ELECTROPHILIC AND NUCLEOPHILIC ADDITION REACTIONS
93
131.46 d (JPC = 2.7 Hz), 131.75 d (JPC = 103.4 Hz),
132.13 d (JPC = 7.9 Hz), 132.24 d (JPC = 7.9 Hz).
31P NMR spectrum: δP 30.76 ppm. Found, %: C 49.17;
H 4.71; Br 35.87; P 7.43. C18H19Br2OP. Calculated, %:
C 48.87; H 4.29; Br 36.19; P 7.01.
(1H, =CHMe, E), 7.19–7.31 m (1H, =CHMe, Z), 7.4–
7.64 m (6H, Ph), 7.71–7.86 m (4H, Ph). 31P NMR
spectrum, δP, ppm: 24.49, 27.24 (intensity ratio 2:1).
Found, %: C 56.38; H 4.75; Br 25.17; P 9.94.
C15H14BrOP. Calculated, %: C 56.07; H 4.36;
Br 24.92; P 9.66.
1,2-Dibromoethyl(diphenyl)phosphine oxide (6)
was synthesized in a similar way from 0.3 g (1.3 mmol)
of 3 and 0.42 g (2.6 mmol) of bromine in 12 mL of
anhydrous chloroform. Yield 0.37 g (74%), mp 150–
Diphenyl(1,1,2-tribromoethyl)phosphine oxide
(9). Bromine, 0.35 g (2.2 mmol), was added dropwise
with vigorous stirring to a solution of 0.54 g
(1.8 mmol) of phosphine oxide 7 in 15 mL of anhy-
drous chloroform under irradiation at a power of
500 W. The mixture was refluxed for 6 h, the solvent
was removed, and the residue was washed with anhy-
drous diethyl ether and dried under reduced pressure.
1
151°C. H NMR spectrum, δ, ppm: 3.64 d.d.d (1H,
CH2Br, J = 11.6, 10.8, 4.8 Hz), 3.91 d.d.d (1H, CH2Br,
J = 11.6, 5.9, 3.0 Hz), 5.43 d.d.d (1H, CHBr, J = 10.8,
3.0, 2.1 Hz), 7.38–7.60 m (6H, Ph), 7.90–8.01 m
(4H, Ph). 13C NMR spectrum, δC, ppm: 32.24 d (JPC
5.0 Hz), 46.59 d (JPC = 61.1 Hz), 127.84 d (JPC
12.4 Hz), 128.29 d (JPC = 11.8 Hz), 130.8 d (JPC
9.4 Hz), 130.96 d (JPC = 9.4 Hz), 131.55 d (JPC
2.8 Hz), 131.71 d (JPC = 2.7 Hz), 133.37 d (JPC
=
=
=
=
=
1
Yield 0.76 g (90.4%), hygroscopic material. H NMR
spectrum, δ, ppm: 4.29 d (2H, CH2Br, J = 4.3 Hz),
7.49–7.7 m (6H, Ph), 8.14–8.26 m (4H, Ph). 13C NMR
spectrum, δC, ppm: 43.20 d (JPC = 8.7 Hz), 62.33 d
(JPC = 53.6 Hz), 127.25, 127.95 d (JPC = 104.5 Hz),
8.8 Hz). 31P NMR spectrum: δP 27.74 ppm. Found, %:
C 42.98; H 3.16; Br 41.59; P 7.71. C14H13Br2OP.
Calculated, %: C 43.29; H 3.35; Br 41.24; P 7.99.
128.03 d (JPC = 12.2 Hz), 128.64, 132.43 d (JPC
=
2.9 Hz), 132.86 d (JPC = 8.6 Hz). 31P NMR spectrum:
δP 29.37 ppm. Found, %: C 36.31; H 2.86; Br 51.13;
P 6.33. C14H12Br3OP. Calculated, %: C 35.97; H 2.57;
Br 51.39; P 6.64.
1-Bromoethenyl(diphenyl)phosphine oxide (7).
