The Journal of Organic Chemistry
Page 8 of 12
0.91 (t, J = 6.9 Hz, 3H) ppm. 13C{1H} NMR (CDCl3, 75
MHz): δ = 167.9, 160.3, 131.4, 128.3, 128.2, 123.3, 97.7, 93.8,
83.2, 33.9, 31.5, 28.7, 26.2, 22.5, 20.8, 14.1 ppm.
(Z)-1-Cyclopropyldec-3-en-1-yn-4-yl acetate (5h): Yellow
oil. Yield: 0.215 g (92%). H NMR (CDCl3, 400 MHz): δ =
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5.15 (s, 1H), 2.22 (t, J = 7.6 Hz, 2H), 2.20 (s, 3H), 1.47-1.40
(m, 2H), 1.36-1.27 (m, 7H), 0.88 (t, J = 6.8 Hz, 3H), 0.83-
0.78 (m, 2H), 0.70-0.66 (m, 2H) ppm. 13C{1H} NMR
(CDCl3, 100 MHz): δ = 168.0, 159.2, 98.1, 97.9, 69.3, 33.6,
31.5, 28.6, 26.2, 22.5, 20.8, 14.0, 8.7, 0.3 ppm. IR (film): ν =
2116 (w, C≡C), 1761 (s, C=O), 1653 (m, C=C) cm-1. HRMS
(ESI): m/z 257.1515, [M+Na+] (calcd for C15H22O2Na:
257.1517).
(Z)-1-(4-Fluorophenyl)dec-3-en-1-yn-4-yl acetate (5b):22a
1
Yellow oil. Yield: 0.277 g (96%). H NMR (CDCl3, 300
MHz): δ = 7.40-7.35 (m, 2H), 7.04-6.98 (m, 2H), 5.43 (s,
1H), 2.33 (t, J = 7.2 Hz, 2H), 2.25 (s, 3H), 1.51-1.49 (m, 2H),
1.36-1.28 (m, 6H), 0.91 (t, J = 6.6 Hz, 3H) ppm. 13C{1H}
NMR (CDCl3, 75 MHz): δ = 167.9, 162.4 (d, J = 249.5 Hz),
160.4, 133.2 (d, J = 8.3 Hz), 119.4 (d, J = 3.5 Hz), 115.5 (d, J =
22.2 Hz), 97.5, 92.7, 82.9, 33.8, 31.5, 28.7, 26.2, 22.5, 20.8,
14.0 ppm. 19F{1H} NMR (CDCl3, 282 MHz): δ = -111.1 ppm.
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(Z)-1-(Cyclohex-1-en-1-yl)dec-3-en-1-yn-4-yl acetate (5i):
1
Colourless oil. Yield: 0.249 g (91%). H NMR (CDCl3, 300
MHz): δ = 6.07 (br, 1H), 5.33 (s, 1H), 2.27 (t, J = 7.2 Hz,
2H), 2.22 (s, 3H), 2.12-2.10 (m, 4H), 1.65-1.59 (m, 4H), 1.48-
1.45 (m, 2H), 1.32-1.29 (m, 6H), 0.89 (t, J = 6.6 Hz, 3H)
ppm. 13C{1H} NMR (CDCl3, 75 MHz): δ = 168.0, 159.2, 134.8,
120.8, 97.9, 95.9, 80.6, 33.8, 31.5, 29.2, 28.7, 26.2, 25.7, 22.5,
22.3, 21.5, 20.8, 14.0 ppm. IR (film): ν = 2194 (w, C≡C), 1763
(s, C=O), 1653 (m, C=C), 1623 (w, C=C) cm-1. HRMS (ESI):
m/z 297.1823, [M+Na+] (calcd for C18H26O2Na: 297.1825).
(Z)-1-(4-Bromophenyl)dec-3-en-1-yn-4-yl acetate (5c):
Yellow oil. Yield: 0.293 g (84%). H NMR (CDCl3, 300
1
MHz): δ = 7.44 (d, J = 8.4 Hz, 2H), 7.26 (d, J = 8.5 Hz, 2H),
5.43 (s, 1H), 2.33 (t, J = 7.8 Hz, 2H), 2.25 (s, 3H), 1.59-1.49
(m, 2H), 1.38-1.31 (m, 6H), 0.91 (t, J = 6.6 Hz, 3H) ppm.
