New Methods of Synthesis of Phosphoryl and Thiophosphoryl Halides from Organylchlorophosphonium Hexachlorophosphorates

Article abstract of DOI:10.1023/A:1024779602690

A new method of synthesis of phosphonic and thiophosphonic chlorides is offered, based on treatment of acyclic and cyclic organylchlorophosphonium hexachlorophosphorates with dimethylformamide, dimethylacetamide, or dimethylthioacetamide. The method involves no formation of phosphoryl chloride and thiophosphoryl chloride, which facilitates isolation of the target products. The reactions of alkenylchlorophos-phonium hexachlorophosphorates with amides and thioamides results in incorporation of the PCl₆^- anion into an insoluble chloroiminium salt which is easily separated by filtration. Removal of the solvent leaves almost pure phosphonic or thiophosphonic chlorides.

Full text of DOI:10.1023/A:1024779602690

Russian Journal of General Chemistry, Vol. 73, No. 2, 2003, pp. 197 201. Translated from Zhurnal Obshchei Khimii, Vol. 73, No. 2, 2003,
pp. 216 221.
Original Russian Text Copyright
2003 by Rozinov, Dmitrichenko, Sultangareev.
New Methods of Synthesis of Phosphoryl
and Thiophosphoryl Halides
from Organylchlorophosphonium Hexachlorophosphorates
V. G. Rozinov, M. Yu. Dmitrichenko, and R. G. Sultangareev
Institute of Petrochemical and Coal Chemical Synthesis, Irkutsk State University, Irkutsk, Russia
Favorskii Irkutsk Institute of Chemistry, Siberian Division, Russian Academy of Sciences, Irkutsk, Russia
Received May 8, 2001
Abstract A new method of synthesis of phosphonic and thiophosphonic chlorides is offered, based on
treatment of acyclic and cyclic organylchlorophosphonium hexachlorophosphorates with dimethylformamide,
dimethylacetamide, or dimethylthioacetamide. The method involves no formation of phosphoryl chloride and
thiophosphoryl chloride, which facilitates isolation of the target products. The reactions of alkenylchlorophos-
phonium hexachlorophosphorates with amides and thioamides results in incorporation of the PCl6 anion into
an insoluble chloroiminium salt which is easily separated by filtration. Removal of the solvent leaves almost
pure phosphonic or thiophosphonic chlorides.
Phosphonic and phosphinic chlorides and their thio
analogs are convenient intermediates in organophos-
the organylchlorophosphonium cations of compounds
I, which allowed us to develop a method for isolation
phorus synthesis. The most common method of forma- of organyltetrachlorophosphoranes [5]:
tion of a phosphoryl group in organic phosphorus acid
R4 N+Cl
R PCl3+PCl6
R PCl4 + R4 N+PCl6 .
chlorides is treatment of organyl-phosphonium tetra-
chlorophosphorates with various oxygen-containing
inorganic and organic compounds [1]. Crystalline
organylchlorophosphonium hexachlorophosphorates
I formed by reactions of phosphorus pentachloride
with organic nucleophiles [2] are easily separated
from soluble phosphorylation and chlorination pro-
ducts, due to which no further purification of the
target products is usually needed. However, one can-
not always gain benefit from the preparative advan-
tages of complex salts I, because known methods of
their conversion to organic phosphorus acid chlorides
involve formation of phosphoryl chloride from the
PCl6 anion of salts I. Removal of phosphoryl chloride,
a very reactive compound, often leads, even in a
vacuum, to contamination and partial tarring of the
target chlorides, especially unsaturated.
It was established that in iminium salts the PCl6
anion forms with the organyliminium cation strong
complexes insoluble in nonpolar and low-polarity
solvents. With this in mind, we offer a new method
for preparing unsaturated phosphonic chlorides by
treatment of complex salts I with dimethylformamide
or dimethylacetamide in benzene or chloroform. This
method permits to avoid formation of phosphoryl
chloride in the reaction mixture, which considerably
facilitates preparative isolation of phosphonic
chlorides.
