Anil Synthesis in the Design of Push?Pull Systems. Synthesis of 2- and 4-(4-Styrylphenyl)-substituted Diphenylpyrimidines

Article abstract of DOI:10.1134/S1070428020020153

Abstract: The potential of anil synthesis for the preparation of 2,4,6-triaryl-substituted pyrimidines with an extended chain of delocalized π-bonds was studied. The reaction of (E)-3-phenyl-1-(p-tolyl)prop-2-en-1-one or chalcone with benzamidine, 4-methylbenzamidine, or 4-isobutoxybenzamidine hydrochlorides in ethanol in the presence of KOH gave 2,4-diphenyl-6-(p-tolyl)pyrimidine, 4,6-diphenyl-2-(p-tolyl)pyrimidine, and 2-(4-isobutoxyphenyl)-4-phenyl-6-(p-tolyl)pyrimidine. The synthesized pyrimidines were reacted with (E)-N-(phenyl- or 2-chlorophenyl)-1-arylmethanimines in DMF in the presence of a KOH/LiH mixture to obtain (E)-4,6-diphenyl-2-(4-styrylphenyl)pyrimidines and (E)-2,6-diphenyl-4-(4-styrylphenyl)pyrimidines were obtained.

Full text of DOI:10.1134/S1070428020020153

ISSN 1070-4280, Russian Journal of Organic Chemistry, 2020, Vol. 56, No. 2, pp. 269–275. © Pleiades Publishing, Ltd., 2020.
Russian Text © The Author(s), 2020, published in Zhurnal Organicheskoi Khimii, 2020, Vol. 56, No. 2, pp. 269–276.
Anil Synthesis in the Design of Push−Pull Systems.
Synthesis of 2- and 4-(4-Styrylphenyl)-substituted
Diphenylpyrimidines
a,b,
b
a,b
A. A. Harutyunyan *, H. A. Panosyan , M. S. Safaryan ,
b
a
a,b
G. K. Harutyunyan , G. T. Gukasyan , and G. G. Danagulyan
a
Russian-Armenian (Slavonic) University, Yerevan, 0051 Armenia
b
Scientific Technological Center of Organic and Pharmaceutical Chemistry (STCOPHCH), Yerevan, 0014 Armenia
e-mail: harutyunyan.arthur@yahoo.com
*
Received September 7, 2019; revised October 18, 2019; accepted December 2, 2019
Abstract—The potential of anil synthesis for the preparation of 2,4,6-triaryl-substituted pyrimidines with an
extended chain of delocalized π-bonds was studied. The reaction of (E)-3-phenyl-1-(p-tolyl)prop-2-en-1-one
or chalcone with benzamidine, 4-methylbenzamidine, or 4-isobutoxybenzamidine hydrochlorides in etha-
nol in the presence of KOH gave 2,4-diphenyl-6-(p-tolyl)pyrimidine, 4,6-diphenyl-2-(p-tolyl)pyrimidine, and
2
-(4-isobutoxyphenyl)-4-phenyl-6-(p-tolyl)pyrimidine. The synthesized pyrimidines were reacted with (E)-N-
(phenyl- or 2-chlorophenyl)-1-arylmethanimines in DMF in the presence of a KOH/LiH mixture to obtain (E)-4,6-
diphenyl-2-(4-styrylphenyl)pyrimidines and (E)-2,6-diphenyl-4-(4-styrylphenyl)pyrimidines were obtained.
Keywords: 2,4-diphenyl-6-(p-tolyl)pyrimidine, 4,6-diphenyl-2-(p-tolyl)pyrimidine, 2-(4-isobutoxyphenyl)-
4
-phenyl-6-(p-tolyl)pyrimidine, (E)-3-phenyl-1-(p-tolyl)prop-2-en-1-one, chalcone, condensation, DMF/KOH/
LiH, (E)-4,6-diphenyl-2-(4-styrylphenyl)pyrimidines, (E)-2,6-diphenyl-4-(4-styrylphenyl)pyrimidines
DOI: 10.1134/S1070428020020153
The growing interest in the synthesis of substituted
pyrimidines with an extended chain of delocalized
π-bonds is associated with the potential use of such
compounds in the design of new organic optical
materials (organic light-emitting diodes (OLED), field
transistors (OFET), solar cells, luminescent sensors,
etc.) [1] and preparations for biomedical applications
[3]. The alternative synthetic approach to π-conjugated
pyrimidine derivatives involves condensation of
methylpyrimidines with arene(hetarene)carbaldehydes
[4] and cross-coupling reactions on the basis of transition
metals [5] or the so-called anil synthesis [6, 7].
