Synthesis, Spectra, and Theoretical Investigations of 1,3,5-Triazines Compounds as Ultraviolet Rays Absorber Based on Time-Dependent Density Functional Calculations and three-Dimensional Quantitative Structure-Property Relationship

Article abstract of DOI:10.1007/s10895-018-2235-2

A series of 1,3,5-triazines were synthesized and their UV absorption properties were tested. The computational chemistry methods were used to construct quantitative structure-property relationship (QSPR), which was used to computer aided design of new 1,3,5-triazines ultraviolet rays absorber compounds. The experimental UV absorption data are in good agreement with those predicted data using the Time-dependent density functional theory (TD-DFT) [B3LYP/6–311 + G(d,p)]. A suitable forecasting model (R > 0.8, P < 0.0001) was revealed. Predictive three-dimensional quantitative structure-property relationship (3D-QSPR) model was established using multifit molecular alignment rule of Sybyl program, which conclusion is consistent with the TD-DFT calculation. The exceptional photostability mechanism of such ultraviolet rays absorber compounds was studied and confirmed as principally banked upon their ability to undergo excited-state deactivation via an ultrafast excited-state proton transfer (ESIPT). The intramolecular hydrogen bond (IMHB) of 1,3,5-triazines compounds is the basis for the excited state proton transfer, which was explored by IR spectroscopy, UV spectra, structural and energetic aspects of different conformers and frontier molecular orbitals analysis.

Full text of DOI:10.1007/s10895-018-2235-2

Journal of Fluorescence
https://doi.org/10.1007/s10895-018-2235-2
ORIGINAL ARTICLE
Synthesis, Spectra, and Theoretical Investigations of 1,3,5-Triazines
Compounds as Ultraviolet Rays Absorber Based on Time-Dependent
Density Functional Calculations and three-Dimensional Quantitative
Structure-Property Relationship
1
1
1
1
1
1
1,2
3
Xueding Wang & Yilian Xu & Lu Yang & Xiang Lu & Hao Zou & Weiqing Yang & Yuanyuan Zhang & Zicheng Li
Menglin Ma
&
1
Received: 27 February 2018 /Accepted: 23 April 2018
#
Springer Science+Business Media, LLC, part of Springer Nature 2018
Abstract
A series of 1,3,5-triazines were synthesized and their UV absorption properties were tested. The computational chemistry
methods were used to construct quantitative structure-property relationship (QSPR), which was used to computer aided design
of new 1,3,5-triazines ultraviolet rays absorber compounds. The experimental UV absorption data are in good agreement with
those predicted data using the Time-dependent density functional theory (TD-DFT) [B3LYP/6–311 + G(d,p)]. A suitable fore-
casting model (R > 0.8, P < 0.0001) was revealed. Predictive three-dimensional quantitative structure-property relationship (3D-
QSPR) model was established using multifit molecular alignment rule of Sybyl program, which conclusion is consistent with the
TD-DFT calculation. The exceptional photostability mechanism of such ultraviolet rays absorber compounds was studied and
confirmed as principally banked upon their ability to undergo excited-state deactivation via an ultrafast excited-state proton
transfer (ESIPT). The intramolecular hydrogen bond (IMHB) of 1,3,5-triazines compounds is the basis for the excited state
proton transfer, which was explored by IR spectroscopy, UV spectra, structural and energetic aspects of different conformers and
frontier molecular orbitals analysis.
.
.
.
Keywords 1,3,5-Triazines 3D-QSPR TD-DFTcalculations Ultraviolet rays absorber
Introduction
order to protect against the damaging effects of UV light,
UV absorbers (UVA) are used to absorb UV light and
thereby prevent the damage.
Due to ozone depletion, more and more ultraviolet rays
(
UVR) has been progressively increased on the earth and
An ideal UVA must have the key property, which is highly
efficient absorption between 280 and 400 nm coupled with
high optical transparency in the visible range. 2-(4,6-
diphenyl-1,3,5- triazin-2-yl)phenol derivatives are one sort
of efficient UVA absorbing in the wavelength region of 270-
400 nm and hardly absorbing visible light.
causes severe photo-induced loss to organic materials [1].
It is widely recognized that UVR in sunlight (wavelengths
between 280 nm and 400 nm) is an important factor caus-
ing skin aging, eye disease and photodegradation to some
organic substances such as polymers and colorants [2]. In
Several endeavours surrounding the spectral character-
ization of 1,3,5-triazine UVA were reported in the litera-
tures [1–7]. There is no systematic study on the theory
and experiment of 1,3,5-triazine derivatives as UVA. In
the present, a combined experimental and theoretical
method was used to investigate the spectral characteriza-
tion of 1,3,5-triazine derivatives, and which provides an
useful tool in designing of 1,3,5-triazines by correlating
theoretical optical properties with their experimental val-
ue. The linear regression analysis method is used to con-
struct the model [8]. Quantum chemistry calculations
*
Menglin Ma
mmlchem@163.com
1
2
Key Lab of Advanced Scientific Computation of Sichuan Province,
School of Science, Xihua University, Chengdu 610039, China
Key lab of Green Chemistry and Technology of Ministry of
Education. Faculty of Chemistry, Sichuan University,
Chengdu 610064, China
3
College of Chemical Engineering, Sichuan University,
Chengdu 610065, China

J Fluoresc
were calculated to investigate the stable structure and UV
electronic absorption bands. Furthermore, three dimen-
sional quantitative structure-property relationship (3D-
QSPR) method is helpful to extract a relation between
theoretical optimal value and experimental value [9, 10].
Especially, the comparative molecular field analysis
2,4-dichloro-6-phenyl-1,3,5-triazine(4a): white solide,
1
yield 30%(0.20 g), H NMR (300 CDC1 ) 7.51–7.55
3
(2H, m), 7.64–7.67 (1H, m), 8.49–8.63 (2H, m);
−
1
IR(KBr): 3444, 2583, 1376,798 cm ; ESI-MS
+
C H Cl N (m/z): 225.0 (M + H) .
9
5
2 3
2,4-dichloro-6-(4-methoxyphenyl)-1,3,5-triazine (4e):
1
(
CoMFA) is an effective method based on statistical tech-
white solide, yield 34%(0.26 g), H NMR (300 MHz,
niques [11–13].
CDCl ) δ 8.47 (2H, d, J = 8.9 Hz), 7.01 (2H, d, J =
3
Where some possible photostabilization mechanisms of
these types of compounds were proposed as formation of in-
tramolecular hydrogen bond (IMHB) between the o-hydroxyl
group of the phenyl ring and the nitrogen atom of the 1,3,5-
triazine moiety [14, 15]. IMHB in title UVA has been explored
by IR spectroscopy, UV spectra, structural and energetic as-
pects of different conformers and frontier molecular orbitals
analysis [16, 17]. This work demonstrates that the first princi-
ple theory-design and organic synthesis can cowork with each
other effectively to develop highly efficiency UV absorbers.
8.9 Hz), 3.92 (3H, s); IR(KBr): 3430. 2851, 1605,
−
1
1525, 1482, 1251, 1110, 847 cm ; ESI-MS
+
C H Cl N O (m/z): 255.0 (M + H) .
1
0
7
2 3
General Procedure for the Preparation 4g, 4k and 4l A THF
solution of aniline (10.0 mmol) was slowly added
dropwise to a solution of cyanuric chloride 3 (1.84 g,
10.0 mmol) and sodium hydrogencarbonate (10% solu-
tion, 1.68 g, 20 mmol) in THF (25 mL) at −5 °C. The
mixture was stirred at 0 °C for 2 h. The mixture was
stirred at room temperature for 2 h. After the completion
of the reaction, the mixture was evaporated. The crude
product was purified by silica gel chromatography (hex-
ane/ethyl acetate = 5/1) and then recrystallized to obtain
Experimental
General Remarks
4
g, 4k and 4l.
All reagents and solvents were purchased from commer-
cial sources and used without further purification. Thin
layer chromatography was performed with Qingdao
Ocean silica gel GF254. Nuclear magnetic resonance
4,6-dichloro-N-phenyl-1,3,5-triazin-2-amine(4g):
white solide, yield 60%(1.44 g), H NMR (300 MHz, d-
1
DMSO) δ 11.14 (1H, s), 7.60 (2H, d, J = 8.4 Hz), 7.40
(2H, t, J = 7.9 Hz), 7.18 (1H, t, J = 7.4 Hz); IR(KBr):
(
NMR) spectra were recorded on a Bruker DPX-300 FT
1
−1
NMR spectrometer at 300 MHz or 400 MHz for H and
were referenced to tetramethylsilane (d values are given in
ppm and J-values in Hz). IR spectra were measured ac-
quired on a Nicolet 380 and obtained by using KBr
platespellet. The UV spectra were recorded on a Hewlett
Packard 8452A spectrophotometer with 2 nm resolution at
room temperature in a dichloromethane solution.
3426, 1554, 1465, 750 cm ; ESI-MS C H Cl N
4
(m/z): 240.0 (M + H) .
9
6
2
+
4,6-dichloro-N-(4-fluorophenyl)-1,3,5-triazin-2-amine
1
(4 k): white solide, yield 56%(1.44 g), H NMR
(300 MHz, d-DMSO) δ 11.16 (1H, s), 7.58 (2H, s),
7.26 (2H, s); IR(KBr): 3429, 1231, 1019, 800 cm-1;IR
(KBr): 3429, 1231, 1019, 800 cm-1 ESI-MS
+
C H Cl FN (m/z): 258.0 (M + H) .
9
5
2
4
Synthesis
4,6-dichloro-N-(2-methoxyphenyl)-1,3,5-triazin-2-
amine (4l): white solide, yield 86%(2.30), H NMR
1
General Procedure for the Preparation 4a and 4e The
(300 MHz, CDCl ) δ 8.31 (1H, d, J = 8.2 Hz), 8.21
3
Grignard (3.0 mmol) solution under dry N protection
(1H, s), 7.16 (1H, s), 7.04 (1H, s), 6.94 (1H, d, J =
2
was added dropwise to a solution of cyanuric chloride
8.2 Hz), 3.91 (3H, s); IR(KBr): 3391, 1393, 1210,
+
3
(0.55 g, 3.0 mmol) in anhydrous THF (25 mL) while
752 cm-1; ESI-MS C H Cl N O (m/z): 270.0 (M + H) .
1
0
8
2 4
the temperature was maintained at 0-10 °C. When the
addition was completed, the mixture was stirred for
4-(4,6-dichloro-1,3,5-triazin-2-yl)morpholine (4m):
An aqueous solution of morpholine (0.87 g, 10 mmol)
was slowly added dropwise to a solution of cyanuric
chloride (1.84 g, 10 mmol) in aqueous at −15 to −5 °C.
The reaction mixture was stirred at −15 °C for 0.5 h and
then at room temperature for 1 h. After removal of the
solvent, the residue was extracted with CH Cl .The ex-
1
0 h at 45 °C and then poured into ice ammonium chlo-
ride solution (30 mL) and boiling steam out THF. The
water suspension was extracted twice with DCM (3 × 10
mL). The organic phase was combined, washed with wa-
ter and brine, dried over anhydrous sodium sulfate, and
then concentrated. The residue was purified by flash
chromatography on silica gel to give the corresponding
products 4a and 4e.
2
2
tract was washed with brine, dried over MgSO and con-
4
centrated to give 1.56 g white solide as 4m, yield 66.3%,
1
H NMR (300 MHz, CDCl ) δ 3.93–3.84 (4H, m), 3.79–
3

