The Journal of Organic Chemistry
Article
(100 MHz, CDCl3, δ ppm): 173.2, 156.8, 134.6, 129.4, 129.0, 127.6,
126.7, 126.3, 123.6, 118.9, 106.6, 66.7, 60.5, 30.9, 24.6, 14.2. MS (EI)
m/z 258.3.
MHz, CDCl3, δ ppm): 173.8, 159.1, 129.4, 120.4, 114.5, 67.8, 60.1,
34.3, 29.2, 29.2, 29.1, 29.0, 26.0, 24.9, 14.2. MS (EI) m/z 278.2;
HRMS (EI-MS) calcd for C17H26O3 278.1882, found 278.1886.
Ethyl 5-(Phenylthio)pentanoate (26b). Yellow oil, 192.3 mg, 68%
Ethyl 4-(Phenylthio)butanoate (16b).17 Yellow oil, 186.6 mg, 70%
1
1
yield, L/B = 100/0. H NMR (400 MHz, CDCl3, δ ppm): 7.36−7.22
yield, L/B = 75/25. H NMR (400 MHz, CDCl3, δ ppm): 7.33−7.22
(m, 4H), 7.20−7.13 (m, 1H), 4.11 (q, J = 7.1 Hz, 2H), 2.95 (t, J = 7.2
Hz, 2H), 2.44 (t, J = 7.2 Hz, 2H), 1.94 (p, J = 7.2 Hz, 2H), 1.23 (t, J =
7.1 Hz, 3H).13C{1H}-NMR (100 MHz, CDCl3, δ ppm): 172.9, 136.1,
129.3, 128.9, 126.0, 60.4, 32.9, 32.9, 24.4, 14.2. MS (EI) m/z 224.3.
Ethyl 4-(4-Methoxyphenylthio)butanoate (17b).18 Yellow oil,
(m, 4H), 7.19−7.12 (m, 1H), 4.09 (q, J = 7.1 Hz, 2H), 2.99−2.84 (m,
2H), 2.29 (t, J = 7.3 Hz, 2H), 1.84−1.59 (m, 4H), 1.22 (t, J = 7.1 Hz,
3H). 13C{1H}-NMR (100 MHz, CDCl3, δ ppm): 173.3, 136.5, 129.2,
129.1, 128.8, 125.8, 60.3, 33.8, 33.2, 28.5, 24.0, 14.2. MS (EI) m/z
238.1; HRMS (EI-MS) calcd for C13H18O2S 238.1028, found
238.1027.
1
209.9 mg, 69% yield, L/B = 100/0. H NMR (400 MHz, CDCl3, δ
Ethyl 2-Methyl-4-(phenylthio)butanoate (26c). Yellow oil, 1H
NMR (400 MHz, CDCl3, δ ppm): 7.34−7.25 (m, 4H), 7.19−7.12 (m,
1H), 4.11. (q, J = 7.1 Hz, 2H), 3.03−2.81 (m, 2H), 2.65−2.56 (m,
1H), 2.08−1.91 (m, 1H), 1.75−1.66 (m, 1H), 1.23 (t, J = 7.1 Hz, 3H),
1.15 (d, J = 7.1 Hz, 3H). 13C{1H}-NMR (100 MHz, CDCl3, δ ppm):
175.9, 136.2, 129.2, 128.9, 125.9, 60.4, 38.5, 33.0, 31.3, 17.0, 14.2. MS
(EI) m/z 238.1; HRMS (EI-MS) calcd for C13H18O2S 238.1028, found
238.1066.
ppm): 7.33 (d, J = 8.8 Hz, 2H), 6.82 (d, J = 8.8 Hz, 2H), 4.09 (q, J =
7.1 Hz, 2H), 3.77 (s, 3H), 2.83 (t, J = 7.1 Hz, 2H), 2.41 (t, J = 7.3 Hz,
2H), 1.86 (p, J = 7.3 Hz, 2H), 1.22 (t, J = 7.1 Hz, 3H). 13C{1H}-NMR
(100 MHz, CDCl3, δ ppm): 173.0, 159.0, 133.3, 126.0, 114.6, 60.3,
55.3, 35.1, 32.8, 24.5, 14.2. MS (EI) m/z 254.3.