A solution containing an unsaturated phosphonic
chloride is readily separated from salt IIa or IIb by
filtration. After removal of a volatile solvent, the
phosphonic chloride is obtained in high yield.
RC(X)=CHPCl+3 PCl6
Previously we showed that N-alkyl-substituted ter-
tiary amides easily react with phosphorus pentachlo-
ride to give crystalline iminium salts containing a
PCl6 anion [3, 4]:
Me2NC(O)H
Me2NC(O)Me
[Me2N=C(Cl)Me]+PCl6
[Me2N=C(Cl)H]+PCl6
IIb
IIa
Alk2NCOR + 2PCl5
[Alk2N=C R]+PCl6 + POCl3.
Cl
RC(X)=CH POCl2
V VII, X
RC(X)=CH POCl2
VIII, IX, XI
R = Ph, X = H (V); R = PhCH =CH , X = Cl (VI);
R = EtO, X = H (VII); R = MeS, X = H (VIII); R = PrO,
X = H (IX); R = PhO, X = H (X); R = Ph2N, X = Cl (XI).
The PCl6 anion forms more stable crystalline com-
plexes with tetraorganylammonium cations than with
1070-3632/03/7302-0197$25.00 2002 MAIK Nauka/Interperiodica

198
ROZINOV et al.
Studying phosphorylation of ureids and thio-
filtration. After removal of the solvent from the
filtrate, an almost pure thiophosphonic chloride
remain.
ureids with phosphorus pentachloride we found
that thionic sulfur is more easily cleaved by phos-
phorus chlorides than carbonyl oxygen [6, 7]. This
leads to different phosphorylation directions.
III
RC(X)=CHPCl+3PCl6
RC(X)=CH PSCl2,
IV
NH2CONHCOMe
R = Ph, X = H (XII); R = MeS, X = H (XIII); R = PhO,
X = H (XIV); R = Ph2N, X = Cl (XV).
PCl5
PCl3=N C(Cl)=N C(Cl)=CHPCl3+PCl6 ,
HCl, POCl3
PCl5
Both salt IV and thiophosphonic chlorides have a
brown color, evidently because of the formation of
small amounts of sulfur chlorides that produce darken-
ing of the reaction mixture [8]. This effect is also
characteristic of the other methods of conversion of
hexachlorophosphorates I to thiophosphonates. It has
almost no effect on the yield of the target products.
NH2CSNHCOMe
POCl2 N=C(Cl) N=C(Cl)Me.
HCl,
PSCl3
Tertiary thioamides have never been reacted with
phosphorus pentachloride. We found that dimethyl-
thioacetamide (III) reacts with PCl5 like tertiary
N,N-dialkylamides. That means that here, too, thionic
sulfur is readily cleaved by phosphorus chloride.
The developed method allowed preparation of P=S-
containing diaza- and azaphosphinines XVII, XIX
from cyclic organylchlorophosphonium hexachloro-
phosphorates XVI, XVIII we obtained previously
[9, 10].
Me2NC(S)Me + 2PCl5
[Me2N=C Me]+PCl6 + PSCl3.
Cl
III
IV
Me2
N
Me2
N
Hence, in the case of thio analogs of tertiary
amides, the PCl6 anion is incorporated in a benzene-
insoluble iminium salt IV. It was expedient to extend
this reaction on various alkenylphosphonium hexa-
chlorophosphorates, aiming at preparing alkenylthio-
phosphonic chlorides.
O
Cl
O
Cl
III
IV
PCl6
+
N
Me1
N
Me1
P
P
S
Cl
Cl
Cl
XVI
XVII
Alkenylthiophosphonic chlorides are usually pre-
pared by treatment of complex salts I with hydrogen,
metal, or phosphorus sulfides [1]. Each of these
methods has drawbacks. Hydrogen sulfide is toxic and
resures thorough drying; moreover, the hydrogen
chloride formed in the course of the reaction adds by
the double bond of alkenylthiophosphonates. In the
case of metal sulfides, the reagent, as well as substrate
I, are insoluble in the reaction mixture, which com-
plicates the reaction. Phosphorus sulfides are toxic
and hardly available. Besides, all the above-described
methods have a common drawback. These reactions
involve formation of thiophosphoryl chloride from
the PCl6 anion. The necessity of removal of PSCl3
from the reaction mixture makes alkenylthiophos-
phonic chlorides even more difficult to isolate than
alkenylphosphonic chlorides contaminated by phos-
phoryl chloride.
