REACTIONS OF HEXAMETHYLPHOSPHORAMIDE WITH SULFUR DICHLORIDE
217
C(1)
C(1)
C(1)
C(1)
b
0
a
N(1)
C(2)
N(1)
C(2)
Cl
Cl
C(2)
C(2)
Cl
Cl
N(1)
C(1)
N(1)
c
C(1)
C(1)
C(1)
Fig. 1. Crystal structure of dimethyliminium chloride II.
(CH3)2N
(CH3)2N
+
+
+
+
SCl2
nSCl2
(CH3)2N P O S[ZnCl4]2–
(CH3)2N P O S SCl2[ZnCl4]2–
(CH3)2N
I + C
–Cl3P=O
–Sn
(CH3)2N
D
+
CH2Cl2
n[(CH3)2N]2[ZnCl4]2–
III + Cl2C=CCl2.
E
Indeed, zinc dichloride eliminates one or two chlo- phosphoryl chloride were obtained on a PerkinElmer-
ride anions in the reagent to convert it into implicit elec- 180 spectrophotometer as thin films. The purity of com-
trophile C, which coordinates to HMPA to form a com- pound II was monitored by TLC on Silufol UV-254
plex reagent D, which generates cation E, involving plates, Silpearl adsorbent, with hexane–ether (10 : 1) as
methylene chloride into the reaction. However, the gem an eluent and iodine as a developer. GLC analysis was
dichloride, as distinct from the first reaction, plays the performed on a Tsvet-110 chromatograph (flame ion-
role of the source of hydride ion and proton to afford ization detection, 3 m × 3 mm column, 15% Carbowax
dichlorocarbene, which dimerizes to give tetrachloro- 6000 on Chromaton N-AW, column thermostat temper-
ethylene.
Compound II is unstable in air, but relatively stable
in a dry nitrogen atmosphere. The crystal and molecular
structure of compound II (Fig. 1) was confirmed by
X-ray diffraction study [2].
The crystal and molecular structure of compound
III was determined by X-ray diffraction analysis and
NMR spectroscopy.
The structural feature of compound III is the pres-
ence of hydrogen bonds Cl…H (2.33(2)–2.48(2) Å),
which are considerably shorter than reduced Cl…H
contacts (2.67 Å) [3]. The crystals of compounds II and
III were grown as described in [4] from an acetonitrile
solution. Tetrachloroethylene was detected by GLC.
ature 80°ë, injector temperature 150°ë, nitrogen car-
rier gas, flow rate 2 L/h). The X-ray diffraction study of
a single crystal of compound II was carried out on a
Smart APEX2 automated diffractometer (MoKα radia-
tion, graphite monochromator, ω–θ scan mode). Crys-
tals of compound II are orthorhombic, Å: a =
6.0466(4), b = 6.9918(4), c = 5.5606(4), α = β = γ =
90°, V = 235.08(3) Å3, Z = 2, space group Pmmn. The
structure was solved by direct methods and refined by
least squares on F2 in the anisotropic approximation for
all non-hydrogen atoms to R = 0.0361 for 549 indepen-
dent reflections with I > 2σ(I) using the SHELXTL V.
5.10 software [5]. The coordinates of the non-hydrogen
atoms are presented in Table 1. The structure of mole-
cule II is shown in Fig. 1.
The X-ray diffraction study of a single crystal of
compound III was carried out on a Smart APEX auto-
mated diffractometer (MoKα radiation, graphite mono-
chromator, ω–θ scan mode).
EXPERIMENTAL
1H NMR spectra were recorded on a Bruker DPX-
200 spectrometer operating at 200 MHz in DMSO-d6
solution using TMS as an internal reference. The IR
spectra of compounds II and III were recorded on an
The crystals of compound III at 100(2) K are mon-
oclinic, Å: a = 8.3760(5), b = 11.3953(7), c =
UR-20 spectrometer as Nujol mulls. The IR spectra of 13.0976(8), β = 90.091(1)°, V = 1250.13(13) A3, Z = 4,
DOKLADY CHEMISTRY Vol. 422 Part 1 2008