SYNTHESIS OF PHOSPHORUS-SUBSTITUTED
1591
3MeOH
II, IV
(HO)2P
O
CHC CХ
_Me3SiOMe
OH
VII, VIII
X = H (VII), Ph (VIII).
The resulting compounds I–VIII contain the
terminal and internal acetylene fragments and are
promising synthons for generating the new types of the
functionalized organophosphorus compounds. The
NMR spectra of compounds I–VIII contain the
characteristic signals of PC1H(ОR)C2≡C3X, X = H, C4
fragments whose parameters are listed below.
According to the NMR spectra compound V is a
mixture of two stereoisomers. The stereoisomers ratio
was determined by the 31P NMR spectroscopy. The
predominant isomer data are given the first.
4.0–4.2 m (2СН2О), 7.1–7.3 m (С6Н5). 13С NMR
1
spectrum, δС, ppm: 60.15 d (С1, JPС 180.4 Hz), 83.96
2
3
d (С2, JPС 4.8 Hz), 87.46 d (С3, JPС 10.4 Hz), 122.05
4
d (С4, JPС 3.2 Hz), 128.19, 128.62 and 131.46 (СРh),
63.4–64.0 m (СН2О), 1.20–1.25 m (Ме), –0.04
(Ме3Si). 31Р NMR spectrum: δР 15.86 ppm. Found, %:
С 56.12; Н 7.29. С16Н25О4PSi. Calculated, %: С 56.45;
Н 7.40.
Bis(trimethylsilyl) (1-trimethylsiloxy-3-phenyl-
prop-2-yn-1-yl)phosphonate (IV). Yield 85%,
bp 154°С (1 mm Hg). 1Н NMR spectrum, δ, ppm: 4.63
2
Diethyl (1-trimethylsiloxyprop-2-yn-1-yl)phos-
phonate (I). To a solution of 21 g of diethyl(tri-
methylsilyl) phosphite in 20 ml of methylene chloride
was added a solution of 3.8 g of propynal in 25 ml of
methylene chloride under stirring and cooling to 10°C.
The mixture was stirred for 0.5 h, the solvent was
distilled off. The residue was distilled. Yield 2.15 g
d (С1Н, JPH 19.2 Hz), 0.09 s (Ме3Si), 0.16 s
(Ме3SiОР), 7.1–7.3 m (С6Н5). 13С NMR spectrum, δС,
1
2
ppm: 60.72 d (С1, JPС 187.5 Hz), 85.65 d (С2, JPС
4.7 Hz), 87.01 d (С3, JPС 10.4 Hz), 122.30 d (С4,
3
4JPС 3.2 Hz), 128.18, 128.44 and 131.35 (СРh), 0.04
(Ме3Si), 0.84 (Ме3SiОР). 31Р NMR spectrum: δР
–1.48 ppm. Found, %: С 50.26; Н 7.69. С18Н33О4PSi3.
Calculated, %: С 50.43; Н 7.76.
1
(82%), bp 112°С (2 mm Hg). Н NMR spectrum, δ,
2
4
ppm: 4.41 d.d (С1Н, JPH 18.4, JНH 2.4 Hz), 2.51 d.d
Bis(1-hydroxy-3-phenylprop-2-yn-1-yl)phos-
phinic acid (V). A mixture of 2.9 g of ammonium
hypophosphite, 9.2 g of phenylpropynal, 10 g of tri-
methylchlorosilane in 30 ml of methylene chloride was
boiled with stirring for 1 h. Then ammonium chloride
was filtered off, the solvent was distilled off. To the
residue was added 30 ml of ethanol. After the mixture
was heated to reflux, ethanol was removed. The
residue was washed with 10 ml of diethyl ether and
kept in a vacuum of 1 mm Hg for 1 h. Yield 8.4 g
(С3Н, JPH 5.6, JНH 2.4 Hz), –0.01 s (Ме3Si), 1.1–1.5
4
4
m (2Ме), 3.9–4.1 m (СН2О). 13С NMR spectrum, δС,
1
ppm: 59.34 d (С1, JPС 180.4 Hz), 78.57 d (С2,
2JPС 4.0 Hz), 76.13 d (С3, JPС 10.4 Hz), –0.29 s
3
(Ме3Si), 16.1–16.3 m (Ме), 63.4–63.7 m (СН2О). 31Р
NMR spectrum: δР 15.74 ppm. Found, %: С 45.11; Н
7.92. С10Н21О4PSi. Calculated, %: С 45.44; Н 8.01.
Phosphonates II–IV were similarly obtained.
Bis(trimethylsilyl) (1-trimethylsiloxyprop-2-yn-
1-yl)phosphonate (II). Yield 84%, bp 104°С (1 mm
Hg). 1Н NMR spectrum, δ, ppm: 4.02 d.d (С1Н,
1
(74%), viscous oil. The first isomer, content 70%. Н
2
NMR spectrum, δ, ppm: 4.77 d (С1Н, JPH 14.0 Hz),
7.3–7.5 m (С6Н5). 13С NMR spectrum, δС, ppm: 61.23
d (С1, 1JPС 111.7 Hz), 85.25 d (С2, 2JPС < 1 Hz), 87.63
d (С3, 3JPС 8.8 Hz), 126.63 d (С4, 4JPС < 1 Hz), 128.93,
129.39 and 131.78 (СРh). 31Р NMR spectrum: δР
4
4
2JPH 19.2, JНH 2.4 Hz), 2.67 d.d (С3Н, JPH 6.0,
4JНH 2.4 Hz), –0.17 s (2Ме3SiОР), –0.21 s (Ме3Si). 13С
NMR spectrum, δС, ppm: 59.16 d (С1, JPС 187.2 Hz),
1
78.66 d (С2, JPС 4.7 Hz), 75.93 d (С3, JPС 10.2 Hz),
–0.21 (Ме3Si), –0.17 (Ме3SiОР). 31Р NMR spectrum:
δР –1.99 ppm. Found, %: С 40.72; Н 8.18. С12Н29О4·
PSi3. Calculated, %: С 40.88; Н 8.29.
2
3
1
24.98 ppm. The second isomer. Н NMR spectrum, δ,
2
ppm: 5.13 d (С1Н, JPH 10.4 Hz), 7.3–7.5 m (С6Н5).
13С NMR spectrum, δС, ppm: 69.18 d (С1, 1JPС 111.0 Hz),
2
3
85.15 d (С2, JPС < 1 Hz), 87.28 d (С3, JPС 7.9 Hz),
127.38 d (С4, 4JPС < 1 Hz), 128.87, 129.13 and 131.86
(СРh). 31Р NMR spectrum: δР 26.87 ppm. Found, %: С
65.98; Н 4.57. С18Н15О4P. CAlculated, %: С 66.26; Н
4.63.
Diethyl (1-trimethylsiloxy-3-phenylprop-2-yn-1-
yl)phosphonate (III). Yield 87%, bp 157°С (1 mm
Hg). 1Н NMR spectrum, δ, ppm: 4.75 d (С1Н,
2JPH 18.8 Hz), 0.11 s (Ме3Si), 1.15–1.25 m (2Ме),
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 82 No. 9 2012