The anil synthesis is known to involve the reaction
of para-tolyl-substituted heterocycles, in particular,
pyrimidines with Schiff bases from aromatic and hetero-
cycle aldehydes and aniline or 2- or 4-chloroanilines in
anhydrous DMF in the presence of strong bases: alkali
metals and their hydroxides, alkoxides, and amides,
preferentially potassium hydroxide or tert-butoxide
[
2]. The π-deficient aza-aromatic system of pyrimidine
acts as the electron-acceptor part of the molecular system
π-acceptor), which, having bound to an electron-donor
(
group (π-donor), forms, through delocalized π-bonds,
an integral push–pull system. The latter exhibits
optoelectronic properties due to charge transfer between
the parts of the molecule.
[6]. However, it is slightly surprising that this method
of synthesis of pyrimidines with extended π-conjugated
chains, even though it allows one to vary synthons,
uses accessible reagents, and simple in experimental
implementation has not gained wide acceptance. Note
that π-conjugated pyrimidines synthesized in this way
over the past years contained one phenyl or one methyl
substituent in the pyrimidine ring or phenyl and alkyl
or alkoxyl together [7], whereas derivatives with two
phenyl substituents in the pyrimidine ring have never
been approached by this method. In this connection, we
Polyunsaturated conjugated chains can be introduced
intothepyrimidinecorecanformallybecarriedoutintwo
ways: by constructing the ring from simple precursors
bearing the required functional groups and by chemically
modifying of the available functional groups. It should
be noted that the reported uses of the former approach to
the target pyrimidines via acyclic precursors are limited
to the synthesis of 4(6)-(2-arylethenyl)pyrimidines from
substituted cinnamaldehydes by the Biginelli reaction
2
69

270
HARUTYUNYAN et al.
Scheme 1.
R
O
NH
2
KOH
R1
.HCl
+
EtOH
NH2
N
R
N
R1
1a, 1b
2a–2c
3a–3c
N
N
R2
N
R3
a–4d
R2
4
5a–5d
KOH/LiH/DMF
N
N
R2
R1
6
a–6e
1
1
1
a, 1b, R = H (a), Me (b). 2a–2c, R = H (a), Me (b), iꢀ%XɈꢁꢂc). 3a–3c, R, R = H, Me (a), Me, H (b), Me, iꢀ%XɈꢁꢂc).
2
3
2
4
a–4d, R , R = H, H (a), 4-MeO, Cl (b), 4-i-Pr, Cl (c), 3,4(CH O ), Cl (d). 5a–5d, R = H (a), MeO (b),
2 2
1
2
i-Pr (c), 3,4-(CH O ) (d). 6a–6e, R , R = H, H (a), H, 4-MeO (b), H, 3,4-(CH O ) (c), H, i-Pr (d), iꢀ%XɈꢃꢁ+ꢁꢂe).
2
2
2
2
decided to explore the potential of the anil synthesis as a
convenient and efficient method of synthesis of the target
π-conjugated pyrimidines from isomeric 2,4,6-triaryl-
substituted pyrimidines. The synthesis was performed
as shown in Scheme 1.
anil synthesis. 4-Isobutoxybenzamidine hydrochloride
(4a) was prepared similarly to benzamidine [8].
We studied the anil synthesis with pyrimidines 3a–3c
and Schiff bases from aniline or 2- or 4-chloroanilines
and aromatic aldehydes and modified the experimental
procedure, which allowed use to optimize and simplify
the process not sacrificing the yield of the target products.
We found that the reported methods of synthesis,
isolation, and purification of Schiff bases from aniline
or 2- or 4-chloroanilines and aromatic aldehydes, except
that for (E)-N,1-diphenylmethanimine (4a) [9], are not
quite satisfactory [10].
The reaction of (E)-3-phenyl-1-arylprop-2-en-1-ones
1
a and 1b with benzamidine (2a), 4-methylbenzamidine
(
(
2b), and 4-isobutoxybenzamidine hydrochlorides
2c) in ethanol in the presence of KOH involved
cyclocondensation and concurrent dehydrogenation–
aromatization to give 2,4,6-trisubstituted pyrimidines
3
a–3c. The latter were use the starting compounds in the
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 56 No. 2 2020

ANIL SYNTHESIS IN THE DESIGN OF PUSH−PULL SYSTEMS.
271
Scheme 2.