13C{1H} NMR (CDCl3, 75 MHz): δ = 167.8, 160.7, 132.8, 131.5,
122.4, 122.3, 97.5, 92.6, 84.4, 33.9, 31.5, 28.7, 26.2, 22.5, 20.8,
14.0 ppm. IR (film): ν = 2210 (w, C≡C), 1759 (s, C=O), 1653
(m, C=C) cm-1. HRMS (ESI): m/z 371.0607, [M+Na+] (calcd
for C18H21O2BrNa: 371.0617).
(Z)-2-Hydroxy-2-methyldodec-5-en-3-yn-6-yl acetate (5j):
1
Orange oil. Yield: 0.219 g (87%). H NMR (CDCl3, 300
MHz): δ = 5.18 (s, 1H), 2.68 (s, 1H), 2.22 (t, J = 6.9 Hz, 2H),
2.18 (s, 3H), 1.49 (s, 6H), 1.43-1.41 (m, 2H), 1.31-1.24 (m,
6H), 0.86 (t, J = 6.3 Hz, 3H) ppm. 13C{1H} NMR (CDCl3, 75
MHz): δ = 167.9, 160.2, 98.7, 97.1, 75.8, 65.3, 33.7, 31.5, 31.3,
28.6, 26.1, 22.5, 20.7, 14.0 ppm. IR (film): ν = 3434 (br,
OH), 2222 (w, C≡C), 1763 (s, C=O), 1655 (m, C=C) cm-1.
HRMS (ESI): m/z 275.1621, [M+Na+] (calcd for C15H24O3Na:
275.1618).
(Z)-1-(4-Methylphenyl)dec-3-en-1-yn-4-yl acetate (5d):
1
Yellow oil. Yield: 0.275 g (97%). H NMR (CDCl3, 300
MHz): δ = 7.31 (d, J = 8.1 Hz, 2H), 7.12 (d, J = 8.1 Hz, 2H),
5.44 (s, 1H), 2.36 (s, 3H), 2.33 (t, J = 8.1 Hz, 2H), 2.26 (s,
3H), 1.52-1.50 (m, 2H), 1.37-1.32 (m, 6H), 0.92 (t, J = 7.2 Hz,
13
3H) ppm. C{1H} NMR (CDCl3, 75 MHz): δ = 168.0, 160.0,
138.3, 131.3, 129.0, 120.3, 97.8, 94.0, 82.6, 33.8, 31.5, 28.7,
26.3, 22.5, 21.5, 20.8, 14.0 ppm. IR (film): ν = 2201 (w, C≡C),
1761 (s, C=O), 1652 (m, C=C) cm-1. HRMS (ESI): m/z
307.1659, [M+Na+] (calcd for C19H24O2Na: 307.1669).
(Z)-1-Phenyldec-3-en-1-yn-4-yl benzoate (6a): Yellow oil.
Yield: 0.319 g (96%). 1H NMR (CDCl3, 300 MHz): δ = 8.25-
8.22 (m, 2H), 7.65-7.50 (m, 3H), 7.22-7.18 (m, 5H), 5.58 (s,
1H), 2.52 (t, J = 6.9 Hz, 2H), 1.63-1.60 (m, 2H), 1.43-1.32 (m,
(Z)-1-(4-Methoxyphenyl)dec-3-en-1-yn-4-yl acetate (5e):22a
1
Yellow oil. Yield: 0.282 g (94%). H NMR (CDCl3, 300
13
6H), 0.94 (t, J = 6.6 Hz, 3H) ppm. C{1H} NMR (CDCl3, 75
MHz): δ = 7.34 (d, J = 8.7 Hz, 2H), 6.84 (d, J = 8.7 Hz, 2H),
5.43 (s, 1H), 3.81 (s, 3H), 2.32 (t, J = 7.5 Hz, 2H), 2.25 (s,
3H), 1.54-1.49 (m, 2H), 1.38-1.31 (m, 6H), 0.91 (t, J = 6.6 Hz,
3H) ppm. 13C{1H} NMR (CDCl3, 75 MHz): δ = 168.0, 159.6,
159.5, 132.8, 115.5, 113.9, 97.8, 93.8, 81.9, 55.2, 33.8, 31.5, 28.7,
26.3, 22.5, 20.8, 14.0 ppm.
