Reactions of 4-oxo-1,3-benzoxazinium perchlorates with guanidines

Article abstract of DOI:10.1134/S1070428007100259

Condensation of 2-methyl-4-oxo-1,3-benzoxazinium perchlorate with various aromatic and heterocyclic aldehydes provided previously unknown arylvinyl-and hetarylvinyl-substituted salts whose recyclization under treatment with guanidine resulted in formerly undescribed 1,3,5-triazines. The reaction of perchlorates obtained with guanidinebenzoxazole led to the formation of bishetarylamines, with guanidinebenzimidazole formed triazinebenzimidazoles, the cyanoguanidine reacted with 4-oxo-1,3-benzoxazinium perchlorates to give cyanamides.

Full text of DOI:10.1134/S1070428007100259

ISSN 1070-4280, Russian Journal of Organic Chemistry, 2007, Vol. 43, No. 10, pp. 1553−1558. © Pleiades Publishing, Ltd., 2007.
Original Russian Text © E.Yu. Suvorova, N.I. Vikrishchuk, L.D. Popov, Z.A. Starikova, A.D. Vikrishchuk, Yu.A. Zhdanov, 2007, published in Zhurnal
Organicheskoi Khimii, 2007, Vol. 43, No. 10, pp. 1556−1561.
Reactions of 4-Oxo-1,3-benzoxazinium Perchlorates
with Guanidines
E. Yu. Suvorovaa, N. I. Vikrishchuka, L. D. Popova, Z. A. Starikovab,
†
A. D. Vikrishchukc, and Yu. A. Zhdanov a
aRostov State University, Rostov-on-Don, 344090 Russia
e-mail: natvi2004@mail.ru
bNesmeyanov Institute of Organoelemental Compounds, Russian Academy of Sciences, Moscow, Russia
cSouthern Scientific Center, Russian Academy of Sciences, Rostov-on-Don, Russia
Received December 2, 2006
Abstract—Condensation of 2-methyl-4-oxo-1,3-benzoxazinium perchlorate with various aromatic and heterocyclic
aldehydes provided previously unknown arylvinyl- and hetarylvinyl-substituted salts whose recyclization under
treatment with guanidine resulted in formerly undescribed 1,3,5-triazines. The reaction of perchlorates obtained
with guanidinebenzoxazole led to the formation of bishetarylamines, with guanidinebenzimidazole formed
triazinebenzimidazoles, the cyanoguanidine reacted with 4-oxo-1,3-benzoxazinium perchlorates to give
cyanamides.
DOI: 10.1134/S1070428007100259
Substituted 1,3,5-triazines are extensively used in
various fields of agrochemistry and pharmaceutics [1,
2]. We performed recyclization under treatment with
guanidine of hetarylvinyl- and arylvinyl-substituted
4-oxo-1,3-benzoxazinium salts II synthesized by con-
densation of 2-methyl-4-oxo-1,3-benzoxazinium (I) with
heterocyclic and aromatic aldehydes as described in [3]
and thus obtained a series of previously unknown hetaryl-
vinyl- and arylvinyl-substituted 1,3,5-triazines III
(Scheme 1).
with salts I, IIc, and IIe, and of benzimidazoleguanidine
with salts I, IIb, IIc, IIf, and IIg. Therewith in the
reaction with guanidinebenzoxazole triazinebenz-
oxazoleamines IV were obtained, but reaction of
perchlorates I and II with guanidinebenzimidazole led
instead of expected triazinebenzimidazoleamines V to
the formation of compounds whose structure based on
elemental analysis, 1H NMR and mass spectra was first
described as triazolebenzoxazepines [4] (Scheme 2).
However the X-ray diffraction analysis carried out
on compound VIa showed that in this reaction formed
1,3,5-triazino[1,2-a]benzimidazoles VI.
In order to prepare new biologically active substances
we carried out recyclization of salts I and II under
treatment of hetarylguanidines, of benzoxazoleguanidine
Scheme 1.
