1H NMR (250 MHz, CDCl3)
d
: 4.78–4.77 (m, 2H),
2H), 7.42 (d, J¼8.5 Hz, 2H), 3.72 (s, 2H), 2.86–2.53 (m, 4H), 2.07 (s,
4.03 (t, J¼6.6 Hz, 2H), 3.06 (s, 2H), 2.65–2.59 (m, 2H), 2.53–2.46 (m,
3H); 13C NMR (62.5 MHz, CDCl3)
43.1, 36.2, 30.0, 25.2; IR (neat):
d
: 206.4, 146.9, 146.2, 129.8, 123.8,
2H), 1.75 (s, 3H), 1.60–1.49 (m, 2H), 1.39–1.27 (m, 2H), 0.86 (t,
n
(cmꢂ1)¼1713 (C]O), 1601 (aro-
J¼7.3 Hz, 3H); 13C NMR (62.5 MHz, CDCl3)
d
: 172.0,141.0,113.6, 64.5,
matic C]C), 1520, 1346 (NO2); MS (m/e)¼239 [Mþ]. Anal. Calcd for
C11H13NO3S: C, 55.21; H, 5.48; N, 5.85; S, 13.40. Found: C, 55.25; H,
5.56; N, 5.78; S, 13.43.
39.3, 34.4, 30.6, 25.8, 20.5, 19.1, 13.7; IR (neat):
n
(cmꢂ1)¼1736
(C]O), 1647 (C]C). Anal. Calcd for C11H20O2S: C, 61.07; H, 9.32; S,
14.82. Found: C, 61.01; H, 9.35; S, 14.87.
4.2.32. 3-((4-Nitrophenyl)methylsulfanyl)propionitrile (32)
4.2.25. Ethyl 3-(2-methylallylthio)butanoate (25)
Colourless oil; 1H NMR (250 MHz, CDCl3)
d
: 8.06 (d, J¼8.4 Hz,
Colourless oil; 1H NMR (250 MHz, CDCl3)
d
: 4.59–4.55 (m, 2H),
2H), 7.46 (d, J¼8.4 Hz, 2H), 3.83 (s, 2H), 2.66–2.52 (m, 4H); 13C NMR
3.88 (q, J¼7.0 Hz, 2H), 2.88 (s, 2H), 2.83–2.74 (m, 1H), 2.32 (dd,
(62.5 MHz, CDCl3) d: 147.1, 145.3, 129.3, 123.9, 118.4, 35.7, 26.8, 18.7;
J¼15.3, 6.3 Hz, 1H), 2.13 (dd, J¼15.3, 8.2 Hz, 1H), 1.53 (s, 3H), 1.03–
IR (neat):
n
(cmꢂ1)¼2249 (CN), 1601 (aromatic C]C), 1520, 1346
0.94 (m, 6H); 13C NMR (62.5 MHz, CDCl3)
41.9, 38.4, 21.0, 20.8, 20.6, 14.1; IR (neat):
1647 (C]C). Anal. Calcd for C10H18O2S: C, 59.37; H, 8.97; S, 15.85.
d
: 171.2, 141.3, 113.3, 60.3,
n
(NO2); MS (m/e)¼222 [Mþ]. Anal. Calcd for C10H10N2O2S: C, 54.04;
(cmꢂ1)¼1736 (C]O),
H, 4.53; N,12.60; S, 14.43. Found: C, 53.98; H, 4.50; N,12.65; S, 14.41.
Found: C, 59.41; H, 8.90; S, 15.89.
4.2.33. Butyl 3-((4-nitrophenyl)methylsulfanyl)propanoate (33)
Colourless oil; 1H NMR (250 MHz, CDCl3)
d
: 7.96 (d, J¼8.4 Hz,
4.2.26. 4-((4-Methylphenyl)methylsulfanyl)butan-2-one28 (26)
2H), 7.32 (d, J¼8.4 Hz, 2H), 3.89 (t, J¼6.7 Hz, 2H), 3.71 (s, 2H), 2.54–
Colourless oil; 1H NMR (250 MHz, CDCl3)
d
: 7.07 (d, J¼8.0 Hz,
2.48 (m, 2H), 2.40–2.34 (m, 2H), 1.46–1.35 (m, 2H), 1.24–1.12 (m,
2H), 6.98 (d, J¼8.0 Hz, 2H), 3.53 (s, 2H), 2.48 (s, 4H), 2.17 (s, 3H),1.95
2H), 0.75–0.69 (m, 3H); 13C NMR (62.5 MHz, CDCl3)
d: 171.6, 146.9,
(s, 3H); 13C NMR (62.5 MHz, CDCl3)
d
: 206.6, 136.5, 135.2, 129.2,
146.1, 129.6, 124.1, 64.6, 35.7, 34.4, 30.5, 26.9, 19.0, 13.6; IR (neat): n
128.9, 43.5, 36.2, 29.9, 25.1, 21.1; IR (neat):
n
(cmꢂ1)¼1717 (C]O),
(cmꢂ1)¼1732 (C]O), 1601 (aromatic C]C), 1520, 1346 (NO2); MS
(m/e)¼297 [Mþ]. Anal. Calcd for C14H19NO4S: C, 56.55; H, 6.44; N,
4.71; S, 10.78. Found: C, 56.60; H, 6.40; N, 4.73; S, 10.72.