_
N
N
N
N
N
N_
_
H C
2
H2C
H C
2
A
_
CH2
A1
CH
A2
CH2
2
_
N
N
N
N
N
N_
B
B1
B2
We synthesized Schiff bases 4a–4d from aromatic
aldehydes and 2-chloroaniline by heating the reagents
in the absence of solvents. The products were further
reacted without isolation and purification. Of the bases
mentioned in the original protocol we chose KOH, but,
for the sake of convenience and simplicity, instead of
the recommended 7–10 molar excess of anhydrous
KOH, we used a mixture of 5 mol of anhydrous KOH
and 5 mol of LiH in DMF.
in one canonical formula (boundary formula B1) and
through a chain including four conjugated double bonds
in the another (boundary formula B2) (Scheme 2).
The mesomeric forms, where the negative charge
5
delocalized over phenyl carbons and the C atom of
the pyrimidine ring, but these forms are less favored
by energy and contribute much less of the mesomeric
stabilization of the carbanions.
Thereactionpresumablyinvolvestheinitialformation
of such carbanions, where the energetically most
efficient stabilization of the negative change through the
most extended π-conjugated chain takes place, and just
such cations further react with electrophilic imines.
It was found that 4,6-diphenyl-2-(p-tolyl)pyrimidine
(3a),2,4-diphenyl-6-(p-tolyl)pyrimidine(3b),and4,6-di-
phenyl-2-(4-isobutoxyphenyl)pyrimidine (3c) smoothly
reactwith(E)-N-(2-chlorophenyl)-1-(aryl)methanimines
4
a–4d in a KOH/LiH mixture in DMF at 95–105°С to
Conclusive evidence for the structure of the synthe-
form target trisubstituted pyrimidines 5a–5d and 6а–6e.
1
13
sized compounds was obtained by IR and Н and
NMR spectroscopy. Analysis of the С NMR spectra
С
1
3
To explain the reactivity of isomeric pyrimidines
a–3c in the anil synthesis in the presence of alkalis,
3
gave a lot of useful information.
we considered, as a working hypothesis, the possible
boundary mesomeric structures formed by deprotonation
of the methyl group of the 2-(p-tolyl) substituent
in the pyrimidine ring. The negative charge in the
two canonical forms of the resulting carbanion A is
effectively delocalized by the nitrogen atoms through a
chain including five conjugated double bonds (boundary
formulas A1 and A2). At the same time, in carbanion B,
formed due to deprotonation of the 4-(p-tolyl) substituent
in the pyrimidine ring is stabilized in a similar way
For example, starting pyrimidine 3a and its
derivative 5a with the 2-(p-tolyl) substituent on has a
symmetry plane, which passes through the methyl group
and pyrimidine C atom (compound 3a) or through the
methyl and 2-(4-styrylphenyl) groups (compound 5a);
as a result, the С13 NMR spectra of compounds 3a and
5
5a contain as little as 11 and 17 signals, respectively. At
1
3
the same time, in the С NMR spectra of their isomeric
pyrimidines 3b and 6b, which have no symmetry
elements, we observe 17 and 22 signals, respectively.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 56 No. 2 2020

272
HARUTYUNYAN et al.
ʌ-A
ʌ-D
ʌ-A/D
ʌ-A/D
R2
ʌ-A/D
ʌ-D
N
ʌ-A
ʌ-A
N
N
N
R2
ʌ-A/D
ʌ-D
ʌ-A/D
ʌ-D, ʌ-A/D ʌ-A ʌ-A/D
ʌ-D, ʌ-A/D ʌ-A ʌ-D , ʌ-A/D
Fig. 1. Electron cloud distribution in synthesized systems 5 and 6.
The structures of the synthesized series of isomeric
had gained 0.5 g, after which it was allowed to stand
overnight at room temperature. The ether was evaporated
at reduced pressure, and the residue was cooled on
ice bath and poured with 20 mL of absolute alcohol
saturated with gaseous ammonia. After 2 days, ethanol
was evaporated, the residue was treated with dry ether,
and the precipitate was filtered off. Yield 1.9 g (83.1%),
pyrimidines 5a–5d and 6a–6e comprise the main
elements of V-shaped push–pull systems, where the
π-acceptor (π-A) and π-donor parts of the molecule
π-D) are conjugated by the type π-A/D–π-A–π-A/D
11] (Fig. 1).
(
[
The central positions in both compound 5 and 6 is
–
1
mp 238–240°С. IR spectrum, ν, cm : 3360, 3120,
occupied by the π-deficient pyrimidine ring (π-А), which
is directly linked with the unsubstituted phenyl group
with the stabilizing ±M effect (π-A/D), phenyl group
+
+
2
740 (NH , NH ), 1669 (NH ), 1608 (C=C–C=N). The
3 2 2
product was further reacted without purification.