NH2
O
O
NH
NH2
OH
N
N
ClO4_
H2N
_
NH
NH
RCHO
ClO4
+
+
N
O
CH3
O
R
R
IIIa_IIIh
IIa_IIh
I
R = 2-pyridinyl (a), 4-ClC6H4 (b), 4-Me2NC6H4 (c), 4-MeSC6H4 (d), 1-methylindol-3-yl (e), 2-thienyl (f),
4-HOOCCH2OC6H4 (g), Ph (h).
† Deceased.
1553

SUVOROVA et al.
1554
Scheme 2.
NH
NH
N
N
I, II
N
N
H2N
N
N
NH2
O
N
H
H
HN
N
H
H
O
NH
NH
N
N
OH
N
N
N
NH2
N
H
OH
N
N
H
N
R'
N
N
N
R'
V
NH2
IVa_IVc
N
R'
VIa_VIe
IV, R' = 4-Me2NC6H4CH=CH (a), 1-methylindol-3-yl-CH=CH (b), Me (c); VI, R' = 4-ClC6H4CH=CH (a),
4-Me2NC6H4CH=CH (b), 2-thienyl-CH=CH (c), 4-HOOCCH2C6H4CH=CH (d), Me (e).
...
In the unit cell of compound VIa are located
4 molecules of unique structure (a single molecule is
presented on Fig. 1). The tricyclic 1,3,5-triazino[1,2-a]-
benzimidazole system is planar, the phenyl ring is tilted
to it on the average by 19°. Geometrical parameters of
the molecules are similar. The main bond lengths are
compiled in the table. The accuracy attained does not
provide a possibility to perform a comparative analysis
of the geometry of the independent molecules. The main
difference between the molecules is the variation of the
phenyl ring position with respect to the double bond
C10=C11, torsion angle N1C1C10C11 being 32°. The
structure is layer-like, the layers are fixed by inter-
molecular hydrogen bonds between the hydrogens of the
amino group and nitrogen atoms of the heterocycle.
(dH N 2.04 Å) result in dimers formation, and these
are combined into layers by weaker hydrogen bonds N31–
...
...
...
H N14A, N34A–H N1 (dH N 2.40 Å) (Fig. 2). The outer
surface of layers consists of chlorine atoms which are
not involved into any short contacts.
Previously 1,3,5-triazino[1,2-a]benzimidazoles were
obtained by reaction of guanidine(amidine) benzimid-
azoles with orthoesters [5, 6].
The reaction presumably proceeds by the following
mechanism: the guanidinebenzimidazole adds into the
position 2 of the benzoxazine ring of perchlorates I and
II providing benzoxazine VII that further opens into
Selected bond lengths (d, Å) in four molecules in the unit cell
of compound VIa
...
Within the layer stronger hydrogen bonds N31H N41A
No. of the molecule in the cell
Bond
1
2
3
4
N1–C1
N1–C2
C2–N2
N2–C3
C3–N5
N5–C1
N4–C3
N4–C4
N5–C9
C2–N3
C1–C10
C10–C11
C11–C12
1.30(1)
1.292(9) 1.288(9) 1.303(9)
1.41(1)
1.30(1)
1.35(1)
1.440(9)
1.355(9)
1.291(9)
1.384(7)
1.384(7)
1.32(1)
1.49(1)
1.29(1)
1.490(7)
1.387(9) 1.40(1)
1.309(9) 1.31(1)
1.391(9)
1.324(9)
1.344(9) 1.340(9) 1.335(9)
1.414(9) 1.441(9) 1.415(9)
1.370(9) 1.354(9) 1.364(9)
1.341(9) 1.285(9) 1.320(9)
1.384(7) 1.382(7) 1.392(7)
1.431(7) 1.375(7) 1.411(7)
1.307(9) 1.340(9) 1.315(9)
1.471(9) 1.48(1)
1.31(1) 1.30(1)
1.469(9)
1.31(10
1.490(8) 1.479(7) 1.486(9)
Fig. 1. Geometry of a molecule of compound VIa.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 43 No. 10 2007

REACTIONS OF 4-OXO-1,3-BENZOXAZINIUM PERCHLORATES
1555
Scheme 3.