Ethyl 4-(4-Fluorophenylthio)butanoate (18b). Yellow oil, 207.1
1
mg, 71% yield, L/B = 100/0. H NMR (400 MHz, CDCl3, δ ppm):
7.35−7.31 (m, 2H), 7.00−7.95 (m, 2H), 4.10 (q, J = 7.1 Hz, 2H), 2.89
(t, J = 7.1 Hz, 2H), 2.42 (t, J = 7.2 Hz, 2H), 1.89 (p, J = 7.1 Hz, 2H),
1.23 (t, J = 7.0 Hz, 3H). 13C{1H}-NMR (100 MHz, CDCl3, δ ppm):
172.9, 163.0, 160.6 (d, 1JC-F = 245 Hz), 132.5, 132.4, 130.8, 116.1,
115.9, 60.4, 34.3, 32.8, 24.3, 14.2. MS (EI) m/z 242.1; HRMS (EI-MS)
calcd for C12H15O2SF 242.0777, found 242.0759.
Ethyl 6-(Phenylthio)hexanoate (27b). Yellow oil, 207.9 mg, 70%
1
yield, L/B = 87/13. H NMR (400 MHz, CDCl3, δ ppm): 7.33−7.22
(m, 4H), 7.18−7.11 (m, 1H), 4.10 (q, J = 7.1 Hz, 2H), 2.90 (t, J = 7.3
Hz, 2H), 2.27 (t, J = 7.5 Hz, 2H), 1.71−1.55 (m, 4H), 1.51−1.38 (m,
2H), 1.23 (t, J = 7.1 Hz, 3H). 13C{1H}-NMR (100 MHz, CDCl3, δ
ppm): 173.6, 136.7, 129.0, 128.8, 125.8, 60.2, 34.1, 33.4, 28.8, 28.2,
24.5, 14.2. MS (EI) m/z 252.1; HRMS (EI-MS) calcd for C14H20O2S
252.1184, found 252.1164.
Ethyl 4-(2-Naphthalenylthio)butanoate (19b).19 Yellow oil, 228.8
1
mg, 70% yield, L/B = 100/0. H NMR (400 MHz, CDCl3, δ ppm):
7.78−7.72 (m, 4H), 7.49−7.37 (m, 3H), 4.11 (q, J = 7.1 Hz, 2H), 3.06
(t, J = 7.2 Hz, 2H), 2.47 (t, J = 7.2 Hz, 2H), 1.99 (p, J = 7.2 Hz, 2H),
1.23 (t, J = 7.1 Hz, 3H). 13C{1H}-NMR (100 MHz, CDCl3, δ ppm):
172.9, 133.8, 133.6, 131.7, 128.4, 127.7, 127.4, 127.0, 127.0, 126.5,
125.6, 60.4, 32.9, 32.8, 24.3, 14.2. MS (EI) m/z 274.4.
Ethyl 2-Methyl-5-(phenylthio)pentanoate (27c). Yellow oil, 1H
NMR (400 MHz, CDCl3, δ ppm): 7.34−7.22 (m, 4H), 7.19−7.11 (m,
1H), 4.08 (q, J = 7.1 Hz, 2H), 2.89 (t, J = 7.1 Hz, 2H), 2.46−2.34 (m,
1H), 1.83−1.70 (m, 1H), 1.69−1.48 (m, 3H), 1.21 (t, J = 7.1 Hz, 3H),
1.12 (d, J = 7.0 Hz, 3H). 13C{1H}-NMR (100 MHz, CDCl3, δ ppm):
176.4, 136.5, 129.1, 128.8, 125.8, 60.2, 39.1, 33.5, 32.8, 26.8, 17.1, 14.2.
MS (EI) m/z 252.1; HRMS (EI-MS) calcd for C14H20O2S 252.1184,
found 252.1192.
Ethyl 5-Phenylpentanoate (20b) and Ethyl 2-Methyl-4-phenyl-
1
butanoate (20c). The mixture cannot be distinguished in H NMR.
Yellow oil, 176.7 mg, 74% yield, L/B = 65/35. 13C{1H}-NMR (100
MHz, CDCl3, δ ppm): 176.1, 173.5, 166.5, 141.4, 139.4, 129.0, 128.6,
128.5, 128.3, 128.3, 126.2, 125.9, 60.2, 41.5, 39.7, 35.1, 33.7, 26.5, 16.8,
14.2, 14.1.
