Intramolecular transformation of 2-benzylideneaminoethoxybenzo[d]-1,3,2- dioxaphosphorin-4-one into 3,4-benzo-10-phenyl-1-aza-5,7-dioxa-6-phosphabicyclo- [4.3.1]decane-2,6-dione

Full text of DOI:10.1134/S107036321010035X

ISSN 1070-3632, Russian Journal of General Chemistry, 2010, Vol. 80, No. 10, pp. 2073–2074. © Pleiades Publishing, Ltd., 2010.
Original Russian Text © M.N. Dimukhametov, L.M. Abdrakhmanova, V.F. Mironov, R.Z. Musin, 2010, published in Zhurnal Obshchei Khimii, 2010, Vol. 80,
No. 10, pp. 1752–1753.
LETTERS
TO THE EDITOR
Intramolecular Transformation
of 2-Benzylideneaminoethoxybenzo[d]-1,3,2-dioxaphosphorin-4-
one into 3,4-Benzo-10-phenyl-1-aza-5,7-dioxa-6-phosphabicyclo-
[4.3.1]decane-2,6-dione
M. N. Dimukhametov, L. M. Abdrakhmanova, V. F. Mironov, and R. Z. Musin
Arbuzov Institute of Organic and Physical Chemistry, Kazan Research Centre,
Russian Academy of Sciences, ul. Arbuzova 8, Kazan, Tatarstan, 420088 Russia
e-mail: mironov@iopc.ru
Received January 14, 2010
DOI: 10.1134/S107036321010035X
Alkylideneaminoalkoxy derivatives of Р(III) A
readily undergo cyclization in the presence of proton-
donating reagents to form 1,4,2-oxazaphosphacyclanes
B [1–3], which are difficultly accessible by other
methods. The derivatives A obtained from chloro-
phosphites, β- or γ-iminoalcohols in the presence of a
base are stable and some of them are distilled under
reduced pressure [4]. This behavior of the imino-
phosphites A is due to the formation of immonium
derivatives in the presence of the proton donor leading
to the increase in electrophilic properties of the imino
group carbon atom and to the intramolecular
cyclization of the phosphites А by the nucleophilic
attack of the atom Р(III) on the imino group.
O
O
O
H+
N
P
O
C
NH
P
B
A
The similar intramolecular cyclization to form Р–С
bond can be initiated not only by the proton-donating
reagents, but by any suitable electrophilic group,
which is present in the iminophosphite molecule. The
acylphosphite fragment POС(О), which is capable of
suffering the nucleophilic attack, proved to be such
electrophilic group [5]. Thus, Р-cyclic derivative of
salicylic acid II containing benzylideneaminoethoxyl
group as an exocyclic substituent, which was obtained
by the reaction of 2-chlorobenzo[d]-1,3,2-dioxa-
Ph
O
O
+
P
O
Cl
HO
O
O
N
P
P
N
CHPh
NEt3
O
O
O
N
O
_O
Ph
O
II
I
C
O
6P
5
O
O7
14
11
4
13
12
8
10
3
18
15
2
9
N
16
17
1
O
III
2073

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).
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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