O
HN
NH
NH2
N
O
R'
NH
O
N
H
HN
HN
HN
NH
ClO4_
NH
+
MeONa/MeOH
N
O
R'
I, II
VII
NH
N
N
N
OH
O
N
O
N
N
N
H
H
NH2
NH2
N
N
R'
H
R'
IX
VI
OH
VIII
imide VIII. The latter undergoes cyclization into triazino-
benzimidazole VI with elimination of salicylamide (IX)
(Scheme 3).
after the reaction with o-phenylenediamine. In the
1H NMR spectra of cyanaminotriazines X the signals
are observed from the protons of R' group, of aromatic
protons in the region 6.62–8.45 ppm, of groups OH and
NH in the region 11–14 ppm as singlets and broadened
singlets.
A similar cleavage of 4-oxo-1,3-benzoxazinium per-
chlorates was formerly observed in reactions with indole
and o-phenylenediamine [7].
The structure of bisheterylamines V is consistent with
Reaction of salts I and II with cyanoguanidine led to
the formation of previously unknown cyanaminotriazines
X containing several functional groups and capable of
further chemical transformations. The reaction of azines
Xb and Xc with o-phenylenediamine gave rise to tri-
azinebenzimidazoleamines V (Scheme 4). In the IR
spectra of compounds X the absorption bands of cyano
group appeared at 2170–2155 cm–1, and they disappeared
their IR and 1H NMR spectra.
EXPERIMENTAL
IR spectra of compounds obtained were registered
on a spectrophotometer Specord 75IR from mulls in
1
mineral oil, H NMR spectra were taken on a spec-
Fig. 2. Hydrogen bonds forming dimers and layers in the crystal of compound VIa.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 43 No. 10 2007

SUVOROVA et al.
Scheme 4.
1556
NHCN
NH
O
H2N
H2N
N
N CN
NH2
ClO4_
OH
N
N
HN
NH
H
N
H
+
MeONa/MeOH
AcOH
N
R'
OH
N
N
O
R'
I, IIf, IIh
Xа_Xc
N
R'
Va, Vb
V, X, R' = Me (a), PhCH=CH (b), 2-thienyl-CH=CH (c).
trometer Varian Unity-300 (300 MHz) at 20°C in acetone-
d6 and DMSO-d6, mass spectra were measured on a VG
7070E instrument (electron impact, 70 eV).
2-[2-(2-thienyl)vinyl]-4-oxo-1,3-benzoxazinium
perchlorate (IIf). Yield 98%, dark-green crystals, mp >
260°C. IR spectrum, ν, cm–1: 1650 (C=N), 1620, 1600
(C=C). Found, %: C 47.30; H 2.60; Cl 9.20; N 3.70;
S 8.80. C14H10ClNO6S. Calculated, %: C 47.26; H 2.81;
Cl 9.99; N 3.94; S 9.00.
Perchlorates I and IIh were described in [3], com-
pounds IIa–IIg were prepared by procedure described
in the same paper.
2-{2-[4-(Carboxymethoxy)phenyl]vinyl}-4-oxo-
1,3-benzoxazinium perchlorate (IIg). Yield 91%, light-
brown crystals, mp > 270°C. IR spectrum, ν, cm–1: 1670
(C=N), 1610, 1600 (C=C). Found, %: C 51.40; H 2.90;
Cl 8.50; N 2.90. C18H13ClNO9. Calculated, %: C 51.12;
H 3.08; Cl 8.40; N 3.31.
