Reaction of tert-butyl tetraethylphosphorodiamidite with bromomalonic ester [4]

Full text of DOI:10.1023/A:1023479716198

Russian Journal of General Chemistry, Vol. 72, No. 12, 2002, p. 1955. Translated from Zhurnal Obshchei Khimii, Vol. 72, No. 12, 2002, p. 2063.
Original Russian Text Copyright
2002 by Sal’keeva, Nurmagambetova, Kurmanaliev.
LETTERS
TO THE EDITOR
Reaction of tert-Butyl Tetraethylphosphorodiamidite
with Bromomalonic Ester
L. K. Sal’keeva, M. T. Nurmagambetova, and O. Sh. Kurmanaliev
Buketov Karaganda State University, Karaganda, Kazakhstan
Received March 6, 2002
Previously we showed that tert-butyl tetraethyl-
phosphorodiamidite (I) reacts with CH acids by way
of protonation of the phosphorus atom to form a
hydrogen phosphite [1].
bromomalonic ester (II) which contains, on the one
hand, a very labile hydrogen atom and, on the other,
an acidic proton, we found that in the absence of sol-
vent an exothermal reaction occurs accompanied by
vigorous isobutylene evolution and leading to poly-
aminophosphine and tetraethyl ethanetetracarboxylate.
While studying the reaction of phosphite I with
O
(
Et N) POBu-t + BrCH(COOEt)
(Et N) P + (EtOOC) CH CH(COOEt)2
2 2 2
2
2
2
Me C=CH
2
2
n
This reaction pathway agrees with the results of
Arbuzov [2] for reactions of sodium dialkyl phos-
hites with bromomalonic ester. The reaction in sol-
ents yields phosphorous bis(diethylamide) (III). The
latter reaction is accompanied by vigorous isobutylene
evolution and regeneration of bromomalonic ester (II).
OBu-t
O
+
(
Et N) POBu-t + BrCH(COOEt)
(Et N) P CBr(COOEt)2
(Et N) P H + II + Me C=CH
2
2
2
2
2
2
2
2
2
I
II
H
III
The formation of compound III can be explained
in no other way than by initial protonation of the
phosphorus atom.
measured on
(32.44 MHz) against external 85% phosphoric acid.
a
Bruker WP-80 spectrometer
REFERENCES
Phosphorous bis(diethylamide) (III), bp 54 55 C
1
2
. Gazizov, T.Kh., Sal’keeva, L.K., and Chugunov, Yu.V.,
Zh. Obshch. Khim., 1989, vol. 59, no. 11, p. 2462.
. Arbuzov, A.E., Izbrannye trudy po khimii fosfororga-
nicheskikh soedinenii (Selected Works on the Che-
mistry of Organophosphorus Compounds), Moscow:
Nauka, 1976, p. 292.
2
0
20
(
0.04 mm), d4 0.9621, nD 1.4540. IR spectrum, ,
1
31
cm : P=O (1225), P H (2470). P NMR spectrum:
9 ppm (JHP 570 Hz). Published data [3]: bp 76
1
P
2
0
8
0 C (0.5 mm), d 1.4545, 18 ppm (JHP 570 Hz).
D P
The IR spectra were recorded on a Specord IR-75
spectrometer in thin layer. The P NMR spectra were
3. Shilov, I.V. and Nifant’ev, E.E., Zh. Prikl. Khim., 1971,
3
1
vol. 44, no. 11, p. 2581.
1
070-3632/02/7212-1955$27.00 2002 MAIK Nauka/Interperiodica