New example of trigonal triphosphine trioxides
Russ.Chem.Bull., Int.Ed., Vol. 53, No. 9, September, 2004
2011
firmed by 1H NMR spectroscopy of the residue after the reꢀ
moval of the chloroform. 1H NMR (CDCl3), δ: 3.51 (t, 2 H,
CH23, 2JP,H = 14.6 Hz); 7.27 (m, 8 H, Hm, Ph); 7.37 (t, 4 H, Hp,
Ph, JH,H = 7.0 Hz); 7.70 (m, 8 H, Ho, Ph). A mixture of the
residue and an authentic sample of 6 had m.p. 180—182 °C (lit.
data5: m.p. 180—181 °C). The chloroformꢀinsoluble precipitate
was dissolved in acetone. The second decomposition product,
viz., complex 7, was isolated after storage of the solution over a
long period.
Destruction of complex 9 in the presence of atmospheric
oxygen was complete in 15 days. The sample obtained after
decomposition was worked up analogously to the sample obꢀ
tained after destruction of complex 5. One of the decomposition
products, viz., compound 6, was isolated from the solution in
chloroform. The formation of compound 6 was confirmed by
1H NMR spectroscopy and m.p. of a mixed sample.
Experimental
NMR spectra were recorded on a Bruker AMXꢀ400 instruꢀ
ment in CDCl3 or CHCl3 (c 0.03 mol L–1) using residual signals
for the protons of a deuterated solvent as the internal standard
(1H) and 85% H3PO4 as the external standard (31P).
Xꢀray diffraction study. Crystals of 7 (C54H54Li2O10P4) at
298 K are monoclinic: a = 12.040(2), b = 9.788(2), c =
22.915(5) Å, β = 104.39(3)°, V = 2615.9(9) Å3, dcalc
=
1.271 g cm–1, space group P21/n, Z = 2, M = 1000.73,
F(000) = 1048, µ = 2.01 cm–1. The intensities of 6115 reꢀ
flections were measured on an automated Nonius CADꢀ4
diffractometer at 298 K (MoꢀKα radiation, graphite monochroꢀ
mator, θ/2θ scannning technique, 2θ
= 52°), and 5699 obꢀ
max
served reflections (Rint = 0.0174) were used in calculations. The
structure was solved by direct methods and refined by the fullꢀ
matrix leastꢀsquares method in the anisotropicꢀisotropic apꢀ
proximation against F2. The hydrogen atoms were revealed from
the difference electron density maps and refined isotropically.
The hydrogen atoms of the methyl groups were refined using the
riding model. The final reliability factors were wR2 = 0.1196,
GOOF = 1.031 based on all reflections (R1 = 0.0377 based on
3930 reflections with I > 2σ(I )). All calculations were carried
out using the SHELXTL PLUS program package.
1,1,1ꢀTris(chloromethyl)propane was synthesized according
to a known procedure9 from 1,1,1ꢀtris(hydroxymethyl)propane
(6.0 g, 45 mmol), thionyl chloride (19.6 g, 160 mmol), and
pyridine (2.2 g). The yield was 5.9 g (70%), b.p. 65—67 °C
(10 Torr).
1,1,1ꢀTris(diphenylphosphinomethyl)propane (10).9 A soluꢀ
tion of NaOH (1.25 g, 22 mmol) in water (1 mL) was added
to a mixture of K2CO3 (10.5 g, 75 mmol) and diphenylphosꢀ
phine (3.7 g, 20 mmol) in DMSO (15 mL). After 15 min,
1,1,1ꢀtris(chloromethyl)propane (1.18 g, 0.625 mmol) was added
portionwise to the brightꢀred solution. The reaction mixture was
heated at 90 °C for 1 h and then at 120 °C for 1 h until the
reaction mixture became colorless. Then water (120 mL) was
added and the mixture was vigorously stirred. The solid precipiꢀ
tate that formed was dried in vacuo at 80 °C over P2O5 for 1 h
and recrystallized from ethanol. The yield of trisphosphine 10
was 2.7 g (62.8%), m.p. 105—106 °C. Found (%): C, 78.56;
H, 6.52; P, 14.53. C42H41P3. Calculated (%): C, 79.0; H, 6.43;
P, 14.58. 31P{H} NMR (CHCl3), δ: –26.1.