A mixture of 0.25 g (0.64 mmol) of phosphine oxide 6
and 0.052 g (1.3 mmol) of sodium hydroxide in 12 mL
of anhydrous benzene was stirred for 3 h at room
temperature. The mixture was filtered, and the precip-
itate was washed with anhydrous benzene (2×10 mL).
The filtrate was combined with the washings and
dried over MgSO4, the solvent was distilled off under
reduced pressure, and the residue was washed with
diethyl ether and dried under reduced pressure. Yield
1-Bromo-2-methoxyethyl(diphenyl)phosphine
oxide (10). A mixture of 0.3 g (0.98 mmol) of
phosphine oxide 7 and 0.04 g (0.98 mmol) of sodium
hydroxide in 8 mL of methanol was stirred for 7 h at
room temperature. The solvent was removed, the
residue was extracted with chloroform, the extract was
washed with water, dried over MgSO4, and evaporated
under reduced pressure, and the residue was washed
with anhydrous diethyl ether and dried under reduced
pressure. Yield 0.31 g (93.3%), hygroscopic material.
1H NMR spectrum, δ, ppm: 3.25 s (3H, OMe), 3.67–
3.81 m (2H, OCH2), 5.19–5.25 m (1H, CHBr), 7.42–
7.56 m (6H, Ph), 7.88–7.96 m (4H, Ph). 13C NMR
spectrum, δC, ppm: 44.00 d (JPC = 67.4 Hz), 57.79,
71.2 d (JPC = 4.3 Hz), 127.7 d (JPC = 12.2 Hz),
127.99 d (JPC = 11.7 Hz), 130.71 d (JPC = 9.2 Hz),
130.98 d (JPC = 9.2 Hz), 131.1 d (JPC = 104.6 Hz),
131.19 d (JPC = 2.3 Hz), 131.29 d (JPC = 3.1 Hz).
31P NMR spectrum: δP 26.85 ppm. Found, %: C 53.48;
H 5.01; Br 23.18; P 8.86. C15H16BrO2P. Calculated, %:
C 53.09; H 4.72; Br 23.59; P 9.14.
1
0.14 g (70.2%), white crystals, mp 70–74°C. H NMR
spectrum, δ, ppm: 6.65 d.d (1H, =CH2, J = 29.7,
2.1 Hz), 6.77 d.d (1H, =CH2, J = 12.4, 2.1 Hz), 7.50–
7.65 m (6H, Ph), 7.71–7.79 m (4H, Ph). 13C NMR
spectrum, δC, ppm: 125.5 d (JPC = 93.3 Hz), 128.0 d
(JPC = 12.4 Hz), 129.2 d (JPC = 108.6 Hz), 131.5 d
(JPC = 9.8 Hz), 131.6, 131.9 d (JPC = 2.8 Hz), 134.5 d
(JPC = 10.5 Hz). 31P NMR spectrum: δP 24.74 ppm.
Found, %: C 54.48; H 4.26; Br 25.87; P 10.42.
C14H12BrOP. Calculated, %: C 54.72; H 3.91;
Br 26.06; P 10.09.
1-Bromoprop-1-en-1-yl(diphenyl)phosphine
oxide (8). A mixture of 0.31 g (0.77 mmol) of phos-
phine oxide 4 and 0.06 g (1.5 mmol) of sodium hy-
droxide in 15 mL of anhydrous THF was refluxed for
3 h. The mixture was then treated as described above
for the synthesis of 7. Yield 0.22 g (89%), a hygro-
scopic mixture of E and Z isomers at a ratio of 2:1.
1H NMR spectrum, δ, ppm: 2.02 d.d (3H, Me, E, J =
6.6, 2.5 Hz), 2.16–2.21 m (3H, Me, Z), 7.05–7.17 m
2-Methoxypropyl(diphenyl)phosphine oxide (11)
was synthesized in a similar way by reaction of 0.3 g
(1.2 mmol) of phosphine oxide 1 with 0.05 g
(1.2 mmol) of sodium hydroxide in 8 mL of methanol.
The product was isolated by double reprecipitation.
1
Yield 0.2 g (61%), hygroscopic material. H NMR
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 56 No. 1 2020