1582 (aromatic C]C); MS (m/e)¼208 [Mþ]. Anal. Calcd for
C12H16OS: C, 69.19; H, 7.74; S,15.39. Found: C, 69.25; H, 7.80; S,15.32.
4.2.27. 3-((4-Methylphenyl)methylsulfanyl)propionitrile (27)
4.2.34. Ethyl 3-((4-nitrophenyl)methylsulfanyl)butanoate (34)
Colourless oil; 1H NMR (250 MHz, CDCl3)
d
: 7.07 (d, J¼8.0 Hz,
Colourless oil; 1H NMR (250 MHz, CDCl3)
d
: 8.09 (d, J¼8.7 Hz,
2H), 6.99 (d, J¼8.0 Hz, 2H), 3.61 (s, 2H), 2.52–2.46 (m, 2H), 2.38–
2H), 7.44 (d, J¼8.7 Hz, 2H), 4.03 (q, J¼7.1 Hz, 2H), 3.77 (s, 2H), 3.10–
2.31 (m, 2H), 2.19 (s, 3H); 13C NMR (62.5 MHz, CDCl3)
d: 137.0, 134.3,
2.96 (m, 1H), 2.53 (dd, J¼15.5, 6.5 Hz, 1H), 2.36 (dd, J¼15.5, 7.8 Hz,
129.3, 128.7, 118.4, 35.9, 26.5, 21.0, 18.5; IR (neat):
n
(cmꢂ1)¼2249
1H), 1.24–1.13 (m, 6H); 13C NMR (62.5 MHz, CDCl3)
d: 171.1, 147.9,
(CN), 1512 (aromatic C]C); MS (m/e)¼191 [Mþ]. Anal. Calcd for
C11H13NS: C, 69.07; H, 6.85; N, 7.32; S, 16.76. Found: C, 69.01; H,
6.80; N, 7.37; S, 16.82.
146.2, 129.7, 123.8, 60.7, 42.0, 36.2, 34.8, 21.3, 14.2; IR (neat): n
(cmꢂ1)¼1732 (C]O), 1601 (aromatic C]C), 1520, 1346 (NO2); MS
(m/e)¼283 [Mþ]. Anal. Calcd for C13H17NO4S: C, 55.11; H, 6.05; N,
4.94; S, 11.32. Found: C, 55.17; H, 6.02; N, 5.00; S, 11.37.
4.2.28. Butyl 3-((4-methylphenyl)methylsulfanyl)propanoate (28)
Colourless oil; 1H NMR (250 MHz, CDCl3)
d
: 7.11 (d, J¼8.0 Hz,
4.2.35. 4-(Isopropylthio)butan-2-one30 (35)
2H), 7.03 (d, J¼8.0 Hz, 2H), 4.00 (t, J¼6.6 Hz, 2H), 3.61 (s, 2H), 2.62–
2.56 (m, 2H), 2.48–2.42 (m, 2H), 2.24 (s, 3H), 1.55–1.46 (m, 2H),
1.33–1.24 (m, 2H), 0.85 (t, J¼7.3 Hz, 3H); 13C NMR (62.5 MHz, CDCl3)
Colourless oil; 1H NMR (250 MHz, CDCl3)
d: 2.91–2.80 (m, 1H),
2.68–2.65 (m, 4H), 2.11 (s, 3H), 1.19 (d, J¼6.7 Hz, 6H); 13C NMR
(62.5 MHz, CDCl3) d: 207.0, 43.7, 35.2, 30.1, 24.2, 23.3; IR (neat): n
d
: 172.0, 136.7, 135.0, 129.2, 128.7, 64.5, 35.9, 34.5, 30.6, 26.2, 21.1,
(cmꢂ1)¼1717 (C]O). Anal. Calcd for C7H14OS: C, 57.49; H, 9.65; S,
19.1, 13.7; IR (neat):
n
(cmꢂ1)¼1736 (C]O), 1589 (aromatic C]C);
