New approaches to pyrimido[4,3-b][1,3,5]selenadiazines

Article abstract of DOI:10.1007/s11172-012-0051-4

The Mannich reactions of (arylmethylidene)(cyano)selenoacetamides with primary amines and formaldehyde gave 3,7-disubstituted 8-R-3,4,7,8-tetrahydro- 2H,6H-pyrimido[4,3-b]-[1,3,5]selenadiazine-9-carbonitriles. Alternatively, these compounds can be obtaine

Full text of DOI:10.1007/s11172-012-0051-4

Russian Chemical Bulletin, International Edition, Vol. 61, No. 2, pp. 366—369, February, 2012
366
New approaches to pyrimido[4,3ꢀb][1,3,5]selenadiazines
K. A. Frolov, V. V. Dotsenko, and S. G. Krivokolysko
Research Laboratory "ChemEx", Vladimir Dal´ EastꢀUkrainian National University,
20a Molodezhnyi kv., 91034 Lugansk, Ukraine.
Fax: +38 (0642) 50 5967. Eꢀmail: ka.frolov@inbox.ru
The Mannich reactions of (arylmethylidene)(cyano)selenoacetamides with primary amines
and formaldehyde gave 3,7ꢀdisubstituted 8ꢀRꢀ3,4,7,8ꢀtetrahydroꢀ2H,6Hꢀpyrimido[4,3ꢀb]ꢀ
[1,3,5]selenadiazineꢀ9ꢀcarbonitriles. Alternatively, these compounds can be obtained by reacꢀ
tions of 4ꢀRꢀ2,6ꢀdiaminoꢀ4Hꢀselenopyranꢀ3,5ꢀdicarbonitriles with primary amines and formꢀ
aldehyde or by multicomponent condensation of an appropriate aldehyde, cyanoselenoacetꢀ
amide, a primary amine, and formaldehyde.
Key words: pyrimido[4,3ꢀb][1,3,5]selenadiazines, the Mannich reaction, recyclization,
4ꢀRꢀ2,6ꢀdiaminoꢀ4Hꢀselenopyranꢀ3,5ꢀdicarbonitriles, aminomethylation.
Scheme 1
Interest in the chemistry of seleniumꢀcontaining heteroꢀ
cycles is largely due to a broad spectrum of their biological
activity.1,2 1,3,5ꢀSelenadiazines are relatively poorly studꢀ
ied. Only a few ways are currently available for constructꢀ
ing the 1,3,5ꢀselenadiazine ring. They include (1) multiꢀ
component reactions between benzylamine, sodium hyꢀ
droselenide, formaldehyde, and aryl isoselenocyanates in
acidic media,3 (2) reactions of 1,3ꢀdichloroꢀ1,3ꢀbisꢀ
(dimethylamino)ꢀ2ꢀazapropenylium chlorides with selenꢀ
amides or selenoureas,4,5 (3) reactions of N,Nꢀdialkylꢀ3ꢀ
arylꢀ3ꢀchloroꢀ2ꢀazapropꢀ1ꢀenylideneammonium perchloꢀ
rate with Nꢀacylselenoureas,6 and (4) recyclization of
1,3,5ꢀoxaselenazines7,8 and a 1,2,4ꢀselenadiazolium salt.9
Nevertheless, the literature provides only one example10
of the synthesis of fused 1,3,5ꢀselenadiazines, while
1,3,5ꢀthiadiazine derivatives are studied much better.11—13
(Arylmethylidene)(cyano)selenoacetamides 1, which are
easily prepared from aromatic aldehydes 2 and cyanoseleꢀ
noacetamide (3),14,15 can serve as convenient starting maꢀ
terials for the synthesis of fused 1,3,5ꢀselenadiazines
(Scheme 1). Earlier, we have found that brief heating of
(cyano)(2ꢀthienylmethylidene)selenoacetamide (1a) with
an excess of aqueous formaldehyde and two equivalents of
primary amine 4 under argon gives the corresponding pyrꢀ
imido[4,3ꢀb][1,3,5]selenadiazines 5 in 38—50% yields (see
Scheme 1, pathway A).10 The goal of the present work was
to obtain novel pyrimido[4,3ꢀb][1,3,5]selenadiazines acꢀ
cording to this method, as well as to study (1) recyclizaꢀ
tion of selenopyrans 6 in their Mannich aminomethylaꢀ
tion and (2) multicomponent cyclocondensation of aldeꢀ
hydes, cyanoselenoacetamide 3, primary amines, and
HCHO as possible routes to compounds of the type 5.
