PHOSPHORUS HALIDES COMPLEXES
917
tribromide. Yield 7.05 g (95 %), mp (decomp.) 180°С.
of individual compounds we were unable to measure
accurately their melting points.
31
The P NMR spectrum (CHCl ) (concentrated reac-
3
tion mixture), δ, ppm: 90 s. Found, %: С 35.35; Н
Complexation of phosphorus sulfochloride with
-dimethylaminopyridine. Weighed samples of 4-di-
5
.15; Br 39.54; N 13.96. C H Br N P. Calculated, %:
18 30 3 6
4
C 35.96; H 5.03; Br 39.88; N 13.98.
methylaminopyridine of 1, 2, 3, and 6 g were dissolved
in 18 ml of chloroform, and to each solution was added
a solution of 1.39 g of phosphorus sulfochloride in 2 ml
Complexation of phosphorus oxychloride with 4-
dimethylaminopyridine. A weighed sample of 4-di-
methylaminopyridine of 1, 3, or 6 g was dissolved in
31
of chloroform. The reaction was monitored by Р NMR
spectroscopy at dilution and concentration of the re-
action mixtures.
1
8 ml of chloroform, and to the solution was added a
solution of 1.12 g of phosphorus oxychloride in 2 ml
31
of chloroform. The reaction was monitored by
Р
Complexation of phosphorus pentabromide with
-dimethylaminopyridine. To a solution of 6.37 g of
-dimethylaminopyridine in 20 ml of chloroform was
NMR spectroscopy at dilution and concentration of the
reaction mixtures.
4
4
For isolation of individual products to a solution of
added dropwise at stirring a suspension of 3.21 g of
phosphorus pentabromide in 10 ml of chloroform. The
suspension gradually dissolved. A newly formed pre-
cipitate was filtered off, washed with chloroform and
dried in a vacuum. Yield 4.1 g (92 %). mp (decomp.)
3
g of 4-dimethylaminopyridine in 18 ml of chloro-
form was added at stirring a solution of 1.26 g of
PОСl in 2 ml of chloroform. The reaction mixture was
3
concentrated and left standing for 17 days, and then the
crystals precipitated were filtered off and dried in a
vacuum. The precipitate was identified as complex
31
1
1
76°С. Registration of the P and H NMR spectra
failed because the substance formed was insoluble in
3
1
XIX. Yield 2.5 g (59 %). In the P NMR spectrum
CDCl ) appeared a signal at δ, ppm: 15.5 s. Some
chloroform and reduced DMSO-d . Found, %: С
6
(
3
3
9.44; Н 4.71; Br 37.10; N 12.90; Р 4.76.
time later in the mixture established an equilibrium of
C H Br N P. Calculated, % C 39.58; H 4.75; Br
2
1
30
3
6
several complexes and appeared signals at δ, ppm (J,
3
7.62; N 13.19; P 4.86.
3
Hz): –161 quintet, J 15, corresponding to the com-
PH
1
By reaction of the obtained complex XI with
plex XVIII, and 9 s (complex XVII). The Н NMR
anhydrous methanol we obtained quantitatively
spectrum (CDCl ) d, ppm (J, Hz): 3.20 s (18H, N–
3
3
1
31
3
trimethylphosphite (by the Р NMR data). The
P
CH ), 6.79 d (6H arom., J 7), 8.26 d (6H arom.,
3
HH
3
NMR spectrum (in methanol) δ, ppm (J, Hz): 142 m,
JPH 15.
JHH 7). Found, %: C 48.31; H 5.45; Cl 20.31; N 16.62;
P 5.97. C H Cl N OP. Calculated, % C 48.52; H
3
21
30
3
6
5
.82; Cl 20.46; N 16.17; P 5.96.
In the filtrate of this reaction mixture was registered
the formation of 3-bromo-4-dimethylaminopyridine as
confirmed by the spectrum of the mixed sample with
authentic substance.
When the filtrate after isolation of complex XIX
was evaporated an oil formed that crystallized at the
addition of acetonitrile. The precipitate was identified
as XVIII solvate with chloroform molecule. It was
filtered off, washed with acetonitrile, and dried in a
REFERENCES
31
vacuum. Yield 0.53 g (12%). In the P NMR spectrum
1
. Trost, W.R., Can. J. Chem., 1954, vol. 32, p. 356.
(
DMSO-d ) appears a signal at δ, ppm:–161 quintet,
6
3
2. Holmes, R.R. and Bertaut, E.F., J. Am. Chem. Soc.,
JPH 15. In some time in the mixture an equilibrium
1
958, vol. 80, p. 2980.
was established with other complexes, and the
following signals appeared, δ, ppm (J, Hz): –15 s, that
3
. Holmes, R.R., J. Phys. Chem., 1960, vol. 64, p. 1295.
corresponds to complex XIX, and 9 s (complex XVII).
4. Holmes, R.R., J. Am. Chem. Soc., 1960, vol. 82, p. 5285.
5. Beattie, I.R. and Webster, M., J. Chem. Soc., 1961,
p. 1730.
6. Dillon, K.B., Reeve, R.N., and Waddington, T.C., J. Chem.
Soc., Dalton Trans., 1977, p. 1410.
1
The Н NMR spectrum (DMSO-d ) δ, ppm: 3.19 s
6
3
4
(
12H, N–CH ), 6.84 d.d (4H arom., J 7, J 2), 8.06
3 HH PH
3
3
d.d (4Н arom., J 7, J 15), 8.30 с. (0.8H, CHCl3).
HH
PH
Found, %: C 38.87; H 4.83; Cl 34.34; N 12.92; P 6.07.
C14.5H20.5Cl N OP. Calculated, % C 38.08; H 4.52; Cl
7. Dillon, K.B., Reeve, R.N., and Waddington, T.C., J. Chem.
Soc., Dalton Trans., 1977, p. 2382.
4.5
4
34.88; N 12.25; P 6.77. Compounds XVIII and XIX
were not isolated as individual products probably due
to their equilibrium in solution. Owing to the absence
8. Il’in, E.G., Shcherbakova, M.N., and Buslaev, Yu.A.,
Dokl. Akad. Nauk SSSR, 1976, vol. 231, no. 1, p. 107.
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 79 No. 5 2009