K. Kiyokawa, I. Suzuki, M. Yasuda, A. Baba
FULL PAPER
HRMS (EI, 70 eV): calcd. for C13H25O3P [M]+ 260.1541; found
260.1539.
1.64 mmol, 84% purity), and 2h (0.250 g, 0.85 mmol) gave the
crude product. Purification by flash column chromatography (hex-
ane/ethyl acetate, 50:50) afforded product 3h (0.040 g, 21%). Fur-
ther purification by distillation under reduced pressure gave 3h as
Diisopropyl (2-Cyclopropylethyl)phosphonate (3e): According to the
typical procedure, InBr3 (0.287 g, 0.81 mmol),
1 (0.632 g,
a colorless liquid (0.020, 11%); b.p. 130 °C/0.2 Torr. IR (neat): ν =
˜
1.54 mmol, 84% purity), and 2e (0.251 g, 0.81 mmol) gave the
crude product. Purification by flash column chromatography (hex-
ane/ethyl acetate, 70:30) afforded product 3e (0.130 g, 68%). Fur-
ther purification by distillation under reduced pressure gave 3e as
1
1033 cm–1. H NMR (400 MHz, CDCl3): δ = 4.18–4.02 (m, 4 H, 2
CH3CH2), 2.10–2.02 (m, 2JP,H = 7.5 Hz, 2 H, PCH2), 1.57–1.48 (m,
2 H, 2 PCH2CH2), 1.29 (td, J = 7.0 Hz, JP,H = 1.0 Hz, 6 H, 2
4
CH3), 0.80–0.70 (m, 1 H, PCH2CH2CH), 0.47–0.42 (m, 2 H), 0.10–
0.06 (m, 2 H) ppm. 13C NMR (100 MHz, CDCl3): δ = 62.1, 34.6,
28.0, 16.1, 11.4, 4.5 ppm. 31P NMR (160 MHz, CDCl3): δ =
113.9 ppm. MS (EI, 70 eV): m/z (%) = 222 (51) [M]+, 194 (41) [M –
CH3CH2]+, 154 (29) [(CH3CH2O)2PS]+, 150 (25), 125 (23), 121
(100), 97 (45), 93 (50), 69 (21) [M – (CH3CH2O)2P(S)]+, 65 (33).
HRMS (EI, 70 eV): calcd. for C9H19O2PS [M]+ 222.0843; found
222.0842. C9H19O2PS (222.28): calcd. C 48.63, H 8.62, O 14.40, P
13.93, S 14.43; found C 48.40, H 8.33.
a colorless liquid; b.p. 85 °C/0.25 Torr. IR (neat): ν = 1250 (P=O)
˜
cm–1. 1H NMR (400 MHz, CDCl3): δ = 4.69–4.58 (m, 2 H, 2
Me2CH), 1.83–1.74 (m, including 2JP,H = 18 Hz, 2 H, PCH2), 1.50–
4
1.42 (m, PCH2CH2), 1.32 (dd, J = 8.2 Hz, JP,H = 1.9 Hz, 12 H, 2
Me2CH), 0.81–0.71 (m, 1 H, PCH2CH2CH), 0.46–0.42 (m, 2 H),
0.08–0.04 (m, 2 H) ppm. 13C NMR (100 MHz, CDCl3): δ = 69.6,
27.7, 26.9, 23.9, 11.6, 4.5 ppm. 31P NMR (160 MHz, CDCl3): δ =
44.8 ppm. MS (CI, 200 eV): m/z (%) = 235 (100) [M + 1]+, 193 (6)
[M – 41]+, 191 (1) [M – 43]+. HRMS (CI, 200 eV): calcd. for
C11H24O3P 235.1463; found 235.1456. C11H23O3P (234.27): calcd.
C 56.39, H 9.90, O 20.49, P 13.22; found C 56.12, H 9.61.