Apart from (cyano)(2ꢀthienylmethylidene)selenoacetꢀ
amide (1a), we successfully used its analog, namely,
i. HCHO, EtOH, t; ii. EtOH, B, t (B is Nꢀmethylmorpholine).
1: R = C4H3S (a), 4ꢀMе2NC6H4 (b)
2: R = C4H3S (a), 4ꢀMе2NC6H4 (b), Ph (c), CH2Me (d), CHMe2 (e)
4: R´ = 4ꢀMeC6H4 (a), CH2Ph (b), 4ꢀFC6H4 (c)
6: R = CHMe2 (a), Ph (b), CH2Me (c), CH2CH2Me (d)
(cyano)(4ꢀdimethylaminophenylmethylidene)selenoacetꢀ
amide (1b), in the Mannich reaction with amines 4 and
HCHO to give pyrimido[4,3ꢀb][1,3,5]selenadiazines 5a,d
in 46 and 47% yields, respectively (see Scheme 1, pathway A).
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 2, pp. 364—367, February, 2012.
1066ꢀ5285/12/6102ꢀ366 © 2012 Springer Science+Business Media, Inc.

Pyrimido[4,3ꢀb][1,3,5]selenadiazines
Russ.Chem.Bull., Int.Ed., Vol. 61, No. 2, February, 2012
367
Table 1. The yields of compounds 5 obtained by methods A—C
Pyrimido[4,3ꢀb][1,3,5]selenadiazines 5 can be obtained
by "one pot" condensation of aldehydes, cyanoselenoacetꢀ
amide 3, primary amines, and HCHO (pathway C) withꢀ
out isolation or purification of unsaturated selenamides 1,
which are generated in situ and undergo further transforꢀ
mations. Another advantage of this approach is that the
range of documented14 unsaturated selenamides of the type 1
is very limited. We found that benzaldehyde and aliphatic
aldehydes react with cyanoselenoacetamide 3, primary
amines 4, and an excess of formaldehyde in boiling EtOH
to give selenadiazines 5 in 14—32% yields (see Scheme 1).
The structural data and yields of compounds 5 are given
in Table 1.
Compound
R
R1
Yield (%) (method)
5а
5b
2ꢀThienyl
2ꢀThienyl
4ꢀFC6H4
4ꢀMeC6H4
46 (A)
50 (A)
32 (C)
38 (A)
29 (C)
47 (A)
16 (B)
22 (C)
20 (B)
28 (C)
0 (B)
5c
2ꢀThienyl
CH2Ph
5d
5e
4ꢀMe2NC6H4 4ꢀMeC6H4
CHMe2
4ꢀMeC6H4
4ꢀMeC6H4
4ꢀMeC6H4
5f
Ph
5g
Et
Method C (see Scheme 1) also allows the synthesis of
pyrimido[4,3ꢀb][1,3,5]selenadiazines 5 containing either
alkyl or aryl substituent at the C(8) atom in higher yields
compared to method B. It should be noted that the yields of
compounds 5 from aromatic aldehydes are low and comꢀ
parable with those achieved by method A. The compounds
obtained are fine crystalline powders varying in color from
light beige to claret; they are well soluble in acetone, DMF,
and DMSO and moderately soluble in EtOH.
The structures of the compounds obtained were conꢀ
firmed by spectroscopic and elemental analysis data.
Among the most characteristic signals in the 1H NMR
spectra of pyrimido[4,3ꢀb][1,3,5]selenadiazines 5a—d,f,
note a singlet at  4.35—5.13 for the C(8)H proton. For
selenadiazines 5e,g containing aliphatic substituents at the
C(8) atom, the signal for the C(8)H proton appears as
a doublet shifted upfield ( 3.23—3.62, 3J = 6.6—8.6 Hz).