J Fluoresc
3
.71 (4H, m); IR(KBr): 3414, 1617, 1362, 841 cm-1;
4,4′-(6-chloro-1,3,5-triazine-2,4-diyl)dimorpholine
(5m). An aqueous solution of morpholine (1.74 g,
20 mmol) in acetone (50 mL) at 0 to 10 °C. The reac-
tion mixture was stirred at 0 °C for 2 h and then at room
temperature for 18 h. After removal of the solvent, the
residue was extracted with CH Cl . The extract was
+
ESI-MS C H Cl N O (m/z): 234.0 (M + H) .
7
8
2 4
4
,6-dichloro-N,N-diphenyl-1,3,5-triazin-2-amine (4n).
A solution of diphenylamine (1.70 g, 10 mmol) in THF
50 mL) was added dropwise to a mixture of
(
diisopropylethylamine (1.30 g, 10 mmol) and cyanuric
chloride (1.84 g, 10 mmol) in THF (30 ml) at 20 °C under
2
2
washed with brine, dried over MgSO and concentrat-
4
N ,. After stirring for 3 h, the solvent was removed by
rotatory evaporation and the residue was purified by col-
umn chromatography over silica gel (hexane/ethyl ace-
ed. The residue was column-chromatographed on silica
gel (hexane/ethyl acetate = 8/2) to give 2.36 g white
color solid as 5m, 65.9% yield. H NMR (300 MHz,
2
1
tate = 4/1) to give 2.37 g white color solid as 4n, yield
CDCl ) δ 3.78 (8H, s), 3.74–3.67 (8H, m); IR(KBr):
3
1
7
7
7
1
5%, H NMR (300 MHz, CDCl ) δ 7.41 (4H, d, J =
3434, 1447, 1005, 751 cm-1; ESI-MS C H ClN O2
3
11 16
5
+
.7 Hz), 7.33 (2H, d, J = 7.5 Hz), 7.28 (3H, d, J = 1.4 Hz),
.26–7.23 (1H, m); IR(KBr): 3416, 1723, 1038, 792 cm-
(m/z): 285.1 (M + H) .
2,4,6-triphenoxy-1,3,5-triazine (6a). A mixture
(1.84 g, 10 mmol) cyanuric chloride and 25 mL of
acetone was added vigorously to a solution of
+
; ESI-MS C H Cl N (m/z): 316.0 (M + H) .
1
5
10
2 4
(
2.91 g, 31 mmol) phenol and (1.24 g, 31 mmol)
General Procedure for the Preparation 5a-5d The Grignard
18.4 mmol) solution under dry N protection was added
sodium hydroxide in 50 mL of water. The reaction
temperature was held at 25 °C and stirred for an
additional 3 h. There was solid precipitation and
then the crystalline solid was filtered, washed with
water and with methanol and dried at 110 °C to get
(
2
dropwise to a solution of cyanuric chloride 3 (0.55 g,
.0 mmol) in anhydrous THF (25 mL) while the temper-
3
ature was maintained at 0-10 °C. When the addition was
completed, the mixture was stirred for 10 h at 45 °C and
then poured into ice ammonium chloride solution (30 mL)
and boiling steam out THF. The water suspension was
extracted twice with DCM (3 × 10 mL). The organic
phase was combined, washed with water and brine, dried
over anhydrous sodium sulfate, and then concentrated.
The residue was purified by flash chromatography on sil-
ica gel (hexane) to give the corresponding products.
1
2.93 g white solide as 6a, yield 82.1%. H NMR
(300 MHz, CDCl ) δ 7.35 (6H, t, J = 7.7 Hz),
3
7.29–7.20 (3H, m), 7.18–7.08 (6H, m); IR (KBr):
3431, 1209, 1025, 764 cm-1; ESI-MS C H N O
1 15 3 3
2
+
(m/z):357.1 (M + H) .
2,4,6-tris(benzyloxy)-1,3,5-triazine (6b). A THF solu-
tion of phenylmethanol (3.25 g, 30 mmol) was slowly
added dropwise to a solution of cyanuric chloride
(
1.84 g, 10 mmol) and sodium hydroxide (0.8 g,
2
-chloro-4,6-diphenyl-1,3,5-triazine (5a): white solide,
20 mmol) in THF (20 ml) at −5 °C. The mixture
1
yield 20%(0.32 g), H NMR (300 MHz, CDCl ) δ 8.76–
was stirred at 0 °C for 2 h to obtain3.39 g 6b as white
3
1
8
7
8
2
.61(4H, m,), 7.63–7.60 (2H, d, J = 7.5 Hz), 7.57–
solide, 85.0% yield, H NMR (300 MHz, CDCl ) δ
3
.52(4H, m); IR(KBr): 3423 1760, 1508, 1171,
7.47–7.28 (15H, m), 5.45 (6H, s); IR (KBr): 3411,
−1
+
31 cm ; ESI-MS C H ClN (m/z): 267.1 (M + H) .
1568, 1134, 651 cm-1; ESI-MS C24H21N O
3
1
5
10
3
3
+
-chloro-4,6-dip-tolyl-1,3,5-triazine (5b): white solide,
(m/z):399.2 (M + H) .
1
yield 23%(0.41 g), H NMR (400 MHz, CDCl ): δ 7.62
4,4′,4″-(1,3,5-triazine-2,4,6-triyl)tris(benzene-1,3-di-
ol) (6c). To 30 mL of dry chlorobenzene was added
cyanuric chloride (1.00 g, 5.42 mmol) and resorcinol
(1.8 g, 16.3 mmol). The solution was heated to 70 °C for
10 min. To allow the solids to dissolve in solution. The
reaction was then cooled to 0 °C and anhydrous aluminum
chloride (2.16, 16.2 mmol) was added to the stirring solu-
tion in three portions over a course of 10 min. The solution
was then heated to 60 °C for 6 h. After the solution cooled
room temperature, the solvent was removed in vacuo. The
mixture was filtered and washed with water (10mLx3),the
filter cake was recrystallized with EtOA to give the corre-
sponding products 1.61 g 6c as a dark yellow solide,
3
(4H, d, J = 8.5 Hz,), 7.36 (4H, d, J = 8.5 Hz,), 2.52 (6H,
−1
s); IR (KBr): 1613, 1518, 1366, 1245, 1183, 802 cm ;
ESI-MS C H ClN (m/z): 295.1 (M + H) .
6
+
1
7
2
14
4
3
-chloro-N ,N -diphenyl-1,3,5-triazine-2,4-diamine
(5g). Triethylamine (3.6 mL,25 mmol) and aniline
(1.95 g, 21 mmol) were added dropwise upon cooling
(t < 35 °C) to 30 mL of acetic acid and the solution was
combined with cyanuric chloride (1.84 g, 10 mmol) dis-
solved in 30 mL of AcOH. After 6 h a precipitate was
filtered, washed with boling water (2 × 20 ml) to neutral
pH, and dried to furnish of 1.96 g white color solid as 5g,
yield 66%, H NMR (300 MHz, d-DMSO) δ 10.26 (2H,
s), 7.63 (4H, s), 7.33 (4H, t, J = 7.9 Hz), 7.09 (2H, t, J =
1
1
73.0% yield, H NMR (300 MHz, d-DMSO) δ 12.85
7
.6 Hz); IR(KBr): 3206, 1575, 1227, 806 cm-1; ESI-MS
(3H, s), 10.50 (3H, s), 8.14 (3H, d, J = 8.8 Hz), 6.51
(3H, dd, J = 8.8, 2.2 Hz), 6.39 (3H, d, J = 2.1 Hz). IR
+
C H ClN (m/z): 297.1 (M + H) .
1
5
12
5

