Behavior of 2-phenyl-2,3-dihydro-1H-1,3-phenalenediones in formylation by Vilsmeier - Haak procedure

Full text of DOI:10.1023/A:1020938601869

Russian Journal of Organic Chemistry, Vol. 38, No. 8, 2002, pp. 1222 1223. From Zhurnal Organicheskoi Khimii, Vol. 38, No. 8, 2002,
pp. 1273 1274.
Original English Text Copyright
2002 by Artyukhova, Patsenker, Baumer, Musatov.
SHORT
COMMUNICATIONS
Behavior of 2-Phenyl-2,3-dihydro-1H-1,3-phenalenediones
in Formylation by Vilsmeier Haak Procedure
E. E. Artyukhova, L. D. Patsenker, V. N. Baumer,
and V. I. Musatov
Institute of Single Crystals, National Academy of Sciences of the Ukraine, Kharkov, 61001 Ukraine
Received February 8, 2002
We discovered formerly [1, 2] that at heating
4-dimethylamino-substituted imines and anhydride of
naphthalic acid Ia c with POCl3 and DMF (under
conditions of Vilsmeier Haak reaction) instead of
expected 3-formyl derivatives arose quinazolinium
salts IIa c.
R = H (III, VI), Cl (IV, VIIa, b).
phenalenone (VIII). Apparently the reaction proceeds
via iminium salt A formation, and the latter is
hydrolyzed at treating the reaction mixture with
water.
X = NAr (a), NMe (b), O (c).
In extension of these investigations we studied the
reaction with Vilsmeier complex of 2-phenyl-2,3-di-
hydro-1H-1,3-phenalenedione (III), and also its
6-chloro (IV) and 6-dimethylamino (V) derivatives.
It was found that compound III readily reacted
with POCl3 and DMF at 20 C and within 40 min was
completely converted into 3-chloro-2-phenyl-1H-1-
phenalenone (VI). The chlorine-substituted compound
IV began to react at 35 C and within 25 min formed
an equimolar mixture of isomeric 3,7-dichloro-
(VIIa) and 3,6-dichloro- (VIIb) 2-phenyl-1H-1-
phenalenones.
However the dimethylamino-substituted compound
V under similar conditions (35 C, 30 min) un-
expectedly furnished 4,6-dichloro-5-phenyl-1H-1-
1070-4280/02/3808-1222$27.00 2002 MAIK Nauka/Interperiodica

BEHAVIOR OF 2-PHENYL-2,3-DIHYDRO-1H-1,3-PHENALENEDIONES
1223
The structure of all compounds synthesized III
1
VIII was confirmed by H NMR spectra, and that of
phenalenone VIII also by X-ray diffraction analysis
(see figure).
2-Phenyl-3-chloro-1H-1-phenalenone (VI). Yield
74%, mp 147 147.5 C. 1H NMR spectrum, ( ,
ppm): 8.49 d.d (1H, H9, J1 8.3, J2 1.0 Hz), 8.47 d
(1H, H4, J 8.3 Hz), 8.41 d.d (1H, H7, J1 8.3, J2
1.0 Hz), 8.35 d (1H, H6, J 8.3 Hz), 7.91 t (1H, H5,
J 7.8 Hz), 7.83 t (1H, H8, J 7.8 Hz), 7.31 7.53 m
(5H, arom). Found, %: C 78.41; H 3.67; Cl 12.24.
C19H11ClO. Calculated, %: C 78.49; H 3.79; Cl
12.22.
Spatial structure of phenalenone VIII molecule according
to the data of X-ray diffraction analysis.
2-Phenyl-3,7-dichloro-1H-1-phenalenone (VIIa).
1H NMR spectrum, ( , ppm): 8.66 d (1H, H6, J
8.3 Hz), 8.58 d.d (1H, H4, J1 7.4, J2 1.0 Hz), 8.32 d
(1H, H3, J 8.1 Hz), 8.04 d (1H, H8, J 8.0 Hz),
8.03 d.d (1H, H5, J1 8.0, J2 0.7 Hz), 7.29 7.57 m
(5H arom). Found, %: C 70.10; H 3.07; Cl 21.84.
C19H10Cl2O. Calculated, %: C 70.15; H 3.08; Cl
21.85.
The reaction progress was monitored and the
purity of compounds obtained was checked by TLC
on Sorbfil PTLC-AF-A-UV plates, eluent for phena-
lones VI and VIIa, b hexane benzene, 2: 1, for
1
phenalone VIII chloroform ethanol, 20:1. H NMR
spectra were registered on spectrometer Varian
Mercury-VX-200 (operating frequency 200 MHz)
from solutions in DMSO-d6, internal reference TMS.
2-Phenyl-3,6-dichloro-1H-1-phenalenone (VIIb).
1H NMR spectrum, ( , ppm): 8.52 d (1H, H7, J
8.1 Hz), 8.48 d (1H, H9, J 7.4 Hz), 8.43 d (1H, H4,
J 8.1 Hz), 7.97 d (1H, H5, J 8.0 Hz), 7.95 t (1H,
H8, J 8.1 Hz), 7.29 7.57 m (5H arom). Found, %:
C 70.10; H 3.07; Cl 21.84. C19H10Cl2O. Calculated,
%: C 70.15; H 3.08; Cl 21.85.
Initial compounds III V were synthesized by
procedures described in [3, 4]. Their melting point
corresponded to the published values.
REFERENCES
5-Phenyl-4,6-dichloro-1H-1-phenalenone (VIII).
1
Yield 78%, mp 273 274 C. H NMR spectrum, ( ,
1. Patsenker, L.D., Yermolenko, I.G., Artyukho-
va, Ye.Ye., Baumer, V.N., and Krasovitskii B.M.,
Tetrahedron, 2000, vol. 56, no. 37, pp. 7319 7323.
2. Patsenker, L.D., Ermolenko, I.G., Artyukhova, E.E.,
and Krasovitskii, B.M., Khim. Geterotsikl. Soed.,
2000, no. 5, pp. 696 697.
3. Kazhoka, Kh.A. and Meirovits, I.A., Izv. Akad. Nauk
LatvSSR, Ser. Khim.. 1984, no. 4, pp. 492 495.
4. Kazhoka, Kh.A. and Meirovits, I.A., Izv. Akad. Nauk
LatvSSR, Ser. Khim., 1985, no. 1, pp. 86 88.
ppm): 8.73 d.d (1H, H9, J1 8.4, J2 1.1 Hz), 8.61 d.d
(1H, H7, J1 8.5, J2 1.1 Hz), 8.30 d (1H, H4, J 10.1
Hz), 8.06 d.d (1H, H8, J1 8.5, J2 1.1 Hz), 7.33
7.68 m (5H arom), 6.83 d (1H, H5, J 10.1 Hz).
Found, %: C 70.01; H 3.01; Cl 21.54. C19H10Cl2O.
Calculated, %: C 70.15; H 3.08; Cl 21.85. Data of
X-ray study: space group P1 at 17 C, a 7.029(1),
b 10.144(2), c 10.310(2)
,
82.38(1) , 81.26(1) ,
80.11(1) , V 711.6(2) , Z 2, R 0.0386.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 38 No. 8 2002