The protons of the fragment N—CH2—Se are manifested as
a doublet of doublets at  3.82—4.48 (2J = 12.0—12.8 Hz),
while the protons of the fragment N—CH2—N—CH2—N,
as two doublets of doublets at  4.13—5.28 (2J =
= 10.2—13.6 Hz).
14 (C)
Alternatively, pyrimido[4,3ꢀb][1,3,5]selenadiazines 5
can be obtained by recyclization of easily accessible16—18
2,6ꢀdiaminoꢀ4Hꢀselenopyranꢀ3,5ꢀdicarbonitriles 6, which
are "masked" synthetic analogs of unsaturated selenoacetꢀ
amides 1. For instance, reactions of selenopyrans 6a,b
with an excess of formaldehyde and a twofold amount of
pꢀtoluidine in boiling EtOH gave compounds 5e,f in 15
and 20% yields, respectively (see Scheme 1, pathway B).
Aminomethylation of selenopyrans 6c,d was accompanied
by strong resinification and the formation of inseparable
complex mixtures of unidentified products. At the same
time, method B allows the synthesis of compound 5e
(R = CHMe2, R´ = 4ꢀMeC6H4), which cannot be obꢀ
tained by method A because (alkylidene)(cyano)selenoꢀ
acetamides of the type 1 (R is alkyl) are inaccessible.
A possible mechanism of the recyclization of selenopyrans 6
can involve elimination of malononitrile and the formaꢀ
tion of unsaturated selenamides 1 followed by their aminoꢀ
methylation leading to compounds 5 (Scheme 2). The low
yields of the final products can be attributed to the aminoꢀ
methylation of malononitrile as a side process.
Thus, we proposed three approaches to the synthesis of
pyrimido[4,3ꢀb][1,3,5]selenadiazines: aminomethylation
Scheme 2

368
Russ.Chem.Bull., Int.Ed., Vol. 61, No. 2, February, 2012
Frolov et al.
B. A mixture of an appropriate selenopyran 6a,b (1 mmol)
prepared according to a known procedure,16,18 pꢀtoluidine 4a
(0.23 g, 2.1 mmol), and an excess of 37% formalin (2.5 mL,
33.6 mmol) in EtOH (30 mL) was refluxed for 3 min, filtered
through a paper filter, and left at ~20 C for 72 h. The crystals
that formed were filtered off and washed with EtOH and hexane.
C. A drop of Nꢀmethylmorpholine was added to a mixture of
cyanoselenoacetamide 2 (0.2 g, 1.4 mmol) and an appropriate
aldehyde 1a,c,d,e (1.4 mmol) in EtOH (15 mL). The mixture
was stirred for 0.5 h to homogenization. Then an appropriate
primary amine (4a,b) (3 mmol) and an excess of 37% formalin
(2.0 mL, 10 mmol) were added. The reaction mixture was reꢀ
fluxed for 3 min, filtered through a paper filter, and left at ~20 C
for 24 h. Products 5b,c,e,f,g were filtered off and washed with
EtOH and hexane. The yields of compounds 5 obtained by
methods A—C are given in Table 1.
of (arylmethylidene)(cyano)selenoacetamides (method A),
cross recyclization of 4ꢀRꢀ2,6ꢀdiaminoꢀ4Hꢀselenopyranꢀ
3,5ꢀdicarbonitriles in the presence of primary amines and
excess formaldehyde (B), and "one pot" condensation of
appropriate aldehydes, cyanoselenoacetamide, primary
amines, and formaldehyde (C).
When comparing these three approaches, one can conꢀ
clude that the highest yields of the target products are
achieved by method A. However, because (alkylidene)ꢀ
(cyano)selenoacetamides (1, R = alkyl) are inaccessible,
this approach is suitable only for the synthesis of 8ꢀarylꢀ
pyrimido[4,3ꢀb][1,3,5]selenadiazines 5. Method B proꢀ
vides a route to 8ꢀalkylpyrimidoselenadiazines 5. However,
the yields of the target products are much lower because
this method involves an additional step (preparation of
selenopyran 6) and is not economical. On the whole, the
above drawbacks makes the recyclization of selenopyrans 6
not very suitable for preparative synthesis of compounds 5.
Method C ("one pot" multicomponent condensation)
combines the advantages of methods A and B and seems to
be most versatile and convenient, though not providing
the highest yields of the target products.