J Fluoresc
(
1
KBr):3440, 2923, 1630, 1610, 1541, 1509, 1401, 1304,
(3H, d, J = 7.4 Hz). IR (KBr): 3446, 1445, 1155, 748 cm-
−
1
290, 1263 1173, 1104, 978, 832 cm ; ESI-MS
1; ESI-MS C H N (m/z):354.2 (M + H) + .
2
1 18 6
+
2
4
6
C H N O (m/z): 405.1 (M + H) .
N ,N ,N -tri-p-tolyl-1,3,5-triazine-2,4,6-triamine (6h).
White solide, yield 52% (2.06 g), White solide, yield 52%
(2.06 g), (400 MHz, d-DMSO) δ 9.43 (3H, s), 7.61 (6H,
s), 7.11 (6H, d, J = 7.7 Hz), 2.29 (9H, d, J = 10.5 Hz); IR
(KBr): 3230, 1478, 1580, 1200 cm-1; ESI-MS
C H N (m/z):396.2 (M + H) + .
2
1 15 3 6
2
4
4
6
6
N ,N ,N ,N ,N -hexamethyl-1,3,5-triazine-2,4,6-
triamine (6d). To the vigorously stirred solution of
cyanuric chloride (1.84 g, 10 mmol) in dichloromethane
(
20 mL), N-dimethylbenzylamine (4.51 mL, 30 mmol)
was added dropwise. Then, the mixture was heated under
reflux for additional 30 min and dichloromethane was
distilled off. The residue was heated for additional
2
4 24 6
4 , 4 ′ , 4 ″ - ( ( 1 , 3 , 5 - t r i a z i n e - 2 , 4 , 6 -
triyl)tris(azanediyl))tribenzoic acid (6i): White solide,
1
6
0 min and benzyl chloride was distilled off. The residue
yield 43%(2.06 g), H NMR (400 MHz, d-DMSO) δ
was dissolved in chloroform (30 mL) and then washed
10.61 (3H, s), 7.92 (6H, d, J = 8.6 Hz), 7.83 (6H, s);
with 1 M aqueous KHSO (40 mL) and water (40 mL).
IR(KBr): 3260, 1550, 1480, 1212 cm-1; ESI-MS
4
+
The organic layer was dried with Na SO , filtered, and
C H N O (m/z):486.1 (M + H) .
2
4
24 18 6 6
2
4
6
concentrated to dryness. After crystallization from hex-
N ,N ,N -tris(2-fluorophenyl)-1,3,5-triazine-2,4,6-
1
1
ane 1.89 g 6d was obtained as white solide, yield 90%, H
triamine (6j): White solide, yield 65%(2.65 g), H NMR
NMR (300 MHz, CDCl ) δ 3.10 (18H, s); IR (KBr): 3426,
(400 MHz, d-DMSO) δ 9.02 (3H, s), 7.70 (3H t, J =
7.3 Hz), 7.25–7.07 (9H, m); IR(KBr): 3250, 1590, 1498,
3
1
541, 1212, 805 cm-1; ESI-MS C H N (m/z):210.2
9 18 6
+
+
(M + H) .
1300 cm-1; ESI-MS C H F N (m/z):408.1 (M + H) .
21 15 3 6
2
,4,6-trimorpholino-1,3,5-triazine (6m). An ice-
cooled solution of cyanuric chloride (1.84 g,
.01 mol) in acetone (25 mL) was treated with
General Procedure for the Preparation 6e and 6f An ice-
cooled solution of cyanuric chloride (1.84 g, 0.01 mol) in
acetone (25 mL) was treated with pyrrolidine or piperidine
0
morpholine (2.61 g, 0.03 mol). The reaction temper-
ature was gradually raised to 40 °C until the complete
disappearance of the cyanuric chloride. The solvent
was removed under reduced pressure and 30 mL wa-
ter was added to the residue. The precipitate was fil-
tered, washed with water (3 × 20 mL), and dried to
(
2
0.03 mol). The reaction temperature was kept at 0 °C, After
h a precipitate was filtered, washed with water (2 × 30 ml),
and dried to furnish of 6e or 6f.
2
,4,6-tri(pyrrolidin-1-yl)-1,3,5-triazine (6e): white
1
afford compound 3.29 g 6m as a white solid, yield
solide, yield 95%(2.60 g), H NMR (300 MHz, CDCl )
3
1
9
8%, H NMR (300 MHz, CDCl ) δ 3.72 (24H, d,
3
δ 3.54 (12H, dt, J = 13.4, 6.7 Hz), 2.00–1.85 (12H, m);
J = 5.1 Hz); IR (KBr): 3431, 1400, 1070, 805 cm-1;
IR(KBr): 3449, 1438, 1023, 804 cm-1; ESI-MS
+
+
ESI-MS C15H N O (m/z):336.2 (M + H) .
24 6 3
C H N (m/z):288.2 (M + H) .
1
5 24 6
2
,4,6-tri(piperidin-1-yl)-1,3,5-triazine(6f): White
1
solide, yield 94%(3.10 g), H NMR (300 MHz, CDCl )
3
General Procedure for the Preparation 7a-7x A mixture of
aldehyde 1 (6.8 mmol), amidine hydrochloride 2 (2 g,
δ 3.76–3.64 (12H, m), 1.57 (18H, dd, J = 16.2,
5
.2 Hz);IR(KBr): 3409, 1340, 1049, 879 cm-1; ESI-MS
+
11.4 mmol), Na
CO (1.21 g, 11.4 mmol, 1.0 equiv) and
2 3
C H N (m/z): 330.3 (M + H) .
1
8 30 6
Cu(OAc) (10 mol%) was stirred in toluene (20 mL) under
2
100 °C in air for 24 h. After completion of the reaction, the
General Procedure for the Preparation 6g-6j Cyanuric chlo-
ride (1.84 g, 10 mmol) was added in one portion to a
stirred solution of the aromatic amine (33 mmol) in
mixture was cooled to room temperature. The water was
added to the reaction system and atmospheric distillation until
toluene was evaporated. The resulting solution was filtered
and residue with hot water washed 3 times. The crude product
was purified by column chromatography on silica gel using
petroleum ether/EtOAc (100:1) as an eluent to give the corre-
sponding products 7a-7x.
7
5 mL of glacial acetic acid, and the mixture was heated
at refluxing temperature (118 °C) 15 min then cooled to
room temperature. The products precipitated from solu-
tion as white or yellow solids and were recovered by
filtration. The solid products were washed with boiling
water (approximately 20 mL × 3) to neutral pH and dried
to afford compounds 6g-6j with high purity.
2,4,6-triphenyl-1,3,5-triazine (7a): White solid; yield
1
74% (1.30 g); H NMR (300 MHz, d-DMSO) δ 8.76
(
6H, d, J = 7.2 Hz), 7.68 (9H, d, J = 6.9 Hz); IR (KBr):
2
4
6
N ,N ,N -triphenyl-1,3,5-triazine-2,4,6-triamine (6g).
3425, 2923, 1630, 1590, 1525, 1448, 1400, 1369, 1174,
1028, 841, 744, 684, 644 cm ; ESI-MS C H N (m/z):
309.1 (M + H) .
1
−1
White solide, yield 73% (2.58 g), H NMR (300 MHz,
CDCl ) δ 10.50 (3H, s), 7.50 (6H, s), 7.23 (6H, s), 7.09
2
1 15 3
+
3

