Synthesis of arylmethylpyrimidinetriones and pyrimidoquinolinediones with fluorescent and nonlinear-optical properties

Article abstract of DOI:10.1134/S1070427207070178

5-Arylmethyl-2,4,6-(1H,3H,5H)pyrimidinetriones and 12-aryl-8,12- dihydrobenzo[f]pyrimido[4,5-b]quinoline-9,11-(7H,10H)diones were synthesized, and their spectral-luminescence and nonlinear-optical properties were examined.

Full text of DOI:10.1134/S1070427207070178

ISSN 1070-4272, Russian Journal of Applied Chemistry, 2007, Vol. 80, No. 7, pp. 1101 1104. Pleiades Publishing, Ltd., 2007.
Original Russian Text
N.G. Kozlov, S.L. Bondarev, B.A. Odnoburtsev, L.I. Basalaeva, 2007, published in Zhurnal Prikladnoi Khimii, 2007, Vol. 80,
No. 7, pp. 1131 1134.
ORGANIC SYNTHESIS
AND INDUSTRIAL ORGANIC CHEMISTRY
Synthesis of Arylmethylpyrimidinetriones
and Pyrimidoquinolinediones with Fluorescent
and Nonlinear-Optical Properties
N. G. Kozlov, S. L. Bondarev, B. A. Odnoburtsev, and L. I. Basalaeva
Institute of Physical Organic Chemistry, National Academy of Sciences of Belarus, Minsk, Belarus
Institute of Molecular and Atomic Physics, National Academy of Sciences of Belarus, Minsk, Belarus
Received February 28, 2006
Abstract 5-Arylmethyl-2,4,6-(1H,3H,5H)pyrimidinetriones and 12-aryl-8,12-dihydrobenzo[f ]pyrimido-
[
4,5-b]quinoline-9,11-(7H,10H)diones were synthesized, and their spectral-luminescence and nonlinear-optical
properties were examined.
DOI: 10.1134/S1070427207070178
Organic luminophores containing a carbonyl group,
either in the open chain or incorporated into the cyclic
system, are of great practical significance. These com-
pounds include, in particular, arylmethylpyrimidine-
triones, both known and new, and pyrimidoquinoline-
diones prepared by the scheme
IIIa IIIh
Ia Il
II
IV
IV
Vd, Vf, Vh Vl
where R = N(CH ) (a), N(C H ) (b), 3,4-di-(OH)
Refluxing equimolar amounts of appropriate benz-
aldehyde Ia Ih and 2,4,6-(1H,3H,5H)pyrimidine-
trione (barbituric acid) II in an alcohol solution
resulted in selective formation of 5-arylmethyl-2,4,6-
(1H,3H,5H)pyrimidinetriones IIIa IIIh.
3
2
2 5 2
(
3
2
c), 2,4-di-OMe (d), 3,4-di-OMe (e), 3-OEt-4-OH (f),
-OMe-4-OCOEt (g), 3-OMe-4-OCO(CH ) Me (h),
2 2
,4-di-Cl (i), 3-OMe-4-OH (j), 3-OMe-4-OCOC H
6
5
(k), and 2-F-6-Cl (l).
1101