1
1
with the ±M effect (R = H, π-A/D) or +M effect (R =
isobutyl, π-D), and phenyl group π-conjugated through
the 4-ethenyl spacer with the phenyl group, whose
substituents determine the electronic characteristics
of the entire 4-(4-styrylphenyl) substituent in the
pyrimidine ring.
Pyrimidines 3a–3c (general procedure). A mixture
of 0.01 mol of amidine hydrochloride 2a–2c, 0.01 mol
of (E)-1-aryl-3-phenylprop-2-en-1-one 3a–3c, and
1.12 g (0.02 mol) of KOH in 30 mL of absolute ethanol
was left to stand overnight at room temperature and then
refluxed for 3 h, and the solvent was evaporated. The
residue was poured with 50 mL of water, left to stand
for 3 h in the cold, and the precipitate was filtered off.
Some representatives of both series of pyrimidines
exhibit well-defined fluorescence, which is undoubtedly
associated with the high mobility of the electron cloud
and provides evidence of the push–pull nature of the
synthesized conjugated systems.
4,6-Diphenyl-2-(p-tolyl)pyrimidine (3a) was pre-
pared from 4-methylbenzamidine hydrochloride [13]
and (E)-N,1-diphenylmethanimine (4a). Yield 65.0%,
–
1
mp 188–190°С, R 0.62. IR spectrum, ν, cm : 1605,
f
1
EXPERIMENTAL
1
595 (C=C–C=N). H NMR spectrum (DMSO-d –CCl ,
1 : 3), δ, ppm: 2.47 s (3H, CH ), 7.27–7.32 m (2H, H
, C H ), 8.24 s (1H,
), 8.34–8.42 m (4H, 2H , C H ), 8.54–8.59 m
(2H, H , C H ). C NMR spectrum, δ, ppm: 21.0
6
4
,
3
',5'
The IR spectra were measured on a Nicolet Avatar
3
1
3',4',5'
3
30 FTIR spectrophotometer in mineral oil. The Н
C H ), 7.48–7.58 m (6H, 2H
H
6
5
4
6 5
2',6'
NMR spectra were obtained on a Varian Mercury-300
spectrometer at 300 МHz and a Bruker Avance Neo 400
spectrometer at 400 МHz, internal reference TMS. The
elemental analyses were obtained on a EuroVector ЕА
pyrimidine
6
5
2
',6'
13
6
4
(CH ), 109.5, 126.9, 127.8, 128.1, 128.4, 130.0, 134.9,
3
136.8, 139.6, 163.4, 163.7. Found, %: C 85.54; H 5.77;
N 8.45. C H N . Calculated, %: C 85.68; H 5.63; N
3
000 elemental analyzer. Thin layer chromatography
2
3
18
2
was performed on Silufol UV-254 in 1 : 8 ethyl acetate–
hexane (3a–3c, 5a–5c, 6a, 6c–6e) and 1 : 4 ethyl acetate–
hexane (6b), spot visualization under UV light.
8.69.
2
,4-Diphenyl-6-(p-tolyl)pyrimidine (3b) was pre-
pared from benzamidine hydrochloride and (E)-3-
phenyl-1-(p-tolyl)prop-2-en-1-one [14]. Yield 72.3%,
mp 150–152°С (150–152°С [15]). H NMR spectrum
4
-Isobutoxybenzamidine (2c). Dry gaseous HCl
1
stream was bubbled through a solution of 1.75 g
(
0.01 mol) of 4-isobutoxybenzonitrile [12] and 0.6 g
0.013 mol) of absolute ethanol in 5 mL of dry ether
(DMSO-d –CCl , 1 : 3), δ, ppm: 2.48 s (3H, CH ), 7.32–
6
4
3
3
',5'
3',4',5'
2',6'
(
7.36 m (2H, H , C H ), 7.44–7.58 m (6H, 2H
,
,
6
4
5
with cooling on an ice bath until the reaction mixture
C H ), 8.23 s (1H, Hpyrimidine), 8.27–8.31 m (4H, 2H
6
5
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ANIL SYNTHESIS IN THE DESIGN OF PUSH−PULL SYSTEMS.
273
2
',6'
–1
1
C H ), 8.36–8.41 m (2H, H , C H ), 8.65–8.70 m (2H,
ν, cm : (C=C–C=N). H NMR spectrum (DMSO-d –
6
2
4
',6'
6
5
6
13
H
, C H ). C NMR spectrum, δ, ppm: 20.9 (CH3),
09.4, 126.80, 126.84, 127.7, 127.8, 128.1, 128.9, 129.8,
30.0, 134.0, 136.8, 137.6, 140.1, 163.2, 163.7, 163.8.
