REACTIONS OF AROMATIC ALDEHYDES AND THEIR ACETALS
2715
1
Bis(trimethylsilyl) pyrid-3-yl(trimethylsiloxy)-
46.82 (Me2N), 48.33 t (C1, JPC = 135.9 Hz), 120.28
2
methylphosphonate (1c). Yield 89%, bp 152°C
(CPh), 132.12 t (CPh, JPC = 5.9 Hz), 135.42 t (CPh,
1
(1 mmHg). H NMR spectrum, δ, ppm: –0.11 s (9H,
3JPC = 8.5 Hz), 141.60 (CPh). 31Р NMR spectrum: δР
–1.47 ppm. Found, %: C 43.06; H 8.06. C21H47NО6P2Si4.
Calculated, %: C 43.20; H 8.11.
Me3Si), –0.10 s (9H, Me3Si), 0.02 s (9H, Me3Si), 4.72
2
d (1H, C1H, JPH = 15.2 Hz), 7.09–7.13 m (1H, CHPy),
3
7.65 d (1H, CHPy, JHH = 8.0 Hz), 8.32–8.34 m (1H,
Bis(trimethylsilyl) 4-bromophenyl(ethoxy)methyl-
phosphonate (3a). A solution of 1.0 g of trimethylsilyl
trifluoromethylsulfonate in 5 mL of methylene chloride
was added to a solution of 3.9 g of 4-bromobenz-
aldehyde diethyl acetal and 19.0 g of tris(trimethyl-
silyl)phosphite in 15 mL of methylene chloride. The
mixture was heated on a boiling water bath for 2 h to
distill off methylene chloride, then the residue was
CHPy), 8.43 s (1H, CHPy). 13C NMR spectrum, δC,
ppm: –0.26 (Me3Si), 0.62 (Me3Si), 0.74 (Me3Si), 69.90
1
d (C1, JPC = 179.3 Hz), 123.05 (CPy), 134.32 (CPy),
3
3
135.37 d (CPy, JPC = 4.6 Hz), 147.85 d (CPy, JPC
=
6.5 Hz), 148.39 (CPy). 31Р NMR spectrum: δР 2.43
ppm. Found, %: C 44.26; H 7.89. C15H32NО4PSi3. Cal-
culated, %: C 44.41; H 7.95.
1
Bis(trimethylsilyl) pyrid-4-yl(trimethylsiloxy)me-
thylphosphonate (1d). Yield 86%, bp 149°C (1 mmHg).
1H NMR spectrum, δ, ppm: –0.09 s (Me3Si), –0.07 s
distilled. Yield 5.0 g (74%), bp 104°C (2 mmHg). H
NMR spectrum, δ, ppm: 0.07 s (18H, Me3Si), 1.05 t
3
(3H, Ме, JHH = 7.2 Hz), 3.30–3.40 m (2H, CH2О),
(Me3Si), 0.06 s (Me3Si), 4.68 d (C1H, JPH = 17.2 Hz),
4.43 d (1H, C1H, JPH = 7.2 Hz), 7.15 d (2H, CHPh,
2
2
3
3
2
7.18 d (CHPy, JHH = 5.6 Hz), 8.35 d (CHPy, JHH
=
2JHH = 8.0 Hz), 7.30 d (2H, CHPh, JHH = 8.0 Hz). 13C
5.6 Hz). 13C NMR spectrum, δC, ppm: –0.70 s (Me3Si),
NMR spectrum, δC, ppm: 0.67 (Me3Si), 15.03 (Ме),
0.15 s (Me3Si), 0.38 s (Me3Si), 70.59 d (C1, JPC
=
66.38 d (CH2О, JPC = 13.8 Hz), 78.11 d (C1, JPC
=
1
3
1
2
174.7 Hz, CPy), 121.45 s (CPy), 147.21 br.s (CPy),
148.54 d (3JPC = 2.0 Hz, CPy). 31Р NMR spectrum: δР
1.85 ppm. Found, %: C 44.28; H 7.86. C15H32NО4PSi3.
Calculated, %: C 44.41; H 7.95.