Me
N
Me
N
Cl
Cl
Cl
Cl
PCl6
POCl2
III
IV
+
POCl2
Cl
P
P
S
Cl
Cl
XVIII
XIX
Hexachlorophosphorate XVIII was used in the
synthetic procedures as coarse crystals. This circum-
stance together with the fact that the reactivity of the
dichlorophosphonium group of the heterocycle is
decreased by conjugation stipulate a longer reaction
time in this case compared with the other syntheses
of thiophosphonic chlorides. Decreased activity of the
dichlorophosphonium group toward sulfur dioxide we
earlier observed with 1,4-dihydro1,4-diazaphosphi-
nines and 1,4-oxa- and 1,4-thiaphosphininonium hexa-
chlorophosphorates [12, 14]. Hence, dimethylthio-
acetamide III is a promising reagent for introduction
of a thiocarbonyl group into organylchlorophos-
phoranes and chlorophosphonium hexachlorophos-
phorates.
Using dimethylthioacetamide III permits to avoid
the above-mentioned complications in the synthesis
of alkenylthiophosphonic chlorides from compounds I.
The reaction of acyclic and cyclic alkenylchlorophos-
phonium hexachlorophosphorates with compound III
involves incorporation of the PCl6 anion into an in-
soluble iminium salt IV which is easily separated by
The structure of the synthesized alkenylphospho-
nates and thiophosphonates was established by NMR
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 73 No. 2 2003

NEW METHODS OF SYNTHESIS OF PHOSPHORYL AND THIOPHOSPHORYL HALIDES
199
Physicochemical characteristics and 31P NMR spectral parameters of phosphonic and thiophosphonic chlorides
Calculated, %
Comp. Yield,
bp,
(p, mm)
C
mp,
C
31P NMR spec-
trum, P, ppm
no.
%
C
H
Cl
N
P
S
V
VI
VII
VIII
IX
90
99
69
63
88
85
88
88
60
52
72
42
20
183 (18)
71 72
94 95
31.9
24.3
34.0
30.3
33.7
31.2
28.8
71.8
69.2
68.3
62.7
53.2
40.5
31.8
43.44
42.64
25.40
18.85
29.56
40.51
48.48
40.51
17.39
37.94
46.34
24.49
16.42
3.17
2.84
3.70
2.62
4.43
2.95
3.17
2.95
2.42
2.77
3.03
2.86
1.09
32.13
37.83
37.57
37.17
34.98
29.96
30.74
29.96
34.30
28.06
29.38
28.98
48.56
14.03
11.01
16.40
16.23
15.27
13.08
8.95
13.08
14.98
12.25
8.55
60 61 (0.1)
93 96 (3)
94 95 (2)
105 (0.1)
16.75
X
XI
86 88
4.04
XII
XIII
XIV
XV
XVII
XIX
116 117 (1)
90 97 (1)
159 161 (4)
13.50
30.92
12.65
8.83
13.06
8.76
104 106
120 122
195 197
3.86
11.43
3.83
12.65
16.96
Found, %
Comp.
no.
Formula
C
J
Cl
31.9
N
P
S
V
VI
VII
VIII
IX
C8H7Cl2OP
43.30
3.01
2.82
3.78
2.94
4.41
2.93
3.13
3.00
3.08
1.94
3.09
2.98
1.23
14.06
10.90
15.80
15.54
14.50
12.65
8.44
C10H8Cl3OP
C4H7Cl2O2P
C3H5Cl2OPS
C5H9Cl2O2P
C8H7Cl2O2P
C14H11Cl3NOP
C8H7Cl2PS
C3H5Cl2PS2
C8H7CI2OPS
C14H11Cl3NPS
C5H7Cl2N2OPS
C5H4Cl5NOP2S
42.65
25.54
19.50
30.10
40.47
48.23
40.35
18.09
42.04
46.11
24.51
16.11
38.05
37.02
37.51
34.85
29.25
31.04
29.45
34.97
29.39
25.55
28.84
49.06
16.88
X
XI
4.21
XII
XIII
XIV
XV
XVII
XIX
13.52
14.28
12.71
8.40
14.15
31.43
11.66
8.72
3.95
11.44
3.59
11.42
16.87
12.39
8.43
spectroscopy. The physicochemical characteristics and
31P NMR spectral parameters are listed in the table.
