PRISHCHENKO Et al.
5
|
9H, Me3Si), 4.72 (d, 1H, JPH = 15.2 Hz, C1H), 7.09-7.13
(t, JPC = 5.9 Hz), 135.4 (t, JPC = 8.5 Hz), 141.6 (s). 31P
NMR (CDCl3, 162 MHz), δ, ppm: −1.5 (s). Anal. Calcd for
C21H47NO6P2Si4 C 43.20 H, 8.11. Found: C 43.06; H 8.06.
2
3
3
3
(m, 2H, CHPy), 7.65 (d, 1H, JHH = 8.0 Hz, CHPy), 8.32-
8.34 (m, 1H, CHPy), 8.43 (s, 1H, CHPy). 13C NMR (CDCl3,
100 MHz), δ, ppm: −0.3 (s, Me3Si), 0.6 (s, Me3Si), 0.7 (s,
Me3Si), 69.9 (d, 1JPC = 179.3 Hz, C1), 123.05 (s), 134.3 (s),
135.4 (d, 3JPC = 4.6 Hz), 147.9 (d, 3JPC = 6.5 Hz), 148.4 (s).
31P NMR (CDCl3, 162 MHz), δ, ppm: 2.4 (s). Anal. Calcd
for C15H32NO4PSi3 C 44.41; H 7.95. Found: C 44.26; H 7.89.
4.7
Bis(trimethylsilyl) (4-bromophenyl)
|
ethoxymethylphosphonat (3a)
Trimethylsilyl trifluoromethanesulfonate (1.0 g, 0.0045 mol)
in 5 mL of methylene chloride was added with the stirring to
a mixture of tris(trimethylsilyl) phosphite (19.0 g, 0.08 mol),
4-bromobenzaldehyde diethylacetal (3.9 g, 0.015 мol), and
methylene chloride (15 mL). The mixture was heated under
a boiling water bath to complete the stripping of low-boiling
compounds and then distilled to give 5.0 g of phosphonate 3a,
yield 74%, bp 104°C (2 mm Hg). 1H NMR (CDCl3, 400 MHz),
4.4
Bis(trimethylsilyl) pyrid-4-
|
yl(trimethylsiloxy)methylphosphonate (1d)
Yield86%,bp149°C(1 mmHg).1HNMR(CDCl3,400 MHz),
δ, ppm: −0.09 (s, 9H, Me3Si), −0.07 (s, 9H, Me3Si), 0.06 (s,
9H, Me3Si), 4.68 (d, 1H, 2JPH = 17.2 Hz, C1H), 7.18 (d, 2H,
3JHH = 5.6 Hz, 2 CHPy), 8.35 (d, 2H, 3JHH = 5.6 Hz, 2 CHPy).
13C NMR (CDCl3, 100 MHz), δ, ppm: −0.7 (s, Me3Si), 0.2 (s,
3
δ, ppm: 0.07 (s, 18H, 2 Me3Si), 1.05 (t, 3H, JHH 7.2 Hz,
2
CH3), 3.30-3.40 (m, 2H, CH2O), 4.43 (d, 1H, JPH = 7.2 Hz,
Me3Si), 0.4 (s, Me3Si), 70.6 (d, JPC = 174.7 Hz, C1), 121.5
C1H), 7.15 (d, 2H, JHH = 8.0 Hz, 2 CHPh), 7.30 (d, 2H,
1
2
(s), 147.2 (br. s), 148.5 (d, 3JPC = 2.0 Hz). 31P NMR (CDCl3,
162 MHz), δ, ppm: 1.9 (s). Anal. Calcd for C15H32NO4PSi3 C
44.41; H 7.95. Found: C 44.28; H 7.86.
2JHH = 8.0 Hz, 2 CHPh). 13C NMR (CDCl3, 100 MHz), δ, ppm:
0.7 (s, 2 Me3Si), 15.0 (s, Me), 66.4 (d, 3JPC = 13.8 Hz, CH2O),
78.1 (d, 1JPC = 175.6 Hz, C1), 121.9 (d, 2JPC = 4.6 Hz), 129.5
(d, JPC = 5.6 Hz), 131.2 (s), 134.7 (s). 31P NMR (CDCl3,
2
162 MHz), δ, ppm: 0.7 (s). Anal. Calcd for C15H28BrO4PSi2 C
41.00; H 6.42. Found: C, 40.86; H, 6.33.
