Addition of Bis(trimethylsiloxy)phosphine to Diphenyl(vinyl)-and Phenyldivinylphosphines [1]

Full text of DOI:10.1023/A:1024720911776

Russian Journal of General Chemistry, Vol. 73, No. 2, 2003, pp. 315 316. Translated from Zhurnal Obshchei Khimii, Vol. 73, No. 2, 2003,
pp. 339 340.
Original Russian Text Copyright
2003 by Livantsov, Prishchenko, Livantsova, Nikolaev, Grigor’ev.
LETTERS
TO THE EDITOR
Addition of Bis(trimethylsiloxy)phosphine to Diphenyl(vinyl)-
and Phenyldivinylphosphines
M. V. Livantsov, A. A. Prishchenko, L. I. Livantsova, S. N. Nikolaev, and E. V. Grigor’ev
Lomonosov Moscow State University, Moscow, Russia
Received April 30, 2002
Addition of diphenylphosphine to substituted vinyl-
phosphines is a convenient method for preparing a
series of ligands widely used as components of cata-
lytic systems [1]. In the present work we have pre-
pared new derivatives of functionally substituted
organophosphorus acids containing P(III) fragments.
Hence, bis(trimethylsiloxy)phosphine easily adds to
diphenyl(vinyl)- and phenyldivinylphosphines in the
presence of azobis(isobutyronitrile) at 120 C to give
phosphonites I and II in high yields (cf. [2]).
NaO
H
nMeONa, nMeOH
2nMe3SiOMe
PCH2CH2
O
I, II
PPh3 n
n
IV, V
CH2CH2PPh2
CH2NR2
MeONa, MeOH
IIIa, IIIb
NaOP
O
Me3SiOMe
VIa, VIb
(b); n = 1 (IV), 2 (V).
N
n(Me3SiO)2PH + (CH2=CH)nPPh3
n
(a), O
R2N =
N
R
[(Me3SiO)2PCH2CH2]nPPh3
,
n
I, II
1
the H NMR spectra of these fragments partially or
completely overlap.
R = Me2(NC)C ; n = 1 (I), 2 (II).
Bis(trimethylsilyl) [2-(diphenylphosphino)ethyl]-
phosphonite (I). A mixture of 17 g of bis(trimethyl-
siloxy)phosphine, 10.7 g of diphenyl(vinyl)phosphine,
and 0.2 g of azobis(isobutyronitrile) was heated to
100 C and then, within 1 h, to 120 C. Distillation of
the reaction mixture gave 17.7 g (83%) of phosphonite
I, bp 164 C (1 mm). 13C NMR spectrum, C, ppm:
Phosphonite I is smoothly aminomethylated with
bis(dialkylamino)methanes at 130 C in the presence
of catalyst (zinc chloride) to form phosphinates IIIa,
IIIb in high yields.
CH2CH2PPh2
CH2NR2
(R2N)2CH2, ZnCl2
Me3SiNR2
I
Me3SiOP
O
1
2
36.44 d.d (C1, JPC 27.2, JPC 10.7 Hz), 18.54 t (C2,
1JPC 13.3 Hz). 31P NMR spectrum, P, ppm: 157.23 d
IIIa, IIIb
(b).
(a), O
N
3
(P1), 15.17 d (P2), JPP 22.5 Hz.
Phosphine II was obtained analogously.
R2N =
N
Bis[2-bis(trimethylsiloxy)phosphinoethyl]-
phenylphosphine (II). Yield 87%, bp 192 C (1 mm).
13C NMR spectrum, C, ppm: 35.75 d.d (C1, 1JPC 26.4,
Treatment of phosphonites I, II and phosphinates
III with dilute solutions of sodium methylate in metha-
nol gives sodium phosphonites IV, V and phosphina-
tes VI which show promise as water-soluble ligands.
1
2
2JPC 8.4 Hz), 17.63 d.d (C2, JPC 15.1, JPC
12.2 Hz). 31P NMR spectrum, P, ppm: 156.96 d
3
(2P1), 20.67 t (P2), JPP 20.0 Hz.
Salts IV VI are white hygroscopic crystals. The 1H
NMR spectra of compounds I IV contain characteris-
tic signals of the P1C1H2P2Ph and PC3H2NC4H2 frag-
ments. Their parameters are listed below. Signals in
Trimethylsilyl [2-(diphenylphosphino)ethyl]-
(N-piperidinomethyl)phosphinate (IIIa). A mixture
of 4.2 g of phosphinite I, 3.6 g of bis(N-piperidino)-
methane, and 0.1 g of zinc chloride was heated at
1070-3632/03/7303-0315$25.00 2002 MAIK Nauka/Interperiodica

