Three-component condensation of 2,4-diaminoselenazole with aldehydes and meldrum's acid: Synthesis of 7-aryl(alkyl)-substituted 2-amino-6,7-dihydro-4H- selenazolo[4,5-b]pyridin-5-ones

Article abstract of DOI:10.1080/10426501003773753

A method for the synthesis of 7-aryl(alkyl)-substituted 2-amino-6,7-dihydro-4H-selenazolo [4,5-b]pyridin-5-ones 5 based on three-component condensation of in situ-generated 2,4-diaminoselenazole 7 with aromatic (aliphatic) aldehydes 9 and Meldrum's acid 10 was developed. Copyright Taylor & Francis Group.

Full text of DOI:10.1080/10426501003773753

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Phosphorus, Sulfur, and Silicon and the
Related Elements
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Three-Component Condensation of
2,4-Diaminoselenazole with Aldehydes
and Meldrum’s Acid: Synthesis of 7-
Aryl(alkyl)-Substituted 2-Amino-6,7-
dihydro-4H-selenazolo[4,5-b]pyridin-5-
ones
Arkady A. Dudinov a , Andrey N. Komogortsev a , Boris V. Lichitsky a
& Mikhail M. Krayushkin a
a N. D. Zelinsky Institute of Organic Chemistry, Russian Academy of
Sciences, Moscow, Russian Federation
Version of record first published: 27 May 2010
To cite this article: Arkady A. Dudinov, Andrey N. Komogortsev, Boris V. Lichitsky & Mikhail M.
Krayushkin (2010): Three-Component Condensation of 2,4-Diaminoselenazole with Aldehydes and
Meldrum’s Acid: Synthesis of 7-Aryl(alkyl)-Substituted 2-Amino-6,7-dihydro-4H-selenazolo[4,5-
b]pyridin-5-ones, Phosphorus, Sulfur, and Silicon and the Related Elements, 185:5-6, 1230-1234
To link to this article: http://dx.doi.org/10.1080/10426501003773753
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Phosphorus, Sulfur, and Silicon, 185:1230–1234, 2010
Copyright ꢀC Taylor & Francis Group, LLC
ISSN: 1042-6507 print / 1563-5325 online
DOI: 10.1080/10426501003773753
THREE-COMPONENT CONDENSATION OF
2,4-DIAMINOSELENAZOLE WITH ALDEHYDES
AND MELDRUM’S ACID: SYNTHESIS OF
7-ARYL(ALKYL)-SUBSTITUTED 2-AMINO-6,7-DIHYDRO-
4H-SELENAZOLO[4,5-b]PYRIDIN-5-ONES
Arkady A. Dudinov, Andrey N. Komogortsev,
Boris V. Lichitsky, and Mikhail M. Krayushkin
N. D. Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences,
Moscow, Russian Federation
A method for the synthesis of 7-aryl(alkyl)-substituted 2-amino-6,7-dihydro-4H-selenazolo
[4,5-b]pyridin-5-ones 5 based on three-component condensation of in situ–generated 2,4-
diaminoselenazole 7 with aromatic (aliphatic) aldehydes 9 and Meldrum’s acid 10 was
developed.
Keywords 7-Aryl(alkyl)-substituted 2-amino-6,7-dihydro-4H-selenazolo[4,5-b]pyridin-5-
ones; 2,4-diaminoselenazole; Meldrum’s acid; three-component condensation
INTRODUCTION
Previously, we developed a convenient method for the preparation of 7-aryl(alkyl)-
substituted 2-amino-6,7-dihydro-4H-thiazolo[4,5-b]pyridin-5-ones 1 based on a three-
component condensation of aromatic or aliphatic aldehydes 2, Meldrum’s acid 3, and
unstable 2,4-diaminothiazoles generated in situ from the corresponding stable 2-amino-4-
iminothiazolidinium hydrochlorides 41 (Scheme 1).
RESULTS AND DISCUSSION
The purpose of this study was to extend the proposed approach to the synthesis
of unknown 7-aryl(alkyl)-substituted 2-amino-6,7-dihydro-4H-selenazolo[4,5-b]pyridin-
5-ones 5 (Scheme 2).
4-Imino-4-aminoselenazolidine hydrochloride 6 was prepared by a known method.2,3
It should be emphasized that the use of 2,4-diaminoselenazole 7 in a free state is almost
impossible due to its low stability. In addition, diamine occurs in solution in equilibrium
Received 23 November 2008; accepted 24 November 2008.
Dedicated to Professor Naomichi Furukawa on the occasion of his 70th birthday.
Address correspondence to Mikhail M. Krayushkin, N. D. Zelinsky Institute of Organic Chemistry, Russian
Academy of Sciences, Leninsky prosp 47, 119991 Moscow, Russian Federation. E-mail: mkray@ioc.ac.ru
1230