EXPERIMENTAL
The H and 31P NMR spectra were registered on a
Bruker DPX-400 spectrometer (400 and 161.98 MHz,
respectively) for CDCl3 solutions.
1
The 31P NMR spectrum of iminium salt IV, in-
dependent of the nature of hexachlorophosphorate I
reacted with amide III, contains only one singlet at
295.7 ppm characteristic of the PCl6 anion (nitro-
benzene soluton). The H NMR spectrum contains
Styrylphosphonic dichloride (V). To a dispersion
of 8.6 g of trichloro(styryl)phosphonium hexachloro-
phosphorate in 100 ml of benzene, a solution of 1.3 g
of dimethylformamide in 5 ml of benzene was added
in portions with stirring. Slight heat release was ob-
served, and the crystalline became denser and heavier.
After 1 h, the crystals of iminium salt IIa were
filtered off, the benzene was removed, and the product
P
1
three singlets at
2.98 [MeC(Cl)=], 3.80, and 3.87
(Me2N) ppm. ThePnonequivalence of the alkyl groups
in the dialkylamino fragment reflects a high degree of
double bonding of the C=N bond. This effect we also
established for other iminium salts [3]. The struc-
ture of iminium salts II has been thoroughly studied
in [4].
1
was distilled in a vacuum. Yield 3.53 g. H NMR
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 73 No. 2 2003

200
ROZINOV et al.
3
2
3
2
spectrum, , ppm: 6.69 d.d (1H, H , JHH 17.0, JHP
(1H, H , JHH 13.2 Hz, JPH 23.2 Hz), 7.36 d.d (1H,
3
3
3
3
34.5 Hz), 7.69 d.d (1H, H , JHH 17.0, JPH 31.0 Hz),
H , JHH 13.2 Hz, JPH 13.9 Hz).
7.4 7.6 m (5H, Ph).
( -Phenoxyvinyl)phosphonic dichloride (X) was
(2-Chloro-4-phenyl-1,3-butadienyl)phosphonic
dichloride (VI). To a dispesion of 33.4 g of trichloro-
(2-chloro-4-phenyl-1,3-butadienyl)phosphonium hexa-
chlorophosphorate prepared from 1-phenylbut-1-en-
3-one and phosphorus pentachloride, a solution of
4.5 g of dimethylformamide in 5 ml of benzene was
added dropwise with stirring. On the next day the
precipitate of iminium salt IIa was filtered off, and
the benzene was removed from the filtrate in a water-
jet-pump vacuum. Crystallization of the residue from
CCl4 gave phosphonic chloride VI as white crystals.
prepared analogously from 14.5 g of trichloro( -
phenoxyvinyl)phosphonium
and 2.1 g of dimethylformamide. Yield 5.8 g. H
hexachlorophosphorate
1
3
NMR spectrum, , ppm: 5.79 d.d (1H, H , JHH
2
3
12.9 Hz, JPH 23.2 Hz), 7.76 d.d (1H, H , JPH 12.9,
3JPH 13.2 Hz), 7.2 7.6 m (5H, Ph).
[2-Chloro-2-(N,N-diphenylamino)ethenyl]phos-
phonic dichloride (XI). A solution of 0.13 g of dime-
thylacetamide in 5 ml of benzene was quickly added
with stirring to a dispersion of 0.9 g of trichloro[2-
chloro-2-(N,N-diphenylamino)ethenyl]phosphonium
hexachlorophosphorate. Several minutes later, the
precipitate turned yellow and pasty. After 1 h,
iminium salt IIb was filtered off. Yield 0.48 g (92%).