J Fluoresc
2
-(2-fluorophenyl)-4,6-diphenyl-1,3,5-triazine (7b):
8.6 Hz), 7.88 (2H, d, J = 8.5 Hz), 7.70 (6H, dd, J = 12.2,
1
White solid; yield 54% (1.00 g); H NMR (400 MHz,
d-DMSO) δ 8.78–8.61 (4H, m), 8.49 (1H, td, J = 7.9,
1
7.2 Hz); IR(KBr): 3439, 2925, 1628, 1589, 1522, 1400,
−
1
1369, 1170, 1072, 1013, 762, 685 cm ; ESI-MS
+
.8 Hz), 7.83–7.59 (7H, m), 7.55–7.39 (2H, m);
C H BrN (m/z):387.0 (M + H) .
2
1
14
3
IR(KBr): 3435, 2924, 1630, 1523, 1384, 1122,
2,4-diphenyl-6-(o-tolyl)-1,3,5-triazine (7k): White sol-
id; yield 82% (1.50 g); H NMR (400 MHz, d-DMSO) δ
−1
+
1
6
89 cm ; ESI-MS C H FN (m/z): 327.1 (M + H) .
2
1
14
3
2
-(3-fluorophenyl)-4,6-diphenyl-1,3,5-triazine (7c):
8.74–8.62 (4H, m), 8.33–8.26 (1H, m), 7.76–7.60 (6H,
m), 7.57–7.51 (1H, m), 7.46 (2H, t, J = 7.1 Hz), 2.80 (3H,
1
White solid; yield 81% (1.50 g), H NMR (400 MHz,
d-DMSO) δ 8.77 (4H, dd, J = 11.6, 4.6 Hz), 8.65–8.55
−1
s); IR (KBr): 3437, 1630, 1524, 1385, 1118, 608 cm ;
+
(1H, m), 8.48 (1H, d, J = 10.2 Hz), 7.77–7.63 (6H, m),
ESI-MS C H N (m/z): 323.1 (M + H) .
2
2 17 3
7
1
.59 (2H, d, J = 6.7 Hz).; IR (KBr): 3434, 2925, 1629,
2,4-diphenyl-6-(m-tolyl)-1,3,5-triazine (7l). White sol-
id; yield 76% (1.40 g); H NMR (400 MHz, d-DMSO)
−
1
1
524, 1440, 1381, 1268, 764, 688 cm ; ESI-MS
+
C H FN (m/z): 327.1 (M + H) .
2
White solid; yield 86% (1.60 g); H NMR
δ 8.79–8.69 (4H, m), 8.65 (2H, d, J = 8.2 Hz), 7.77–7.59
(6H, m), 7.48 (2H, d, J = 8.1 Hz), 2.47 (3H, s); IR (KBr):
2
1
14
3
-(4-fluorophenyl)-4,6-diphenyl-1,3,5-triazine (7d):
1
−1
3437, 1630, 1524, 1385, 1118, 608 cm ; ESI-MS
+
(
(
300 MHz, d-DMSO) δ 8.89–8.78 (2H, m), 8.75
4H, d, J = 6.8 Hz), 7.83–7.55 (6H, m), 7.49 (2H,
C H N (m/z): 323.1 (M + H) .
2
2 17 3
2,4-diphenyl-6-(p-tolyl)-1,3,5-triazine (7m). White sol-
1
s); IR (KBr): 3434, 2924, 1740, 1605, 1525, 1405,
1
C H FN (m/z): 327.1 (M + H) .
2
id; yield 87% (1.60 g); H NMR (300 MHz, d-DMSO) δ
−
1
368, 1228, 1146, 857, 766, 688 cm ; ESI-MS
8.82–8.66 (6H, m), 7.76–7.61 (6H, m), 7.20 (2H, d, J =
+
9.0 Hz), 3.91 (3H, s); IR (KBr): 3432, 2923, 1617, 1519,
2
1
14
3
−1
-(2-chlorophenyl)-4,6-diphenyl-1,3,5-triazine (7e):
1442, 1368, 1176, 1112, 1023, 824, 762, 689 cm ; ESI-
1
+
White solid; yield 77% (1.50 g); H NMR (300 MHz,
MS C H N (m/z): 323.1 (M + H) .
2
2 17 3
d-DMSO) δ 8.68 (4H, d, J = 7.1 Hz), 8.18 (1H, d, J =
2-(2-methoxyphenyl)-4,6-diphenyl-1,3,5-triazine (7n).
Yellow solid; yield 41% (0.80 g); H NMR (400 MHz, d-
1
8
2
6
2
.9 Hz), 7.67 (9H, dq, J = 15.1, 7.4 Hz); IR (KBr): 3440,
925, 1630, 1524, 1401, 1367, 1156, 1041, 744, 685,
DMSO) δ 8.66 (4H, dd, J = 5.3, 3.2 Hz), 8.03 (1H, dd,
J = 7.6, 1.8 Hz), 7.76–7.56 (7H, m), 7.28 (1H, d, J =
8.3 Hz), 7.18 (1H, t, J = 7.5 Hz), 3.93 (3H, s); IR
(KBr): 3436, 2925, 1602, 1520, 1446, 1366, 1250,
−1
+
39 cm ; ESI-MS C H ClN (m/z): 343.1 (M + H) .
2
1
14
3
-(3-chlorophenyl)-4,6-diphenyl-1,3,5-triazine (7f):
1
White solid; yield 82% (1.60 g); H NMR (400 MHz,
−
1
d-DMSO) δ 8.78–8.73 (4H, m), 8.69 (2H, d, J =
1174, 1022, 846, 747, 691, 639 cm ; ESI-MS
+
1
.3 Hz), 7.82–7.77 (1H, m), 7.76–7.62 (7H, m); IR
C H N O(m/z): 339.1 (M + H) .
2
2 17 3
−
1
(
KBr): 3432, 1632, 1523, 1383, 760 cm ; ESI-MS
2-(3-methoxyphenyl)-4,6-diphenyl-1,3,5-triazine (7o).
+
1
C H ClN (m/z): 343.1 (M + H) .
Yellow solid; yield 52% (1.00 g); H NMR (400 MHz,
2
1
14
3
2
-(4-chlorophenyl)-4,6-diphenyl-1,3,5-triazine (7g):
d-DMSO) δ 8.74 (4H, dd, J = 5.3, 3.2 Hz), 8.34 (1H, d,
J = 7.8 Hz), 8.28–8.20 (1H, m), 7.79–7.63 (6H, m), 7.59
(1H, t, J = 8.0 Hz), 7.30 (1H, dd, J = 7.8, 2.3 Hz), 3.94
(3H, s); IR (KBr): 3426, 1627, 1522, 1451, 1380, 1367,
1
White solid; yield 82% (1.60 g); H NMR (300 MHz, d-
DMSO) δ 8.79–8.71 (6H, m), 7.71 (8H, dd, J = 16.4,
8.1 Hz); IR (KBr): 3433, 2924, 1628, 1522, 1739, 1093,
−
1
+
−1 13
763, 675 cm ; ESI-MS C H ClN (m/z): 343.1 (M + H) .
1278, 1233, 1041, 893, 763, 690, 639 cm ; C NMR
21
14
3
2
-(2-bromophenyl)-4,6-diphenyl-1,3,5-triazine (7h):
(100 MHz, d-DMSO): δ 171.50, 171.33, 160.19, 137.29,
135.78, 133.58, 130.65, 129.49, 129.18, 121.56, 119.26,
113.97, 55.84;HRMS (EI) calcd. For 339.1372;
1
White solid; yield 59% (1.30 g); H NMR (300 MHz,
d-DMSO) δ 8.69 (4H, d, J = 6.7 Hz), 8.12 (1H, d, J =
+
7
.7 Hz), 7.90 (1H, d, J = 7.4 Hz), 7.74–7.63 (7H, m), 7.56
C H N O, found (M + H) 340.1450.
2
2 17 3
(
1H, s); IR (KBr): 3439, 2925, 1630, 1523, 1401, 1367,
2-(4-methoxyphenyl)-4,6-diphenyl-1,3,5-triazine (7p).
Yellow solid; yield 57% (1.10 g); H NMR
−1
1
1
3
2
156, 1026, 744, 685 cm ;ESI-MS C H BrN (m/z):
2
1
14
3
+
87.0 (M + H) .
-(3-bromophenyl)-4,6-diphenyl-1,3,5-triazine (7i):
(300 MHz, d-DMSO) δ 8.82–8.66 (6H, m), 7.76–
7.61 (6H, m), 7.20 (2H, d, J = 9.0 Hz), 3.91 (3H, s);
IR (KBr): 3433, 2926, 1607, 1520, 1402, 1370, 1255,
1
White solid; yield 68% (1.50 g); H NMR (300 MHz, d-
DMSO) δ 8.81 (1H, s), 8.77–8.65 (5H, m), 7.92 (1H, d, J =
7
1
6
2
−
1
1173, 1029, 835, 771, 733, 693 cm ; ESI-MS
+
.2 Hz), 7.79–7.56 (7H, m); IR (KBr): 3430. 2925, 1780,
C H N O(m/z): 339.1 (M + H) .
2
2 17 3
710, 1625, 1524, 1449, 1401, 1365, 1261, 1152, 761,
2-(2-nitrophenyl)-4,6-diphenyl-1,3,5-triazine (7q).
−1
+
1
88 cm ; ESI-MS C H BrN (m/z): 387.0 (M + H) .
Yellow solid; yield 30% (0.60 g); H NMR (300 MHz,
21
14
3
-(4-bromophenyl)-4,6-diphenyl-1,3,5-triazine (7j):
d-DMSO) δ 8.62 (4H, d, J = 6.9 Hz), 8.53–8.47 (1H, m),
8.10–8.05 (1H, m), 7.94 (2H, dd, J = 9.2, 3.9 Hz), 7.78–
7.60 (6H, m); IR (KBr): 3434, 2924, 1741, 1633, 1518,
1
White solid; yield 68% (1.50 g); H NMR (300 MHz,
d-DMSO) δ 8.75 (4H, d, J = 6.8 Hz), 8.68 (2H, d, J =