Diethyl (3-Cyclopropylpropyl)phosphonate (6): According to the
typical procedure, InBr3 (0.283 g, 0.80 mmol),
1
(0.644 g,
1.60 mmol, 86% purity), 5 (0.232 g, 0.79 mmol), and AIBN
(0.013 g, 0.08 mmol) gave the crude product. Purification by flash
column chromatography (hexane/ethyl acetate, 70:30) afforded the
product 6 (0.032 g, 18%). Further purification was performed by
distillation under reduced pressure; b.p. 80 °C/0.26 Torr. IR (neat):
2-(1-Methyl-2-cyclopropylethyl)-5,5-dimethyl-1,3,2-dioxaphos-
phorinan-2-one (3f): According to the typical procedure, InBr3
(0.283 g, 0.80 mmol), 1 (0.748 g, 1.62 mmol, 75% purity), and 2f
(0.243 g, 0.80 mmol) gave the crude product. Purification by flash
column chromatography (hexane/ethyl acetate, 70:30) afforded
product 3f (0.130 g, 58%). Further purification by distillation
under reduced pressure gave 3f as a colorless liquid (0.070 g, 38%);
ν = 1246 (P=O) cm–1. 1H NMR (400 MHz, CDCl ): δ = 4.17–4.03
˜
3
(m, 4 H, 2 CH2OP), 1.82–1.65 (m, 4 H, PCH2 and PCH2CH2),
1.42–1.26 (m, 2 H, PCH2CH2CH2), 1.33 (t, J = 7.0 Hz, 6 H, 2
CH3), 0.69–0.60 (m, 1 H, PCH2CH2CH2CH), 0.44–0.40 (m, 2 H),
0.07–0.01 (m, 2 H) ppm. 13C NMR (100 MHz, CDCl3): δ = 61.3,
35.4, 25.4, 22.4, 16.4, 10.3, 4.3 ppm. 31P NMR (160 MHz, CDCl3):
δ = 47.3 ppm. MS (EI, 70 eV): m/z (%) = 220 (14) [M]+, 191 (23)
[M – CH2CH3]+, 165 (53) [M – CH2C3H5]+, 152 (100) [M –
CH2CH2C3H5]+, 147 (31), 138 (71) [(CH3CH2O)2PO]+, 125 (65),
124 (23), 111 (64), 110 (23), 109 (31), 108 (21), 97 (52), 96 (26), 82
(31) [CH2CH2CH2C3H5]+, 81 (38), 41 (23) [C3H5]+. HRMS (EI,
70 eV): calcd. for C10H21O3P 220.1228; found 220.1221.
b.p. 130 °C/0.47 Torr. IR (neat): ν = 1268 (P=O) cm–1. 1H NMR
˜
3
(400 MHz, CDCl3): δ = 4.21 (dd, J = 11, JP,H = 6 Hz, 2 H, two
protons of 4-H and/or 6-H), 3.67 (dd, JP,H = 17 Hz, J = 11 Hz, 2
3
H, two protons of 4-H and/or 6-H), 2.08–1.95 (m, 1 H, PCH),
1.64–1.54 (m, 1 H, PCHCHH), 1.43–1.33 (m, 1 H, PCHCHH),
1.25 (dd, 3JP,H = 19 Hz, J = 7.5 Hz, 3 H, PCHCH3), 1.11 (s, 5-Me),
0.87 (s, 5-Me), 0.82–0.71 (m, 1 H, PCHCH2CH), 0.50–0.33 (m, 2
H), 0.11 to –0.06 (m, 2 H) ppm. 13C NMR (100 MHz, CDCl3): δ
= 73.9, 73.8, 34.5, 32.6, 30.3, 21.8, 21.2, 12.8, 9.0, 5.4, 3.7 ppm. 31
P
NMR (160 MHz, CDCl3): δ = 110.5 ppm. MS (EI, 70 eV): m/z (%)
= 232 (55) [M]+, 217 (51) [M – CH3]+, 191 (48) [M – C3H5]+, 178
(59), 177 (37) [M – CH2C3H5]+, 164 (31), 163 (36), 150 (39), 149
(67) [M – CH3CHCH2C3H5]+, 147 (46), 136 (23), 123 (51), 111
(82), 110 (36), 109 (28), 97 (21), 83 (34) [CH3CHCH2C3H5]+, 82
(99), 81 (50), 71 (27), 69 (98), 68 (71), 67 (56), 57 (40), 56 (52), 55 (78)
[CH2C3H5]+, 43 (20), 41 (100) [C3H5]+. HRMS (EI, 70 eV): calcd.
for C11H21O3P [M]+ 232.1228; found 232.1225.
1,1-Diphenyl-3-cyclopropyl-1-propene (10): According to the typical
procedure, 3h (0.050 g, 0.23 mmol), sBuLi (1.0 m in hexane,
0.30 mL), and benzophenone (0.043 g, 0.24 mmol) gave the crude
product. Purification by flash column chromatography (hexane,
200 mL) gave the product 10 as a colorless liquid (0.030 g, 57%).