The solvent was removed from the filtrate, and the re-
sidue was recrystallized from a 10:1 hexane benzene
mixture to obtain 0.45 g of compound XI as white
1
Yield 17.3 g. H NMR spectrum, , ppm: 6.21 d (1H,
2
3
H , JPH 24.6 Hz); 7.98 d.d (1H, H , JHH 15.1 Hz,
4JPH 2.4 Hz), 7.2 7.5 m (6H, H , Ph).
( -Ethoxyvinyl)phosphonic dichloride (VII).
To a dispersion of 18.6 g of trichloro( -ethoxyvinyl)-
phosphonium hexachlorophosphorate in 30 ml of ben-
zene, 3 g of dimethylformamide was added with stir-
ring. After 4-h stirring, the thickened precipitate of
salt IIa was filtered, the benzene was removed in a
water-jet-pump vacuum, and compound VII was
distilled in a vacuum. Yield 7.9 g. 1H NMR spectrum,
1
crystals. H NMR spectrum, , ppm: 5.24 d (1H, H ,
2JPH 20.8 Hz), 7.2 7.4 m (10H, Ph).
Styrylthiophosphonic dichloride (XII). A solu-
tion of 0.3 g of dimethylthioacetamide in 5 ml of
benzene was added in portions with stirring to a dis-
persion of trichloro(styryl)phosphonium hexachloro-
phosphorate. In the course of the reaction, the crystall-
ine precipitate thickened and acquired a brown color.
After 5 h, the crystals of iminium salt IV were filtered
off, and the benzene was removed in a water-jet-pump
vacuum. The residue was distilled in a vacuum to give
3
, ppm: 1.08 t (3H, Me, JHH 8.1 Hz), 3.86 q (2H,
3
3
CH2, JHH 8.1 Hz), 5.43 d.d (1H, H , JHH 13.4 Hz,
2JPH 23.2 Hz), 7.38 d.d (1H, H , JHH 13.4 Hz, JPH
3
3
13.9 Hz).
( -Methylthiovinyl)phosphonic dichloride
(VIII). To a dispersion of 3.05 g of trichloro( -methyl-
thiovinyl)phosphonium hexachlorophosphorate in
15 ml of benzene, a solution of 0.6 g of dimethylacet-
amide in 5 ml of benzene was added with stirring. The
precipitate quickly thickened, and the reaction mixture
became yellow. After 4 h, iminium salt IIb was fil-
tered off. Yield 2.1 g (92%). Distillation of the re-
1
0.6 g of stytylthiophosphonic dichloride. H NMR
3
spectrum, , ppm: 6.96 d.d (1H, H , JHH 16.4 Hz,
3
3
2JHH 29.1 Hz), 7.66 d.d (1H, H , JHH 16.4 Hz, JPH
33.1 Hz), 7.4 7.5 m (5H, Ph).
( -Methylthiovinyl)thiophosphonic dichloride
(XIII). A solution of 0.5 g of dimethylthioacetamide
in 5 ml of benzene was added with stirring to a dis-
persion of 2.2 g of trichloro( -methylthiovinyl)phos-
phonium hexachlorophosphorate in 15 ml of benzene.
The dispersion practically immediately thickened and
darkened. After 24 h, iminium salt IV was filtered off.
Yield 10 g (58%). The solvent was removed from the
filtrate, and the residue was treated with hot hexane.
Distillation of the extract gave 0.6 g of compound
1
sidue gave 0.8 g of compound VIII. H NMR spec-
trum, , ppm: 2.41 s (3H, Me), 5.89 d.d (1H, H , 3JHH
2
3
15.9 Hz, JPH 31.1 Hz), 7.78 d.d (1H, H , JHH
3
15.9 Hz, JPH 28.1 Hz).
( -Propoxyvinyl)phosphonic dichloride. To a
dispersion of 6.5 g of trichloro( -propoxyvinyl)phos-
phonium hexachlorophosphorate in 50 ml of benzene,
1.2 g of dimethylacetamide was added in portions
with vigorous stirring. The precipitate quickly thicke-
ned, which made the mixture more difficult to stir.