J Fluoresc
−1
1
444, 1401, 1370, 1172, 770, 744, 693, 641 cm ; ESI-
General Procedure for the Preparation 8a, 8e and 9a-9d To a
+
MS C H N O (m/z): 354.1 (M + H) .
stirred anhydrous chlorobenzene (15 mL) under dry N pro-
2
1
14
4
2
2
2
-(3-nitrophenyl)-4,6-diphenyl-1,3,5-triazine (7r).
tection in a 50 mL three-necked flask were added 5 (1.6 mmol)
1
Yellow solid; yield 50% (1.00 g); H NMR (400 MHz,
and anhydrous AlCl (0.32 g, 2.4 mmol),the mixture was
3
d-DMSO) δ 9.42–9.37 (1H, m), 9.17 (1H, d, J = 7.8 Hz),
stirred for 0.5 h at 25 °C. Then resorcinol (0.24 g, 2.2 mmol)
was added, and the mixture was stirred for 5 h at 85 °C. After
cooling to room temperature, ice water (10 mL) was added
slowly and then chlorobenzene was evaporated under reduced
pressure. The mixture was filtered and washed with water
(3 × 10 mL), the filter cake was recrystallized with EtOA to
give the corresponding products 8a, 8e 9a-9d.
8
.81–8.74 (3H, m), 8.56 (1H, dd, J = 7.7, 1.9 Hz), 7.98
(
2H, t, J = 8.0 Hz), 7.82–7.57 (6H, m); IR (KBr): 3420,
−
1
1
3
2
628, 1518, 1383 cm ; ESI-MS C H N O (m/z):
21 14 4 2
+
54.1 (M + H) .
-(4-nitrophenyl)-4,6-diphenyl-1,3,5-triazine (7s).
1
Yellow solid; yield 54% (1.10 g); H NMR
300 MHz, d-DMSO) δ 8.96 (2H, d, J = 9.0 Hz),
(
8
7
1
.80–8.69 (4H, m), 8.47 (2H, d, J = 9.0 Hz), 7.80–
4,4′-(6-phenyl-1,3,5-triazine-2,4-diyl)bis(benzene-1,3-
diol) (8a): Yellow solid; yield 83% (0.50 g); H NMR
1
.58 (6H, m); IR (KBr): 3434, 2924, 1630, 1523,
−
1
366, 1113, 749, 688, 649 cm ; ESI-MS
(400 MHz, d-DMSO) δ 13.05 (2H, s), 10.50 (2H, s), 8.37
(4H, dd, J = 25.1, 8.3 Hz), 7.71 (3H, dd, J = 25.4, 7.3 Hz),
6.54 (2H, dd, J = 8.9, 2.0 Hz), 6.40 (2H, d, J = 1.9 Hz); IR
+
C H N O (m/z): 354.1 (M + H) .
2
1 14 4 2
2
-(4,6-diphenyl-1,3,5-triazin-2-yl)phenol (7t). Yellow
1
−1
solid; yield 54% (1.00 g); H NMR (300 MHz, d-
DMSO) δ 13.15 (1H, s), 8.71 (1H, d, J = 8.1 Hz), 8.63
(KBr): 3444, 1633, 1518, 1385, 1239, 1164, 1103 cm ;
+
ESI-MS C H N O (m/z): 373.1 (M + H) .
2
1 15 3 6
(
4H, d, J = 7.1 Hz), 7.85–7.64 (6H, m), 7.60 (1H, t, J =
.6 Hz), 7.16–7.06 (2H, m); IR (KBr): 3443, 2925, 1627,
4,4′-(6-(4-methoxyphenyl)-1,3,5-triazine-2,4-
diyl)bis(benzene-1,3-diol) (8e): Yellow solid; yield 84%
(0.54 g); H NMR (300 MHz, d-DMSO) δ 13.18 (2H, s),
7
1
6
3
1
595, 1518, 1402, 1367, 1252, 1151, 842, 745, 689,
−1
+
44 cm ; ESI-MS C H N O(m/z): 325.1 (M + H) .
10.51 (2H, s), 8.33 (4H, dd, J = 11.3, 8.9 Hz), 7.22 (2H, d,
J = 8.9 Hz), 6.53 (2H, dd, J = 8.8, 2.3 Hz), 6.39 (2H, d,
J = 2.3 Hz), 3.90 (3H, s); IR(KBr): 3435 2856 1519, 1370
2
1 15 3
-(4,6-diphenyl-1,3,5-triazin-2-yl)phenol (7u). Yellow
1
solid; yield 59% (1.10 g); H NMR (400 MHz, d-
DMSO) δ 9.81 (1H, s), 8.80–8.65 (4H, m), 8.27–8.10
−1
+
1255 cm ; ESI-MS C H N O (m/z): 403.1 (M + H) .
2
2 17 3 5
(
2H, m), 7.81–7.57 (6H, m), 7.51–7.39 (1H, m), 7.10
4-(4,6-diphenyl-1,3,5-triazin-2-yl)benzene-1,3-diol
(9a): Yellow solid; yield 73% (0.40 g); H NMR
1
(1H, ddd, J = 8.1, 2.5, 0.9 Hz); IR (KBr): 3437, 1633,
−
1
13
1
(
1
1
3
4
524, 1384, 1121, 760, 678 cm
;
C NMR
(300 MHz, d-DMSO) δ 13.26 (1H, s), 10.51 (1H, s),
8.57 (4H, d, J = 7.3 Hz), 8.53 (1H, d, J = 9.1 Hz), 7.77–
7.63 (6H, m), 6.55 (1H, d, J = 9.0 Hz), 6.40 (1H, s); IR
(KBr):3426, 2924, 1633, 1595, 1519, 1403, 1294, 1170,
100 MHz, d-DMSO): δ 171.51, 171.40, 158.34,
37.16, 135.87, 133.47, 130.49, 129.43, 129.06,
20.60, 120.01, 115.59; HRMS (EI) calcd. For
+
−1
25.1215; C H N O, found (M + H) 326.1280.
1112, 845, 763, 687 cm ; ESI-MS C H N O (m/z):
341.1 (M + H) .
2
1
15
3
21 15 3 2
+
-(4,6-diphenyl-1,3,5-triazin-2-yl)phenol (7v). Yellow
1
solid; yield 59% (1.10 g); H NMR (400 MHz, d-
DMSO) δ 10.35 (1H, s), 8.77–8.67 (4H, m), 8.65–8.58
4-(4,6-di-p-tolyl-1,3,5-triazin-2-yl)benzene-1,3-diol
1
(9b): Yellow solid; yield 76% (0.45 g); H NMR
(
(
1
2H, m), 7.75–7.59 (6H, m), 7.06–6.96 (2H, m); IR
(300 MHz, d-DMSO) δ 13.36 (1H, s), 10.49 (1H, s),
8.50 (1H, d, J = 8.9 Hz), 8.46 (4H, d, J = 8.2 Hz), 7.46
(4H, d, J = 8.2 Hz), 6.54 (1H, dd, J = 8.8, 2.3 Hz), 6.39
(1H, d, J = 2.3 Hz), 2.52–2.48 (6H, m); IR (KBr): 3424,
2924, 1618, 1513, 1402, 1284, 1180, 1149, 1111, 972,
KBr): 3436, 2925, 1610, 1515, 1440, 1366, 1278,
−1
211, 1172, 1144, 1023, 832, 768, 734, 687, 651 cm ;
+
ESI-MS C H N O(m/z):325.1 (M + H) .
2
2
1 15 3
-phenyl-4,6-di-p-tolyl-1,3,5-triazine (7w). White solid;
1
−1
+
yield 78% (1.50 g); H NMR (300 MHz, d-DMSO) δ
.72 (2H, s,), 8.64 (4H, d, J = 8.2 Hz), 7.72–7.62 (3H,
m), 7.47 (4H, d, J = 8.1 Hz), 2.46 (6H, s); IR (KBr): 3432,
924, 1741, 1611, 1586, 1518, 1446, 1407, 1370, 1300,
793 cm ; ESI-MS C H N O (m/z): 369.1 (M + H) .
23 19 3 2
4-(4,6-bis(2,4-dimethylphenyl)-1,3,5-triazin-2-
8
yl)benzene-1,3-diol (9c): Yellow solid; yield 79%
1
2
1
(0.50 g); H NMR (300 MHz, d-DMSO) δ 13.21 (1H, s),
−1
179, 1149, 1022, 815, 776, 696, 656 cm ; ESI-MS
10.51 (1H, s), 8.36 (1H, d, J = 8.8 Hz), 7.99 (2H, d, J =
8.3 Hz), 7.24 (4H, s), 6.52 (1H, d, J = 10.7 Hz), 6.36 (1H,
s), 2.66 (6H, s), 2.36 (6H, d, J = 11.7 Hz); IR (KBr): 3411,
2923, 1613, 1516, 1401, 1241, 1162, 1103, 1037, 978,
+
C H N (m/z): 337.2 (M + H) .
2
6
(
2
3 19 3
,4,6-tri-p-tolyl-1,3,5-triazine (7x). White solid; yield
1
8% (1.30 g); H NMR (300 MHz, d-DMSO) δ 8.61
−1
+
6H, t, J = 9.1 Hz), 7.46 (6H, d, J = 8.1 Hz), 2.45
802 cm ; ESI-MS C H N O (m/z): 397.2 (M + H) .
25 23 3 2
(
1
9H,s); IR (KBr):3433, 2924, 1610, 1515, 1403, 1370,
4-(4,6-di(thiophen-2-yl)-1,3,5-triazin-2-yl)benzene-
1,3-diol (9d): Yellow solid; yield 71% (0.40 g), H NMR
(300 MHz, d-DMSO) δ 12.83 (1H, s), 8.34–8.31 (1H, s,
−
1
1
176, 1149, 1019, 800, 771 cm ; ESI-MS
+
C H N (m/z): 351.2(M + H) .
2
4 21 3

