Reaction of 2H-1,2,3-diazaphosphole with ethanolamine

Full text of DOI:10.1134/S1070363206030248

ISSN 1070-3632, Russian Journal of General Chemistry, 2006, Vol. 76, No. 3, pp. 495 496.
Pleiades Publishing, Inc., 2006.
Original Russian Text
pp. 521 522.
N.G. Khusainova, O.A. Mostovaya, R.A. Cherkasov, 2006, published in Zhurnal Obshchei Khimii, 2006, Vol. 76, No. 3,
LETTERS
TO THE EDITOR
Dedicated to the 90th Anniversary of Corresponding Member
of the Russian Academy of Sciences A.N. Pudovik
Reaction of 2H-1,2,3-Diazaphosphole with Ethanolamine
N. G. Khusainova, O. A. Mostovaya, and R. A. Cherkasov
Kazan State University, ul. Kremlevskaya 18, Kazan, Tatarstan, 420008 Russia
Received October 11, 2005
DOI: 10.1134/S1070363206030248
Reactions of cyclic derivatives of two-coordinate
phosphorus, containing a P=C bond, with difunctional
nucleophilic reagents have scarcely been studied. We
previously found that a mixture of 1,2,3-diazaphos-
pholene and -hydroxybutoxyhydrospirophosphorane
containing a diazaphospholene and a dioxaphospho-
lane ring, formed by the reaction of 2-acetyl-5-methyl-
2H-1,2,3-diazaphosphole (I) with butane-2,3-diol at
10 to 0 C undergoes fragmentation into a sym-
metrical hydroslirotetraoxaphosphorane, its tautomeric
hydrogen phosphite, and acetone hydrazone, as the
temperature increases [1].
and 112.5 ppm (0.5) (2JPH 30.7 Hz); figures in paren-
theses relate to the integral intensity of the signal.
The observation of several signals from 2-acetyl-3-(2-
aminoethoxy)-5-methyl-3,4-dihydro-2H-1,2,3-diaza-
phosphole (III) is explained by the presence of
geometric isomers: The OC2H4NH2 substituent can
be syn and anti with respect to the electronic pair of
the PIII atom of compound III [2]. In addition, the
following signals are observed, P, ppm: 236 (0.08)
(diazaphosphole I), 220 (0.4) (2JPH 44.5 Hz), 57.7
and 57.4 (0.1), 57.6 (0.24) and 52.8 (0.04).
To establish the chemical shift of the PIII atom
bearing the amino group in a diazaphospholene, we
reacted diazaphosphole I with diethylamine. The 31P
In the present communication we report on the
results of the reaction of diazaphosphole I with
ethanolamine (II) at 0 C. Analysis of the 31P NMR
spectrum of the reaction mixture, measured after
mixing of equimolar reagent amounts, established that
the reaction involves preferential attack of the P=C
bond of diazaphosphole I with the -aminoethoxy
group of compound II, as evidenced by the ap-
pearance of strong signals at P 111 (1) (2JPH 29.8 Hz)
NMR spectrum acquired a signal at
59 ppm. We
assigned the signal at
57 ppm to thePPIII nucleus in
2-acetyl-3-[2-(hydroxyPethylamino)-5-methyl-3,4-di-
hydro-2H-1,2,3-diazaphosphole (IV). The presence of
a weak signal at
220 ppm points to formation of
P
a 2H-1,2,3-diazaphosphole bearing no substituents on
N2 [3]. The signals at 57.6 (1JPH 705 Hz) and
Me
Me
Me
C
N
N
C
N
N
C
N
N
H3C
+
H3C
+ H2NC2H4OH
Me
Me
P
P
CH2
C
O
CH2
C
O
II
P
CH
C
O
NHC2H4OH
OC2H4NH2
I
III
IV
Me
C
N
N
CH2
C
O
O
Me
O
H
P
POC2H4NH2
+
+
+ MeC NH N=C
O
NH
P
O
Me
N
H
NH
H2C
NH
CH2
H
V
VI
VII
VIII
495

496
KHUSAINOVA et al.
52.8 ppm (1JPH 737 Hz) relate to 1-acetyl-3-methyl-
ACKNOWLEDGMENTS
1,2,6-triaza-9-oxa-5 5-phosphaspiro[4.4]non-2-ene
5
The work was financially supported by the Univer-
sities of Russia Program and the Program for Support
of Leading Scientific Schools.
(V) and 1,6-diaza-4,9-dioxa-5 -phosphoaspiro[4.4]-
nonane (VI) [4]. The reaction mixture was left to
stand for 1 week at 5 7 C, after which the 31P NMR
spectrum acquired a signal at
140 ppm (0.10), that
P
REFERENCES
we assign to the PIII atom in 2-(2-aminoethoxy)-1,3,2-
oxazaphospholane (VII). Phospholane VII is formed
by partial fragmentation of compounds III and V,
accompanied by elimination of acetone hydrazone
VIII [1, 5].
1. Khusainova,
N.G.,
Mostovaya,
O.A.,
Azan-
cheev, N.M., Litvinov, I.A., Krivolapov, D.B.,
and Cherkasov, R.A., Mendeleev Commun., 2004,
no. 5, p. 212.
2. Germa, H., Sanchez, M., Burgada, R., and Wolf, R.,
Bull. Soc. Chim. Fr., 1970, no. 2, p. 612.
3. Bobkova, R.G., Ignatova, N.P., Shvetsov-Shilov-
skii, N.I., Mel’nikov, N.N., Negrebetskii, V.V., Bo-
gel’fer, L.Ya., and Dymova, S.F., Zh. Obshch. Khim.,
1977, vol. 47, no. 3, p. 576.
4. Germa, H., Wilson, M., and Burgada, R., C. R. Acad.
Sci., 1970, vol. 270, no. 16, p. 1426.
5. Bobkova, R.G., Ignatova, N.P., Shvetsov-Shilov-
skii, N.I., Negrebetskii, V.V., and Vasil’ev, A.F.,
Zh. Obshch. Khim., 1976, vol. 46, no. 3, p. 590.
Thus, the reaction of diazaphosphole I with amino-
ethanol II involves both protic functions of reagent II,
resulting in O-, N-, and O,N-fuctionalization of the P
center (compounds II V, respectively), the O-func-
tionalization products prevailing.
The 31P NMR spectra were obtained on a Varian
Unity-300 spectrometer (121.42 MHz) in CH2Cl2,
external reference 85% H3PO4.
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 76 No. 3 2006