3,7ꢀBis(4ꢀfluorophenyl)ꢀ8ꢀ(2ꢀthienyl)ꢀ3,4,7,8ꢀtetrahydroꢀ
2H,6Hꢀpyrimido[4,3ꢀb][1,3,5]selenadiazineꢀ9ꢀcarbonitrile (5a),
m.p. 158—160 C (Me2CO), beige fine crystalline powder.
Found (%): C, 53.72; H, 4.06; N, 12.53. C23H18F2N4SSe
(M = 499.45). Calculated (%): C, 54.06; H, 4.02; N, 12.61. IR
(Nujol), /cm–1: 2158 (CN); 1590 (C=C). 1H NMR (DMSOꢀd6),
: 4.45 (dd, AB system, 2 H, SeCH2N, 2J = 12.8 Hz); 4.83 (dd,
2
AB system, 2 H, NCH2N, J = 11.5 Hz); 5.10 (s, 1 H, C(8)H);
2
5.27 (dd, AB system, 2 H, NCH2N, J = 11.0 Hz); 6.91—6.97
(m, 8 H, 2 Ar); 7.05—7.09 (m, 2 H, C(3)Hthienyl, C(4)Hthienyl);
7.32 (m, 1 H, C(5)Hthienyl).
Experimental
3,7ꢀBis(4ꢀmethylphenyl)ꢀ8ꢀ(2ꢀthienyl)ꢀ3,4,7,8ꢀtetrahydroꢀ
2H,6Hꢀpyrimido[4,3ꢀb][1,3,5]selenadiazineꢀ9ꢀcarbonitrile (5b),
m.p. 173—175 C (Me2CO), light beige fine crystalline powder.
The spectroscopic characteristics of compound 5b are identical
with the literature data.10
3,7ꢀDibenzylꢀ8ꢀ(2ꢀthienyl)ꢀ3,4,7,8ꢀtetrahydroꢀ2H,6Hꢀpyrꢀ
imido[4,3ꢀb][1,3,5]selenadiazineꢀ9ꢀcarbonitrile (5c), m.p.
127—128 C (Me2CO) (cf. Ref. 10: 127—130 C). The spectroꢀ
scopic characteristics of compound 5c are identical with the
literature data.10
1
H NMR spectra were recorded on a Bruker Avance II 400
instrument (399.97 MHz) in DMSOꢀd6 with SiMe4 as the interꢀ
nal standard. IR spectra (Nujol) were recorded on an IKSꢀ29
spectrophotometer. Elemental analysis was carried out on a Perꢀ
kin—Elmer C,H,Nꢀanalyzer. The purity of the compounds obꢀ
tained was checked by TLC on Silufol UVꢀ254 plates with acetꢀ
one—heptane (1 : 1) as an eluent; spots were visualized in the
iodine vapor or under UV light. Melting points were determined
on a Kofler hot stage and are given uncorrected. All manipulaꢀ
tions were carried out under argon.
8ꢀ(4ꢀDimethylaminophenyl)ꢀ3,7ꢀbis(4ꢀmethylphenyl)ꢀ3,4,
7,8ꢀtetrahydroꢀ2H,6Hꢀpyrimido[4,3ꢀb][1,3,5]selenadiazineꢀ9ꢀ
carbonitrile (5d), m.p. 187—189 C (DMF), dark claret fine
crystalline powder. Found (%): C, 66.24; H, 5.93; N, 13.18.
C29H31N5Se (M = 528.56). Calculated (%): C, 65.90; H, 5.91;
N, 13.25. IR (Nujol), /cm–1: 2170 (CN); 1615 (C=C). 1H NMR
(DMSOꢀd6), : 2.28, 2.31 (both s, 3 H each, 2 H3CC6H4); 2.92,
2.98 (both s, 3 H each, Me2N); 4.27 (dd, AB system, 2 H,
(Cyano)(2ꢀthienylmethylidene)selenoacetamide (1a) was preꢀ
pared according to a general procedure.14
(Cyano)(4ꢀdimethylaminophenylmethylidene)selenoacetamide
(1b) was prepared in a similar way from 4ꢀdimethylaminobenzꢀ
aldehyde 2b (2.03 g, 1.36 mmol) and cyanoselenoacetamide 3
(2.0 g, 1.36 mmol). The yield of compound 1b was 59%, dark
violet fine crystalline powder, decomp. > 150 C. Found (%):
C, 51.91; H, 4.78; N, 14.99. C12H13N3Se (M = 279.23). Calcuꢀ
lated (%): C, 51.81; H, 4.71; N, 15.10. IR (Nujol), /cm–1: 3275
(NH2); 2210 (CN); 1610 (C=C). 1H NMR (DMSOꢀd6), :
3.16 (s, 6 H, 2 Me); 6.75, 7.85 (both d, 2 H each, Ar, 3J = 9.1 Hz);
8.12 (s, 1 H, CH=); 8.26, 9.63 (both br.s, 1 H each, C(Se)NH2).