J Fluoresc
J = 8.8 Hz), 8.21–8.20 (2H, d, J = 2.6 Hz), 8.02–8.01 (2H,
d, J = 4.0 Hz), 7.34–7.31 (2H, d, J = 4.7 Hz), 6.51–6.47
108.97, 103.54; HRMS (EI) calcd. For 353.0293;
+
C H N O S , found (M-H) 352.0190.
17 11 3 2 2
(
2
1H, m), 6.34–6.33 (1H, d, J = 2.3 Hz); IR (KBr): 3439,
−1 13
924, 1632, 1521, 1400, 1243, 1155, 807, 720 cm ;
C
General Procedure for the Preparation 9e and 9f Stirred
DMF (8 mL) in a 50 mL three-necked flask was added
to 9a (1.00 g, 2.9 mmol) and K CO (0.76 g, 5.5 mmol),
NMR (100 MHz, d-DMSO): δ 170.63, 166.02, 164.83,
64.13, 140.33, 134.91, 132.79, 131.88, 129.76, 109.38,
1
2
3
Scheme 1 Preparation of 1,3,5-triazine compounds. Reagents and
conditions: (a) Cu(OAc) .H O (10 mol%), Na CO (2equiv), toluene,
air, 100 °C; (b) ACl , chlorobenzene 60 °C; (c) acetone, NaOH; (d)
DCM, 0 °C; (e) acetone, 0 °C; (f) THF, NaHCO , 0 °C; (g) AcOH,
0~35 °C; (h) AcOH, 0~120 °C; (i) H
(k) acetone, 40 °C; (l) 0 °C, DCM; (m) THF, N
ACl , chlorobenzene, N , 85 °C; (o) K CO , DMF,75 °C; (p) THF, N
45 °C; (q) Resorcinol, ACl , chlorobenzene, N , 85 °C
2
O, −15~-5 °C; (j) H
2
O, 0~10 °C;
, 45 °C; (n) Resorcinol,
2
2
2
3
2
3
3
2
2
3
2
,
3
3
2

J Fluoresc
the mixture was stirred for 0.5 h at 45 °C. Haloalkane
3.1 mmol) in 2 mL DMF was added slowly into the
the filter cake was recrystallized with EtOA to give the
corresponding products 9e and 9f.
(
mixture with stirring. The reaction mixture was stirred
for 6 h at 75 °C. After completion of the reaction, the
mixture was cooled to room temperature and then fil-
tered. The filter washed with hot water (10 mLx3) and
2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-methoxyphenol
(9e): Yellow solid; yield 78% (0.80 g); H NMR (300 MHz,
d-DMSO) δ 13.37 (1H, s), 8.59 (5H, s), 7.70 (5H, s), 6.70
1
Table 1 UV Data of 1,3,5-
triazines calculations and
experiments
max
max
Cal
max
Exp
ε is L(mol.cm)− cm−1
max
ε
Cal
ε is L/(mol.cm)−1 cm−1
Comp
λ
Exp
λ
ε
1
nm
nm
4
4
4
4
4
4
4
5
5
5
5
6
6
6
6
6
6
6
6
6
6
6
7
7
7
7
7
7
7
7
7
7
7
7
7
7
7
7
7
7
7
7
7
7
7
7
8
8
9
9
9
9
9
9
a
e
g
k
l
m
n
a
b
g
m
a
b
c
d
e
f
g
h
i
275.0
324.2
274.0
270.0
303.0
246.0
241.0
276.0
289.8
270.0
235.0
232.0
229.0
337.2
233.0
235.0
238.0
274.0
281.0
338.0
273.0
237.0
270.8
270.0
270.0
272.8
269.2
271.0
276.6
268.4
270.8
277.8
271.0
273.0
275.0
270.0
272.0
273.2
270.8
269.0
279.4
276.6
272.0
275.0
282.4
287.2
300.0
342.0
278.4
291.4
289.0
323.0
277.0
275.8
268.40
330.94
286.43
286.00
313.00
243.00
235.00
284.29
298.23
283.00
230.00
202.00
189.00
329.17
216.00
213.00
223.00
277.00
284.00
310.00
279.00
215.00
282.95
281.87
283.05
284.44
281.23
283.18
288.15
281.14
283.12
290.97
281.43
283.96
287.45
277.08
282.13
284.43
282.21
280.81
294.66
285.35
282.20
288.30
292.42
298.41
303.65
331.32
288.15
302.39
303.70
315.59
288.04
287.33
18,330.72
35,389.06
18,756.49
15,617.92
17,536.03
22,802.29
15,676.76
39,232.90
44,018.60
32,406.98
52,125.23
9472.14
27,868.36
33,254.30
31,707.23
30,743.07
22,308.64
16,401.78
19,083.54
47,119.64
50,727.05
58,257.91
40,910.08
27,865.45
86,407.52
55,327.67
70,970.00
78,119.04
86,151.11
89,088.00
94,992.00
106,340.00
86,730.00
75,249.50
73,433.39
69,618.57
69,326.35
72,386.38
60,339.59
69,202.10
75,140.42
58,702.25
69,159.52
71,490.56
64,763.47
71,996.97
71,134.27
57,554.04
70,262.09
50,039.45
56,907.75
72,360.39
65,067.32
63,553.48
68,024.06
54,540.17
74,530.69
81,383.19
42,325.08
63,296.72
53,207.23
64,925.55
53,156.90
54,480.66
48,378.83
47,064.12
55,714.28
44,578.13
42,792.61
42,430.16
50,830.93
42,113.61
57,349.54
88,100.00
62,635.59
60,993.95
68,446.01
55,651.26
39,595.68
59,625.00
49,055.95
56,220.60
68,600.00
53,937.50
57,487.50
59,354.63
55,884.61
59,709.30
57,693.28
42,693.28
62,806.72
40,801.45
44,960.62
56,875.00
47,806.72
56,520.08
48,260.50
40,888.59
60,164.86
74,939.65
56,321.50
64,703.55
38,496.09
53,998.84
43,930.30
44,177.76
44,668.60
40,529.07
j
m
a
b
c
d
e
f
g
h
i
j
k
l
m
n
o
p
q
r
s
t
u
v
w
x
a
e
a
b
c
d
e
f

J Fluoresc
max
max
Fig. 1 The Relationship between (i) λ
values and (ii) ε
values from experiment and prediction based on calculated by TD-DFT
Table 2 UV Data of 7a-7v calculations and experiments in DCM, calculated Orbital Energies and torsion angles
λmaxExp
λmaxCal
ε
max
ε
max
-1
ELUMO-HOMO
Hartree
Dihedral angle θo
ii
Exp
-1
Cal
-1
Comp
R
-
1
nm
nm
M cm
M cm
i
iii
7
7
7
a
b
c
H
270.8 282.95
270.0 281.87
270.0 283.05
272.8 284.44
269.2 281.23
271.0 283.18
276.6 288.15
268.4 281.14
270.8 283.12
277.8 290.97
271.0 281.43
273.0 283.96
275.0 287.45
270.0 277.08
272.0 282.12
273.2 284.43
270.8 282.21
269.0 280.81
279.4 294.66
68446.01
55651.26
39595.68
59625.00
49055.95
56220.60
68600.00
53937.50
57487.50
59354.63
55884.61
59709.30
57693.28
42693.28
62806.72
40801.45
44960.62
56875.00
47806.72
56520.08
8502.00
73433.39
69618.57
69326.35
72386.38
60339.59
69202.10
75140.42
58702.25
69159.52
71490.56
64763.47
71996.97
71134.27
57554.04
70262.09
50039.45
56907.75
72360.39
65067.32
63553.48
9712.39
0.17561
0.17290
0.17223
0.17381
0.17489
0.17111
0.17040
0.17143
0.16901
0.16793
0.17184
0.17025
0.16825
0.15458
0.15299
0.15423
0.15661
0.14958
0.14229
- 0.00168
0.00543
- 0.02251
0.00000
- 0.00555
- 0.02554
2.21070
- 0.01614
- 0.0029
1.82798
0.01955
- 0.0326
- 2.75673
- 0.01015
0.00669
- 0.01351
0.00068
0.00153
0.02302
- 0.63743
- 0.00083
- 0.0194
- 0.02936
- 0.02456
0.05949
- 2.37386
- 0.01828
- 0.00785
- 0.33845
0.01761
- 0.00985
1.53426
- 0.00087
0.00031
o-F
m-F
p-F
o-Cl
m-Cl
p-Cl
o-Br
m-Br
p-Br
- 0.00096
- 0.00956
- 48.14485
- 0.00390
- 0.00290
- 51.34278
- 0.00314
0.00212
7
d
7
7
e
f
g
7
7
h
7
7
i
j
7
k
o-CH
3
- 36.43625
- 0.00298
- 0.10311
7
l
m-CH
3
7
m
p-CH
o-OCH
m-OCH
p-OCH
o-NO
m-NO
p-NO
3
7
7
7
7
n
o
p
q
3
- 45.95615
0.01202
1.71826
0.01329
0.01675
- 3.44419
0.00000
- 0.00085
-
3
3
- 0.00154
37.92288
0.00118
2
7
7
r
s
2
2
- 0.00048
2
3
76.6 285.35
42.4 350.46
7
t
o-OH
0.14882
- 2.93398
- 1.44051
14.73074
- 0.01217
- 2.50936
7
7
u
v
m-OH
p-OH
272.0 282.20
275.0 288.30
48260.50
40888.59
68024.06
54540.17
0.15688
0.17092
- 0.00514
- 0.69621
- 0.01852
- 2.45855