21.92. Found: C, 57.44; H, 9.64; S, 21.95.
MS (m/e)¼266 [Mþ]. Anal. Calcd for C15H22O2S: C, 67.63; H, 8.32; S,
12.04. Found: C, 67.70; H, 8.25; S, 12.07.
4.2.36. 3-(Isopropylthio)propanenitrile31 (36)
Colourless oil; 1H NMR (250 MHz, CDCl3)
d: 3.04–2.88 (m, 1H),
4.2.29. Ethyl 3-((4-methylphenyl)methylsulfanyl)butanoate (29)
2.77–2.71 (m, 2H), 2.59–2.53 (m, 2H), 1.22 (d, J¼6.7 Hz, 6H); 13C
Colourless oil; 1H NMR (250 MHz, CDCl3)
d
: 7.13 (d, J¼7.9 Hz, 2H),
NMR (62.5 MHz, CDCl3) d: 118.4, 35.2, 26.0, 23.2, 19.0; IR (neat): n
7.03 (d, J¼7.9 Hz, 2H), 4.05 (q, J¼7.2 Hz, 2H), 3.65 (s, 2H), 3.10–2.97
(m, 1H), 2.53 (dd, J¼15.3, 6.0 Hz, 1H), 2.34 (dd, J¼15.3, 8.4 Hz, 1H),
(cmꢂ1)¼2249 (CN). Anal. Calcd for C6H11NS: C, 55.77; H, 8.58; N,
10.84; S, 24.81. Found: C, 55.81; H, 8.55; N, 10.80; S, 24.84.
2.24 (s, 3H), 1.23–1.14 (m, 6H); 13C NMR (62.5 MHz, CDCl3)
d: 171.4,
136.6, 135.1, 129.2, 128.7, 60.5, 42.1, 35.9, 35.0, 21.2, 21.1, 14.2; IR
4.2.37. Butyl 3-(isopropylthio)propanoate (37)
(neat):
n
(cmꢂ1)¼1736 (C]O), 1512 (aromatic C]C); MS (m/e)¼252
Colourless oil; 1H NMR (250 MHz, CDCl3)
d: 4.03 (t, J¼6.6 Hz,
[Mþ]. Anal. Calcd for C14H20O2S: C, 66.63; H, 7.99; S, 12.71. Found: C,
66.66; H, 7.92; S, 12.79.
2H), 2.93–2.83 (m, 1H), 2.76–2.72 (m, 2H), 2.55–2.49 (m, 2H), 1.63–
1.49 (m, 2H), 1.36–1.27 (m, 2H), 1.20 (d, J¼6.7 Hz, 6H), 0.87 (t,
J¼7.3 Hz, 3H); 13C NMR (62.5 MHz, CDCl3)
d: 172.1, 64.5, 35.0, 34.9,
4.2.30. Ethyl 2-methyl-3-((4-methylphenyl)methylsulfanyl)-
propanoate (30)
30.6, 25.5, 23.3, 19.1, 13.7; IR (neat):
n
(cmꢂ1)¼1736 (C]O). Anal.
Calcd for C10H20O2S: C, 58.78; H, 9.87; S, 15.69. Found: C, 58.81; H,
9.82; S, 15.66.
Colourless oil; 1H NMR (250 MHz, CDCl3)
d
: 7.12 (d, J¼8.0 Hz,
2H), 7.04 (d, J¼8.0 Hz, 2H), 4.07 (q, J¼7.1 Hz, 2H), 3.61 (s, 2H), 2.71–
2.63 (m, 1H), 2.59–2.45 (m, 1H), 2.41–2.33 (m, 1H), 2.25 (s, 3H), 1.19
(t, J¼7.1 Hz, 3H), 1.13 (d, J¼6.8 Hz, 3H); 13C NMR (62.5 MHz, CDCl3)
4.2.38. Ethyl 3-(isopropylthio)butanoate (38)
Colourless oil; 1H NMR (250 MHz, CDCl3)
3.25–3.12 (m, 1H), 3.01–2.85 (m, 1H), 2.54 (dd, J¼15.4, 6.1, Hz, 1H),
d
: 4.09 (q, J¼7.1 Hz, 2H),
d
: 175.2, 136.7, 135.0, 129.2, 128.8, 60.5, 39.9, 36.2, 34.5, 21.1, 16.8,