2074
DIMUKHAMETOV et al.
phosphorin-4-one I with 2-benzylideneaminoethanol in
benzene in the presence of triethylamine (δP 137.5 ppm),
was capable of the intramolecular cyclization into the
bicyclic structure III (δP 20.0 ppm). Apparently, this
process includes the nitrogen atom attack on the
endocyclic carbonyl carbon atom with the subsequent
(or simultaneous) attack of the phosphorus atom on the
imino group carbon atom. In this case the intermediate
bipolar ion C is formed, which further is transformed
into the end reaction product III.
The 1H and 31Р NMR spectra were recorded on
Bruker Avance-600 (600 MHz, Н) and Bruker CXP-
1
100 (36.48 MHz, 31Р) spectrometers in CDCl3 relative
to the residual signal of the solvent or to external
H3PO4. The IR spectrum was registered on a Bruker
Vector-22 instrument (from thin film on KBr plates).
The mass spectrum MALDI was obtained on a TOF
mass spectrometer ULTRAFLEX (Bruker, Germany).
Laser desorption was performed with a pulse UV laser
(λ 337 nm). Dihydroxybenzoic acid was used as a
matrix. The sample was prepared by the “dry drop”
method: a mixture of matrix ethanol solution (1 wt %)
and THF solution of the analyzed substance (0.1 wt %)
was applied on the support and dried at 40°C. The
mass spectrum EI was registered on a DFS Thermo
Electron Corporation instrument (USA) at the
ionization electrons energy 70 eV and ion source
temperature 280°С. The capillary column DB-5MS
30 m × 0.254 mm) was used. Gas-carrier helium. The
processing of mass spectral data was carried out with
the use of Xcalibur program.
This transformation is completed in 3 days and is
characterized by the high stereoselectivity (one
diastereomer is formed). The structure of compound
1
III was proved by the Н, 31Р NMR and IR spec-
troscopy, mass-spectrometry (MALDI, EI) methods.
The IR spectrum contains the absorption band at
1673 cm–1 belonging to the amide carbonyl group. The
corresponding absorption bands originating from the
groups Р=О (1220 cm–1) and РОС (1036 cm–1) are also
present.
Compound (III). To a mixture of 0.82 g of 2-
benzylideneaminoethanol and 0.84 g of triethylamine
in 20 ml of anhydrous benzene was dropwise added at
stirring within 20 min a solution of 1.12 g of com-
pound I in 5 ml of anhydrous benzene at room tem-
perature under argon atmosphere. After the phosphite
addition the reaction mixture was stirred for 30 min
and kept for 3 days under argon. The precipitate was
filtered off and washed with diethyl ether. The solvent
was removed. The residue was viscous colorless oily
liquid. Yield 1.5 г (87%). 1Н NMR spectrum (СDCl3),
ACKNOWLEDGMENTS
This work was financially supported by the Russian
Foundation for Basic Research (grant no. 07-03-
00180).
REFERENCES
1. Dimukhametov, М.N., Bajandina, E.V., Davydova, Е.Yu.,
Dobrynin, А.B., Gubaidullin, А.T., Litvinov, I.A., and
Alfonsov, V.A., Mendeleev Comm., 2001, vol. 11, no. 5,
p. 196.
2. Dimukhametov, M.N., Bajandina, E.V., Davydova, E.Yu.,
Litvinov, I.A., Gubaidullin, A.T., Dobrynin, A.B.,
Zyablikova, T.A., and Alfonsov, V.A., Heteroatom.
Chem., 2003, vol. 14, no. 1, p. 56.
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2
3
δ, ppm (J, Hz): 3.74 m (1Н, NC9H, JHH 14.1, JHH
3
2
3
6.9–7.0, JHH 6.8), 4.18 m (1H, NC9H, JHH 14.1, JHH
6.7, JHH 6.7), 4.32 m (1H, OC8H), 4.43 m (1H,
3
OC8H), 5.18 d (1H, 2JРH 15.8 Hz), 7.15 br. d (1H, Н12,
3
3
3JHH 8.3), 7.21 br. d. d (1H, Н14, JHH 7.6, JHH 7.7),
7.27 m, 7.40 m, 7.68 m (7Н, Н11,13, Н16–18). 31Р NMR
spectrum, δ, ppm (J, Hz): 19.9 (2JРСН 16.0). Mass
spectrum (MALDI), m/z (Irel, %): 317 (18.6), 316
(100.0) [М + H]+. Mass spectrum (EI), m/z (Irel, %):
315 (68.4) [M]+·, 287 (34.7) [М – СO]+, 258 (28.7)
[М – СO – СОH]+, 210 (68.9) [М – PhСО]+, 184
(73.1) [С9H13O2P]+, 120 (100.0) [С6H4СO2]+, 91 (76.9)
[PhСH2]+, 77 (19.4) [Ph]+. Found, %: N 4.51; Р 10.01.
С16H14NO4P. Calculated, % : N 4.44; Р 9.84.
5. Mironov, V.F., Konovalova, I.V., Burnayeva, L.M., and
Ofitserov, E.N., Usp. Khim., 1996, vol. 65, no. 11, p. 1013.
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 80 No. 10 2010