One-pot synthesis of 1,2,4-triazines

Article abstract of DOI:10.1081/SCC-120004086

1,2,4-Triazines have been prepared from the one-pot condensation reaction of acid hydrazide (1), ammonium acetate and dicarbonyl compounds (2) on the surface of silica gel in the presence of triethylamine under microwave irradiation.

Full text of DOI:10.1081/SCC-120004086

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ONE-POT SYNTHESIS OF 1,2,4-TRIAZINES
a
a
Shahnaz Rostamizadeh & Kamran Sadeghi
a
Department of Chemistry , K. N. Toosi University of Technology , P.O. Box 15875-4416,
Tehran, Iran
Published online: 17 Oct 2011.
To cite this article: Shahnaz Rostamizadeh & Kamran Sadeghi (2002) ONE-POT SYNTHESIS OF 1,2,4-TRIAZINES, Synthetic
Communications: An International Journal for Rapid Communication of Synthetic Organic Chemistry, 32:12, 1899-1902, DOI:
10.1081/SCC-120004086
To link to this article: http://dx.doi.org/10.1081/SCC-120004086
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SYNTHETIC COMMUNICATIONS, 32(12), 1899–1902 (2002)
ONE-POT SYNTHESIS OF
1,2,4-TRIAZINES
Shahnaz Rostamizadeh* and Kamran Sadeghi
Department of Chemistry, K. N. Toosi University of
Technology, P.O. Box 15875-4416 Tehran, Iran
ABSTRACT
1,2,4-Triazines have been prepared from the one-pot conden-
sation reaction of acid hydrazide (1), ammonium acetate and
dicarbonyl compounds (2) on the surface of silica gel in the
presence of triethylamine under microwave irradiation.
In recent years there has been considerable interest in the use of dry
media as nonconventional reaction medium for the preparation of organic
[1]
compounds.
Microwave irradiation has become a very useful tool in organic syn-
thesis and a great number of classical organic reactions have been success-
[
2]
fully carried out under microwave heating technique.
,2,4-Triazines are a representative class of heterocyclic compounds
with a wide range of interesting properties which are used in medicine and
1
[3–6]
agriculture. These compounds have been prepared by different methods:
a) Condensation of acid hydrazides with benzil in acetic acid containing
*
Corresponding author.
1
899
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1
900
ROSTAMIZADEH AND SADEGHI
ammonium acetate to give 5,6-diphenyl-1,2,4-triazine with various aromatic
[
7]
and heterocyclic groups attached at 3 position. b) Cyclization of aliphatic,
aromatic and heterocyclic acid hydrazide with 1,2-diketone monoacylhydra-
[
8,9]
zones in alcoholic ammonia under pressure.
hydrazones of aromatic (but not aliphatic) 1,2-diketones with formation
c) Condensation of mono-
[
10]
to give 5,6-disubstituted 1,2,4-triazines.
of acid hydrazide and ꢀ-halo acetophenone in the presence of NaOAc
d) Condensation reaction
[11,12]
or AgOAc. e) Reaction of ꢀ-diketones with amidrazones and
S-methylthiosemicarbazide were also reported in the literature.
[
14–16]
In this work, 1,2,4-triazines (3a–i) were obtained from the one-
pot Condensation reaction of acid hydrazides (1), ammonium ace-
tate and dicarbonyl compounds (2) on the surface of silica gel in
the presence of triethylamine under microwave irradiation (Scheme 1,
Table 1).
High yield, short reaction time, products and easy work up are advan-
tages of this procedure in comparison to other methods. The data for the
synthesis of 1,2,4-triazines are shown in Table 2.
Scheme 1.
Table 1. Cyclization of ꢀ-Diketone with
Acid Hydrazide
Product
R
1
R
2
R
3
3
3
3
3
3
3
3
3
3
a
b
c
d
e
f
g
h
i
Ph
Ph
Ph
Ph
Et
Ph
Et
Me
Ph
Me
Ph
Ph
Et
Me
Ph
Me
Ph
Ph
Et
4-MeO-C H
6
4
4-MeO-C H
6
4
4-Me-C
Me
Me
6 4
H
Me
Me
Me

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ONE-POT SYNTHESIS OF 1,2,4-TRIAZINES
1901
Table 2.
Time
(min)
Yield
(%)
M.P.
ꢀ
Lit. M.P.
ꢀ
Product
( C)
( C)
Ref.
3
3
3
3
3
3
3
3
3
a
b
c
d
e
f
g
h
i
593
11
11
7
12
7
7
12
7
146–147
88.5
74
148
12
56
70–81
56
82
8
8
20
71
73.5142–144
158–159
159–160
144–146
138–140 138–140
20
78
74
61
63
19
19
8
89–91
18–21
48–51
92
19
49–51
8
EXPERIMENTAL
All products are known compounds and were characterized by
comparision of their spectral and physical data with those of known
samples.
Melting points were taken on an Electrothermal 9100 apparatus. IR
spectra were recorded with a Shimadzu IR-480 spectrometer (KBr). The
1
H-NMR spectra were determined in chloroform-d on a FT-NMR Bruker
AC-80 (80 MHz).
Microwave irradiation was carried out using commercial microwave
oven Moulinex (2735A). Merck silica gel 60GF254 was used for analytical
and preparative TLC. Acid hydrazides were prepared according to the lit-
[17,18]
erature method.
General Procedure for Synthesis of
,5,6-Trisubstituted-1,2,4-triazines
3
A mixture of acid hydrazide (2 mmol), ꢀ-diketone (2 mmol) and silica
gel (2 g) was well ground with a pestle and introduced to microwave irradia-
tion in an open pyrex beaker for appropriate time (Table 1). After complete
conversion as indicated by TLC, the mixture was extracted with petroleum
ether (3 Â 50 ml) and washed with water (3 Â 50 ml). Then the solvent was
evaporated in vacuum and the product was purified by chromatography on
a short silica gel column with proper solvent or recrystallized directly from
appropriate solvent.

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902
ROSTAMIZADEH AND SADEGHI
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Received in the Netherlands June 27, 2001