CCl , 1 : 3), δ, ppm (J, Hz): 3.83 s (3H, OCH ), 6.86–
6.91 m (2H, H , C H MeO), 7.08 d (1H, CH=CH, J
16.3), 7.20 d (1H, CH=CH, J 16.3), 7.48–7.60 m (8H,
H , C H MeO, H , 2C H ), 7.62–7.66 m (2H,
6
5
4
3
3
,5
1
1
6 4
2
,6
3,4,5
2
-(4-Isobutoxyphenyl)-4-phenyl-6-(p-tolyl)pyri-
midine (3c). Yield 76.7%, mp 120–122°С, R 0.80. IR
6
4
6
5
3
,5
5
H , C H ), 8.26 s (1H, H
), 8.38–8.42 m (4H,
6
4
pyrimidine
2,6
f
1
2
,6
13
–
1
H , 2C H ), 8.63–8.67 m (2H, H , C H ). C NMR
spectrum, δ, ppm: 54.5 (OCH ), 109.6 (C Hpyrimidine),
13.6 (2CH, C , C H MeO), 125.5 (CH), 125.6 (2CH),
26.9 (4CH), 127.4 (2CH), 128.1 (2CH), 128.2 (4CH),
128.8 (CH), 129.3, 130.1 (2CH), 136.2, 136.8, 139.3,
158.9, 163.1, 163.8. Found, %: C 84.35; H 5.63; N 6.44.
spectrum, ν, cm : 1607, 1585 (C=C–C=N). H NMR
spectrum (DMSO-d –CCl , 1 : 3), δ, ppm (J, Hz):
6 5 6 4
5
3
6
4
3
,5
1
1
.09 d (6H, Me , J 6.7), 2.07–2.20 m (1H, CH), 2.47 s
6 4
2
1
(
H
7
8
3H, CH ), 3.83 d (2H, CH , J 6.5), 6.95–7.00 m (2H,
3 2
3
',5'
3',5'
, C H O-i-Bu), 7.31–7.35 m (2H, H , C H Me),
6 4 6 4
3
',4,5'
5
.47–7.57 m (3H, H
, C H ), 8.14 s (1H, Hpyrimidine),
6 5
2
',6'
C H N О. Calculated, %: C 84.52; H 5.49; N 6.36.
.24–8.28 m (2H, H , C H Me), 8.33–8.38 m (2H,
31 24 2
6
4
2',6'
2',6'
13
H
, C H ), 8.56–8.61 m (2H, H , C H O-i-Bu). C
NMR spectrum, δ, ppm: 18.8 (Me ), 20.9 (CH ), 27.7
CH), 73.5 (CH ), 108.6, 113.5 (2CH), 126.7 (2CH),
26.8 (2CH), 128.1 (2CH), 128.8 (2CH), 129.3 (2CH),
29.9, 130.1, 134.1, 137.0, 139.9, 160.7, 163.1, 163.5,
63.6. Found, %: C 82.43; H 6.52; N 7.27. C H N O.
(E)-4,6-Diphenyl-2-[4-(4-isopropylstyryl)phenyl]-
pyrimidine (5c) was prepared from pyrimidine 3a
with (E)-N-(2-chlorophenyl)-1-(4-isopropylphenyl)me-
thanimine (4e). Yield 72.2%, mp 172–174°С, R 0.52.
IR spectrum, ν, cm : 1583, 1574 (C=C–C=N). H NMR
spectrum (DMSO-d –CCl , 1 : 3), δ, ppm (J, Hz): 1.29 d
(6H, Me ), 2.92 septet (1H, CHMe , J 6.9), 7.18 d (1H,
CH=CH, J 16.3), 7.18–7.22 m (2H, H , C H C H ),
.23 d (1H, CH=CH, J 16.3), 7.46–7.51 m (2H, H ,
6
5
6
4
2
3
(
2
1
1
f
–
1
1
1
2
7
26
2
6
4
Calculated, %: C 82.20; H 6.64; N 7.10.
2 2
3
,5
Pyrimidines 5a–5d and 6a–6e (general procedure).