SYNTHESIS OF 4H-SELENAZOLO[4,5-b]PYRIDIN-5-ONES
1231
-
Cl
+
NH2
O
N
O
O
O
O
N
N
S
N
ArCHO
AcONa
+
+
+
R
EtOH
R
S
O
Ar
3
4
2
1
Scheme 1
H
-
Cl
+
NH2
O
N
N
O
O
N
O
NH2
O
O
N
Se
R'CHO
+
AcONa
EtOH
+
NH2
Se
R'
5 a-j
6
10
9
R’ = 3-Cl-C6H4 (a); 3-F-C6H4 (b); 3,4-methylenedioxy-C6H3 (c); 4-MeO-C6H4 (d); 3-MeO-C6H4
(e); 3,4,5- (MeO)3C6H2 (f); 3-CF3-C6H4 (g); 3-OH-4-MeO-C6H3 (h); 4-Cl-C6H4 (i);
(CH3)2CHCH2 (j).
Scheme 2
with its tautomer, 2-amino-4-iminoselenazolidine;4 the imino form predominates and, in
turn, it can be easily hydrolyzed.
The three-component condensation of compound 6 with aldehydes 2 and Meldrum’s
acid 3 was carried out in refluxing ethanol in the presence of a slight excess of anhydrous
sodium acetate and a catalytic amount of N-methylmorpholine. Presumably, free 2,4-
diaminoselenazole 7 is formed initially in the reaction mixture under the action of sodium
acetate, the process being accompanied by evolution of an equimolar amount of acetic
acid and the arylmethylene Meldrum’s acid derivative 8 (from aldehyde 2 and Meldrum’s
acid 3). This is followed by conjugate Michael addition of 2,4-diaminoselenazole 7 to
the arylmethylene Meldrum’s acid derivative, and subsequent cyclization of the resulting
Michael adduct accompanied by CO2 and acetone elimination (Scheme 3).
The reaction products 5 were crystalline solids; their structures were confirmed by
data of IR and NMR spectroscopy, mass spectrometry, and elemental analysis (Tables I
and II).
EXPERIMENTAL
1
IR spectra were recorded on a Perkin-Elmer 557 instrument (KBr). H and 13C
NMR spectra were measured on Bruker Avance II 300 and Bruker DRX-500 instruments
in DMSO-d6. Mass spectra were run on a Finnigan MAT INCOS 50 mass spectrometer
(direct injection, electron impact, 70 eV). Melting points were measured on a Boetius hot
stage and were not corrected. The reactions were monitored, and the product purity was
checked by TLC (Merck Silica gel 60 F254 plates, elution with ethyl acetate–hexane).

1232
A. A. DUDINOV ET AL.
O
Ar
NH2
N
O
+
H2N
Se
N
O
O
7
8
NH2
NH
O
O
O
N
O
H2N
O
H2N
Se
Se
O
Ar
Ar
O
O
O
H
N
N
H2N
Se
Ar
5
Scheme 3
Table I Melting points, yields, elemental analysis, and mass spectrometry data for compounds 5
Calculated/Found (%)
Molecular formula
Compound
Mp/ ◦C
Yield (%)
C
H
N
MS, m+/z
5a
5b
5c
5d
5e
5f
221–223 (dec.)
>250 (dec.)
73
60
68
74
80
58
38
53
76
44
44.13
44.30
46.47
46.31
46.44
46.60
48.46
48.28
48.46
48.30
47.13
47.30
43.35
43.17
46.17
46.34
44.13
44.30
44.12
43.95
3.09
3.20
3.25
3.33
3.30
3.39
4.07
4.15
4.07
4.14
4.48
4.56
2.80
2.71
3.87
3.79
3.09
3.18
5.55
5.65
12.86
12.79
13.55
13.48
12.50
12.43
13.04
13.12
13.04
13.11
13.04
13.11
11.67
11.74
12.42
12.50
12.86
12.93
15.44
15.52
C12H10ClN3OSe
327
C
12H10FN3OSe
310
227–229 (dec.)
219–221 (dec.)
217–219 (dec.)
210–212 (dec.)
>250 (dec.)
C
C
C
C
13H11N3O3Se
336
13H13N3O2Se
322
13H13N3O2Se
322
15H17N3O4Se
382
5g
5h
5i
C
13H10F3N3OSe
360
209–211 (dec.)
221–224 (dec.)
223–225 (dec.)
C13H13N3O3Se
338
C12H10ClN3OSe
327
5j
C
10H15N3OSe
272

1233

1234
A. A. DUDINOV ET AL.
7-Aryl(alkyl)-2-amino-6,7-dihydro-4H-selenazolo[4,5-b]pyridin-5-ones
(5): General Procedure
A mixture of 2-amino-4-iminoselenazolidine hydrochloride 2 (0.60 g, 3 mmol),
Meldrum’s acid (0.49 g, 3.4 mmol), anhydrous sodium acetate (0.25 g, 3.1 mmol), N-
methylmorpholine (0.06 g, 0.6 mmol), and the appropriate aldehyde (3 mmol) in ethanol (8
mL) was refluxed for 4 h. The reaction mixture was cooled, and the precipitate was filtered
off and washed on the filter with ethanol (3 × 5 mL) and water (3 × 5 mL).
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1740 (2008) (English edition).
2. W. Davies, J. A. Maclaren, and L. R. Wilkinson, J. Chem. Soc., 3491 (1950).
3. K. Geisler, W.-D. Pfeiffer, A. Kuenzler, H. Below, E. Bulka, and P. Langer, Synthesis, 6, 875
(2004).
4. S. Angelova, V. Enchev, N. Markova, P. Denkova, and K. Kostova, J. Mol. Struct., 711(1–3), 201
(2004).