After 2 h, the precipitate became greenish-yellow. A
day later, iminium salt IIb was filtered off. Yield 4.2
g. Distillation of the filtrate gave 2.5 g of compound
1
XIII as a yellow oil. H NMR spectrum, , ppm:
2.44 s (3H, Me), 6.17 d.d (1H, H , 3JHH 15.4 Hz, 2JPH
3
2
25.6 Hz), 7.85 d.d, H , JHH 15.4 Hz, JPH 31.1 Hz).
1
3
X. H NMR spectrum, , ppm: 0.95 t (3H, Me, JHH
( -Phenoxyvinyl)thiophosphonic dichloride
(XIV). A solution of 0.47 g of dimethylthioacetamide
in 5 ml of benzene was added to a dispersion of 2.3 g
3
3
7.2 Hz), 1.72 m (2H, CH2 Me, JHH 7.2 Hz, JHH
6.4 Hz), 3.86 t (2H, CH2O, JHH 6.4 Hz), 5.28 d.d
3
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 73 No. 2 2003

NEW METHODS OF SYNTHESIS OF PHOSPHORYL AND THIOPHOSPHORYL HALIDES
201
of trichloro( -phenoxyvinyl)phosphonium hexachloro-
phosphorate in 15 ml of benzene. A day after, the pre-
cipitate got much denser and darker. After 24 h, the
precipitate of iminium salt IV was filtered off, and
the solvent was removed from the filtrate. The brown
residue was treated with boiling hexane. It was re-
moved, and the residue was distilled to obtain 0.6 g
NMR spectrum, , ppm: 4.06 s (3H, MeN), 5.93 d
4
(1H, CH=, JPH 9.1 Hz). The P(S)Cl group appears at
2
40.5 ppm ( JPP 46.6 Hz).
P
REFERENCES
1. Kormachev, V.V. and Fedoseev, M.S., Preparativ-
naya khimiya fosfora (Preparative Phosphorus
Chemistry), Perm, 1992.
1
of compound XIV as a slightly yellow oil. H NMR
3
2
spectrum, ppm: 6.17 d.d (1H, H , JHH 12.5 Hz, JPH
3
3
16.8 Hz), 7.86 d.d (1H, H , JHH 12.5 Hz, JPH
2. Fridland, S.V. and Malkov, Yu.K., Reakts. Metody
Issled. Org. Soedin., 1986, pp. 106 149.
14.8 Hz), 7.2 7.6 m (5H, Ph).
3. Pensionerova, G.A., Rozinov, V.G., Kalabina, A.V.,
Donskikh, V.I., Ratovskii, G.V., and Dmitrichen-
ko, M.Yu., Zh. Obshch. Khim., 1982, vol. 52, no. 11,
pp. 2491 2499.
[2-Chloro-2-(N,N-diphenylamino)ethenyl]thio-
phosphonic dichloride (XV). A solution of 0.18 g of
dimethylthioacetamide in 5 ml of benzene was added
dropwise with stirring and cooling with ice water to a
dispersion of 1.05 g of trichloro[2-chloro-2-(N,N-di-
phenylamino)ethenyl]phosphonium hexachlorophos-
phorate. A day after, the precipitate of iminium salt
IV was filtered off, and the solvent was removed from
the filtrate. The brown residue was treated with boil-
ing hexane. After cooling, 0.45 g of compound XV
4. Rozinov, V.G., Dmitrichenko, M.Yu., Kolbina, V.E.,
and Dolgushin, G.V., Zh. Obshch. Khim., 1999,
vol. 69, no. 9, pp. 1430 1438.
5. Rozinov, V.G., Rybkina, V.V., Kolbina, V.E., Pen-
sionerova, G.A., and Donskikh, V.I., Zh. Obshch.
Khim., 1982, vol. 52, no. 9, pp. 1994 1997.
