1016
TURANOV et al.
O
O
P
O
P
O
P
O
P
O
P
R
Ph
Ph
Ph
Ph
Ph
Ph
P
Ph
Ph
R
(CH2)n
R
R
I
IIа, b
IIа, R = Ph; IIb, R =
III–V
p
ꢀTol III
,
n
= 1; IV
,
n
= 4;
V
,
n
= 5
O
P
O
P
O
Ph
Ph
Ph
Ph
Ph
Ph
CH3
P
O
O
O
Ph
Ph
Ph
P
P
O
Ph
VI
VII
VIII
EXPERIMENTAL
and diluted (1 : 1) HCl and evaporated in a vacuum.
The residue was chromatographed on a column with
silica gel L (eluent used was СHCl3 and СHCl3 :
1,2ꢀPhenyleneꢀbis(methylene)bis(diphenylphosphine
oxide) (I). A mixture of 2.50 g (0.013 mol) of dipheꢀ
i
ꢀPrOH (100 : 1)). Yield 2.60 g (67%), mp 148–150
(benzene–hexane).
For C36H36O2P2 anal. calcd. (%): C, 76.85; H, 6.46;
P, 11.01.
°С
nylphosphinous acid, 1.22 g (0.007 mol) of
dichloride, and 15 mL of hexamethyldisilazane was
stirred for 6 h at 110 in a dry argon flow and evapoꢀ
oꢀxylylene
°С
rated in a vacuum. The residue was dissolved in 15 mL
of CHCl3, the solution was washed with 15% solution
Found (%): C, 76.76, 76.80; H, 6.34, 6.43; P,
11.00, 10.97.
of Na2CO3 (2
(1 : 1) HCl (
×
15 mL), water (
15 mL) and evaporated in a vacuum.
2 15 mL), and diluted
×
2
×
1H NMR (СDCl3
, , ppm): 2.99 (s, 6Н, 2ArꢀСН3),
δ
3.50 (d, 4H, 2JH P = 13.80 Hz, Р(О)CH2ꢀAr), 6.93 (m,
The residue was chromatographed on a column with
silica gel L (eluent used was СHCl3 and СHCl3 :
−
4H, Ar–H), 7.02–7.56 (m, 8H, Ar–H).
i
ꢀPrOH (100 : 1)). Yield 3.15 g (89%), mp 282–284
°С
31P NMR (СDCl3,
, ppm): 39.18.
δ
(ethanol) (283–284 [14]).
°С
We described the synthesis of tetraphenylmethylꢀ
enediphosphine dioxide III earlier [16].
1,4ꢀbis(Diphenylphosphoryl)ꢀ2ꢀoxabutane (VI).
Potassium hydroxide (0.1 g, 1.8 mmol) and 2.3 g
(10.0 mmol) of diphenylvinylphosphine oxide were
added to a solution of 2.3 g (10.0 mmol) of 2ꢀdipheꢀ
nylphosphorylmethanol in 25 mL of dry dioxane. The
mixture was heated to 80°C, cooled to 20°С and kept
for 48 h, then the solvent was removed in a vacuum.
Twenty five milliliters of water was added to the residue
1,3ꢀPhenyleneꢀbis(methylene)bis(diphenylphosphine
oxide) (IIa). Diphenylphosphinous acid–acetone
complex (3.05 g, 0.012 mol) was kept for 3 h at
1 mmHg and 150–160
ethyldisilazane was added, and the mixture was kept for
3 h at 110 in a dry argon flow, next 0.87 g (0.005 mol)
of ꢀxylylene dichloride was added, the mixture was
stirred at 110 for 8 h and concentrated in a vacuum.
The residue was dissolved in 15 mL of CHCl3, the
solution was washed with 15% solution of Na2CO3 (2
15 mL), water ( 15 mL), and diluted (1 : 1) HCl (
°С (in a bath), 10 mL of hexamꢀ
°С
m
°С
×
2
×
2
×
and the mixture was extracted with CHCl3 (3
The extract was washed with diluted (1 : 1) HCl
(25 mL), water ( 20 mL) and the solvent was
×
20 mL).
15 mL) and evaporated in a vacuum. The residue was
chromatographed on a column with silica gel L (eluent
3
×
used was СHCl3 and СHCl3 :
1.90 g (75.0%), mp 89–92
93 [15]).
1H NMR (СDCl3,
iꢀPrOH (100 : 1)). Yield
(benzene–hexane) (91–
removed in a vacuum. The residue was chromatoꢀ
graphed on a column with silica gel (eluent used was
°С
°С
CHCl3). Yield 2.5 g (52%), mp 179–180
hexane).
For C27H26O3P2 anal. calcd. (%): C, 70.70; H, 5.67;
P, 1 3 . 4 7 .
°С (benzene–
2
δ
, ppm): 3.53 (d, 4H, JH–P
=
13.80 Hz, Р(О)CH2ꢀAr), 6.88 (m, 4H, Ar–H), 7.41–
7.68 (m, 10H, Ar–H).
31P NMR (СDCl3,
δ
, ppm): 39.02.
1,3ꢀPhenyleneꢀbis(methylene)bis(di(
oxide) (IIb). A mixture of 3.66 g (0.016 mmol) of di(
tolyl)phosphinous acid and 16 mL of hexamethyldisiꢀ
lazane was stirred for 3 h at 110 , next 1.23 g
(0.007 mol) of ꢀxylylene dichloride was added, the
mixture was stirred at 110 for additional 15 h and
Found (%): C, 76.70, 70.56; H, 5.45, 5.43; P,
13.20, 13.35.
p
ꢀtolyl)phosphine
pꢀ
1H NMR (СDCl3,
δ, ppm): 2.64 (m, 2Н,
ОСН2СН2Р(O)Ph2), 3.88 (m, 2Н, СН2СН2Р(O)Ph2),
°
С
2
4.20 (2H, JH–P = 8.0 Hz, СH2P(O)Ph2) 7.44
m
(m, 12H, Ar–H), 7.72 (m, 8H, Ar–H).
°С
31P NMR (СDCl3,
δ, ppm): 27.55, 29.39.
evaporated in a vacuum. The residue was dissolved in
15 mL of CHCl3, the solution was washed with 15%
Compounds IV, V, VII, and VIII were obtained as
solution of Na2CO3 (2
×
15 mL), water (
2
×
15 mL), described in [17–19].
RUSSIAN JOURNAL OF INORGANIC CHEMISTRY Vol. 60 No. 8 2015