175.6 Hz), 121.89 d (CPh, JPC = 4.6 Hz), 129.49 d
(CPh, JPC = 5.6 Hz), 131.16 (CPh), 134.70 (CPh). 31Р
2
NMR spectrum: δР 0.65 ppm. Found, %: C 40.86; H
6.33. C15H28BrО4PSi2. Calculated, %: C 41.00; H 6.42.
Bis(trimethylsilyl) 4-dimethylaminophenyl(tri-
Bis(trimethylsilyl) {[4-(dimethylamino)phenyl](eth-
oxy)methyl}phosphonate (3b). A mixture of 3.4 g of
4-dimethylaminobenzaldehyde diethyl acetal and
6.12 g of diethyl(trimethylsilyl) phosphite, 0.1 g of cad-
mium iodide, and 0.1 g of zinc chloride was heated at
140°C until complete distillation off of ethoxytri-
methylsilane (bp 74°C). The residue was distilled.
Yield 4.2 g (86%), bp 195°C (2 mmHg). 1H NMR spec-
methylsiloxy)methylphosphonate (1e). Yield 89%,
1
bp 164°C (1 mmHg), mp 55°C. H NMR spectrum, δ,
ppm: –0.29 s (9H, Me3Si), –0.19 s (9H, Me3Si), –0.16
s (9H, Me3Si), 2.59 s (6H, Me2N), 4.64 d (1H, C1H,
2JPH = 16.0 Hz), 6.43 d (2H, CHPh, 3JHH = 7.2 Hz), 6.93
3
d (2H, CHPh, JHH = 7.2 Hz). 13C NMR spectrum, δC,
ppm: –0.68 (Me3Si), 0.12 (Me3Si), 40.47 (Me2N),
1
3
71.40 d (C1, JPC = 181.4 Hz), 112.22 (CPh), 127.79 d
trum, δ, ppm: 0.97 t (3H, Ме, JHH = 7.2 Hz), 0.98 t
3
3
3
(CPh, JPC = 6.0 Hz), 130.52 (CPh), 148.76 (CPh). 31Р
(3H, Ме, JHH = 7.2 Hz), 1.05 t (3H, Ме, JHH =
NMR spectrum: δР 4.44 ppm.
6.8 Hz), 2.72 s (6H, Me2N), 3.20–3.35 m (2H, CH2О),
2
3.60–3.90 m (4H, CH2О), 4.29 d (1H, C1H, JPH
=
Tetra(trimethylsilyl) 4-dimethylaminophenyl-
methylenediphosphonate (2). A solution of 0.9 g of
trimethylsilyl trifluoromethylsulfonate in 5 mL of
methylene chloride was added to a solution of 3.4 g of
4-dimethylaminobenzaldehyde diethyl acetal and
18.0 g of tris(trimethylsilyl) phosphite in 15 mL of me-
thylene chloride. After completion of the exothermic
reaction, the mixture was kept overnight at 20°C. The
solvent was removed in a vacuum, the crystals were
washed with cold hexane. Yield 8.6 g (96%), mp 144°C.
1H NMR spectrum, δ, ppm: 0.07 s (36H, Me3Si), 3.22
s (6H, Me2N), 3.48 t (1H, C1H, 2JPH = 25.2 Hz), 7.53 d
3
15.2 Hz), 6.47 d (2H, CHPh, JHH = 8.8 Hz), 7.08 d
(2H, CHPh, JHH = 8.8 Hz). 13C NMR spectrum, δC,
2
3
ppm: 14.93 (Me), 16.17 d (Me, JPC = 5.5 Hz), 40.15
2
(Me2N), 62.37 d (CH2О, JPC = 6.5 Hz), 62.58 d
(CH2О, 2JPC = 6.41 Hz), 65.39 d (CH2О, 3JPC = 14.7 Hz),
77.99 t (C1, JPC = 171.0 Hz), 111.84 (CPh), 121.87
1
(CPh), 128.86 d (CPh, JPC = 5.5 Hz), 150.33 (CPh). 31Р
3
NMR spectrum: δР 19.97 ppm. Found, %: C 56.94; H
8.26. C15H26NО4P. Calculated, %: C 57.13; H 8.31.
NMR spectra (CDCl3) were obtained on a Bruker
Avance 400 spectrometer, internal reference TMS (1H,
13C) or external reference 85% solution of H3PO4 in
D2O (31Р).
3
3
(2H, CPhH, JHH = 8.4 Hz), 7.65 d (2H, CPhH, JHH
=
8.4 Hz). 13C NMR spectrum, δC, ppm: 0.32 (Me3Si),
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 86 No. 12 2016