1
precipitated as coarse yellow plates. H NMR spec-
6. Dmitrichenko, M.Yu., Donskikh, V.I., Rozinov, V.G.,
Dolgushin, G.V., Ratovskii, G.V., Efremov, V.G.,
and Rybkina, V.V., Zh. Obshch. Khim., 1989, vol. 59,
no. 1, pp. 227 228.
2
2
trum, , ppm: 5.61 d (1H, H , JPH, JPH 23.4 Hz),
7.2 7.4 m (10H, Ph).
2,4-Dichloro-1,5-dimethyl-6-oxo-1,2,5,6-tetra-
hydro-1,5,2 5-diazaphosphinine 2-sulfide (XVII)
was obtained in a similar way from 2.4 g of complex
salt XVI and 0.5 g of dimethylthioacetamide. After 3
days, the light brown precipitate of iminium salt IV
was filtered off, the benzene was removed, and the
residue was recrystallized from a 10:1 hexane ben-
zene mixture to obtain 0.5 g of compound XVII as
7. Rozinov, V.G., Dmitrichenko, M.Yu., Dolgushin, G.V.,
and Donskikh, V.I., Zh. Obshch. Khim., 1990, vol. 60,
no. 3, pp. 706 707.
8. Buehler, C.A. and Pearson, D.E., Survey of Organic
Syntheses, New York: Wiley, 1970, vol. 1. Translated
under the title Sintezy organicheskikh soedinenii,
1973, vol. 1, p. 349.
1
light yellowish prisms. H NMR spectrum, , ppm:
9. Dmitrichenko, M.Yu., Rozinov, V.G., Donskikh, V.I.,
Ratovskii, G.V., Sergienko, L.M., Dolgushin, G.V.,
and Valeev, R.B., Zh. Obshch. Khim., 1988, vol. 58,
no. 10, pp. 2252 2261.
3
3.34 d (3H, Me1, JPH 10.2 Hz), 3.52 s (3H, Me2),
2
5.87 d (1H, CH=, JPH 15.8 Hz).
1-Methyl-2,4,6-trichloro-3-(dichlorophosphoryl)-
10. Dmitrichenko, M.Yu., Rozinov, V.G., Donskikh, V.I.,
Doilgushin, G.V., Feshin, V.P., and Kaslabina, A.V.,
Zh. Obshch. Khim., 1987, vol. 57, no. 8, pp. 1912
1913.
5
1,4-dihydro-1,4 -azaphosphinine 4-sulfide (XIX).
A solution of 0.07 g of dimethylthioacetamide in 2 ml
of benzene was added in portions with stirring to a
dispersion of 0.4 g of 2,4,4,6-tetrachloro-1-methyl-3-
(dichlorophosphoryl)-1,4-dihydro-1,4 5-azaphosphi-
nonium hexachlorophosphorate (XVIII) in 8 ml of
benzene. Within 4 h, the reaction mixture slowly
darkened. A day after, the brownish precipitate of
iminium salt IV was filtered off. Yield 0.25 g. The
solvent was removed from the filtrate, and the residue
was recrystallized from a 10:1 hexane benzene mix-
ture to obtain 0.05 g of compound XIX as yellow
crystals. Evaporation of the mother liquor gave 0.05 g
11. Rozinov, V.G., Izhboldina, L.P., Donskikh, V.I., Ra-
tovskii, G.V., Sergienko, L.M., Dolgushin, G.V., and
Dmitrichenko, M.Yu., Zh. Obshch. Khim., 1989,
vol. 59, no. 5, pp. 997 1018.
12. Rozinov, V.G., Kolbina, V.E., and Donskikh, V.I.,
Zh. Obshch. Khim., 1987, vol. 57, no. 4, pp. 954 956.
13. Rozinov, V.G., Kolbina, V.E., Donskikh, V.I., Ra-
tovskii, G.V., Dolgushin, G.V., Gavrilova, G.M., Gos-
tevskaya, V.I., and Amosova, S.V., Zh. Obshch. Khim.,
1990, vol. 60, no. 8, pp. 1780 1789.
1
of crude compound XIX as a brownish powder. H
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 73 No. 2 2003