316
LIVANTSOV et al.
1
110 130 C for 1.5 h. Distillation of the reaction
mixture gave 2.9 g of phosphinate IIIa, yield 65%,
spectrum, , ppm: 6.90 d (PH, JPH 506.4 Hz). 13C
NMR spectrum, P, ppm: 27.70 d.d (C1, JPC 86.8,
1
bp 208 C (1 mm), n2D0 1.5495. 13C NMR spectrum,
,
2JPC 10.3 Hz), 18.47 d (C2, JPC 7.9 Hz). 31P NMR
1
C
ppm: 24.91 d.d (C1, JPC 91.2, JPC 15.0 Hz),
spectrum, P, ppm: 27.43 d (2P1), 19.29 t (P2), JPP
1
2
3
1
2
19.87 d.d (C2, JPC 14.9, JPC3 4.6 Hz), 57.84 d (C3,
46.4 Hz. Found, %: C 35.30, H 4.59. C10H15Na2O4P3.
Calculated, %: C 35.52; H 4.47.
1JPC 113.5 Hz), 16.31 d (C4, JPC 9.2 Hz). 31P NMR
spectrum, P, ppm: 41.32 d (P1), 14.69 d (P2),
Sodium [2-(diphenylphosphino)ethyl](N-piperi-
dinomethyl)phosphinate (VIa). Yield 95%. 13C
3JPP 50.5 Hz.
NMR spectrum, C, ppm: 28.08 d.d (C1, JPC 92.6,
1
Phosphinate IIIb was obtained analogously.
2JPC 12.1 Hz), 21.57 d.d (C2, JPC 11.8, JPC 4.5 Hz),
59.27 d (C3, 1JPC 105.2 Hz), 56.80 d (C4, 3JPC 4.9 Hz).
31P NMR spectrum, P, ppm: 34.09 d (P1), 14.43 d
1
2
Trimethylsilyl (N-morpholinomethyl)[2-(di-
phenylphosphino)ethyl]phosphinate (IIIb). Yield
68%, bp 202 C (1 mm), n2D0 1.5505. 13C NMR spec-
(P2), JPP 47.1 Hz. Found, %: C 60.26; H 6.69.
3
trum, P, ppm: 24.43 d.d (C1, 1JPC 91.5, 2JPC 15.2 Hz),
1
2
19.52 d.d (C2, JPC 14.8, JPC3 2.6 Hz), 56.86 d (C3,
C20H26NNaO2P2. Calculated, %: C 60.45; H 6.60.
1JPC 112.6 Hz), 54.83 d (C4, JPC 9.1 Hz). 31P NMR
Sodium (N-morpholinomethyl)[2-(diphenyl-
phosphino)ethyl]phosphinate (VIb). Yield 95%. 13C
spectrum, P, ppm: 39.95 d (P1), 15.18 d (P2), JPP
3
NMR spectrum, C, ppm: 27.81 d.d (C1, JPC 89.7,
49.7 Hz.
1
2JPC 12.5 Hz), 21.79 d (C2, JPC 12.1 Hz), 58.78 d
1
Sodium 2-(diphenylphosphino)ethylphosphonite
(IV). To a solution of 0.54 g of sodium methylate in
30 ml of methanol, a solution of 4.2 g of phosphonite
I in 5 ml of diethyl ether was added with stirring at
10 C. The resulting mixture was heated to boil, the
solvent was distilled off, and the residue was kept in a
vacuum (1 mm) for 1 h. Salt IV, 2.9 g (96%), was
(C3, JPC 103.3 Hz), 55.60 d (C4, JPC 7.5 Hz). 31P
1
3
NMR spectrum, P, ppm: 34.16 d (P1), 14.97 d (P2),
3JPP 48.4 Hz). Found, %: C 56.83; H 6.16. C19H24
NNaO3P2. Calculated, %: C 57.15; H 6.06.
The NMR spectra were obtained on a Varian VXR-
400 spectrometer in CDCl3 or D2O (salts IV VI)
against TMS (1H, 13C) and 85% H3PO4 in D2O (31P).
1
1
obtained. H NMR spectrum, ppm: 6.88 d (PH, JPH
,
508.0 Hz). 13C NMR spectrum, C, ppm: 28.99 d (C1,
1JPC 87.5 Hz, JPC 13.8 Hz), 19.32 d (C2, JPC
2
1
REFERENCES
10.1 Hz). 31P NMR spectrum, P, ppm: 27.29 d (P1),
15.61 d (P4), JPP 53.7 Hz. Found, %: C 55.87;
3
1. Jemilev, U.M., Popod’ko, N.R., and Kozlova, E.V.,
Metallokompleksnyi kataliz v organicheskom sinteze
(Metal Complex Catalysis in Organic Synthesis),
Moscow: Khimiya, 1999, pp. 137 144.
2. Prishchenko, A.A., Livantsov, M.V., Livantsova, L.I.,
Pol’shchikov, D.G., Nikolaev, S.N., and Grigor’ev, E.V.,
Zh. Obshch. Khim., 1999, vol. 69, no. 1, pp. 156 157.
H 5.12. C14H15NaO2P2. Calculated, %: C 56.01;
H 5.04.
Salts V, VI were obtained analogously.
(3-Phenyl-3-phosphapentane-1,5-diyl)bis(sodium
1
hydrogen phosphonite) (V). Yield 93%. H NMR
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 73 No. 2 2003