2-[2-(2-Pyridyl)vinyl]-4-oxo-1,3-benzoxazinium
perchlorate (IIa). Yield 99%, brown crystals, mp >
250°C. IR spectrum, ν, cm–1: 1750 (C=O), 1680, 1640
(C=N), 1620 (C=C). Found, %: C 49.50; H 2.70;
Cl 10.00; N 9.10. C15H11ClNO6. Calculated, %: C 49.11;
H 3.00; Cl 9.69; N 9.69.
2-[2-(4-Chlorophenyl)vinyl]-4-oxo-1,3-benz-
oxazinium perchlorate (IIb). Yield 79%, red crystals,
mp 255–258°C. IR spectrum, ν, cm–1: 1760 (C=O), 1680,
1640 (C=N), 1620 (C=C). Found, %: C 49.80; H 2.70;
Cl 18.60; N 3.10. C16H11Cl2NO6. Calculated, %: C 50.00;
H 2.86; Cl 18.49; N 3.65.
2-Amino-4-(2-hydroxyphenyl)-6-[2-(2-pyridyl)-
vinyl]-1,3,5-triazine (IIIa). To a solution of 10 mmol of
sodium methylate (0.23 g of sodium in 10 ml of methanol)
was added 1.08 g (5 mmol) of guanidine sulfate, 10 min
later 1.8 g (5 mmol) of perchlorate IIa was added. After
16 h the reaction mixture was diluted with ice water, the
separated precipitate was filtered off and washed with
water. Yield 0.36 g (24%), brown crystals, mp 285°C
(2-propanol). IR spectrum, ν, cm–1: 3470 (NH2), 3050
(OH), 1650, 1615 (C=N), 1600, 1525 (C=C). 1H NMR
spectrum, δ, ppm: 6.97–8.68 m (10H, HAr, 2H, NH2),
13.16 s (1H, OH). Found, %: C 64.80; H 4.70; N 25.10.
C16H13N5O. Calculated, %: C 64.51; H 4.66; N 25.08.
2-[2-(4-Dimethylaminophenyl)vinyl]-4-oxo-1,3-
benzoxazinium perchlorate (IIc). Yield 79%, violet
crystals, mp > 250°C. IR spectrum, ν, cm–1: 1755 (C=O),
1680, 1650 (C=N), 1610 (C=C). Found, %: C 55.40;
H 4.00; Cl 9.30; N 6.90. C18H17ClN2O6. Calculated, %:
C 55.03; H 4.33; Cl 9.04; N 7.13.
2-[2-(4-Methylthiophenyl)vinyl]-4-oxo-1,3-
benzoxazinium perchlorate (IId). Yield 99%, red
crystals, mp > 260°C. IR spectrum, ν, cm–1: 1680, 1640
(C=N), 1620 (C=C). Found, %: C 51.20; H 3.60; Cl 9.00;
N 3.10; S 8.50. C17H14ClNO6S. Calculated, %: C 51.58;
H 3.54; Cl 8.98; N 3.54; S 8.09.
Compounds IIIb–IIIf were obtained similarly.
2-Amino-4-(2-hydroxyphenyl)-6-[2-(4-chloro-
phenyl)vinyl]-1,3,5-triazine (IIIb). Yield 43%, yellow
crystals, mp 222–224°C (2-butanol). IR spectrum, ν,
cm–1: 3400, 3300 (NH2), 3180 (OH), 1625, 1610 (C=N),
2-[2-(1-Methylindol-3-yl)vinyl]-4-oxo-1,3-benz-
oxazinium perchlorate (IIe). Yield 96%, red crystals,
mp 235°C. IR spectrum, ν, cm–1: 1640 (C=N), 1610, 1590
(C=C). Found, %: C 56.70; H 3.70; Cl 8.70; N 6.20.
C19H15ClN2O6. Calculated, %: C 56.65; H 3.73; Cl 8.82;
N 6.96.