Pyrimido[4,3ꢀb][1,3,5]selenadiazines (5). Method A. For the
detailed synthesis of compounds 5b,c by this method, see Ref. 10.
Compounds 5a,d were obtained according to a modified proceꢀ
dure as follows. A mixture of 2ꢀcyanoꢀ3ꢀ(4ꢀdimethylaminoꢀ
phenyl)propꢀ2ꢀeneselenamide (1b) (0.7 g, 2.5 mmol), an approꢀ
priate primary amine 4a—c (5.2 mmol), and 37% formalin
(1.0 mL, 12.5 mmol) in DMF (5 mL) was refluxed to complete
homogenization (~1—2 min), immediately filtered through a paꢀ
per filter, and left at ~20 C for 24 h. The precipitate of comꢀ
pound 5 that formed was filtered off and washed with EtOH
and hexane.
2
SeCH2N, J = 12.5 Hz); 4.80 (dd, AB system, 2 H, NCH2N,
2J = 13.6 Hz); 4.85 (s, 1 H, C(8)H); 5.27 (dd, AB system, 2 H,
NCH2N, 2J = 10.9 Hz); 6.55—7.04 (m, 12 H, 3 Ar).
8ꢀIsopropylꢀ3,7ꢀbis(4ꢀmethylphenyl)ꢀ3,4,7,8ꢀtetrahydroꢀ
2H,6Hꢀpyrimido[4,3ꢀb][1,3,5]selenadiazineꢀ9ꢀcarbonitrile (5e),
m.p. 164—166 C (EtOH), beige fine crystalline powder. Found (%):
C, 64.13; H, 6.29; N, 12.28. C24H28N4Se (M = 451.48). Calcuꢀ
lated (%): C, 63.85; H, 6.25; N, 12.41. IR (Nujol), /cm–1: 2177
(CN); 1605 (C=C). 1H NMR (DMSOꢀd6), : 0.98, 1.07 (both d,
3
3 H each, (CH3)2CH, J = 6.6 Hz); 1.82 (m, 1 H, Me2CH);
2.25, 2.28 (both s, 3 H each, 2 H3CC6H4); 3.25 (d, 1 H, C(8)H,
3J = 8.6 Hz); 4.47 (dd, AB system, 2 H, SeCH2N, 2J = 12.0 Hz);
4.77 (pseudo s, 2 H, NCH2N); 5.22 (dd, AB system, 2 H,
NCH2N, 2J = 11.0 Hz); 6.66—6.98 (m, 8 H, 2 MeC6H4).
3,7ꢀBis(4ꢀmethylphenyl)ꢀ8ꢀphenylꢀ3,4,7,8ꢀtetrahydroꢀ2H,6Hꢀ
pyrimido[4,3ꢀb][1,3,5]selenadiazineꢀ9ꢀcarbonitrile (5f), m.p.

Pyrimido[4,3ꢀb][1,3,5]selenadiazines
Russ.Chem.Bull., Int.Ed., Vol. 61, No. 2, February, 2012
369
176—178 C (DMF), yellowꢀgreen fine crystalline powder.
