Formylation and acylation of naphthalen-1-ol in the system 1,3,5-triazine-polyphosphoric acid

Full text of DOI:10.1134/s1070428008010247

ISSN 1070-4280, Russian Journal of Organic Chemistry, 2008, Vol. 44, No. 1, pp. 151–152. © Pleiades Publishing, Ltd., 2008.
Original Russian Text © A.V. Aksenov, I.V. Aksenova, A.A. Zamorkin, I.V. Borovlev, 2008, published in Zhurnal Organicheskoi Khimii, 2008, Vol. 44, No. 1,
pp. 152–153.
SHORT
COMMUNICATIONS
Formylation and Acylation of Naphthalen-1-ol
in the System 1,3,5-Triazine–Polyphosphoric Acid
A. V. Aksenov, I. V. Aksenova, A. A. Zamorkin, and I. V. Borovlev
Stavropol State University, ul. Pushkina 1a, Stavropol, 355009 Russia
e-mail: k-biochem-org@stavsu.ru
Received June 25, 2007
DOI: 10.1134/S1070428008010247
We previously showed that the system 1,3,5-tri-
azine–polyphosphoric acid (PPA) acts as an effective
formylating and acylating agent toward perimidine
[1, 2]. In the present communication we report on the
reaction of 1,3,5-triazines Ia–Ic with naphthalen-1-ol
(II) in PPA. Polyphosphoric acid containing 86% of
P2O5 was prepared according to the procedure de-
scribed in [3]. When a mixture of compound II and tri-
azine Ia–Ic was heated in polyphosphoric acid, we ob-
tained the corresponding 4,5-diformyl and 4,5-diacyl
derivatives VIa–VIc.
tion at the 4-position of naphthalen-1-ol by protonated
triazine gives dihydrotriazine derivative III. Opening
of the triazine ring in the latter by the action of acid
yields cationic species IV, intramolecular electrophilic
substitution in IV leads to azaphenalenes V, and the
subsequent hydrolysis results in the formation of com-
pounds VI.
Thus the described reaction ensures regioselective
diacylation (diformylation) at positions 4 and 5 of the
naphthalene ring.
4,5-Diacyl(diformyl)-1-hydroxynaphthalenes
VIa–VIc (general procedure). A mixture of 0.144 g
(1 mmol) of naphthalen-1-ol (II) and 3–4 g of PPA was
Presumably, the process follows the mechanism
shown below. In the first step, electrophilic substitu-
R
OH
N
R
H
N
R
R
NH2
R
N
N
R
N
R
R
N
H
R
H+
H+
N
N
N
N
II
R
N
R
R
OH
OH
IVa–IVc
Ia–Ic
IIIa–IIIc
R
NH
HN
R
O
N
R
O
R
R
H2O
OH
Va–Vc
OH
VIa–VIc
R = H (a), Me (b), Ph (c).
151

AKSENOV et al.
7.47 d (1H, 5-H, J5,6 = 7.1 Hz), 8.53 d (1H, 7-H, J6,7
152
vigorously stirred for 1 h at 60–65°C, 1.5 mmol of
triazine Ia–Ic was added, and the mixture was stirred
for 3 h at 60–65°C in the synthesis of VIa, for 3 h at
85–90°C in the synthesis of VIb, or for 4 h at 110–
115°C in the synthesis of VIc. The mixture was
cooled, poured into 30 ml of cold water under stirring,
made alkaline by adding a solution of ammonia, and
extracted with ethyl acetate (50×3 ml). The extract was
evaporated, and the residue was purified by chroma-
tography using ethyl acetate as eluent.
=
8.1 Hz). Found, %: C 73.79; H 5.22. C14H12O3. Calcu-
lated, %: C 73.67; H 5.30.
4,5-Dibenzoylnaphthalen-4-ol (VIc). Yield 0.19 g
(54%), yellow crystals, mp 172–174°C (from octane),
1
Rf 0.72. H NMR spectrum (CDCl3), δ, ppm: 6.68 d
(1H, 3-H, J2, 3 = 9.2 Hz), 6.93 d (1H, 2-H, J2, 3
9.2 Hz), 7.05 br.s (1H, OH), 7.45 d.d (1H, 6-H, J5,6
=
=
7.1, J6, 7 = 8.0 Hz), 7.47 d (1H, 5-H, J5, 6 = 7.1 Hz),
7.56 m (10H, C6H5), 8.58 d (1H, 7-H, J6,7 = 8.0 Hz).
Found, %: C 81.92; H 4.52. C24H16O3. Calculated, %:
C 81.80; H 4.58.
4-Hydroxynaphthalene-1,8-dicarbaldehyde
(VIa). Yield 0.058 g (29%), yellow crystals, mp 172–
174°C (from octane), Rf 0.46. H NMR spectrum
(CDCl3), δ, ppm: 7.46 d (1H, 3-H, J2,3 = 9.2 Hz),
7.71 d.d (1H, 6-H, J5,6 = 7.1, J6,7 = 8.1 Hz), 8.04 d
1
1
The H NMR spectra were measured on a Bruker
WP-200 spectrometer (200 MHz) relative to tetrameth-
ylsilane as internal reference. The progress of reactions
and the purity of products were monitored by TLC on
Silufol UV-254 plates using ethyl acetate as eluent.
(1H, 5-H, J5,6 = 7.1 Hz), 8.28 d (1H, 2-H, J2,3
=
9.2 Hz), 9.14 d (1H, 7-H, J6,7 = 8.1 Hz), 10.26 s (1H,
CHO), 12.2 br.s (1H, OH), 12.67 s (1H, CHO). Found,
%: C 72.16; H 3.98. C12H8O3. Calculated, %: C 72.00;
H 4.03.
REFERENCES
4,5-Diacetylnaphthalen-1-ol (VIb). Yield 0.082 g
1. Aksenov, A.V., Borovlev, I.V., Lyakhovnenko, A.S., and
Aksenova, I.V., Russ. J. Org. Chem., 2007, vol. 43,
p. 1579.
(36%), yellow crystals, mp 172–174°C (from octane),
1
Rf 0.51. H NMR spectrum (CDCl3), δ, ppm: 2.83 s
2. Aksenov, A.V., Borovlev, I.V., Lyakhovnenko, A.S., and
(3H, Me), 2.91 s (3H, Me), 6.79 d (1H, 3-H, J2, 3
9.3 Hz), 7.18 d (1H, 2-H, J2,3 = 9.3 Hz), 7.03 br.s (1H,
OH), 7.46 d.d (1H, 6-H, J5, 6 = 7.1, J6, 7 = 8.1 Hz),
=
Aksenova, I.V., Khim. Geterotsikl. Soedin., 2007, p. 629.
3. Uhlig, F., Angew. Chem., 1954, vol. 66, p. 435.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 44 No. 1 2008