1,1,1ꢀTris(diphenylphosphorylmethyl)propane (11). A mixꢀ
ture of trisphosphine 10 (0.7 g, 1.1 mmol) and 5.7% hydrogen
peroxide in tertꢀbutyl alcohol (10 mL) was heated at 50 °C
for 4 h. Trisphosphine oxide 11 was isolated in a yield of 0.77 g
(~100%) as monohydrate, m.p. 178—181 °C. Found (%):
C, 71.80; H, 6.30; P, 13.10. C42H41O3P3•H2O. Calculated (%):
C, 71.59; H, 6.10; P, 13.21. Drying of a sample of the monoꢀ
hydrate to a constant weight in vacuo at 80 °C over P2O5 for 3 h
led to the loss of the water molecule; the weight loss was ~2.5%,
m.p. 181—183 °C. 31P{H} NMR (CHCl3), δ: 31.21.
Bis(diphenylphosphoryl)methane was synthesized according
to a procedure described earlier.5
Complex of bis(diphenylphosphoryl)diphenylphosphinoꢀ
methane with lithium chloride (5). A solution of chloride 3 (0.5 g,
2.3 mmol) in benzene (10 mL) was added to a hexane solution of
methanide 2, which was prepared from bis(diphenylphosꢀ
phoryl)methane (0.9 g, 2.16 mmol) and butyllithium (0.15 g,
2.3 mmol).3 The solution was refluxed for 10 h. The precipitate
that formed was filtered off (0.9 g) and extracted with chloroꢀ
form (15 mL). The extract was concentrated to dryness to give
complex 5 in a yield of 0.8 g (57.6%), t.decomp. 280 °C.
Found (%): Cl, 5.51; P, 14.14. C37H31O2P•LiCl. Calcuꢀ
lated (%): Cl, 5.52; P, 14.47. The benzeneꢀhexane filtrate of the
reaction mixture was concentrated to dryness. An additional
amount (~0.1 g) of complex 5 was precipitated with diethyl
ether from the syrupꢀlike residue (0.35 g). The ethereal filꢀ
trate was concentrated and a solution of 30% hydrogen peroxide
in acetone was added. Butyldiphenylphosphine oxide was isoꢀ
lated in ~15% yield, m.p. 89—92 °C. 31P{H} NMR (CHCl3),
δ: 27.55. Lit. data11: m.p. 89.5—90.5 °C; 31P{H} NMR (CHCl3),
δ: 27.60.
Complex of tris(diphenylphosphoryl)methane with lithium
chloride (9). A solution of chloride 8 (0.6 g, 2.3 mmol) in benꢀ
zene (20 mL) was added to a hexane solution of methanide 2,
which was prepared from bis(diphenylphosphoryl)methane
(0.9 g, 2.16 mmol) and butyllithium (0.15 g, 2.3 mmol). The
solution was refluxed for 20 h. The precipitate that formed was
filtered off and extracted with chloroform. The extract was conꢀ
centrated to dryness. The yield of complex 9 was 0.3 g (30%),
t.decomp. >300 °C. Found (%): C, 63.07; H, 4.61; Cl, 10.30;
P, 13.30. C37H31O3P3•2LiCl. Calculated (%): C, 63.34; H, 4.42;
Cl, 10.13; P, 13.27.
This study was financially supported by the Russian
Foundation for Basic Research (Project No. 02ꢀ03ꢀ33073)
and the Foundation of the President of the Russian Fedꢀ
eration (Federal Program for the Support of Leading Sciꢀ
entific Schools, Grant NShꢀ1100.2003.3).
References
Oxidative destruction of complexes 5 and 9. Complex 5 was
kept in air for 10 days and then chloroform (15 mL) was added.
One of the decomposition products, viz., bis(diphenylphosꢀ
phoryl)methane 6, passed into the solution, which was conꢀ
1. A.S. 710205, Chem. Abstr., 1993, 119, 107846x.
2. A. P. Baranov, V. G. Dashevskii, T. Ya. Medved´, and M. I.
Kabachnik, Teor. Eksp. Khim., 1979, 15, 514 [Theor. Exp.
Chem., 1979, 15 (Engl. Transl.)].
Pisareva