4.5
Bis(trimethylsilyl) 4-dimethylaminophe
|
nyl(trimethylsiloxy)methylphosphonate (1e)
Yield 89%, bp 164°C (1 mm Hg), mp 55°C. 1H NMR
(CDCl3, 400 MHz), δ, ppm: −0.29 (s, 9H, Me3Si), −0.19 (s,
9H, Me32Si), −0.16 (s, 9H, Me3Si), 2.59 (s, 6H, Me2N), 4.64
4.8
Diethyl (4-dimethylaminophenyl)
|
ethoxymethylphosphonate (3b)
(d, 1H, JPH = 16.0 Hz, C1H), 6.43 (d, 2H, JHH = 7.2 Hz,
A mixture of 4-dimethylaminobenzaldehyde diethylacetal
(3.4 g, 0.015 mol), diethyl trimethylsilyl phosphite (12.6 g,
0.060 mol), zinc chloride (0.1 g, 0.0004 mol), and cadmium
iodide (0.1 g, 0.0003 mol) was heated at 140°C to com-
plete distillation of ethoxytrimethylsilane (bp 74°C). The
residue was distilled to give 4.2 g of phosphonate 3b, yield
3
2 CHPh), 6.93 (d, 2H, JHH = 7.2 Hz, 2 CHPh). 13C NMR
3
(CDCl3, 100 MHz), δ, ppm: −0.7 (s, Me3Si), 0.1 (s, Me3Si),
40.5 (s, Me2N), 71.4 (d, JPC = 181.4 Hz, C1), 112.2 (s),
1
127.8 (d, JPC = 6.0 Hz), 130.5 (s), 148.8 (s). 31P NMR
3
(CDCl3, 162 MHz), δ, ppm: 4.4 (s) (cf [5]).
1
86%, bp 195°C (2 mm Hg). H NMR (CDCl3, 400 MHz),
3
δ, ppm: 0.97 (t, 3H, JHH = 7.2 Hz, CH3), 0.98 (t, 3H,
4.6
Tetra(trimethylsilyl)
|
3JHH = 7.2 Hz, CH3), 1.05 (t, 3H, 3JHH = 6.8 Hz, CH3), 2.72
(4-dimethylaminophenyl)
(s, 6H, Me2N), 3.20-3.35 (m, 2H, CH2O), 3.60-3.90 (m, 4H,
methylenediphosphonate (2a)
2 CH2O), 4.29 (d, 1H, JPH = 15.2 Hz, C1H), 6.47 (d, 2H,
2
Trimethylsilyl trifluoromethanesulfonate (0.9 g, 0.004 mol)
in 5 mL of methylene chloride was added with the stir-
ring to a mixture of tris(trimethylsilyl) phosphite (18.0 g,
0.060 mol), 4-dimethylaminobenzaldehyde diethylacetal
(3.4 g, 0.015 mol), and methylene chloride (15 mL). At once
the exothermic reaction proceeded, then the mixture was kept
for 24 hour at 20°C, the solvent was removed, the residue
was washed with cooled hexane to give 8.6 g of diphospho-
3JHH = 8.8 Hz, 2 CHPh), 7.08 (d, 2H, 2JHH = 8.8 Hz, 2 CHPh).
13C NMR (CDCl3, 100 MHz), δ, ppm: 14.9 (s, Me), 16.2 (d,
3JPC = 5.5 Hz, Me), 40.2 (s, Me2N), 62.4 (d, JPC = 6.5 Hz,
3
2
CH2O), 62.6 (d, JPC = 6.4 Hz, CH2O), 65.4 (d, CH2O,
3JPC = 14.7 Hz), 78.0 (t, 1JPC 171.0 Hz, C1), 111.8 (s), 121.9
(s), 128.9 (d, JPC = 5.5 Hz), 150.3 (s). 31P NMR (CDCl3,
3
162 MHz), δ, ppm: 20.0 (s). Anal. Calcd for C15H26NO4P: C
57.13; H 8.31. Found: C 56.94; H 8.26.
1
nate 2a as white crystals, yield 96%, mp 144°C. H NMR
(CDCl3, 400 MHz), δ, ppm: 0.07 (s, 36H, 4 Me3Si), 3.22 (s,
4.9
Diethyl chloro(4-fluorophenyl)
|
6H, Me2N), 3.48 (t, 1H, JPH = 25.2 Hz, C1H), 7.53 (d, 2H,
2
methylphosphonate (4a)
3JHH = 8.4 Hz, 2 CPhH), 7.65 (d, 2H, 3JHH = 8.4 Hz, 2 CPhH).
13C NMR (CDCl3, 100 MHz), δ, ppm: 0.3 (s, 2 Me3Si), 46.8
A mixture of 4-fluorobenzal chloride (3 g, 0.017 mol), tri-
1
(s, Me2N), 48.3 (t, JPC = 135.9 Hz, C1), 120.3 (s), 132.1
ethyl phosphite (7 g, 0.042 mol), and zinc chloride (0.1 g,