1938 J . Org. Chem., Vol. 62, No. 7, 1997
Ando
Eth yl [bis(p-ch lor op h en yl)p h osp h on o]a ceta te (1c): col-
orless oil (yield 62%); H NMR δ 1.28 (3H, t, J ) 7 Hz), 3.26
(2H, d, J ) 22 Hz), 4.23 (2H, q, J ) 7 Hz), 7.14-7.24 (4H, m),
7.26-7.37 (4H, m); MS m/ e 388, 390 (M+), 233, 235; bp 270
°C/3 mmHg (bulb-to-bulb). Anal. Calcd for C16H15Cl2PO5: C,
49.38; H, 3.89; Cl, 18.22; P, 7.96. Found: C, 49.35; H, 3.78;
Cl, 18.21; P, 8.01.
Eth yl [bis(p-m eth oxyp h en yl)p h osp h on o]a ceta te (1d ):
colorless oil (yield 54%); 1H NMR δ 1.28 (3H, t, J ) 7 Hz),
3.22 (2H, d, J ) 22 Hz), 3.77 (6H, s), 4.23 (2H, q, J ) 7 Hz),
6.82-6.89 (4H, m), 7.12-7.18 (4H, m); MS m/ e 380 (M+), 334,
229; bp 280 °C/3 mmHg (bulb-to-bulb). Anal. Calcd for
C18H21PO7: C, 56.84; H, 5.57; P, 8.14. Found: C, 57.11; H,
5.56; P, 8.13.
Eth yl (d i-p-tolylp h osp h on o)a ceta te (1e): colorless oil
(yield 63%); 1H NMR δ 1.28 (3H, t, J ) 7 Hz), 2.31 (6H, s),
3.22 (2H, d, J ) 22 Hz), 4.23 (2H, q, J ) 7 Hz), 7.11 (8H, s);
MS m/ e 348 (M+), 241, 213; bp 250 °C/3 mmHg (bulb-to-bulb).
Anal. Calcd for C18H21PO5: C, 62.07; H, 6.08; P, 8.89.
Found: C, 61.90; H, 6.01; P, 8.90.
(6H, m), 7.19-7.24 (2H, m). MS m/ e 348 (M+), 213. bp 230
°C/3 mmHg (bulb-to-bulb). Anal. Calcd for C18H21PO5: C,
62.07; H, 6.08; P, 8.89. Found: C, 62.21; H, 5.78; P, 8.67.
Eth yl [bis(o-d im eth ylp h en yl)p h osp h on o]a ceta te (1o):
colorless needles (yield 57%). mp 83-84 °C (recrystallized
from hexane-CH2Cl2). 1H NMR δ 1.27 (3H, t, J ) 7 Hz), 2.27
(12H, s), 3.37 (2H, d, J ) 22 Hz), 4.22 (2H, q, J ) 7 Hz), 6.96-
7.04 (6H, m). MS m/ e 376 (M+), 255, 227. Anal. Calcd for
C20H25PO5: C, 63.82; H, 6.69. Found: C, 63.57; H, 6.60.
Hor n er -Em m on s Rea ction w ith Ben za ld eh yd e: P r o-
ced u r e 1. A solution of 1 (0.50 mmol) in THF (10 mL) was
treated with Triton B (0.27 mL, 0.60 mmol) at -78 °C for 15
min. Benzaldehyde (0.054 mL, 0.53 mmol) was then added,
and the resulting mixture was stirred at -78 °C. The reaction
was quenched with saturated NH4Cl, and the mixture was
extracted with AcOEt (10 mL × 3). The combined extracts
were washed with water (15 mL × 2) followed by brine, dried
(MgSO4), and concentrated. After determining the Z/E ratio
1
1
of the crude mixture by 500 MHz H NMR, ethyl cinnamate
was isolated by flash chromatography as a colorless oil. The
Z/E ratio did not change by flash chromatography.
Eth yl (Z)-cin n a m a te:12 1H NMR δ 1.24 (3H, t, J ) 7 Hz),
4.17 (2H, q, J ) 7 Hz), 5.95 (1H, d, J ) 12 Hz), 6.94 (1H, d, J
) 12 Hz), 7.29-7.39 (3H, m), 7.56-7.59 (2H, m); GCMS m/ e
176 (M+), 131.
Eth yl (biph en ylph osph on o)acetate (1f): colorless needles
(yield 24%); mp 81-82 °C (recrystallized from hexane-CH2-
Cl2); 1H NMR δ 1.27 (3H, t, J ) 7 Hz), 3.23 (2H, d, J ) 21 Hz),
4.20 (2H, q, J ) 7 Hz), 7.33-7.40 (4H, m), 7.44-7.48 (2H, m),
7.51-7.55 (2H, m); MS m/ e 318 (M+). Anal. Calcd for C16H15
PO5: C, 60.38; H, 4.75. Found: C, 60.28; H, 4.67.