1102
KOZLOV et al.
Table 1. Properties of 5-arylmethyl-2,4,6-(1H,3H,5H)pyrimidinetriones IIIf IIIh and 12-aryl-8,12-dihydrobenzo[f ]-
pyrimido[4,5-b]quinoline-9,11-(7H,10H)diones Vd, Vf, and Vh Vl
Found, %
H
Calculated, %
H
Com-
pound
Yield, %
mp,
C
Formula
C
N
C
N
IIIf
75
70
63
40
59
52
61
62
37
64
275
283
292
>350
>350
>350
>350
>350
>350
>350
56.55
54.92
56.24
68.77
68.87
68.25
61.58
68.24
70.88
64.14
4.34
4.58
5.02
4.78
4.76
5.00
3.15
4.42
4.27
3.36
10.12 C H N O
56.52
54.90
56.25
68.82
68.82
68.27
61.61
68.20
70.87
64.12
4.35
4.57
5.00
4.74
4.74
5.03
3.18
4.39
4.28
3.31
10.14
9.15
8.75
10.47
10.48
9.19
10.27
10.85
8.55
1
3
12
2
5
6
6
4
4
5
IIIg
IIIh
Vd
Vf
Vh
Vi
Vj
Vk
Vl
9.15 C H N O
14 14 2
8.77 C H N O
1
5 16 2
10.50 C H N O
2
3 19 3
10.51 C H N O
2
3 19 3
9.21 C H N O
26 23 3
10.3 C H Cl N O
2
1
13
2 3 2
10.88 C H N O
22 17 3 4
8.58 C H N O
29 21 3 5
10.71 C H FClN O
10.68
2
1
13
3 2
Pyrimidoquinolinediones Vd, Vf, Vh and Vi Vl
can be prepared both by the reaction of arylmethylpy-
rimidinetriones with 2-naphthylamine and three-com-
ponent condensation of benzaldehydes Ii Il, barbituric
acid, and 2-naphthylamine via formation of arylidene-
triones which further react with 2-naphthylamine.
The latter, having the highest electron density on
which is the strongest (Irel 100%), and several frag-
ment peaks. The mass spectra of pyrimidoquinoline-
diones Vd, Vf, and Vh Vl contain a peak with the
maximal intensity (Irel 100%) at m/z 264, correspond-
+
ing to the [M C H ] ion, a peak with m/z 265
6
4
corresponding to the [M C H + 1] + ion (I 65
6
4
rel
+
70%), and peaks of the molecular ion M (28 35%)
the carbon atom in the
position with respect to
and positive ions with m/z 111 (29 33%), 134 (56
the amino group, enters into the addition reaction at
the double bond of arylmethylpyrimidinetriones III.
Previously [1] we reported that this pathway is pos-
sible for multicomponent condensation of benzalde-
hydes, 1,3-diketones, and 2-naphthylamine. In this
study, we prepared pyrimidoquinolinediones by two
pathways: Vd, Vf, Vh by the first pathway, and
Vi Vl, by the second pathway. Physicochemical con-
stants of arylmethylpyrimidinetriones IIIa IIIe are
identical to those published in [2 4]; for constants of
IIIf IIIh and Vd, Vf, Vh and Vi Vl, see Table 1.
6
0%), 139 (90 96%), 148 (72 78%), 153 (47 55%),
166 (32 39%), and 222 (18 23%) formed from the
+
[M
C H ] fragment ion and constant for all these
6
4
compounds.
The electronic absorption spectra of arylmethyl-
pyrimidinetriones IIIa IIIh and pyrimidinequinoline-
diones Vd, Vf, and Vh Vl in ethanol are charac-
terized by a number of vibronic bands (their
relative intensities are listed in Table 2); the spectra
and
max
of IIIa and Vl are shown in the figure.
Pyrimidoquinolinediones Vd, Vf, and Vh Vl in
an ethanol solution exhibit a weak fluorescence with
a maximum near 380 nm. Arylmethylpyrimidine-
triones IIIa IIIh in an ethanol solution also exhibit
weak fluorescence, with the spectra shifted to long
waves relative to those of Vd, Vf, and Vh Vl.
The position and multiplicity of the aromatic pro-
ton signals in the H NMR spectra of arylmethyl-
pyrimidinetriones IIIa IIIh and pyrimidinequinoline-
diones Vd, Vf, and Vh Vl correspond to the struc-
tures of compounds of this kind [5].
1
The IR spectra of arylmethylpyrimidinetriones
IIIa IIIh and pyrimidinequinolinediones Vd, Vf,
and Vh Vl contain bands associated with the stretch-
All the compounds examined in the crystalline
state at room temperature exhibit fluorescence of dif-
ferent intensities. The fluorescence spectra were re-
ing vibrations of secondary amines (a band at 3520
1
1
3
1
185 cm ) and carbonyl groups (a band at 1729
corded at
= 340 nm. Arylmethylpyrimidine-
exc
701 cm ). Pyrimidoquinolinediones Vi and Vl ex-
triones IIIa, IIIb, IIIe and pyrimidinequinolinediones
Vd, Vf, Vh, Vl are characterized by intense fluores-
cence, and the remaining compounds examined, by
weak fluorescence. The maxima in the fluorescence
spectra vary over a wide spectral range. Fluorescence
of polycrystals of Vd, Vf, and Vh Vl is charac-
1
hibit an intense absorption band at 860 and 830 cm ,
respectively, associated with the stretching vibrations
of the C Cl bond.
The mass spectra of arylmethylpyrimidinetriones
+
IIIa IIIh synthesized contain a molecular peak [M] ,
RUSSIAN JOURNAL OF APPLIED CHEMISTRY Vol. 80 No. 7 2007

