Addition of bis(trimethylsiloxy)phosphine to aryl-substituted acetylenes [1]

Full text of DOI:10.1007/s11176-005-0122-4

Russian Journal of General Chemistry, Vol. 74, No. 12, 2004, pp. 1943 1944. Translated from Zhurnal Obshchei Khimii, Vol. 74, No. 12, 2004,
pp. 2056 2057.
Original Russian Text Copyright
2004 by Prishchenko, Livantsov, Novikova, Livantsova, Pol’shchikov, Krut’ko.
LETTERS
TO THE EDITOR
Addition of Bis(trimethylsiloxy)phosphine
to Aryl-substituted Acetylenes
A. A. Prishchenko, M. V. Livantsov, O. P. Novikova,
L. I. Livantsova, D. G. Pol’shchikov, and D. P. Krut’ko
Lomonosov Moscow State University, Moscow, Russia
Received June 22, 2004
Addition of bis(trimethylsiloxy)phosphine to
ONa
H
NaO
H
styrene, its heterocyclic analogs, and vinylferrocene
is a convenient method for preparing functionalyzed
phosphonites and their derivatives [1]. In the present
work we showed that bis(trimethylsiloxy)phosphine A
reacts with aryl-substituted acetylenes in a way much
different from its exothermic addition to dimethyl
acetylenedicarboxylate [2], i.e. by a radical me-
chanism and only in the presence of a catalyst, azo-
diisobutyronitrile, under conditions of its thermolysis
at 100 120 C. Thus the reactions of phosphine A with
phenyl- and anisylacetylenes involve double regio-
selective addition to the acetylene fragment to form
diphosphonites I.
Ia, Ib 2MeONa, MeOH
PCH2CH(Ar)P
4Me3SiOMe
IIIa, IIIb
Ar = Ph (a), 4-MeOC6H4 (b).
PC1=C2H fragments, whose parameters are given
below. In the H and 13C NMR spectra, the proton
1
and 13C signals of the CH2 fragment of compound II
overlap with the respective signals of the phenyl
fragments. For compound II, the NMR data for the
preferred isomer are given first.
1,2-Bis[bis(trimethylsiloxy)phosphino]-1-phenyl-
ethane (Ia). A mixture of 42 g of bis(trimethylsiloxy)-
phosphine, 6.1 g of phenylacetylene, and 0.3 g of
azodiisobutyronitrile was heated to 100 C, after which
the temperature was raised to 130 C over the course
of 1 h. Distillation gave 24.3 g (78%) of diphos-
2(Me3SiO)2PH + HC CAr
A
R
(Me3SiO)2PCH2CH(Ar)P(OSiMe3)2,
Ia, Ib
1
Ar = Ph (a), 4-MeOC6H4 (b).
phonite Ia, bp 133 C (0.5 mm Hg). H NMR spec-
trum, , ppm: 1.85 2.0 m (C1HAHB), 2.84 m ABMX
system [C2HM, 2J(P2HM) 3.6, 3J(HBHM) 11.6,
3J(HBHM) 9.2 Hz]. 13C NMR spectrum, C, ppm:
Under the same conditions, the reaction of excess
phosphine A with tolane stops on the formation of
substituted vinylphosphonite II which, according to
NMR data, is 2:1 mixture of the E and Z isomers.
1
40.27 d.d (C1, JPC 31.7, 2JPC 15.5 Hz), 50.72 d.d (C2,
2
2
3
1JPC 30.3, JPC 9.6 Hz), 139.81 d.d (C3, JPC 9.1, JPC
3.1 Hz). 31P NMR spectrum, P, ppm: 160.89 d (P1,
3JPP 7.0 Hz), 148.94 d (P2, JPP 7.0 Hz).
PhC CPh
3
Ph
H
Ph
Ph
A, R
C=C
C=C
+
Compounds Ic and II were obtained analogously.
Ph
H
(Me3SiO)2P
(Me3SiO)2P
(E)-II
(Z)-II
1-Anisyl-1,2-bis[bis(trimethylsiloxy)phosphino]-
1
ethane (Ib). Yield 74%, bp 139 C (0.5 mm Hg). H
NMR spectrum, , ppm: 1.85-2.05 m (C1HAHB), 2.80
m ABMX [C2HM, 2J(P2HM) 4.0, 3J(HAHM) 12.4,
3J(HBHM) 8.6 Hz], 3.91 s (OCH3). 13C NMR spect-
Treatment of compounds I with dilute solutions of
sodium methylate in methanol provides water-soluble
salts as white hygroscopic crystals.
1
2
rum, C, ppm: 39.60 d (C1, JPC 30.0, JPC 14.9 Hz),
1
2
The NMR spectra of compounds I III contain
49.07 d.d (C2, JPC 27.6, JPC 11.3 Hz), 130.75 d.d
characteristic signals of the P1C1H2C2H(C3)P2 and
(C3, JPC 9.0, JPC 3.4 Hz), 55.02 s (OCH3), 157.85 s
2
3
1070-3632/04/7412-1943 2004 MAIK Nauka/Interperiodica