A mixture of 0.0055 mol of aromatic aldehyde and
.0055 mol of 2-chloroaniline was heated for 4 h at
40–150°С in a 20-mLround-bottomed flask. After
cooling, 1.61 g (0.005 mol) of pyrimidine 3a, 3b, or
c, 1.4 g (0.025 mol) of single melted KOH, 0.20 g
0.025 mol) of LiH, and 10 mL of dry DMF was added,
and the resulting mixture was heated for 3 h at 90–
00°С. Already after 5 min, the yellowish color of the
solution changes to dark crimson. The mixture was then
cooled to room temperature, poured onto 50 g of ice,
and left in the cold. The product was filtered off through
a paper filter and recrystallized from 80% AcOH.
6
4
3
7
2
,6
7
C H C H ), 7.52–7.60 m (8Нarom), 7.64–7.68 m (2Н,
0
1
6
3
4
3
7
,5
5
H , C H ), 8.26 s (1H, H
), 8.38–8.43 m (4H,
6
4
pyrimidine
2,6
2
,6
13
H , 2C H ), 8.64–8.68 m (2H, H , C H ). C NMR
6
5
6
4
3
(
spectrum, δ, ppm: 23.5 (Me2), 33.2 (CH), 109.6, 125.8,
126.0, 126.2, 126.8, 126.9 (4CH), 128.1, 128.2 (4CH),
129.1, 130.1, 134.2, 136.5, 136.8, 139.1, 147.6, 163.1,
163.8. Found, %: C 87.73; H 6.17; N 6.37. C33H28N2.
Calculated, %: C 87.57; H 6.24; N 6.19.
1
(
E)-2-{4-[2-(Benzo[d][1,3]dioxol-5-yl)vinyl]phe-
nyl}-4,6-diphenylpyrimidine (5d) was prepared from
pyrimidine 3a and (E)-1-benzo[d][1,3]dioxol-5-yl-N-
(2-chlorophenyl)methanimine (4d). Yield 73.1%, mp
183–185°С, R 0.28. IR spectrum, ν, cm : 1586, 1573
(C=C–C=N). HNMRspectrum(DMSO-d –CCl , 1:3),
(
E)-4,6-Diphenyl-2-(4-styrylphenyl)pyrimidine
5a) was prepared from pyrimidine 3a and (E)-N,1-
diphenylmethanimine(4a).Yield64.3%,mp202–204°С,
–
1
(
f
1
6
4
–
1
7
R 0.64. IR spectrum, ν, cm : 1585, 1574 (C=C–C=N).
δ, ppm (J, Hz): 6.01 s (2H, CH ), 6.80 d (1H, H , C H ,
J 8.0), 7.01 d.d (1H, H , C H , J 8.0, 1.7), 7.08 d (1H,
6 3
f
2 6 3
1
7
H NMR spectrum (DMSO-d –CCl , 1 : 3), δ, ppm:
6
4
4
7
.21–7.27 m (1H, H , C H CH=CH), 7.25 s (2H,
CH=CH, J 16.3), 7.18 d (1H, CH=CH, J 16.3), 7.18 d
6
5
3
,5
4
3,4,5
C H CH=CH), 7.32–7.38 m (2H, H , C H CH=CH),
(1H, H , C H , J 1.7), 7.50–7.60 m (6H, H , 2C H ),
6
5
6
5
6 3 6 5
3
,4,5
2,6
3,5
5
7
7
8
.50–7.60 m (8H, H , 2C H and H , C H CH=CH),
7.62–7.66 m (2H, H , C H ), 8.27 s (1H, H
),
6
5
6
5
6
4
pyrimidine
2,6
3
,5
5
2,6
.66–7.71 m (2H, H , C H ), 8.27 s (1H, H
),
8.38–8.43 m (4H, H , 2C H ), 8.63–8.67 (2H, H ,
6
4
pyrimidine
2,6
6 5
2
,6
13
.38–8.43 m (4H, H , 2C H ), 8.66–8.71 m (2H, H ,
C H ). C NMR spectrum, δ, ppm: 100.5 (CH ), 105.1
6 4 2
6
5
13
C H ). C NMR spectrum, δ, ppm: 109.7, 125.9, 126.1,
26.9, 127.1, 127.8, 128.0, 128.1, 128.2, 129.2, 130.1,
36.6, 136.7, 136.8, 138.9, 163.1, 163.8. Found, %:
(CH), 107.7 (CH), 109.6 (CH), 121.3 (CH), 125.7 (2CH),
126.0(CH),126.9(4CH),128.1(2CH),128.2(4CH),128.9
(CH), 130.1 (2CH), 131.1, 136.3, 136.8, 139.1, 146.9,
147.6, 163.1, 163.8. Found, %: C 81.78; H 4.75; N 6.31.