J Fluoresc
(
1
2H, s), 6.60 (1H, s), 3.87 (3H, s); IR (KBr):3442, 2924,
−1
636, 1590, 1535, 1354, 1262, 1168, 1109, 732, 688 cm ;
+
ESI-MS C H N O (m/z): 355.1 (M + H) .
22 17 3 2
2
-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-(hexyloxy)phenol
1
(
(
9f): Yellow solid; yield 81% (1.00 g), H NMR
300 MHz, d-DMSO) δ 13.55 (1H, s), 8.66–8.64 (4H,
d, J = 8.3 Hz), 8.62 (1H, s),7.74–7.57 (7H, m), 6.63–
.55 (1H, d, J = 8.6 Hz), 4.16–4.12 (2H, t), 1.86–1.80
2H, m), 1.67–1.64 (2H, m), 1.40–1.35 (4H, m), 1.00–
6
(
0
1
.96 (3H, t); IR (KBr):3433, 2925, 1594, 1532, 1449,
−1
265, 1163, 1111, 730, 683 cm ; ESI-MS C H N O
7 27 3 2
2
+
(m/z): 426.5 (M + H) .
Computational Details
Density functional theory (DFT) and time dependent (TD)
calculations are done to determine the optimized geometry
and UV absorption spectra. Therefore, in this work, by
allowing the relaxation of all the parameters, calculation has
been found to converge to a optimized geometry at B3LYP/6–
Fig. 2 3D-views of 7a-7v congeners by RMSD-based fitting
Results and Discussion
TD-DFT Analysis of the UV Data of 1,3,5-Triazines
3
11 + G (d,p) level. The optimized structural parameters are
used in the vibrational frequency calculations at DFT level to
characterize all stationary points as minima. The vertical ex-
citation energies at the ground state equilibrium geometries
are calculated with TD-DFT [1]. The low-lying first singlet
excited state (S1) of each conformer is relaxed using the TD-
DFT to obtain its minimum energy geometry. The difference
between the energies of the optimized geometries at the first
singlet excited state and the ground state is used in computing
Representing the synthesis processes of 1,3,5-triazine deriva-
tives are given in Scheme 1 and the UV data of 1,3,5-triazines
calculations and experiments in DCM were collected and re-
sults shown in Table 1.
On the basis of these data, the theoretical and experimental
max
values of the maximum absorption wavelength (λ ) and the
max
maximum molar absorption coefficient (ε ) were used to
build the linear relationship respectively. In Fig. 1 (i), the
maximum absorption wavelength from observed and predic-
tion calculated by TD-DFT have certain linear relationship
with high correlation coefficient with R = 0.9098,
P < 0.0001. In Fig. 1 (ii), the maximum molar absorption co-
efficient has results with R = 0.8136, P < 0.0001. The above
theoretical method provides a simple, relatively precise meth-
3
e
the emissions. All the computations are carried out using the
Polarizable Continuum Model (PCM) in CH Cl . All the
2
2
quantum mechanical calculations in this paper were carried
out in the Gaussian 09 program [18] and analytical data use
Multiwfn analyzer software [19].
The 3D-QSPR studies of the 1,3,5-triazine compounds
using the CoMFA performed on the Sybyl 8.0 package run-
ning on the Linux operating system. Partial atomic charges of
all compounds were calculated by the Gasteigere-Marsili
method, and then were optimized for their geometry using
Tripos field [20] with a distance-dependent dielectric function
and energy convergence criterion of 0.21 kcal/mol Å using the
maximum iterations set to 1000 [21]. The improvement of
QSPR may originate from the choice of DFT-optimized tem-
plate and the usage of RMSD-based molecular alignment
strategy. To derive the CoMFA descriptor fields, the aligned
training set molecules were placed in a 3D cubic lattice with
grid spacing of 2 Å in x, y, and z directions such that the entire
set could be included in it [22]. The CoMFA steric and elec-
max
max
od to obtain λ
and ε
of 1,3,5- triazines.
In Table 2, with 7a as the parent compound, the
effecting of different structures on the photophysical prop-
erties of 1,3,5-triazines are summarized as follows: (i) all
the maximum absorption wavelengths are red shifted when
R is a para-substituted group (e.g. 7d, 7g, 7j, 7m, 7p,7s,
Table 3 The statistical parameters for the 3D-QSAR CoMFA models
Comp
Statistical results
Filed contribution
2
2
R
F
SE
q
Steric Electrostatic
7
7
a-7v(except 7t) 0.918 44.585 0.955 0.501 0.127 0.873
3
a-7v
0.682 18.391 1.807 0.244
–
–
trostatic field energies were calculated using a sp carbon
probe atom with a van der Waals radius of 1.52 Å and a charge
of +1.0. Cut-off values for both steric and electrostatic fields
were set to 30.0 kcal/mol [23].
2
Method is CoMFA, q = The leave-one-out (LOO) cross-validation co-
2
efficient; SE = Standard error of estimate. R = The predictive correlation
coefficient; F = test value

J Fluoresc
3D-QSPR of 1,3,5-Triazines
In order to further modify the molecule, the 3D-QSPR
studies were applied on the maximum absorption wave-
length by using CoMFA protocol for the first time. The
data-based fitting procedure was finally adopted through
careful comparison. Each analogs (7a-7v) were
superimposed to the template based on the common sub-
structure of 1,3,5-triazines. The aligned molecules were
illustrated in Fig. 2 and the statistical parameters were
listed in Table 3.
For 1,3,5-triazines molecules, as shown in Table 3, the
better predictions are obtained by the 3D-QSPR/CoMFA for
2
absorption properties. The model has a high R (0.918) for 7a-
7
v except 7t, showed in Table 3, with a low standard deviation
Fig. 3 Plots of experimental activities versus the corresponding predicted
activities by QSAR/CoMFA models
(SE, 0.955) and a high Fischer ratio (F, 44.585), while a QSPR
2
model is generally acceptable if R is approximately 0.9 or
higher Specially, the cross-validation related coefficient q is
2
7
v). According to the theoretical optimization of the mo-
lecular structure, ortho-substituted due to the steric hin-
drance effect destroys the coplanarity leading to blue shift
or little change of the maximum absorption wavelength
0.501 (>0.5), suggesting a good prediction ability of this mod-
el. The contribution of steric field and electrostatic field are
0.127 and 0.873 respectively. The plots of the predicted versus
actual the maximum absorption wavelength for the QSPR/
CoMFA model were displayed in Fig. 3, which shows a good
correlation among them. Electrostatic field is the main factor
influencing the maximum absorption. When the model is
added to 7t, R = 0.682, q = 0.244, F = 18.391, SE = 1.807,
their results were not ideal compared with 7t be removed. The
major different form 7t to other compounds is that there is
ortho hydroxy in the structure of 7t. It indicated that the in-
troduction of ortho hydroxy has a great influence on the elec-
trostatic field and steric field of this kind of structure. The
reasons were further studied and discussed following.
(
e.g. 7b, 7e, 7h, 7k, 7n, 7q). Molar absorption coefficient
of the para-substituted is also generally higher than that of
m-substituted and ortho-substituted (e.g. 7d vs 7b and 7c,
7
g vs 7e and 7f, 7j vs 7 h and 7i, 7m vs 7k, 7s vs 7q). (ii)
2
2
Compared to para-substituted, meta-substituted and orth-
substituted compounds respectively, introduced the
electron-withdrawing group in para or ortho position or
electron-donating in meta position makes the maximum
absorption wavelength red shift more obvious (e.g. 7s vs
7
p, 7q vs 7n, 7s vs 7r). The introduction of electron-
withdrawing group has relative high molar absorption co-
efficient. Comprehensive analysis of halogen-substituted,
the Cl- substituted showed better UV absorption properties
To view the field effect on the target property, CoMFA
contour maps were generated and shown in Fig. 4. For steric
fields, the green is means bulky group favourable and the
yellow is bulky group unfavourable. Similarly, the blue means
(
e.g. 7b-7j). (iii) There bigger maximum absorption wave-
LUMO-HOMO
length can be get by a smaller E
.
Fig. 4 Stereoview of CoMFA
steric filed (i) and electrostatic
filed (ii) of 7a-7v except 7t

J Fluoresc
Fig. 5 Simulated IR spectra of 7t
and the reference compound
7
v.Calculation was done at DFT/
B3LYP/6–311 + G(d,p) level of
theory
electropositive charge favourable and red is electronegative
charge favourable. These can be explained by the fact that
interested chemicals shows a larger red shift when p-substitut-
ed, m-substituted introduce bulky group and o-substituted in-
troduce small group. At the same time, p-substituted was elec-
tronegative charge favourable and m-substituted, o-substituted
were electropositive charge favourable. This conclusion is
consistent with the TD-DFT calculation.
steric hindrance effect, the compounds with ortho hydroxy
have better UV absorption properties with wider absorption
band and adding a new absorption peak in about 342 nm. It
can be proved that a hydrogen is formed between the hydro-
gen atom of the hydroxyl group and the nitrogen atom of
1,3,5-triazine ring. In order to prove the existence of hydrogen
bonding, the further research work was done.
The IR spectroscopy has long been recognized as a fruitful
technique for characterization of H-bond present in a mole-
cule. Herein, we endeavour to exploit the strategy to rational-
ize the presence of IMHB in 7t from theoretically calculated
IR spectra. Figure 5 illustrates the simulated IR spectra of 7t
and a reference compound lacking of the IMHB interaction.
Here 7v has been taken as the reference which is devoid of the
The IMHB Analysis of of 1,3,5-Triazines
Significantly, the introduction of -OH group to o-position
bringing lots of interesting properties. In contrast with the
previous results, although the ortho hydroxy does not cause
32
Scheme 2 Simplified paradigm
showing the ESIPT process in 7t
29
31
*
.
Numbering of atoms used in the
2
7
2
8 O39
present study in indicated
26
hv
O
1
H 38
36
H
N
N37
1
7
6
N
N
2
2
0
N
34
9
15
N
3
5
2
2
5
11
16
18
7
E-form
ESIPT
O
*
Reverse PT
O
-
H
N
N
H
N
N
N
+
N
PT-form