SYNTHESIS OF ARYLMETHYLPYRIMIDINETRIONES
1103
Table 2. Spectral-luminescence properties of arylmethylpyrimidinetriones IIIf IIIh and pyrimidoquinolinediones Vd, Vf,
and Vh Vl in ethanol solution and as polycrystals at room temperature
Fluorescence, max, nm (Irel)
Absorption max, nm (Irel),
Compound
ethanol
ethanol
polycrystals
IIIa
IIIb
IIIc
IIId
IIIe
IIIf
IIIg
IIIh
Vd
Vd
Vh
Vi
Vj
465(1.0), 275(0.12), 244(0.23)
470(1.0), 278(0.14), 239(0.26)
410(1.0), 256(0.46), 233(0.53)
410(1.0), 252(0.45)
395(0.83), 259(1.0), 230(0.86)
483(0.55), 407(1.0), 256(0.71), 232(0.67)
358(0.59), 257(1.0)
396(0.40), 257(1.0)
323(0.43), 284(1.0)
320(0.42), 279(1.0)
320(0.39), 285(1.0), 275(0.96)
323(0.34), 286(1.0), 275(0.88)
320(0.43), 263(1.0)
319(0.34), 284(0.96), 274(1.0)
322(0.30), 384(1.0)
522
529
590(0.37), 634(1.0)
637
609
515
588
524
401
443(1.0), 517(0.83)
460
452(0.3), 573(0.9), 604(1.0)
461
420
458
382
379
378
380
380
377
381
403(0.46), 547(1.0)
400
393
393
405(1.0), 550(0.32)
398(0.73), 426(1.0)
394
Vk
Vl
410
terized primarily by maxima near 400 nm, while that
EXPERIMENTAL
of IIIa IIIh, by maxima varying within 400 650 nm
(see figure and Table 2).
The IR spectra of the arylmethylpyrimidinetriones
and pyrimidoquinolinedions examined were recorded
on a Nicolet Protege-460 Fourier spectrophotometer
from a thin layer or KBr pellets, and mass spectra, on
a Hewlett Packard 5890/5979 Chrommas GC/MS
chromatograph mass spectrometer, HP-5MS column
Polycrystals of some compounds display nonlinear-
optical properties, i.e., are able of converting the laser
radiation frequency. For example, when excited by the
3+
first harmonics of radiation of a YAG : Nd laser
( exc = 1.06 m, Eexc = 80 mJ, pulse length 20 ns)
polycrystalline arylmethylpyrimidinetriones IIIa and
IIIb exhibited bright red two-photon-excited fluores-
(
70 eV). The absorption spectra of the solutions were
measured at room temperature on a Cary-500 (Varian,
the United States) spectrophotometer, and the fluores-
cence (TEF) with
pyrimidinetrione IIIa, less intense yellow TEF at
640 nm, and arylmethyl-
max
6
00 nm.
Arylmethylpyrimidinetriones IIIf and IIIg ex-
hibited a different nonlinear-optical effect, generation
of the second harmonics of laser radiation (GSG). It
consists in converting the wavelength of the first
harmonics of a neodymium laser (1.06 m) into the
second harmonics wavelength (532 nm) by the poly-
crystals. Thus, both these substances emit bright red
luminescence at 532 nm when irradiated with intense
invisible IR radiation (1.06 m). For arylmethylpyri-
midinetrione IIIh we recorded a weak GSG effect.
The nonlinear-optical effects revealed for arylmeth-
ylpyrimidinetriones IIIa, IIIb, IIIe (TEF) and IIIf
IIIh (GSG) make these compounds candidate materi-
als for preparing elements for visual imaging of in-
visible IR laser radiation, optical recording of infor-
mation, and development of nonlinear-optical ele-
ments for GSG.
,
nm
(
(
1, 4) Absorption and (2, 3, 5, 6) fluorescence spectra of
4 6) IIIa and (1 3) Vl in (1, 2, 4, 5) ethanol and
(3, 6) polycrystals at 293 K. (I) Intensity and ( ) wave-
length.
RUSSIAN JOURNAL OF APPLIED CHEMISTRY Vol. 80 No. 7 2007