1944
PRISHCHENKO et al.
1
(OC=). 31P NMR spectrum, P, ppm: 164.33 d (P1,
ppm: 6.52 d (P1H, JPH 519.4 Hz), 6.81 d.d (P2H,
1JPH 522.1, JHH 2.6 Hz). 13C NMR spectrum,
,
3
3
3JPP 8.4 Hz), 151.46 d (P2, JPP 8.4 Hz).
C
ppm: 30.05 d (C1, JPC 90.3 Hz), 41.89 d (C2, JPC
83.7 Hz), 135.1 135.3 m (C3), 54.92 s (OCH3),
158.01 s (OC=). 31P NMR spectrum, P, ppm: 35.83
1
1
Bis(trimethylsilyl) (1,2-diphenylvinyl)phos-
phonite (II). Yield 69%, bp 152 C (0.5 mm Hg). 13C
1
3
1
d.d (P1, JPH 519.4, JPP 57.1 Hz), 29.55 d.d (P2, JPH
1
NMR spectrum, C, ppm: 151.34 d (C1, JPC 36.6 Hz)
3
1
3
522.1, JPP 57.1 Hz). Found, %: C 34.94; H 3.98.
C9H12Na2O5P2. Calculated, %: C 35.08; H 3.92.
and 152.41 d (C1, JPC 45.2 Hz), 1.57 d (CSi, JPC
3.2 Hz) and 1.45 d (CSi, 3JPC 2.9 Hz). 31P NMR spec-
trum, P, ppm: 144.26 and 139.99 s.
The NMR spectra were obtained on a Varian VXR-
400 spectrometer in CDCl3 or D2O (salts III) against
1-Phenylethylenebis(sodium hydrogen phos-
phonite) (IIIa). To a solution of 3.2 g of sodium
methylate in 50 ml of methanol, a solution of 15.7 g
of phosphonite Ia in 30 ml of diethyl ether was added
with stirring at 10 C. The resulting mixture was
heated to boiling, the solvent was removed, and the
residue was kept in a vacuum (1 mm Hg) for 1 h to
TMS (1H, 13C) or 85% of H3PO4 in D2O (31P).
REFERENCES
1. Prishchenko, A.A., Livantsov, M.V., Livantsova, L.I.,
Novikova, O.P., and Grigor’ev, E.V., Zh. Obshch.
Khim., 1996, vol. 66, no. 12, p. 2055; Prishchenko, A.A.,
Livantsov, M.V., Livantsova, L.I., Pol’shchikov, D.G.,
and Grigor’ev E.V., Zh. Obshch. Khim., 1999, vol. 69,
no. 2, p. 346; Livantsova, L.I., Prishchenko, A.A., Li-
vantsov, M.V., Nikolaev, S.N., and Grigor’ev, E.V.,
Zh. Obshch. Khim., 2000, vol. 70, no. 7, p. 1220; Li
vantsov, M.V., Prishchenko, A.A., Livantsova, L.I.,
Nikolaev, S.N., Meleshonkova, N.N., and Grigor’-
ev, E.V., Zh. Obshch Khim., 2003, vol. 73, no. 1,
p. 163.
1
obtain 8.2 g (98%) of salt IIIa. H NMR spectrum,
1
, ppm: 6.65 d (P1H, JPH 516.3 Hz), 6.78 d.d (P2H,
3
1JPH 515.5, JHH 2.4 Hz). 13C NMR spectrum,
,
C
ppm: 29.66 d (C1, JPC 89.5 Hz), 43.04 d (C2, u1JPC
1
82.9 Hz), 136.4 134.4 m (C3). 31P NMR spectrum,
P, ppm: 29.06 d.d (P1, JPH 516.3, JPP 55.6 Hz),
1
3
23.56 d.d (P2, JPH 515.5, JPP 55.6 Hz). Found, %:
C 34.43; H 3.69. C8H10Na2O4P2. Calculated, %: C
34.55; H 3.62.
1
3
Salt IIIb was obtained analogously.
2. Prishchenko, A.A., Livantsov, M.V., Livantsova, L.I.,
Grigor’ev, E.V., Goncharova, Zh.Yu., and Noviko-
va, O.P., Zh. Obshch. Khim., 1997, vol. 67, no. 11,
p. 1912.
1-Anisylethylenebis(sodium hydrogen phos-
1
phonite) (IIIb). Yield 96%. H NMR spectrum,
,
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 74 No. 12 2004