MHz): δ = 163.9, 160.8, 133.5, 131.3, 130.2, 129.6, 128.6, 128.1,
128.0, 123.3, 97.9, 94.1, 83.5, 34.0, 31.6, 28.8, 26.4, 22.6, 14.1
ppm. IR (film): ν = 2198 (w, C≡C), 1733 (s, C=O), 1646 (m,
C=C) cm-1. HRMS (ESI): m/z 355.1661, [M+Na+] (calcd for
C23H24O2Na: 355.1669).
(Z)-1-(4-Fluorophenyl)dec-3-en-1-yn-4-yl benzoate (6b):
(Z)-1-(Trimethylsilyl)dec-3-en-1-yn-4-yl acetate (5f): Col-
1
1
Yellow oil. Yield: 0.318 g (91%). H NMR (CDCl3, 300
ourless oil. Yield: 0.232 g (87%). H NMR (CDCl3, 400
MHz): δ = 8.21-8.18 (m, 2H), 7.68-7.63 (m, 1H), 7.54-7.49
(m, 2H), 7.14-7.09 (m, 2H), 6.90-6.85 (m, 2H), 5.52 (s, 1H),
2.48 (t, J = 7.2 Hz, 2H), 1.60-1.58 (m, 2H), 1.38-1.29 (m,
6H), 0.91 (t, J = 6.3 Hz, 3H) ppm. 13C{1H} NMR (CDCl3, 100
MHz): δ = 163.8, 162.2 (d, J = 249.2 Hz), 160.9, 133.5, 133.0
(d, J = 8.4 Hz), 130.1, 129.5, 128.5, 119.3, 115.4 (d, J = 22.0
Hz), 97.6, 92.7, 83.1, 34.0, 31.5, 28.7, 26.3, 22.5, 14.0 ppm.
19F{1H} NMR (CDCl3, 282 MHz): δ = -111.3 ppm. IR (film): ν
= 2204 (w, C≡C), 1739 (s, C=O), 1646 (m, C=C) cm-1. HRMS
(ESI): m/z 373.1578, [M+Na+] (calcd for C23H23O2FNa:
373.1574).
MHz): δ = 5.23 (s, 1H), 2.25 (t, J = 7.6 Hz, 2H), 2.20 (s, 3H),
1.49-1.44 (m, 2H), 1.34-1.28 (m, 6H), 0.88 (t, J = 6.4 Hz,
3H), -0.18 (s, 9H) ppm. 13C{1H} NMR (CDCl3, 100 MHz): δ =
167.7, 161.6, 99.3, 98.7, 97.7, 33.8, 31.5, 28.6, 26.1, 22.5, 20.7,
14.0, -0.1 ppm. IR (film): ν = 2136 (m, C≡C), 1766 (s, C=O),
1649 (m, C=C) cm-1. HRMS (ESI): m/z 289.1593, [M+Na+]
(calcd for C15H26O2NaSi: 289.1594).
(Z)-Tetradec-7-en-9-yn-7-yl acetate (5g): Yellow oil.
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Yield: 0.210 g (84%). H NMR (CDCl3, 300 MHz): δ = 5.20
(s, 1H), 2.35-2.30 (m, 2H), 2.25 (t, J = 7.2 Hz, 2H), 2.21 (s,
3H), 1.49-1.44 (m, 6H), 1.32-1.29 (m, 6H), 0.95-0.87 (m,
13
6H) ppm. C{1H} NMR (CDCl3, 75 MHz): δ = 168.0, 158.9,
(Z)-1-(4-Bromophenyl)dec-3-en-1-yn-4-yl benzoate (6c):
1
Yellow oil. Yield: 0.362 g (88%). H NMR (CDCl3, 300
98.0, 94.9, 74.1, 33.6, 31.5, 30.8, 28.6, 26.2, 22.5, 21.8, 20.7,
19.1, 14.0, 13.5 ppm. IR (film): ν = 2220 (w, C≡C), 1763 (s,
C=O), 1653 (m, C=C) cm-1. HRMS (ESI): m/z 273.1825,
[M+Na+] (calcd for C16H26O2Na: 273.1825).
MHz): δ = 8.21-8.19 (m, 2H), 7.68-7.63 (m, 1H), 7.55-7.50
(m, 2H), 7.31 (d, J = 8.4 Hz, 2H), 6.99 (d, J = 8.5 Hz, 2H),
5.53 (s, 1H), 2.49 (t, J = 7.2 Hz, 2H), 1.67-1.56 (m, 2H), 1.46-
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