Ethyl 6-(Phenylthio)heptanoate (28b). Yellow oil, 145.8 mg, 46%
1
yield, L/B = 86/14. H NMR (400 MHz, CDCl3, δ ppm): 7.33−7.21
Ethyl 4-Phenylbutanoate (21b). Yellow oil, 207.1 mg, 71% yield,
(m, 4H), 7.18−7.11 (m, 2H), 4.10 (q, J = 7.1 Hz, 2H), 2.89 (t, J = 7.3
Hz, 2H), 2.26 (t, J = 7.5 Hz, 2H), 1.77−1.54 (m, 4H), 1.51−1.27 (m,
4H), 1.23 (t, J = 7.1 Hz, 3H). 13C{1H}-NMR (100 MHz, CDCl3, δ
ppm): 173.7, 136.9, 128.9, 128.8, 125.7, 60.2, 34.2, 33.5, 28.9, 28.6,
28.4, 24.8, 14.2.
1
L/B = 80/20. H NMR (400 MHz, CDCl3, δ ppm): 7.38−7.22 (m,
3H), 7.22−7.09 (m, 2H), 4.11 (q, J = 7.1 Hz, 2H), 2.70−2.58 (m,
2H), 2.31 (t, J = 7.5 Hz, 2H), 2.03−1.82 (m, 2H), 1.24 (t, J = 7.1 Hz,
3H). 13C{1H}-NMR (100 MHz, CDCl3, δ ppm): 173.5, 141.4, 128.5,
128.3, 125.9, 60.2, 35.1, 33.7, 26.5, 14.2.
Ethyl 9-(Phenylthio)nonanoate (29b). Yellow oil, 206.8 mg, 62%
1
Ethyl 5-(Phenoxy)pentanoate (22b). Yellow oil, 201.7 mg, 76%
yield, L/B = 95/5. H NMR (400 MHz, CDCl3, δ ppm): 7.33−7.20
1
yield, L/B = 100/0. H NMR (400 MHz, CDCl3, δ ppm): 7.34−7.20
(m, 4H), 7.18−7.11 (m, 1H), 4.10 (q, J = 7.1 Hz, 2H), 2.92−2.86 (m,
2H), 2.26 (t, J = 7.5 Hz, 2H), 1.68−1.54 (m, 4H), 1.41−1.36 (m, 2H),
1.28−1.21 (m, 9H). 13C{1H}-NMR (100 MHz, CDCl3, δ ppm):
173.8, 137.0, 128.8, 128.8, 125.6, 60.1, 34.3, 33.5, 29.1, 29.0, 28.9, 28.7,
24.9, 14.2. MS (EI) m/z 294.2; HRMS (EI-MS) calcd for C17H26O2S
294.1654, found 294.1648.
(m, 2H), 6.98−6.83 (m, 3H), 4.12 (q, J = 7.1 Hz, 2H), 3.96 (t, J = 5.6
Hz, 2H), 2.37 (t, J = 5.9 Hz, 2H), 1.82−1.79 (m, 4H), 1.24 (t, J = 7.1
Hz, 3H). 13C{1H}-NMR (100 MHz, CDCl3, δ ppm): 173.5, 158.9,
129.4, 120.6, 114.4, 67.2, 60.3, 33.9, 28.7, 21.6, 14.2. MS (EI) m/z
222.1; HRMS (EI-MS) calcd for C13H18O3 222.1256, found 222.1248.
Ethyl 6-(Phenoxy)hexanoate (23b).20 Yellow oil, 193.4 mg, 70%
Ethyl 11-(Phenylthio)undecanoate (30b). Yellow oil, 73.8 mg, 21%
1
1
yield, L/B = 99/1. H NMR (400 MHz, CDCl3, δ ppm): 7.30−7.22
yield, L/B = 98/2. H NMR (400 MHz, CDCl3, δ ppm): 7.31−7.23
(m, 2H), 6.95−6.84 (m, 3H), 4.11 (q, J = 7.1 Hz, 2H), 3.94 (t, J = 6.4
Hz, 2H), 2.32 (t, J = 7.5 Hz, 2H), 1.86−1.74 (m, 2H), 1.73−1.65 (m,
2H), 1.56−1.44 (m, 2H), 1.24 (t, J = 7.1 Hz, 3H).13C{1H}-NMR (100
MHz, CDCl3, δ ppm): 173.6, 159.0, 129.4, 120.5, 114.4, 67.5, 60.2,
34.2, 28.9, 25.6, 24.7, 14.2. MS (EI) m/z 236.3.