-
Eth yl (E)-cin n a m a te:12,13 1H NMR δ 1.34 (3H, t, J ) 7 Hz),
4.27 (2H, q, J ) 7 Hz), 6.44 (1H, d, J ) 16 Hz), 7.33-7.43
(3H, m), 7.51-7.53 (2H, m), 7.69 (1H, d, J ) 16 Hz); GCMS
m/ e 176 (M+), 131.
P r ep a r a tion of th e E-Isom er : P r oced u r e 2. To a
solution of triethyl phosphonoacetate (0.205 mL, 1.00 mmol)
in THF (3 mL) was added BuLi in hexane (0.75 mL, 1.20 mmol)
at 0 °C. After 10 min, the mixture was treated with benz-
aldehyde (0.112 mL, 1.10 mmol) for 30 min and the reaction
quenched in the same way as in procedure 1 (E:Z ) 99.7:0.3)
(yield 99%).
Hor n er -Em m on s Rea ction w ith 2(E)-Hexen a l. A solu-
tion of 1 (0.50 mmol) in THF (2 mL) was treated with Triton
B (0.27 mL, 0.60 mmol) at -78 °C for 15 min. 2(E)-Hexenal
(0.066 mL, 0.55 mmol) in THF (0.5 mL) was then added, and
the resulting mixture was gradually warmed to the indicated
temperature over 1-2 h. The following reaction procedure was
the same as procedure 1. For characterization, the isomers
were separated by pTLC.
Eth yl (d i-2-n a p h th ylp h osp h on o)a ceta te (1g): colorless
viscous oil (yield 64%); 1H NMR δ 1.25 (3H, t, J ) 7 Hz), 3.35
(2H, d, J ) 22 Hz), 4.23 (2H, q, J ) 7 Hz), 7.38-7.47 (6H, m),
7.71-7.81 (8H, m); MS m/ e 420 (M+), 249; HRMS calcd for
C24H21PO5 420.1125, found 420.1128.
Eth yl (d i-1-n a p h th ylp h osp h on o)a ceta te (1h ): colorless
viscous oil (yield 57%); 1H NMR δ 1.19 (3H, t, J ) 7 Hz), 3.49
(2H, d, J ) 22 Hz), 4.20 (2H, q, J ) 7 Hz), 7.35-7.38 (2H, m),
7.46-7.56 (6H, m), 7.66-7.68 (2H, m), 7.81-7.85 (2H, m),
8.10-8.14 (2H, m); MS m/ e 420 (M+), 249; HRMS calcd for
C24H21PO5 420.1125, found 420.1129.
Eth yl [bis(o-ch lor op h en yl)p h osp h on o]a ceta te (1i): col-
1
orless oil (yield 46%); H NMR δ 1.24 (3H, t, J ) 7 Hz), 3.46
(2H, d, J ) 22 Hz), 4.21 (2H, q, J ) 7 Hz), 7.12-7.18 (2H, m),
7.20-7.25 (2H, m), 7.40-7.44 (4H, m); MS m/ e 388, 390 (M+),
233, 235; bp 260 °C/3 mmHg (bulb-to-bulb). Anal. Calcd for
C16H15Cl2PO5: C, 49.38; H, 3.89; Cl, 18.22; P, 7.96. Found:
C, 49.45; H, 3.75; Cl, 18.33; P, 7.78.
Eth yl 2(Z),4(E)-octa d ien oa te: 1H NMR δ 0.93 (3H, t, J )
7 Hz), 1.30 (3H, t, J ) 7 Hz), 1.47 (2H, sex, J ) 7 Hz), 2.18
(2H, q, J ) 7 Hz), 4.18 (2H, q, J ) 7 Hz), 5.56 (1H, d, J ) 11
Hz), 6.06 (1H, dt, J ) 15, 7 Hz), 6.55 (1H, t, J ) 11 Hz), 7.37
(1H, dd, J ) 15, 11 Hz); GCMS m/ e 168 (M+); HRMS calcd
for C10H16O2 168.1150, found 168.1150.
Eth yl [bis(o-m eth oxyp h en yl)p h osp h on o]a ceta te (1j):
colorless oil (yield 57%); 1H NMR δ 1.26 (3H, t, J ) 7 Hz),
3.42 (2H, d, J ) 22 Hz), 3.83 (6H, s), 4.22 (2H, q, J ) 7 Hz),
6.85-6.90 (2H, m), 6.93-4.96 (2H, m), 7.11-7.15 (2H, m),
7.21-7.25 (2H, m); MS m/ e 381 ((M + H)+), 257, 211; bp 280
°C/3 mmHg (bulb-to-bulb). Anal. Calcd for C18H21PO7: C,
56.84; H, 5.57; P, 8.14. Found: C, 56.87; H, 5.30; P, 7.88.
