Formylation of perimidine derivatives in a system 1,3,5-triazine- polyphosphoric acid

Full text of DOI:10.1134/S1070428007100351

ISSN 1070-4280, Russian Journal of Organic Chemistry, 2007, Vol. 43, No. 10, pp. 1579−1580. © Pleiades Publishing, Ltd., 2007.
Original Russian Text © A.V. Aksenov, I.V. Borovlev, A.S. Lyakhovnenko, I.V. Aksenova, 2007, published in Zhurnal Organicheskoi Khimii, 2007,
Vol. 43, No. 10, p. 1581.
SHORT
COMMUNICATIONS
Formylation of Perimidine Derivatives in a System
1,3,5-Triazine−Polyphosphoric Acid
A. V. Aksenov, I. V. Borovlev, A. S. Lyakhovnenko, and I. V. Aksenova
Stavropol’ State University, Stavropol’, 355009 Russia
e-mail: k-biochem-org@stavsu.ru
Received April 2, 2007
DOI: 10.1134/S1070428007100351
Formerly [1] formylation of perimidines I was report-
ed to be performed by Vilsmeier reaction, but the yield
of the corresponding perimidine-6(7)-carbaldehydes IV
was from 1 to 7%. We developed a new method of com-
pounds I formylation based on their reaction with 1,3,5-
triazine (II) (see Scheme).
4. g of PPA was stirred at 55–60°C for 1 h. Then the
reaction mixture was poured into 50 ml of water,
alkalinized with ammonia solution, and extracted with
ethyl acetate (3 × 80 ml), and the extract was evaporated.
Perimidine-6(7)-carbaldehyde (IVa). Yield 0.178 g
(91%), mp 212–214°C (from acetic acid) (212–214°C
The application of compound II in the role of
formylating agent is well known [2]. In the classical
version the reaction is carried out without catalyst or in
the presence of Lewis acids. We demonstrated that under
these conditions the perimidine formylation did not occur.
Therefore another combination of reagents was used as
formylating agent: 3-fold excess of 1,3,5-triazine II in
80% polyphosphoric acid (PPA) at 55–60°C. The yield
of aldehydes IV under these conditions was 83–91%.
1
[1]). H NMR spectrum (CDCl3), δ, ppm: 6.57 br.s (1H,
H9), 6.91 br.s (1H, H4), 7.50 s (1H, H2), 7.54 d.d (1H,
H8, J87 8.9, J89 8.3 Hz ), 7.68 d (1H, H5, J54 8.1 Hz),
8.77 d.d (1H, H7, J78 8.9 Hz), 9.97 s (1H, CHO). Found,
%: C 73.31; H 4.01; N 14.03. C12H8N2O. Calculated, %:
C 73.45; H 4.11; N 14.28.
2-Methylperimidine-6(7)-carbaldehyde (IVb).
Yield 0.187 g (89%), mp 196–198°C (from octane).
1
(196–198°C [1]). H NMR spectrum (CDCl3), δ, ppm:
Formylation of perimidines in a system 1,3,5-
triazine−PPA. General procedure.Amixture of 1 mmol
of perimidine I, 0.243 g (3 mmol) of 1,3,5-triazine, and
2.28 s (3H, CH3), 6.57 br.d (1H, H4, J45 7.7 Hz),
6.84 br.d (1H, H9, J98 7.9 Hz), 7.51 d.d (1H, H8, J87 8.7,
Scheme.
R
H
N
H
N
R
R
R
H
H
H
H
N
N
N
N
N
N
H2O
N
N
PPA
+
N
N
N
N
CHO
CHO
IVа IVc, 84 91%
_
_
_
_
II
Iа Ic
IIIа IIIc
R = H (a), Me (b), Ph (c).
1579

AKSENOV et al.
1580
J89 7.9 Hz ), 7.67 d (1H, H5, J54 7.7 Hz), 8.72 d (1H, H7,
J78 8.7 Hz), 9.95 s (1H, CHO). Found, %: C 74.05;
H 4.50; N 13.19. C13H20N2O. Calculated, %: C 74.26;
H 4.80; N 13.33.
NMR spectra were registered on a spectrometer
Bruker WP-200 (200 ΜHz) using TMS as internal
reference. The reaction progress was monitored and the
homogeneity of compounds synthesized was checked by
TLC on Silufol UV-254 plates, eluent ethyl acetate.
2-Phenylperimidine-6(7)-carbaldehyde (IVc).
Yield 0.226 g (83%), mp 238–239°C (from benzene).
1H NMR spectrum (CDCl3), δ, ppm: 6.52 br.s (1H, H9),
REFERENCES
6.82 br.s (1H, H4), 7.50 s (1H, H2), 7.55 m (4H, H8,
1. Filatova, E.A., Borovlev, I.V., Pozharskii, A.F., Goncha-
rov, V.I., and Demidov, O.P., Khim. Geterotsikl. Soedin.,
2006, p. 104.
2. Fieser, L. F. and Fieser, M., Reagents for Organic Synthesis,
New York: Wiley-Intersci., 1972.
mp
H
, 7.72 d (1H, H5, J54 8.1 Hz), 8.93 d (2H, HPoh, J54
Ph
7.2 Hz), 8.78 d.d (1H, H7, J78 8.9 Hz), 10.03 s (1H,
6-CHO). Found, %: C 79.22; H 4.49; N 10.34.
C18H12N2O. Calculated, %: C 79.40; H 4.44; N 10.29.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 43 No. 10 2007