(m, 4H), 7.18−7.11 (m, 1H), 4.10 (q, J = 7.1 Hz, 2H), 2.97−2.80 (m,
2H), 2.26 (t, J = 7.5 Hz, 2H), 1.68−1.54 (m, 5H), 1.45−1.18 (m,
14H). 13C{1H}-NMR (100 MHz, CDCl3, δ ppm): 173.9, 137.0, 128.8,
128.8, 125.6, 60.1, 34.3, 33.5, 29.4, 29.3, 29.2, 29.1, 28.8, 24.9, 14.2.
MS (EI) m/z 322.2; HRMS (EI-MS) calcd for C19H30O2S, 322.1967
found 322.1964.
Ethyl 7-(Phenoxy)heptanoate (24b). Yellow oil, 83.7 mg, 35%
Methyl 4-(2-Hydroxyphenoxy)butanoate (31b).21 Yellow oil,
1
yield, L/B = 85/15. H NMR (400 MHz, CDCl3, δ ppm): 7.28−7.24
1
(m, 2H), 7.05−6.76 (m, 3H), 4.11 (q, J = 7.1 Hz, 2H), 3.93 (t, J = 6.5
Hz, 2H), 2.30 (t, J = 7.5 Hz, 2H), 1.86−1.71 (m, 2H), 1.69−1.61 (m,
2H), 1.52−1.34 (m, 4H), 1.24 (t, J = 7.1 Hz, 3H). 13C{1H}-NMR
(100 MHz, CDCl3, δ ppm): 173.7, 159.1, 129.4, 120.5, 114.5, 67.6,
60.1, 34.2, 29.1, 28.9, 25.7, 24.9, 14.2. MS (EI) m/z 250.2; HRMS (EI-
MS) calcd for C15H22O3 250.1569, found 250.1550.
169.3 mg, 68% yield, L/B = 100/0. H NMR (400 MHz, CDCl3, δ
ppm): 6.95−6.75 (m, 4H), 5.83 (s, 1H), 4.06 (t, J = 6.0 Hz, 2H), 3.69
(s, 3H), 2.51 (t, J = 7.0 Hz, 2H), 2.21−2.10 (m, 2H). 13C{1H}-NMR
(100 MHz, CDCl3, δ ppm): 174.1, 146.0, 145.7, 121.7, 120.0, 114.8,
111.9, 68.0, 51.8, 31.0, 24.6. MS (EI) m/z 210.2.
Propyl 6-(Phenoxy)hexanoate (32b). Yellow oil, 195.9 mg, 62%
1
Ethyl 9-(Phenoxy)nonanoate (25b). Yellow oil, 147.7 mg, 45%
yield, L/B = 92/8. H NMR (400 MHz, CDCl3, δ ppm): 7.28−7.23
1
yield, L/B = 90/10. H NMR (400 MHz, CDCl3, δ ppm): 7.32−7.21
(m, 2H), 6.96−6.83 (m, 3H), 4.02 (t, J = 6.7 Hz, 2H), 3.94 (t, J = 6.4
Hz, 2H), 2.33 (t, J = 7.5 Hz, 2H), 1.87−1.44 (m, 8H), 0.92 (t, J = 7.4
Hz, 3H). 13C{1H}-NMR (100 MHz, CDCl3, δ ppm): 173.7, 159.0,
129.4, 120.5, 114.4, 67.5, 65.9, 34.2, 28.9, 25.7, 24.7, 22.0, 10.4. MS
(m, 2H), 6.98−6.81 (m, 3H), 4.11 (q, J = 7.1 Hz, 2H), 3.93 (t, J = 6.5
Hz, 2H), 2.27 (t, J = 7.5 Hz, 2H), 1.83−1.70 (m, 2H), 1.66−1.53 (m,
2H), 1.50−1.28 (m, 8H), 1.24 (t, J = 7.1 Hz, 3H).13C{1H}-NMR (100
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J. Org. Chem. 2016, 81, 3860−3867