C H N O . Calculated, %: C 81.92; H 4.88; N 6.16
6
4
1
1
C 88.15; H 5.32; N 6.64. C H N . Calculated, %: C
3
0
22
2
8
7.77; H 5.40; N 6.82.
3
1
22
2
2
(
E)-4,6-Diphenyl-2-[4-(4-methoxystyryl)phenyl]-
(E)-2,4-Diphenyl-6-(4-styrylphenyl)pyrimidine
pyrimidine (5b) was prepared from pyrimidine 3a s (E)-
N-(2-chlorophenyl)-1-(4-methoxyphenyl)methanimine
(6a) was prepared from pyrimidine 3b and (E)-N,1-
diphenylmethanimine(4a).Yield63.8%,mp186–188°С,
–
1
(
4b). Yield 77.6%, mp 234–236°С, R 0.24. IR spectrum,
R 0.59. IR spectrum, ν, cm : 1600, 1589 (C=C–C=N).
f
f
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 56 No. 2 2020

274
HARUTYUNYAN et al.
1
6'
H NMR spectrum (DMSO-d –CCl , 1 : 3), δ, ppm
J 8.0), 7.12 d.d (1H, H , C H , J 8.0, 1.5), 7.25 d (1H,
6 3
6
4
4
'
(J, Hz): 7.24 d (1H) and 7.29 d (1H, CH=CH, J 16.0),
CH=СН, J 16.5), 7.35 d (1H, H , C H , J 1.5), 7.38 d
6 3
7
7
.22–7.27 m (1Нarom), 7.32–7.39 m (2Нarom), 7.48–
(1H,CH=СН,J16.5),7.58–7.65m(6Нarom),7.77–7.81m
(2Harom), 8.49–8.54 m (4Н ), 8.55 s (1H, H 5p yrimidine),
.60 m (8Нarom), 7.70–7.75 m (2Нarom), 8.30 s (1H,
arom
5
13
H
pyrimidine), 8.39–8.44 m (4Нarom), 8.66–8.71 m (2Нarom).
8.64–8.69 m (2Нarom). C NMR spectrum, δ, ppm: 101.1
13
C NMR spectrum, δ, ppm: 109.6, 126.2, 126.3, 126.9,
(CH ), 105.4 (CH), 108.4 (CH), 110.1 (CH), 122.1 (CH),
2
1
1
1
6
27.2, 127.3, 127.4, 127.7, 127.8, 128.06, 128.14,
29.6, 129.9, 130.1, 135.7, 136.5, 136.8, 137.6, 139.2,
63.28, 163.32, 163.8. Found, %: C 87.62; H 5.27; N
.93. C H N . Calculated, %: C 87.77; H 5.40; N 6.82.
125.9 (CH), 126.6 (2CH), 127.3 (2CH), 127.7 (2CH),
128.0 (2CH), 128.6 (2CH), 128.9 (2CH), 129.9 (CH),
130.8 (CH), 131.1 (CH), 131.4, 135.1, 136.6, 137.5,
140.2, 147.3, 147.9, 163.3, 163.7, 164.1. Found, %:
C 82.15; H 4.65; N 5.98. C H N O . Calculated, %:
30
22
2
3
1
22
2
2
(
E)-2,6-Diphenyl-4-[4-(4-methoxystyryl)phenyl]-
C 81.92; H 4.88; N 6.16
pyrimidine (6b) was prepared from pyrimidine 3b
and (E)-N-(2-chlorophenyl)-1-(4-methoxyphenyl)me-
thanimine (4b). Yield 78.5%, mp 162–164°С, R 0.42.
IR spectrum, ν, cm : 1601, 1590 (C=C–C=N). H NMR
spectrum (DMSO-d –CCl , 1 : 3), δ, ppm (J, Hz): 3.83 s
(
E)-2-(4-Isobutoxyphenyl)-4-(4-styrylphenyl)-6-
phenylpyrimidine (6e) was prepared from pyrimidine
3c and (E)-N,1-diphenylmethanimine (4a). Yield 64.7%,
f
–
1
1
–
1
mp 162–164°С, R 0.61. IR spectrum, ν, cm : 1607
f
6
4
1
3
',5'
(C=C–C=N). HNMRspectrum(DMSO-d –CCl , 1:3),
(3H, CH ), 6.87–.92 m (2H, H , C H MeO), 7.08 d
6
4
3
6
4
δ, ppm (J, Hz): 1.09 d (6H, 2CH , J 6.7), 2.14 m (1H,
(2H, CH=СН, J 16.3), 7.24 d (2H, CH=СН, J 16.3),
3
CH), 3.84 d (2H, CH , J 6.4), 6.96–7.01 m (2H, C H O-
7
.45–7.60 m (8Нarom), 7.66–7.71 m (2Нarom), 8.30 s (1H,
5p yrimidine), 8.38–8.43 m (4Нarom), 8.66–8.71 m (2Нarom).
