Acylation of perimidine with 1,3,5-triazines in polyphosphoric acid [12]

Full text of DOI:10.1007/s10593-007-0085-y

Chemistry of Heterocyclic Compounds, Vol. 43, No. 4, 2007
ACYLATION OF PERIMIDINE WITH 1,3,5-TRIAZINES
IN POLYPHOSPHORIC ACID
A.V. Aksenov, I. V. Borovlev, A. S. Lyakhovnenko, and I. V. Aksenova
Keywords: perimidine, polyphosphoric acid (PPK). 1,3,5-triazines, acylation, formylation.
The use of 1,3,5-triazines 2 as formylating agents in the presence of a Lewis acid has been reported [1].
The use of substituted 1,3,5-triazines as acylating agent was not known. We have shown that formylation of
perimidine 1 does not occur under these conditions. Formylation has been successfully carried out with a three-
fold excess of 1,3,5-triazine 2 in 80% PPA (4 g per mmol of perimidine) at 55-60°C for 1 h. The yield of
perimidine-6(7) carbaldehyde (3a) was 91% under these conditions. The compound was separated by pouring
the reaction mixture into water with subsequent basification of the solution with ammonia and extraction with
ethyl acetate. Compound 3a was previously successfully obtained in a yield of less than 10% by the Vilsmeier
reaction [2]. We have shown that by using substituted 1,3,5-triazine ketones 3b,c can be obtained. In this case
the reaction time is 2.5 h at a temperature of 80 and 110°C respectively.
R
N
NH
PPA
N
N
+
R
N
R
2a–c
1
N
NH
N
NH
N
HN
H2O
R
N
HN
O
R
R
O
3a–c
R
N
R
2, 3 a R = H, b R = Me, c R = Ph
Perimidine-6(7)-carbaldehyde (3a). Yield 91%; mp 212-214°C ( from acetic acid) (mp 212-214°C [2]).
1
A mixed melting point with a known sample gave no depression of the melting point. The H NMR spectrum
coincided with that cited in [2].
6(7)-Acetylperimidine (3b). Yield 78%; mp 221-222°C (from aqueous ethanol) (mp 221-222°C [3]). A
mixed melting point with a known sample gave no depression of the melting point.
__________________________________________________________________________________________
Stavropol State University, Stavropol 355009, Russia; e-mail: k-biochem-org@stavsu.ru. Translated
from Khimiya Geterotsiklicheskikh Soedinenii, No. 4, 629-630, April, 2007. Original article submitted April 2,
2007
0009-3122/07/4304-0527©2007 Springer Science+Business Media, Inc.
527

6(7)-Benzoylperimidine (3c). Yield 64%; mp 227-229°C (from benzene) (mp 227-229°C [3]). A mixed
melting point with a known sample gave no depression of the melting point.
REFERENCES
1.
2.
3.
L. Fieser and M. Fieser, Reagents for Organic Synthesis. [Russian translation]. Mir, Moscow, Vol. 5,
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Soed., 104 (2006). [Chem. Heterocycl. Comp., 42, 92 (2006)].
A. F. Pozharskii, I. V. Borovlev, and I. S. Kashparov, Khim. Geterotsikl. Soedin., 543 (1975). [Chem.
Heterocycl. Comp., 11, 480 (1975)].
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