J Fluoresc
hydrogen acceptor unit as in 7t. A direct comparison reveals
observed red shift in the IR stretch. (numbering of atoms ac-
cording to Scheme 2).
−1
that the O-H stretching frequency in 7t is about 102 cm red
shifted in comparison to that in the reference compound. The
present scenario is readily understandable in connection with
the IMHB interaction in 7t.The formation of IMHB requires a
hyperconjugative charge transfer from the lone pair of N -
Figure 6 depicts the steady-state absorption spectra of 7n,
7u, 7v and 7t in dichloromethane (DCM). The absorption
spectra show different vibronic structures between 7n, 7u,
7v and 7t, which indicates that the maxima of the absorption
bands of 7n, 7u, 7v and 7t are mainly located near 270, 272,
276 and 276 nm respectively. Especially 7 t appears a new
obvious absorption peak around 342 nm. The width of the
absorption band for 7t is broader than that for 7n, 7u and 7v.
Because the four molecules have similar geometric conforma-
tions, it was thought that the obvious difference in absorption
is caused by IMHBs. The structures of the 7n, 7u, 7v and 7t
molecules are shown in Fig. 6 as well. An IMHB can be
formed between the hydroxyl hydrogen and heterocyclic ni-
trogen in the 7t molecule, in which a quasi-aromatic chelating
ring is created through the IMHB. In contrast, the IMHB is not
formed in the 7n,7u,7v molecule.
3
7
*
atom to the σ (O -H ) orbital, which is necessarily to ac-
3
9
38
company some decrement in the O -H bond order as
3
9
38
reflected in weakening of the O -H bond energy compared
3
9
38
to that in the reference compound which accounts for the
IMHB interaction in these compounds is proposed to
play a pivotal role behind their ability to function as
UVAs. To reveal the mechanism of this phenomenon,
the theoretical analyses using DFT and TD-DFT was
performed. The initial insights into the photophysics
and ESIPT reaction of 7t are deduced from the opti-
mized geometrical parameters and relative stability order
of different possible low energy conformers of the stud-
ied molecule. The optimized geometrical parameters for
the E- and PT-forms of 7t (Scheme 2), which relevant to
the operation of ESIPT reaction, are summarized in
Table 4. As seen in the Table 4, elongation of the O -
3
9
H38 bond and contraction of N …H distance with
37
38
concomitant shortening of ∠N -H -O angle on going
3
7
38 39
from the E-form to the PT-form are some structural
modifications in accord with translocation of the proton
Table 4 Selected optimized geometry parameters for 7t relevant to
occurrence of ESIPT reaction (numbering of atoms according to
Scheme 2)
7
t
7n
a
b
Geometry Parameters
Calculation
E-Form
PT-Form
O
N
N
39–H38
0.990
1.716
1.350
1.470
1.420
1.345
1.340
148.27
118.245
1.819
1.021
1.348
1.497
1.464
1.259
1.302
138.26
117.17
37…H38
37–C
1
C
C
C
C
1
–C26
26–C28
28–O39
1
-C36
∠N
37-H38-O39
37-C -C26
7
u
7v
∠N
1
Fig. 6 Shapes of steady-state absorption spectra of 7n, 7u, 7v and 7t
a
o
molecules in DCM at concentration 2 × 10− mol L . Structures of 7n,
5
−1
Bond lengths in Å and angles in degree ( )
b
7
u, 7v and 7t molecules are also shown in
Calculation at DFT/B3LYP/6–311 + G(d,p) level

J Fluoresc
Fig. 7 Frontier molecular orbital
HOMO and LUMO) pictures for
(
the E-form and PT-form of 7t as
obtained from DFT/B3LYP/6–
3
11 + G(d,p) level of calculation
E-form
PT-form
HOME
LOME
Table 5 UV Data of 9a-9d calculations and experiments in DCM and calculated Orbital Energies
ELUMO-HOMO
Hartree
λmaxCal
λmaxExp
ε
max
ε
max
-1
Cal
-1
Exp
-1
Comp
-
1
nm
nm
M cm
M cm
2
3
3
3
3
3
88.15 278.4
53207.23
23903.79
64925.55
36287.80
53156.90
34608.89
54480.66
38496.99
15633.59
53998.84
18784.48
43930.30
20049.14
44177.76
9
a
0.14751
0.14984
39.68 337.8
02.39 291.4
37.75 333.8
03.70 289.0
33.61 335.0
9
b
9
c
0.15566
0.14340
9
d
315.59 323.0

J Fluoresc
Table 6 UV Data of 7a, 7t, 9a, 9e and 9f calculations and experiments in DCM and calculated Orbital Energies
λmaxExp
λmaxCal
nm
max
max
-1
ELUMO-HOMO
Hartree
ε
Exp
-1
ε
Cal
-1
Comp
-
1
nm
M cm
M cm
7
a
270.8
282.95
285.35
350.46
288.15
339.68
288.04
340.61
287.33
340.80
68446.01
56520.08
8502.01
73433.39
63553.48
9712.39
0.17561
2
3
2
3
2
3
2
3
76.6
42.4
78.4
37.8
77.0
39.8
75.8
41.2
7
t
0.14882
0.14751
0.14682
0.14750
38496.09
15633.59
44668.60
21022.09
40529.07
21577.91
53207.23
23903.79
48378.84
33506.05
47064.12
32309.03
9
a
e
9
9
f
from -OH functional moiety to the N -atom of the
same over O -atom. The presence of nodal plane be-
3
7
39
1
,3,5-triazine ring. Calculations predict the E-form of
tween N -C and N -C bonds prevents electron delo-
3
6
2
37
3
7
t to be the lowest energy conformer in the ground-
calization involving the aromatic nucleus and thereby for-
bidding the reversal of proton transfer in the excite-state.
state (Scheme 2) and thus accounts for the extra degree
of stabilization out of the six member IMHB ring. They
utilize an excited state intramolecular proton transfer
Method Application Validation
(
ESIPT) from a hydroxyl group to dissipate light energy
in a harmless manner to convert the absorbed photon
energy into heat without chemical damage.
In order to get a better absorption property of 1,3,5-triazines,
the 9a is used as the leading compound for future research.
Based on the above TD-DFT theory analysis and predictive
3D-QSPR model, some good absorbent 1,3,5-triazines com-
pounds 9b, 9c and 9d were studied and their UV absorption
properties were shown in Table 5. The result also proved the
good stability of our previous study.
Due to the large molecular weight, the 1,3,5-triazine com-
pounds is not easy to be dissolved in polymer materials. For
their wider application, the para-hydroxyl etherification prod-
ucts are designed and synthesized. From Table 6, the
etherification could be conducive to ultraviolet absorption
was found, but the chain length has little effect on UVabsorp-
tion. The experimental UV absorption data of the
etherification product 9e and 9f are also in good agreement
with those predicted using the TD-DFT. Conclusions.
The nodal plane concept of π-system molecular orbital
to rationalize the phenomenon of ESIPT was first devel-
oped by Nagaoka and Nagashima in the 90s and since
then it has been successfully substantiated to various sys-
tems [24, 25]. Analysis of the HOMO and LUMO of 7t
shows that the HOMO is a π-orbital with bonding char-
acter primarily across C -C -C and C -C -C axes
2
7
29 32
26 28 31
and antibonding character across C -O bond for the E-
2
8
39
form. Similar characteristics prevail for the HOMO of the
PT-form too. As observed in Fig. 7, the HOMO of both E-
and PT-forms consists of a large electronic density projec-
tion over O -atom along with bonding character along
3
9
O -H bond. Thus, transfer of the proton in the ground
3
9
38
-
state does not lead to any further stabilization through
*
electronic redistribution. Whereas, the LUMO is of π
character and excitation of electron from HOMO to
LUMO in the E-form leads to specific modulation of the
π-electron density distribution over the IMHB ring with
antibonding character along N -C and N -C bond ax-
Conclusions
In summary, a series of 1,3,5-triazines were synthesized. All
of experimental values λ
good agreement with those predicted using the TD-DFT
3
6
2
37
3
max
max
es. Transfer of proton in the excited-state produces a
LUMO in which the N -atom undergoes an enrichment
and ε
of 1,3,5-triazines are in
3
7
of electronic density projection and a diminution of the
[B3LYP/6–311 + G(d,p)]. The linear relationships have better

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stability ability with high correlation coefficient with
max
max
R(0.9098 and 0.8136), P < 0.0001 for the λ
and the ε
respectively. So this theoretical calculation provides a relative-
max
max
ly precise method to obtain λ
and ε
of 1,3,5-triazines.
Structure modification with 7a as parent compound revealed
that when p-substituted introduce electronegative charge
bulky group or o-substituted introduce electropositive charge
small group, the 1,3,5-triazines compounds have better UV
absorption properties.
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OH group to o-position brings excellent UVabsorption prop-
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Acknowledgements The financial support of this work was supplied by
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Education Department of Sichuan Province (NO. 12ZB128) and Key
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