1104
KOZLOV et al.
cence spectra, on a wide-aperture setup [6]. Two-pho-
ton excitation was achieved with the first harmonics
was revealed for already known 5-dimethylamino-
(IIIa), 5-diethylamino- (IIIb), and 5-(3,4-dimethoxy)-
phenylmethyl-2,4,6-(1H,3H,5H)-pyrimidinetriones
(IIIe)], and generation of the second harmonics
of the laser radiation, for previously unknown 5-(4-
hydroxy-3-ethoxy- (IIIf), (4-carboxy-3-methyoxy)-
3+
of a YAG : Nd pulse laser with the wavelength of
.06 m.
1
5
-Arylmethyl-2,4,6-(1H,3H,5H)pyrimidine-
triones IIIf IIIh. Barbituric acid II [1.3 g (0.01 mol)]
and 0.01 mol of appropriate aldehyde Ia Ih in an
alcohol solution were refluxed for 20 30 min. The
precipitate formed after cooling the reaction mixture
was filtered off and recrystallized from alcohol.
(
2
IIIg),
5-(4-carbpropoxy-3-methoxy)phenylmethyl-
,4,6-(1H,3H,5H)pyrimidinetriones (IIIh). The effects
revealed make these compounds candidate materials
for preparing elements for visual imaging of invisible
IR laser radiation, optical recording of information,
and development of nonlinear-optical elements for
generation of the second harmonics of laser radiation.
1
2-Aryl-8,12-dihydrobenzo[f]pyrimido[4,5-b]-
quinoline-9,11-(7H,10H)diones Vd, Vf, Vh. A solu-
tion of 0.01 mol of appropriate 5-(4-arylmethyl)-2,4,6-
(
0
1H,3H,5H)pyrimidinetrione IIId, IIIf, IIIh and
.01 mol of 2-naphthylamine IV in 20 ml of butanol
ACKNOWLEDGMENTS
was refluxed until crystals formed. The precipitate
was filtered off and recrystallized from a 1 : 1 al-
cohol benzene mixture.
The authors are grateful to I.I. Kalosha from the
Institute or Atomic and Molecular Physics, National
Academy of Sciences of Belarus, for assistance in
carrying out the nonlinear-optical measurements.
1
2-Aryl-8,12-dihydrobenzo[f]pyrimido[4,5-b]-
quinoline-9,11-(7H,10H)diones Vi Vl. A solution of
.43 g (0.01 mol) of 2-naphthylamine IV, 0.01 mol
of appropriate aromatic aldehyde Ii Il, and 1.3 g
0.01 mol) of barbituric acid II in 20 ml of butanol
1
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and recrystallized from a 1 : 1 alcohol benzene
mixture.
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CONCLUSIONS
(
1) 5-Arylmethyl-2,4,6-(1H,3H,5H)pyrimidine-
triones IIIa, IIIb, IIIe and 12-aryl-8,12-dihydroben-
zo[f ]pyrimido[4,5-b]quinoline-9,11-(7H,10H)diones
Vd, Vf, Vh, Vl exhibit intense fluorescence.
(
2) These compounds exhibit nonlinear-optical ef-
fects. Specifically, two-photon-excited fluorescence
RUSSIAN JOURNAL OF APPLIED CHEMISTRY Vol. 80 No. 7 2007