Eth yl (d i-o-tolylp h osp h on o)a ceta te (1k ): colorless oil
(yield 61%); 1H NMR δ 1.26 (3H, t, J ) 7 Hz), 2.25 (6H, s),
3.33 (2H, d, J ) 22 Hz), 4.22 (2H, q, J ) 7 Hz), 7.05-7.16
(4H, m), 7.18-7.20 (2H, m), 7.27-7.30 (2H, m); MS m/ e 348
(M+), 241, 213; bp 240 °C/3 mmHg (bulb-to-bulb). Anal. Calcd
for C18H21PO5: C, 62.07; H, 6.08; P, 8.89. Found: C, 61.90;
H, 5.93; P, 8.81.
Eth yl 2(E),4(E)-octa d ien oa te: 1H NMR δ 0.92 (3H, t, J )
7 Hz), 1.29 (3H, t, J ) 7 Hz), 1.46 (2H, sex, J ) 7 Hz), 2.15
(2H, q, J ) 7 Hz), 4.20 (2H, q, J ) 7 Hz), 5.78 (1H, d, J ) 15
Hz), 6.08-6.20 (2H, m), 7.26 (1H, dd, J ) 15, 11 Hz); GCMS
m/ e 168 (M+); HRMS calcd for C10H16O2 168.1150, found
168.1149.
The E-isomer was prepared by procedure 2 using DME2e (2
mL) instead of THF (E:Z ) 97:3) (yield 93%).
Eth yl [bis(o-eth ylp h en yl)p h osp h on o]a ceta te (1l): color-
Hor n er -Em m on s Rea ction w ith Octa n a l: P r oced u r e
3. To a solution of 1 (0.50 mmol) in THF (2 mL) was added
NaH (0.028 g, 0.70 mmol) at 0 °C; 15 min later, octanal (0.086
mL, 0.55 mmol) in THF (0.5 mL) was added, and the resulting
mixture was gradually warmed to the indicated temperature
over 1-2 h. The following reaction procedure was the same
as procedure 1. For characterization, the isomers were
separated by pTLC.
1
less oil (yield 53%); H NMR δ 1.16 (6H, t, J ) 7.5 Hz), 1.26
(3H, t, J ) 7 Hz), 2.64 (4H, q, J ) 7.5 Hz), 3.33 (2H, d, J ) 22
Hz), 4.22 (2H, q, J ) 7 Hz), 7.10-7.16 (4H, m), 7.19-7.24 (2H,
m), 7.32-7.35 (2H, m); MS m/ e 377 ((M + H)+), 227; bp 250
°C/3 mmHg (bulb-to-bulb). Anal. Calcd for C20H25PO5: C,
63.82; H, 6.69; P, 8.23. Found: C, 63.70; H, 6.61; P, 8.00.
Eth yl [bis(o-isop r op ylp h en yl)p h osp h on o]a ceta te (1m ):
colorless oil (yield 55%); 1H NMR δ 1.15 (6H, d, J ) 7 Hz),
1.18 (6H, d, J ) 7 Hz), 1.26 (3H, t, J ) 7 Hz), 3.26 (2H, septet,
J ) 7 Hz), 3.34 (2H, d, J ) 22 Hz), 4.22 (2H, q, J ) 7 Hz),
7.08-7.16 (4H, m), 7.24-7.30 (2H, m), 7.31-7.38 (2H, m); MS
m/ e 405 ((M + H)+), 241; bp 250 °C/3 mmHg (bulb-to-bulb).
Anal. Calcd for C22H29PO5: C, 65.33; H, 7.23; P, 7.66.
Found: C, 65.30; H, 7.15; P, 7.56.
1
Eth yl 2(Z)-d ecen oa te: H NMR δ 0.88 (3H, t, J ) 7 Hz),
1.26-1.38 (11H, m), 1.40-1.47 (2H, m), 2.64 (2H, dq, J ) 2, 7
Hz), 4.17 (2H, q, J ) 7 Hz), 5.75 (1H, dt, J ) 12, 2 Hz), 6.21
(1H, dt, J ) 12, 7 Hz); GCMS m/ e 198 (M+), 153; HRMS calcd
for C12H22O2 198.1620, found 198.1620.
(12) Rathke, M. W.; Bouhlel, E. Synth. Commun. 1990, 20, 869-
875.
(13) Tanaka, K.; Yamagishi, N.; Tanikaga, R.; Kaji, A. Bull. Chem.
Soc. J pn. 1979, 52, 3619-3625.
Eth yl (d i-m -tolylp h osp h on o)a ceta te (1n ): colorless oil
(yield 55%). 1H NMR δ 1.28 (3H, t, J ) 7 Hz), 2.33 (6H, s),
3.24 (2H, d, J ) 22 Hz), 4.23 (2H, q, J ) 7 Hz), 6.99-7.06