Reactions of phosphonic and phosphoric dichlorides with sodium cyanate as a general synthesis method of phosphoryldiisocyanates

Full text of DOI:10.1134/S1070363210050324

ISSN 1070-3632, Russian Journal of General Chemistry, 2010, Vol. 80, No. 5, pp. 1039–1040. © Pleiades Publishing, Ltd., 2010.
Original Russian Text © T.V. Baulina, P.V. Petrovskii, E.I. Goryunov, E.E. Nifant’ev, 2010, published in Zhurnal Obshchei Khimii, 2010, Vol. 80, No. 5,
pp. 868–870.
LETTERS
TO THE EDITOR
Reactions of Phosphonic and Phosphoric Dichlorides
with Sodium Cyanate
as a General Synthesis Method of Phosphoryldiisocyanates
T. V. Baulina, P. V. Petrovskii, E. I. Goryunov, and E. E. Nifant’ev
Nesmeyanov Institute of Organoelemental Compounds, Russian Academy of Sciences,
ul. Vavilova 28, Moscow, 119991 Russia,
fax: (095)1355085
e-mail: zaq@ineos.ac.ru
Received April 14, 2009
DOI: 10.1134/S1070363210050324
Phosphoryldiisocyanates XP(O)(NCO) are promis-
cyanate proceeds at room temperature in anhydrous
acetonitrile medium for 4 h, the content of diiso-
cyanate in the mixture formed 93% according to the
P NMR data. After distilling the product yield
comprises 61% (Tables 1, 2).
2
ing precursors for synthesis of various classes of organo-
phosphorus compounds: phosphorylated ureas, urethans,
carbodiimides, heterocycles, etc, which are in turn of
great interest as organophosphorus extractants, complex-
ing agents, sorbates, polymers, biologically active
compounds and other practically useful substances.
3
1
O
O
P
Although various approaches to phosphoryldi-
isocyanates: thermal decomposition of phosphoryldi-
carbamates [1], oxidation of the corresponding
trivalent phosphorus diisocyanates [2–4], etc. are
proposed to date, reaction of the easily available phos-
Cl
NCO
NCO
Ph
P
+ 2 NaOCN
Ph
+ 2 NaCl
Cl
Under the similar conditions the reactions of
methyldichlorophosphonate and phenyldichlorophos-
phate with sodium cyanate either do not go at all or go
very slowly.
phoryldichlorides RP(O)Cl with cyanates is the most
simple and rational method to their obtaining [4–7].
2
At the same time the literary data on the synthesis
of phosphoric diisocyanates given by the different
authors with the use of a last method often do not correlate.
And the end-products were not reliably characterized.
Earlier we proposed an effective catalytic method
to obtain the phosphorus monoisocyanates on the basis
of the corresponding monochlorides and sodium
cyanate [8]. We used this approach to the synthesis of
methyldichlorophosphonate and phenyldichlorophos-
phate. The Lewis acid, anhydrous magnesium chloride,
was used as catalyst in these reactions (Table 1).
In this connection we investigated the reactions of
some typical phosphonic and phosphoric dichlorides
with accesible sodium cyanate. It was established that
reaction of phenyldichlorophosphonate with sodium
Table 1. Reaction of phosphoryldichlorides with sodium cyanate
Content of diisocyanate in the reaction
R
Catalyst
–
Temperature, °С
Reaction time, h
Yield, %
3
1
mixture by the Р NMR spectral data, %
Ph
Me
20
50
4
1
1
93
97
95
61
60
42
MgCl
MgCl
2
2
PhO
~80
1
039

1
040
BAULINA et al.
3
1
1
Table 2. Boiling points, Р{ H} NMR spectra and elemental analysis data for phosphoryldiisocyanates RP(O)(NCO)
2
Found/Calculated, %
31
1
bp, °С
Р{ H} NMR
R
(
p, Тоrr)
spectrum, δ, ppm, s
C
H
N
P
Ph
133.5–134 (5)
77–78 (2)
46.19
2.49
2.42
2.13
2.07
2.49
2.25
13.40
13.46
19.20
19.19
12.33
12.50
14.80
14.88
21.14
21.21
13.85
13.82
–7.1
4
6.17
24.50
4.67
43.00
Me
–3.4
2
PhO
93–94 (1)
–30.1
4
2.87
O
P
O
P
Their structure was confirmed by elemental analysis
data and also by NMR ( Р, Н) and IR spectroscopy.
Cl
Cl
NCO
NCO
31
1
R
+ 2 NaOCN
R
+ 2 NaCl
Hence we pioneered in discovering the effect of
electrophilic catalysis in the reaction of phosphoryl-
dichlorides with sodium cyanate. Using this effect, we
developed the simple and effective synthesis method
of the both phosponic and phosphoric diisocyanates.
R = PhO, Me.
The mixture of dichlorides with sodium cyanate
excess was heated at 50ºC (R = Me) or refluxed (R =
OPh) in absolute acetonitrile medium for 1 h in the
REFERENCES
presence of 2.5 mol % of MgCl . The target
diisocyanates were isolated by vacuum distillation in
2
1
. Derkach, G.I., Slyusarenko, E.I., Libman, B.Ya., and
Lipuga, N.I., Zh. Obshch. Khim., 1965, vol. 35, no. 10,
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4
2–61% yields. They are colorless, labile liquids,
sensitive to the air moisture. Their structure was
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2
3
4
. Steyermark, P.R., USA Patent no. 3177239, 1965, C. A.,
3
1
1965, vol. 62, p. 16129b.
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For the chemical identification of these diiso-
cyanates we used reaction with dialkylamines resulting
in the corresponding phosphorylated bisureas in high
yields.
O
5. Haven, A.C., USA Patent no. 2835652, 1958, C. A.,
1959, vol. 53, p. 221.
6. Utvary, K., Freudlinger, E., and Gutman, V., Monats.
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O
P
O
P
1
2
2
Cl
+ R R NH
Cl
C H
NH
NH
C
NR R
6
6
1
2
R
R
1
C
O
NR R
7
. Derkach, G.I., Slyusarenko, E.I., Doroshenko, V.V., and
Libman, B.Ya., Khimiya organicheskikh soedinenii
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Buyanovskaya, A.G., and Nifantyev, E.E., Izv. Akad.
Nauk Ser. Khim., 2005, no. 11, p. 2543.
1
2
2 5 3 7
R = Ph, Me, PhO; R = R = C H , C H -n.
8
Bisureas isolated are colorless crystalline sub-
stances, which are melted without the decomposition.
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 80 No. 5 2010