1
1525 (C=C). H NMR spectrum (acetone-d6), δ, ppm:
6.82–8.42 m (10H, HAr, 2H, NH2), 13.29 s (1H, OH).
Found, %: C 64.00; H 4.30; Cl 11.20; N 17.00.
C17H13ClN5O. Calculated, %: C 62.87; H 4.01; Cl 10.94;
N 17.26.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 43 No. 10 2007

REACTIONS OF 4-OXO-1,3-BENZOXAZINIUM PERCHLORATES
1557
2-Amino-4-(2-hydroxyphenyl)-6-[2-(4-dimethyl-
aminophenyl)vinyl]-1,3,5-triazine (IIIc). Yield 38%,
orange crystals, mp 255–256°C. IR spectrum, ν, cm–1:
3390, 3300 (NH2), 3150 (OH), 1630 (C=N), 1600, 1520
Compounds IVb and IVc were prepared in the same
way.
1,3-Benzoxazol-2-yl{4-(2-hydroxyphenyl)-6-[2-(1-
methyl-1H-indol-3-yl)vinyl]-1,3,5-triazin-2-yl}amine
(IVb). Yield 30%, yellow crystals, mp > 310°C (i-BuOH–
DMF). IR spectrum, ν, cm–1: 3370 (NH), 3050 (OH),
1680, 1630 (C=N), 1600, 1525 (C=C). 1H NMR spectrum
(acetone-d6), δ, ppm: 3.95 s (3H, NMe), 6.94–8.47 m
(15H, HAr), 13.54 s (1H, OH), 13.60 s (1H, NH). Found,
%: C 67.90; H 4.80; N 20.10. C27H20N6O2. Calculated,
%: C 67.92; H 4.71; N 19.81.
1
(C=C). H NMR spectrum (DMSO-d6), δ, ppm: 3.09 s
(6H, NMe2) 6.65–8.39 m (10H, HAr, 2H, NH2), 13.11 s
(1H, OH). Found, %: C 68.40; H 5.70; N 21.00. C20H17N5O.
Calculated, %: C 68.47; H 5.71; N 21.02.
2-Amino-4-(2-hydroxyphenyl)-6-[2-(4-methyl-
thiophenyl)vinyl]-1,3,5-triazine (IIId). Yield 43%,
yellow crystals, mp 217–219°C. IR spectrum, ν, cm–1:
3380, 3320 (NH2), 3200 (OH), 1635 (C=N), 1595, 1520
(C=C). 1H NMR spectrum (acetone-d6), δ, ppm: 2.45 s
(3H, SMe), 6.82–8.41 m (10H, HAr, 2H, NH2), 13.29 s
(1H, OH). Found, %: C 64.30; H 4.70; N 16.60; S 9.40.
C18H16N4OS. Calculated, %: C 64.29; H 4.76; N 16.67;
S 9.52.
1,3-Benzoxazol-2-yl[4-(2-hydroxyphenyl)-6-
methyl-1,3,5-triazin-2-yl]amine (IVc). Yield 45%, pink
crystals, mp 290°C (i-BuOH). IR spectrum, ν, cm–1: 3350
(NH), 3090 (OH), 1660, 1660 (C=N), 1600 (C=C).
1H NMR spectrum (acetone-d6), δ, ppm: 2.58 s (3H, Me)
6.91–8.43 m (8H, HAr), 12.56 s (1H, OH) 12.98 s (1H,
NH). Found, %: C 63.60; H 4.20; N 21.80. C17H13N5O2.
Calculated, %: C 63.95; H 4.08; N 21.94.
2-Amino-4-(2-hydroxyphenyl)-6-[2-(1-methyl-
indol-3-yl)vinyl]-1,3,5-triazine (IIIe). Yield 40%,
yellow crystals, mp 210–212°C. IR spectrum, ν, cm–1:
3470 (NH2), 3050 (OH), 1680, 1630 (C=N), 1600, 1525
(C=C). 1H NMR spectrum (acetone-d6), δ, ppm: 3.95 s
(3H, NMe), 6.94–8.47 m (11H, HAr, 2H, NH2), 13.54 s
(1H, OH). Found, %: C 70.20; H 4.60; N 20.50.