IR (neat): ν = 1493, 1442, 822, 702 cm–1. 1H NMR (400 MHz,
˜
CDCl3): δ = 7.38–7.16 (m, 10 H, 2 Ar), 6.19 (t, J = 7.0 Hz, 1 H,
2-H), 2.02 (dd, J = 7.0, 7.0 Hz, 2 H, 3-H2), 0.83–0.73 (m, 1 H,
C=CHCH2CH), 0.46–0.41 (m, 2 H), 0.088–0.050 (m, 2 H) ppm.
13C NMR (100 MHz, CDCl3): δ = 142.7, 141.4, 140.2, 129.9, 129.1,
128.1, 128.0, 127.2, 126.8, 126.7, 34.5, 11.1, 4.2 ppm. MS (EI,
70 eV): m/z (%) = 234 (46) [M]+, 205 (100), 193 (37) [M – C3H5]+,
191 (22), 180 (35), 178 (25) [M – CH2C3H5]+, 165 (24), 115 (48),
91 (42). HRMS (EI, 70 eV): calcd. for C18H18 [M]+ 234.1409; found
234.1404. C18H18 (234.34): calcd. C 7.74, H 92.26; found C 7.66,
H 92.12.
(2-Cyclopropylethyl)diphenylphosphane Oxide (3g): According to
the typical procedure, InBr3 (0.285 g, 0.80 mmol), 1 (0.660 g,
1.61 mmol, 84% purity), and 2g (0.272 g, 0.80 mmol) gave the
crude product. Purification by flash column chromatography (hex-
ane/ethyl acetate, 60:40) afforded product 3g as a white solid
(0.140 g, 52%); m.p. 95 °C. IR (KBr): ν = 1438, 1172, 698 cm–1.
˜
1H NMR (400 MHz, CDCl3): δ = 7.76–7.71 (m, 4 H, o), 7.53–7.43
2
(m, 6 H, m and p), 2.42–2.35 (m, including JP,H = 11 Hz, 2 H,
PCH2), 1.56–1.48 (m, 2 H, PCH2CH2), 0.79–0.69 (m, 1 H,
PCH2CH2CH), 0.43–0.38 (m, 2 H), 0.049–0.012 (m, 2 H) ppm. 13
C
(2-Cyclopropylethylidene)cyclohexane (11): According to the typical
procedure, 3h (0.038 g, 0.17 mmol), sBuLi (1.0 m in hexane,
0.20 mL), and cyclohexanone (0.023 g, 0.23 mmol) gave the crude
product. Purification by flash column chromatography (hexane,
200 mL) afforded product 11 as a colorless liquid (0.012 g, 51%).
NMR (100 MHz, CDCl3): δ = 133.05, 131.5, 130.6, 128.4, 29.6,
26.5, 11.9, 4.6 ppm. 31P NMR (160 MHz, CDCl3): δ = 46.7 ppm.
MS (EI, 70 eV): m/z (%) = 270 (34) [M]+, 269 (28), 215 (33) [M –
CH2C3H5]+, 255 (32), 201 (100) [M – CH2CH2C3H5]+, 186 (34), 77
(23) [C6H5]+. HRMS (EI, 70 eV): calcd. for C17H19OP 270.1174;
found 270.1169. C17H19OP (270.30): calcd. C 75.54, H 7.08, O 5.92,
P 11.46; found: C 75.70, H 6.89.
IR (neat): ν = 1666 (C=C), 1446, 1014, 849, 818 cm–1. 1H NMR
˜
(400 MHz, CDCl3): δ = 5.16 (t, J = 7.0 Hz, 1 H, C=CH), 2.12–
2.07 (m, 4 H), 1.92 (dd, J = 7.0, 7.0 Hz, 2 H, 2-H2), 1.55–1.43 (m,
6 H), 0.74–0.64 [m, 1 H, 2-CH(CH2)2], 0.41–0.37 (m, 2 H), 0.07–
0.03 (m, 2 H) ppm. 13C NMR (100 MHz, CDCl3): δ = 139.8, 120.1,
O,OЈ-Diethyl (2-Cyclopropylethyl)phosphonothioate (3h): According
to the typical procedure, InBr3 (0.286 g, 0.81 mmol), 1 (0.675 g,
2170
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Eur. J. Org. Chem. 2011, 2163–2171