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New Journal of Chemistry
Page 5 of 9
DOI: 10.1039/C6NJ00123H
NJC
PAPER
1.65-1.56 (m, 2H), 0.61-0.56 (m, 2H), 0.02 (s, 9H). 13C NMR
(CDCl3, 100 MHz): δ 52.3 (d, J = 6.6 Hz), 28.7 (d, J = 137.1 Hz),
18.6 (d, J = 15 Hz), 17.4 (d, J = 5.4 Hz), -1.6. 31P NMR (CDCl3,
162 MHz): δ 34.5. HRMS (ESI+) calcd for C8H21O3P: 225.1076
found: 225.1077.
NMR (CDCl3, 100 MHz): δ 155.5 (d, J = 4.7 Hz), 115.0 (d, J =
184.6 Hz), 52.1 (d, J = 5.7 Hz), 31.5, 31.0 (d, J = 8.2 Hz), 28.7,
22.6, 14.10. 31P NMR (CDCl3, 162 MHz): δ 20.2. HRMS (ESI+)
calcd for C9H20O3P: 207.1150, found: 207.1152. For (E) isomer:
1H NMR (CDCl3, 400 MHz): δ 6.80 (ddt, J = 22.1, 17.2, 6.6 Hz,
1H), 5.60 (ddt, J = 21.4, 17.2, 1.6 Hz, 1H), 3.70 (d, J = 11.0 Hz,
6H), 2.30-2.15 (m, 2H), 1.51-1.39 (m, 2H), 1.35-1.24 (m, 4H),
0.94-0.83 (m, 3H). 13C NMR (CDCl3, 100 MHz): δ 155.3 (d, J =
4.3 Hz), 115.3 (d, J = 188.5 Hz), 52.4 (d, J = 5.7 Hz), 34.3 (d, J =
22.2 Hz), 31.4, 28.5, 22.5, 14.1. 31P NMR (CDCl3, 162 MHz): δ
21.7. HRMS (ESI+) calcd for C9H20O3P: 207.1150, found:
207.1151.
4.8. Dimethyl 1-methyl-heptylphosphonate (A) and dimethyl
1-ethyl-hexylphosphonate (B) Table 1, Entry 8). Procedure A,
60 mg (99%), colorless oil (inseparable isomers). 1H NMR
(CDCl3, 400 MHz): δ 3.73 (d, J = 10.5 Hz, 3H, isomer A), 3.73 (d,
3H, J = 10.5 Hz, isomer A), 3.72 (d, J = 10.5 Hz, 6H, isomer B),
1.88-1.24 (m, 23H), 1.15 (dd, J = 7.2, 18.8 Hz, 3H, isomer B),
0.99 (t, J = 7.4 Hz, 3H, isomer A), 0.89-0.85 (m, 6H). 13C NMR
(CDCl3, 100 MHz): δ 52.6-52.3 (m), 37.1 (d, J = 137.2 Hz), 32.0,
31.8, 31.2, 30.0, 29.9, 29.7, 29.2, 27.6-27.2 (m), 22.7, 22.6,
21.2 (d, J = 3.5 Hz), 14.2, 13.2 (d, J = 5 Hz), 12.2 (d, J = 8.9 Hz).
31P NMR (CDCl3, 162 MHz): δ 37.7 (isomer A), 37.5 (isomer B).
HRMS (ESI+) calcd for C10H23O3P: 223.1463 found: 223.1467.
4.11. Dimethyl styrylphosphonate (Table 2, Entry 3) 52
.
Procedure B, 22 mg (40%), yellow oil. 1H NMR (CDCl3, 400
MHz): δ 7.69-7.36 (m, 11H), 7.26 (d, J = 14.2 Hz, 1H, E isomer),
6.22 (t, J = 17.7 Hz, 1H, E isomer), 5.78 (dd, J = 15.6, 14.2 Hz,
1H, Z isomer), 3.78 (d, J = 11.1 Hz, 6H, E isomer), 3.62 (d, J =
11.2 Hz, 6H, Z isomer). 13C NMR (CDCl3, 100 MHz): δ 149.5 (d, J
= 6.6 H, E isomer), 149.0 (Z isomer), 135.0 (d, J = 8.8 Hz, Z
isomer), 134.5 (d, J = 23.4 Hz, E isomer), 130.2 (E isomer), 129.4
(Z isomer), 129.3 (Z isomer), 128.7 (E isomer), 128.1 (Z isomer),
127.6 (E isomer), 114.9 (d, J = 186.4 Hz, Z isomer), 112.2 (d, J =
192.4 Hz, E isomer), 52.3 (d, J = 5.6 Hz, E isomer), 52.1 (d, J =
6.0 Hz, Z isomer). 31P NMR (CDCl3, 162 MHz): δ 22.4 (E isomer),
18.9 (Z isomer). HRMS (ESI+) calcd for C10H14O3P: 213.0681,
found: 213.0682.