C20H17N5O. Calculated, %: C 70.17; H 4.67; N 20.46.
2-[4-(1H-Benzimidazol-2-ylamino)-6-methyl-1,3,5-
triazin-2-yl]phenol (Va). A mixture of 2.27 g (10 mmol)
of compound Xa and 1.08 g (10 mmol) of o-phenyl-
enediamine was boiled for 2 h in 10 ml of acetic acid.
Then the reaction mixture was diluted with cold water,
the separated precipitate was filtered off and washed with
water. Yield 29%, light-yellow crystals, mp > 310°C
(DMΤA). IR spectrum, ν, cm–1: 3380 (NH), 1640, 1610
(C=N), 1525, 1500 (C=C). 1H NMR spectrum (DMSO-
d6), δ, ppm: 2.8 s (3H, Me), 6.85–8.40 m (8H, HAr)
12.1 s (1H, OH), 12.2 s (1H, NH) 13.2 s (1H, NH). Found,
%: C 64.10; H 4.50; N 26.20. C17H14N6O. Calculated,
%: C 64.15; H 4.40; N 26.42.
2-Amino-4-(2-hydroxyphenyl)-6-[2-(thienyl)-
vinyl]-1,3,5-triazine (IIIe). Yield 42%, light-brown
crystals, mp 158–160°C (1-butanol). IR spectrum, ν,
cm–1: 3375, 3320 (NH2), 3180 (OH), 1640, 1610 (C=N),
1
1590, 1570 (C=C). H NMR spectrum (acetone-d6), δ,
ppm: 6.77–8.50 m (9H, HAr, 2H, NH2), 13.11 s (1H, OH).
Found, %: C 60.70; H 4.20; N 18.70; S 10.90.
C15H12N4OS. Calculated, %: C 60.81; H 4.05; N 19.92;
S 10.81.
In the same way from compound Xb compound Vb
was prepared.
1,3-Benzoxazol-2-yl{4-(2-hydroxyphenyl)-6-[2-(4-
dimethylaminophenyl)vinyl]-1,3,5-triazin-2-yl}amine
(IVa). To a solution of 10 mmol of sodium methylate
(0.23 g of sodium in 10 ml of methanol) was added
1.74 g (9.9 mmol) of benzoxazolylguanidine and 3.92 g
(9.9 mmol) of compound IIc. Then the reaction mixture
was twice heated to boiling with an interval of 20 min,
and then it was left standing at room temperature.After
16 h the separated reaction product was diluted with ice
water, filtered off, recrystallized, and dried. Yield 40%,
red crystals, mp 192–194°C (DMF). IR spectrum, ν,
cm–1: 3390 (NH), 3100 (OH), 1670, 1630 (C=N), 1600
2-{4-(1H-Benzimidazol-2-ylamino)-6-[(Ε)-2-
phenylethenyl]-1,3,5-triazin-2-yl}phenol (Vb). Yield
37%, yellow crystals, mp > 310°C (DMF). IR spectrum,
ν, cm–1: 3280 (NH), 1720, 1690, 1635 (C=N), 1600, 1540
1
(C=C). H NMR spectrum (DMSO-d6), δ, ppm: 6.95–
8.71 m (15H, HAr), 12.11 s (1H, OH), 12.29 s (1H, NH),
13.10 s (1H, NH). Found, %: C 70.90; H 4.50; N 20.40.
C24H18N6O. Calculated, %: C 70.94; H 4.43; N 20.69.
