Synthesis of triphenylphosphazoperiindenones by staudinger reaction

Full text of DOI:10.1134/S107036320912024X

ISSN 1070-3632, Russian Journal of General Chemistry, 2009, Vol. 79, No. 12, pp. 2698–2699. © Pleiades Publishing, Ltd., 2009.
Original Russian Text © S.P. Belov, I.V. Komlev, S.V. Kuznetsov, E.E. Nifant’ev, 2009, published in Zhurnal Obshchei Khimii, 2009, Vol. 79, No. 12,
pp. 2061–2062.
LETTERS
TO THE EDITOR
Synthesis of Triphenylphosphazoperiindenones
by Staudinger Reaction
S. P. Belov, I. V. Komlev, S. V. Kuznetsov, and E. E. Nifant’ev
Moscow Pedagogical State University, Nesvizhskii per. 3, Moscow, 119021 Russia
e-mail: chemdept@mtu-net.ru
Received June 19, 2008
DOI: 10.1134/S107036320912024X
We have reported earlier [1] on the synthesis of
new iminophosphorane dyes on the basis of amino
derivatives of phenalenone abd benzanthrone along the
schemes of Appel and Kirsanov reactions. The
compounds obtained are substances with intensive
luminescence, and some of them are promising as dyes
for quantum electronics.
Synthesis of IIa was carried out from the
corresponding 3-hydroxyphenalenone by the procedure
close to that described in [4].
The following systems were used for thin layer
chromatography: chloroform–ethanol, 10:1 (1), chloro-
form–acetone, 331:169 (2) and benzene–dioxane,
88:12 (3). IR spectra were registered on a Fourier
spectrometer FSM-1201, the 31P NMR spectra were
registered on a Bruker WO-80SY instrument with
operating frequency 32.4 MHz, relative to 85% H3PO4.
This communication reports on the alternative
pathway to the triphenylphosphazo compounds on the
basis of periindenones by the method of Staudinger [2].
Initial 6-aminophenalenone (Ia), 3-amino-2-phenyl-
phenalenone (IIa), and 3-aminobenzanthrone (IIIa)
were transformed into the corresponding azido-
derivatives Ib–IIIb by the procedure resembling that
described in [3], and then under mild conditions they
were brought into the reaction with triphenyl-
phosphine. The scheme below shows these trans-
formations by the example of compound Ia.
6-Azido-1H-phenalen-1-one (Ib). A suspension of
1.95 g (0.01 mol) of 6-aminopenalenone and 4 ml
(0.07 mol) of conc. H2SO4 in 10 ml of acetic acid at
stirring and cooling to –5°C was treated with a solution
of 0.76 g (0.07 mol) of sodium nitrite in 5 ml of water.
The stirring was continued for 5 min and then a
solution of 0.25 g (0.04 mol) of sodium azide in 5 ml
of water was added dropwise, and the mixture was
stirred for 2 h at cooling. Then 25 ml of cold water was
added, the precipitate was filtered off, washed with
water to neutral reaction, and dried in a vacuum. The
product was purified by chromatography on silica gel
(eluent chloroform), the process of separation was
monitored by TLC. After removing the solvent, yellow
crystals were obtained, mp 170–172°C. IR spectrum
(KBr): 2110 cm–1 (N3). Yield 1.48 g (72%), Rf 0.78 (1),
0.86 (2), 0.57 (3). Found, %: N 18.78, 18.41.
C13H7N3O. Calculated, %: N 18.99.
NH2
N3
H2SO4
CH3COOH
NaN3
O
O
Ib
Iа
N
PPh3
PPh3
Other azides were prepared similarly to Ib (com-
pound, yield, %, mp, Rf): IIb, 78, 168–169°C (aqueous
alcohol), 0.78 (1), 0.64 (2), 0.73 (3); IIIb, 74, – , 0.78 (1),
0.56 (2), 0.93 (3).
СH2Cl2
O
Ic
2698

SYNTHESIS OF TRIPHENYLPHOSPHAZOPERIINDENONES
2699
6-Triphenylphosphazo-1H-phenalen-1-one (Ic).
To a solution of 1.11 g (5 mmol) of azide Ib in 25 ml
of methylene chloride was added dropwise at stirring
1.5 g (5.7 mmol) of triphenylphosphine in 25 ml of
methylene chloride. The mixture was heated under
reflux for 1 h, then the solvent was removed in a
vacuum and the residue was heated with 40 ml of
hexane for removing triphenylphosphine excess. The
crude product was chromatographed on silica gel
(eluent chloroform). Cherry-red crystals, yield 1.78 g
(78%), mp 155–156°C. 31P NMR spectrum, δP
8.25 ppm (ethanol), Rf 0.72 (1), 0.83 (2), 0.45 (3).
Found, %: C 80.32, 80.58; H 4.35, 4.46; P 6.23, 6.31;
N 2.96, 2.73. C31H22NOP. Calculated, %: C 81.74; H
4.87; P 6.8; N 3.08.
registered, in the 31P NMR spectra of imines Ic–IIIc
typical singlet signals appeared in the region of 7–9 ppm.
We failed to carry out similar sequence of
transformations for 3-amino-1-phenalenone IVa. This
is consistent with the data of [4] mentioning that this
compound like many other β-dicarbonyl compounds
[5] do not form diazo compounds in the reaction with
sodium nitrite.
REFERENCES
1. Nifant’ev, E.E., Belov, S.P., Komlev, I.V., Petukhov, V.A.,
Semenov, M.A., Mezentseva, G.A., Tavrizova, M.A.,
and Ponomareva, O.V., Zh. Obshch. Khim., 2008, vol. 78,
no. 3, p. 400.
2. Staudinger, H. and Hauser, E., Helv. Chim. Acta., 1921,
Under analogous conditions were obtained other
phosphazo compounds (compound, yield, %, mp, Rf):
IIc, 69, 154–155°C, 0.52 (1), 0.82 (2), 0.48 (3); IIIc,
74, 139–141°C, 0.48 (1), 0.72 (2), 0.44 (3).
vol. 4, no. 6, p. 861.
3. Sato, M., Nakayama, M., and Ueno, T., Chem. Pharm.
Bull., 1984, vol. 32, no. 10, p. 3226.
4. Solodar’, S.L. and Kochkin, V.A., Zh. Org. Khim.,
1980, vol. 16, no. 10, p. 2123.
5. Curtin, D.Y., Kampmaier, J.A., and Farmer, M.L., J. Am.
Chem. Soc., 1965, vol. 87, no. 4, p. 874.
All the synthesized compounds showed satisfactory
elemental analyses. In the IR spectra of azides Ib–IIIb
a strong absorption in the region of 2100 cm–1 (N3) is
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 79 No. 12 2009