2
6
4
i-Bu), 7.20–7.28 m (3Нarom), 7.32–7.38 m (2Нarom),
H
13
7.50–7.60 m (5Нarom), 7.69–7.74 m (2Нarom), 8.21 s
C NMR spectrum, δ, ppm: 54.5 (OCH ), 109.5 (CH),
3
5
(
(
(
1H, H
), 8.35–8.42 m (4Нarom), 8.57–8.62 m
1
1
1
13.6 (2CH), 125.1 (CH), 126.0 (2CH), 126.9 (2CH),
pyrimidine
1
3
2Нarom). C NMR spectrum, δ, ppm: 18.9 (Ме ), 27.7
CH), 73.6 (OCH ), 108.8, 113.6 (2CH), 126.2 (2CH),
27.1 (2CH), 127.4 (2CH), 127.7 (2CH), 127.8 (2CH),
28.1 (2CH), 129.1, 129.3 (CH), 129.8 (CH), 130.0
2
2
1
1
1
1
26.4 (2CH), 126.9 (2CH), 127.2 (2CH), 127.3, 127.5,
28.1 (2CH), 128.2 (2CH), 128.3, 129.4 (2CH), 129.6,
30.1, 135.9, 136.6, 137.0, 139.2, 160.8, 163.2, 163.3,
63.7. Found, %: C 84.80; H 6.06; N 5.64. C H N O.
(CH), 135.1, 136.8, 137.6, 139.7, 159.0, 163.2, 163.4,
1
63.7. Found, %: C 84.67; H 5.33; N 6.52. C H N О.
31 24 2
Calculated, %: C 84.52; H 5.49; N 6.36.
3
4
30
2
(
E)-2,6-Diphenyl-4-[4-(4-isopropylstyryl)phenyl]-
Calculated, %: C 84.61; H 6.27; N 5.80.
pyrimidine (6c) was prepared from pyrimidine 3b
and (E)-N-(2-chlorophenyl)-1-(4-isopropylphenyl)me-
FUNDING
thanimine (4c). Yield 73.0%, mp 150–152°С, R 0.67.
The work was financially supported by the State
Committee for Science of the Republic of Armenia (grant no.
8-Т-1D249) and by the Ministry for Education and Science
of the Russian Federation through the subsidy allocated for
research activity of the Russian–Armenian University.
f
–
1
1
IR spectrum, ν, cm : 1588 (C=C–C=N). H NMR spec-
trum (DMSO-d –CCl , 1 : 3), δ, ppm (J, Hz): 1.28 d
1
6
4
(
6H, CH , J 6.9), 2.91 septet (1H, CH, J 6.9), 7.17 d (1H,
3
CH=СН, J 16.4), 7.18–7.23 m (2Harom), 7.26 d (1H,
CH=СН, J 16.4), 7.46–7.59 m (8Нarom), 7.69–7.73 m
CONFLICT OF INTEREST
The authors declare no conflict of interest.
REFERENCES
5
(
8
2Harom), 8.31 s (1H, Hpyrimidine), 8.40–8.44 m (4Нarom),
.67–8.71 m (2Нarom). C NMR spectrum, δ, ppm: 23.6
1
3
(
(
(
(
Ме ), 33.3 (CH), 109.6 (CH), 126.2 (2CH), 126.30
2
1
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1
37.7, 139.5, 147.9, 163.3, 163.4, 163.8. Found, %:
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3
3
28
2
8
7.57; H 6.24; N 6.19.
(
E)-4-{4-[2-(Benzo[d][1,3]dioxol-5-yl)vinyl]phe-
nyl}-2,6-diphenylpyrimidine (6d) was prepared from
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3
. Dhanalakshmi, P. and Shanmugam, S., RSC Adv.,
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2
(
1
2-chlorophenyl)methanimine (4d). Yield 60.4%, mp
–
1
73–174°С, R 0.45. IR spectrum, ν, cm : 1589 (C=C–
f
1
C=N). H NMR spectrum (DMSO-d –CCl , 1 : 3),
δ, ppm (J, Hz): 6.06 s (2H, CH ), 6.95 d (1H, H , C H ,
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6
4
7
'
Yerevan, 2017.
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6
3
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RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 56 No. 2 2020