4-[(Ε)-2-(4-Chlorophenyl)ethenyl][1,3,5]triazino-
[1.2-a]benzimidazol-2-amine (VIa). To a solution of
0.23 g of sodium in 10 ml of methanol was added 1.41 g
(8.2 mmol) of benzimidazoleguanidine and 3.15 g
(8.2 mmol) of compound IIb. The mixture was boiled
for 60 min, then it was diluted with water, the separated
1
(C=C). H NMR spectrum (DMSO-d6), δ, ppm: 3.05 s
(6H, NMe2), 6.62–8.12 m (14H, HAr,), 10.77 C (1H, OH),
11.57 C (1H, NH). Found, %: C 69.00; H 4.50; N 18.90.
C26H22N6O2. Calculated, %: C 69.33; H 4.89; N 18.67.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 43 No. 10 2007

SUVOROVA et al.
1558
precipitate was filtered off and washed with water. Yield
1.62 g (28%), red crystals, mp 280–282°C (DMF). IR
spectrum, ν, cm–1: 3320 (NH2), 1660, 1650 (C=N), 1600,
was added thereto, the separated precipitate was filtered
off, washed with water, and recrystallized. Yield 55%,
light-yellow crystals, mp 255–256°C (butanol). IR
spectrum, ν, cm–1: 3340 (NH), 2155 (C≡N), 1600 (C=N),
1
1520 (C=C). H NMR spectrum (DMSO-d6), δ, ppm:
1
1540 (C=C). H NMR spectrum (DMSO-d6), δ, ppm:
7.22–8.49 m (12H, HAr). Found, %: C 63.40; H 3.60;
Cl 11.10; N 21.70. C17H12ClN5. Calculated, %: C 63.45;
H 3.73; Cl 11.01; N 21.77.
2.37 s (3H, Me), 6.88–8.29 m (4H, HAr), 13.1 s (1H,
OH), 13.78 s (1H, NH). Found, %: C 58.20; H 3.90;
N 30.80. C11H9N5O. Calculated, %: C 58.15; H 3.96;
N 30.84.
Compounds VIb−VIe were prepared in the same way.
4-[(Ε)-2-(4-Dimethylaminophenyl)ethenyl][1,3,5]-
triazino[1,2-a]benzimidazol-2-amine (VIb). Yield
32%, red crystals, mp 304–306°C (DMF). IR spectrum,
ν, cm–1: 1670, 1610 (C=N), 1590, 1500 (C=C). 1H NMR
spectrum (DMSO-d6), δ, ppm: 3.11 s (6H, NMe2), 6.72–
8.19 m (12H, HAr). Found, %: C 69.10; H 5.30; N 25.40.
C19H18N6. Calculated, %: C 69.09; H 5.45; N 25.45.
Compounds Xb and Xc were similarly prepared.
N-{4-(2-Hydroxyphenyl)-6-[(Ε)-2-phenylethenyl]-
1,3,5-triazin-2-yl}cyanamide (Xb). Yield 49%, yellow
crystals, mp 210°C (butanol). IR spectrum, ν, cm–1: 3470
(NH), 2160 (C≡N), 1680, 1630 (C=N), 1600, 1525
1
(C=C). H NMR spectrum (acetone-d6), δ, ppm: 6.72–
8.89 m (11H, HAr), 13.89 s (1H, OH), 14.01 s (1H, NH).
Found, %: C 68.60; H 4.00; N 22.30. C18H13N5O.
Calculated, %: C 68.57; H 4.13; N 22.22.
4-[(Ε)-2-(2-thienyl)ethenyl][1,3,5]triazino[1,2-
a]benzimidazol-2-amine (VIc). Yield 28%, red crystals,
mp 277–279°C (1-butanol). IR spectrum, ν, cm–1: 3340
N-{4-(2-Hydroxyphenyl)-6-[(Ε)-2-(2-thienyl)-
ethenyl]-1,3,5-triazin-2-yl}cyanamide (Xc). Yield 22%,
brown crystals, mp > 310°C (butanol). IR spectrum, ν,
cm–1: 3400 (NH), 2170 (C≡N), 1650, 1605 (C=N), 1510,
1
(NH2), 1650 (C=N), 1525 (C=C). H NMR spectrum
(DMSO-d6), δ, ppm: 7.05–8.42 m (11H, HAr). Found,
%: C 61.70; H 3.50; N 23.70; S 10.70. C15H11N5S.
