A SCHEME OF THE STEPWISE REACTION OF DIPHENYLCHLOROPHOSPHINE
2101
diphenylchlorophosphine (I). After 1 h the reaction
mass became of red-brown color, and deposition of the
analytically pure compound XVIa started. After 18 h,
to the reaction mixture was added 20 ml of benzene,
and the mixture was stirred for 5 min. The precipitate
was filtered off, washed with benzene (3×10 ml) and
dried in a vacuum. 2.42 g (91%) of XVIa was obtained
as colorless needles, mp 92–94°C (decomp.). The
compound is hygroscopic. 31P NMR spectrum, δ, ppm:
22.8 g (2JPH = 11 Hz). 1H NMR spectrum, δ, ppm: 7.97
0.74 g (0.0056 mol) of NaI and 1.47 g (0.0056 mol) of
Ph3P (XVII). The reaction mixture was stirred at 20°C
for 5 h, then diluted with 30 ml of CH2Cl2. After 2 h
the precipitate formed was filtered off and washed with
CH2Cl2 (4×5 ml). The filtrate was evaporated under
vacuum, and to the oily residue was added 30 ml of
benzene, the mixture was stirred for 10 min. The
precipitate formed was reperecipitated from a DMF–
benzene and then CH2Cl2–benzene mixtures. After
filtration, washing with benzene (2×5 ml) and drying
in a vacuum was isolated 1.54 g (82%) of IIIa as a
pale-yellow needle-like crystals, mp 140–142°C
(decomp.) [1]. 1H NMR spectrum, δ, ppm: 9.92 d (1H,
2
m (4H, o-H, Ph), 7.89 d (1H, CH, JPH = 11 Hz), 7.53
m (6H, m,p-H, Ph), 3.08 s [6H, N(CH3)2]. Found, %: C
61.44, H 5.79, N 4.68, P 0.40. C15H17ClNPO. M
293.74. Calculated, %: C 61.34, H 5.83, N 4.77, P
10.55.
2
N=CH, JPH = 6 Hz), 7.82 m (4H, C6H5, o-H), 7.47 m
(6H, C6H5, m,p-H), 3.90 d (3H, CH3, 4JPH = 6 Hz), 3.22
d (3H, CH3, 4JPH = 3 Hz). 31P–{1H} NMR spectrum, δ,
ppm: –2.2 s. Found, %: C 48.94, H 4.67, I 34.40, N
3.65, P 8.33. C15H17INP. M 369.09. Calculated, %: C
48.80, H 4.62, I 34.38, N 3.80, P 8.39.
Synthesis of N,N-dimethyl(diphenylphosphino-
methylene)iminium iodide (IIIa) by reduction of
(diphenylphosphoryl)(N,N-dimethylamino)chloro-
methane (XVIa) with diphenyliodophosphine (IV).
To 1.5 g (0.0051 mol) of (diphenylphosphoryl)-N,N-
dimethylaminochloromethane (XVIa) in 5 ml of DMAA
while stirring in an inert gas atmosphere was added
0.74 g (0.0056 mol) of NaI and 1.75 g (0.0056 mol) of
Ph2PI (IV). The reaction mixture was stirred at 20°C
for 3 h, then diluted with 30 ml of CH2Cl2. After 2 h
the precipitate was filtered off and washed with
CH2Cl2 (4×5 ml). The filtrate was evaporated under
vacuum, and the oily residue was kept in a vacuum
desiccator at 0.1 mm Hg. Over P2O5 for 18 h (to
remove most of solvent). The resulting mixture of oil
and crystals was triturated in 30 ml of diethyl ether, the
solid residue was reprecipitated from DMF to benzene,
and then from CH2Cl2 to benzene. After filtration,
washing with benzene (2×5 ml) and drying in a
vacuum, was isolated 1.33 g (71%) of IIIa as a pale-
yellow needle-like crystals, mp 140–142°C (decomp.)
REFERENCES
1. Nifant’ev, E.E., Morgalyuk, V.P., Petrovskii, P.V., and
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1
[1]. H NMR spectrum, δ, ppm: 9.92 d (1H, N=CH,
7. March, J., Advanced Organic Chemistry, Moscow: Mir,
2JPH = 6 Hz), 7.82 m (4H, C6H5, o-H), 7.47 m (6H,
1987, vol. 1, p. 176.
4
C6H5, m,p-H), 3.90 d (3H, CH3, JPH = 6 Hz), 3.22 d
8. Organicum, Weinheim: Wiley-VCH, GmbH & KGaA,
4
(3H, CH3, JPH = 3 Hz). 31P-{1H} NMR spectrum, δ,
2004, p. 383.
ppm: –2.2 s. Found, %: C 48.87, H 4.50, I 34.30, N
3.79, P 8.30. C15H17INP. M 369.09. Calculated, %: C
48.80, H 4.62, I 34.38, N 3.80, P 8.39.
9. Bosschard, H.H., Mory, R., Schmidt, M., and Zollinger, H.,
Helv. Chim. Acta, 1959, vol. 42, p. 1659.
10. 31P Nuclear Magnetic Resonance, Graison, M. and
Synthesis of N,N-dimethyl(diphenylphosphino-
methylene)iminium iodide (IIIa) by reduction of
(diphenylphosphoryl)-N,N-dimethylaminochloro-
methane (XVIa) with triphenylphosphine (XVII).
To 1.5 g (0.0051 mol) of (diphenylphosphoryl)-N,N-
dimethylaminochloromethane (XVIa) in 5 ml of DMF
while stirring under inert gas atmosphere was added
Griffith, E.J., Eds., New York: Wiley, 1967.
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Phosphorus Chemistry (ICCP-XV), St. Petersburg:
2008, R-89.
12. Morgalyuk, V.P., Petrovskii, P.V., Lysenko, K.A., and
Nifant’ev, E.E., Izv. Ros. Akad. Nauk, Ser. Khim., 2009,
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RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 81 No. 10 2011