4.9. Dimethyl (2-cyclohexylvinyl)phosphonate (Table 2, Entry
1) 16
1
Procedure B, 46 mg (78%), colorless oil. H NMR (CDCl3,
.
OMe
O
400 MHz): δ 6.76 (ddd, J = 6.3, 17.3, 22.7 Hz, 1H, E isomer),
6.32 (ddd, J = 10.4, 13.0, 53.5 Hz, 1H), 5.54 (ddd, J = 1.5, 17.3,
21.1 Hz, 1H, E isomer), 5.42 (ddd, J = 0.7, 13.0, 19.8 Hz, 1H, Z
isomer), 3.71 (d, J = 11.1 Hz, 6H, Z isomer), 3.70 (d, J = 11.0 Hz,
6H, E isomer), 1.79-1.64 (m, 11H), 1.39-1.06 (m, 11H). 13C NMR
(CDCl3, 100 MHz): δ 160.2 (d, J = 5.3 Hz, E isomer), 160.0 (d, J =
3.5 Hz, Z isomer), 112.8 (d, J = 184.7 Hz, E isomer), 112.7 (d, J =
188.7 Hz, Z isomer), 52.4 (d, J = 5.7 Hz, Z isomer), 52.1 (d, J =
5.6 Hz, E isomer), 42.1 (d, J = 20.5 Hz, E isomer), 39.6 (d, J = 7.6
Hz, Z isomer), 32.5, 31.6, 26.0, 25.9, 25.8, 25.3. 31P NMR
(CDCl3, 162 MHz): δ 22.6 (E isomer), 20.3 (Z isomer). HRMS
(ESI+) calcd for C10H19O3P: 219.1150, found: 219.1153.
P
OMe
OMe
OMe
P
O
4.12.
(Z)-
and
(E)-Dimethyl
(3-phenylprop-1-en-1-
yl)phosphonate (Table 2, Entry 4). Procedure B, 55 mg (89%),
colorless oil. Further purification by flash chromatography on
silica gel (cyclohexane/ethyl acetate/ NEt3, 25/75/0.5, v/v/v)
gave pure analytical samples of (Z) and (E) isomers. For (Z)
isomer: 1H NMR (CDCl3, 400 MHz): δ 7.32-7.28 (m, 2H), 7.24-
7.19 (m, 3H), 6.65 (ddt, J = 7.8, 12.9, 52.5 Hz, 1H), 5.64 (ddt, J =
1.5, 12.9, 18.9 Hz, 1H), 3.89 (ddd, J = 1.4, 2.9, 7.7 Hz, 2H), 3.68
(d, J = 11.2 Hz, 6H). 13C NMR (CDCl3, 100 MHz): δ 152.8 (d, J =
3.7 Hz), 138.7 (d, J = 1.7 Hz), 128.8, 128.7, 126.6, 115.6 (d, J =
184.4 Hz), 52.2 (d, J = 5.8 Hz), 47.0 (d, J = 8.4 Hz). 31P NMR
(CDCl3, 162 MHz): δ 19.5. HRMS (ESI+) calcd for C11H15O3P:
227.0837, found: 227.0839. For (E) isomer: 1H NMR (CDCl3, 400
MHz): δ 7.27-7.23 (m, 2H), 7.19-7.16 (m, 1H), 7.10-7.08 (m,
2H), 6.95-682 (m, 1H), 5.58-5.47 (m, 1H), 3.63 (d, J = 11.1 Hz,
6H), 3.50-3.56 (m, 2H). 13C NMR (CDCl3, 100 MHz): δ 152.9 (d, J
= 5.3 Hz), 137.3, 129.0, 128.9, 126.9, 116.8 (d, J = 188.4 Hz),
52.4 (d, J = 5.7 Hz), 40.5 (d, J = 22.9 Hz). 31P NMR (CDCl3, 162
4.10. (Z)- and (E)-Dimethyl hept-1-en-1-ylphosphonate (Table
2, Entry 2). Procedure B, 22 mg (42%), colorless oil. Further
purification by flash chromatography on silica gel
(cyclohexane/ethyl acetate, 6/4, v/v) gave pure analytical
1
samples of (Z) and (E) isomers. For (Z) isomer: H NMR (CDCl3,
400 MHz): δ 6.53 (ddt, J = 53.5, 13.0, 7.7 Hz, 1H), 5.55 (ddt, J =
20.0, 13.0, 1.5 Hz, 1H), 3.72 (d, J = 11.1 Hz, 6H), 2.51 (m, 2H),
1.48-1.41 (m, 2H), 1.34-1.30 (m, 4H), 0.91-0.87 (m, 3H). 13C
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