Calculated, %: C 61.43; H 3.75; N 23.89; S 10.92.
1
1500 (C=C). H NMR spectrum (DMSO-d6), δ, ppm:
{4-[(Ε)-2-(2-Amino[1,3,5]triazino[1,2-a]benz-
imidazol-4-yl)ethenyl]phenoxy}acetic acid (VId).
Yield 26%, red crystals, mp 220–222°C (DMF). IR
spectrum, ν, cm–1: 3380 (NH2), 1640, 1610 (C=N), 1530,
6.65–8.39 m (9H, HAr), 13.91 s (1H, OH), 14.09 s (1H,
NH). Found, %: C 59.70; H 3.30; N 20.50; S 9.80.
C16H11N5OS. Calculated, %: C 59.81; H 3.43; N 21.81;
S 9.97.
1
1500 (C=C). H NMR spectrum (DMSO-d6), δ, ppm:
4.69 s (2H, OCH2), 6.82–8.15 m (12H, HAr). Found, %:
C 63.10; H 4.10; N 19.30. C19H15N5O3. Calculated, %:
C 63.16; H 4.16; N 19.39.
REFERENCES
1. Kuboyama, N., Kozumi, K., Ohki, S., and Wakabaya-
shi, K., J. Pesticid Sci., 1998, vol. 23, no. 3, p. 268.
2. Naito, S., Nishimura, M., and Tamao, Y., J. Pharm.
Pharmacol., 2000, vol. 52, p. 173.
3. Ryabukhin, Yu.I., Mezheritskii, V.V., Karpenko, V.D., and
Dorofeenko, G.N., Khim. Geterotsikl. Soedin., 1975,
p. 1184.
4. Vikrishchuk, N.I., Popov, L.D., Suvorova, E.Yu., and
Zhdanov, Yu.A., Zh. Org. Khim., 2005, vol. 41, p. 1257.
5. Reddy, B.S., Sambaian, T., and Reddy, K.K., Indian J.
Chem. Soc. B., 1998, vol. 37, p. 1293.
6. Dolzhenko, A.V. and Chui, Wai-Keung., J. Heterocycl.
Chem., 2006, vol. 43, p. 95.
4-Methyl[1,3,5]triazino[1,2-a]benzimidazol-2-
amine (VIe). Yield 30%, light-brown crystals, mp 316–
318°C (DMF) (314–315°C [6]). IR spectrum, ν, cm–1:
3430 (NH2), 1640, 1610 (C=N), 1540 (C=C). 1H NMR
spectrum (DMSO-d6), δ, ppm: 2.89 s (3H, Mε) 7.18–
7.85 m (6H, HAr). Mass spectrum, m/z (Irel, %): 199 (96),
158 (100), 131 (10), 104 (9), 90 (20), 63 (9), 42 (34).
Found, %: C 60.20; H 4.50; N 35.10. C10H9N5.
Calculated, %: C 60.30; H 4.52; N 35.18.
N-[4-(2-Hydroxyphenyl)-6-methyl-1,3,5-triazin-2-
yl]cyanamide (Xa). To a solution of 10 mmol of sodium
methylate (0.23 g of sodium in 10 ml of methanol) was
added 0.84 g (10 mmol) of cyanoguanidine and 2.36 g
(10 mmol) of perchlorate I. The reaction mixture was
maintained at room temperature for 12 h, then ice water
7. Dorofeenko, G.N., Ryabukhina, O.Yu., Mezheritskii, V.V.,
and Ryabukhin, Yu.I., Khim. Geterotsikl. Soedin., 1977,
p. 47
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 43 No. 10 2007