Found (%): C, 67.54; H, 5.46; N, 11.41. C27H26N4Se
(M = 485.50). Calculated (%): C, 66.80; H, 5.40; N, 11.54. IR
(Nujol), /cm–1: 2185 (CN); 1610 (C=C). 1H NMR (DMSOꢀd6),
: 2.30, 2.31 (both s, 3 H each, 2 H3CC6H4); 4.31 (dd, AB system,
2 H, SeCH2N, 2J = 12.7 Hz); 4.83 (dd, AB system, 2 H, NCH2N,
2J = 13.6 Hz); 4.98 (s, 1 H, C(8)H); 5.28 (dd, AB system, 2 H,
NCH2N, 2J = 10.8 Hz); 6.91—7.31 (m, 13 H, 3 Ar).
8ꢀEthylꢀ3,7ꢀbis(4ꢀmethylphenyl)ꢀ3,4,7,8ꢀtetrahydroꢀ2H,6Hꢀ
pyrimido[4,3ꢀb][1,3,5]selenadiazineꢀ9ꢀcarbonitrile (5g), m.p.
168—170 C (EtOH), beige fine crystalline powder. Found (%):
C, 63.24; H, 6.03; N, 12.91. C23H26N4Se (M = 437.45). Calcuꢀ
lated (%): C, 63.15; H, 5.99; N, 12.81. IR (Nujol), /cm–1: 2155
(CN); 1610 (C=C). 1H NMR (DMSOꢀd6), : 0.99 (t, 3 H,
CH2CH3, 3J = 7.3 Hz); 1.52—1.76 (m, 2 H, CH2Me); 2.25, 2.27
(both s, 3 H each, 2 H3CC6H4); 3.60 (br.d, 1 H, C(8)H, 3J = 6.6 Hz);
4.48 (dd, AB system, 2 H, SeCH2N, 2J = 12.7 Hz); 4.80 (pseudo s,
2 H, NCH2N); 5.23 (dd, AB system, 2 H, NCH2N, 2J = 11.0 Hz);
6.72—6.99 (m, 8 H, 2 MeC6H4).
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were prepared as described earlier.16,18
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4ꢀRꢀ2,6ꢀDiaminoꢀ4Hꢀselenopyranꢀ3,5ꢀdicarbonitriles (6c,d)
were prepared according to a modified procedure18 as follows.
A mixture of an appropriate aldehyde (10 mmol), malononitrile
(0.66 g, 10 mmol), cyanoselenoacetamide (1.47 g, 10 mmol),
and Nꢀmethylmorpholine (0.1 mL) in EtOH (20 mL) was stirred
at 20 C for 3 h. The precipitate that formed was filtered off and
washed with EtOH and hexane.
2,6ꢀDiaminoꢀ4ꢀethylꢀ4Hꢀselenopyranꢀ3,5ꢀdicarbonitrile (6c).
Yield 17%, m.p. 253—255 C (EtOH—Me2CO, 3 : 1), orange
fine crystalline powder. Found (%): C, 42.13; H, 4.01; N, 21.95.
C9H10N4Se (M = 253.17). Calculated (%): C, 42.70; H, 3.98;
N, 22.13. IR (Nujol), /cm–1: 3285 (2 NH2); 2215, 2235 (2 CN);
1640 (2 C=C). 1H NMR (DMSOꢀd6), : 1.30 (t, 3 H, Me,
3J = 7.6 Hz); 2.79 (m, 2 H, CH2); 2.91 (br.d, 1 H, C(4)H, 3J =
= 6.6 Hz); 7.74 (br.s, 4 H, 2 NH2).
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2,6ꢀDiaminoꢀ4ꢀpropylꢀ4Hꢀselenopyranꢀ3,5ꢀdicarbonitrile
(6d). Yield 29%, m.p. 220—222 C (EtOH—Me2CO, 3 : 1), light
yellow fine crystalline powder. Found (%): C, 45.37; H, 4.57;
N, 20.62. C10H12N4Se (M = 267.19). Calculated (%): C, 44.95;
H, 4.53; N, 20.97. IR (Nujol), /cm–1: 3345 (2 NH2); 2215
(2 CN); 1650 (2 C=C). 1H NMR (DMSOꢀd6), : 1.30 (t, 3 H,
3
Me, J = 7.3 Hz); 1.72 (m, 2 H, MeCH2CH2); 2.76 (m, 2 H,
3
MeCH2CH2); 2.96 (br.d, 1 H, C(4)H, J = 6.7 Hz); 7.76 (br.s,
Received December 22, 2010;
in revised form July 17, 2011
4 H, 2 NH2).