Facile Synthesis of π-Conjugated Quinazoline-Substituted Ethenes from 2-Ethynylanilines and Benzonitriles under Transition-Metal-Free Conditions

Article abstract of DOI:10.1021/acs.joc.8b01494

A new transition-metal-free version for the synthesis of π-conjugated quinazoline-substituted ethene derivatives from readily available starting materials has been developed. Quinazoline-substituted ethenes were obtained in moderate to high yields with completely Z-selectivity, and the resulting quinazoline-substituted ethenes show typical aggregation-induced emission (AIE) properties.

Full text of DOI:10.1021/acs.joc.8b01494

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Article
Facial Synthesis of #-Conjugated Quinazoline-Substituted Ethenes from 2-
Ethynylanilines and Benzonitriles under Transition-Metal-Free Conditions
Xu Wang, Jiawei Li, Yubing Huang, Jiayi Zhu, Rongrong Hu, Wanqing Wu, and Huanfeng Jiang
J. Org. Chem., Just Accepted Manuscript • DOI: 10.1021/acs.joc.8b01494 • Publication Date (Web): 13 Aug 2018
Downloaded from http://pubs.acs.org on August 13, 2018
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Facial Synthesis of πꢀConjugated QuinazolineꢀSubstituted
Ethenes from 2ꢀEthynylanilines and Benzonitriles under
TransitionꢀMetalꢀFree Conditions
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Xu Wangb, Jiawei Lib, Yubing Huangb, Jiayi Zhub, Rongrong Hua, Wanqing Wu*,a,b
and Huanfeng Jiang*,b
a. State Key Laboratory of Luminescent Materials and Devices, South China University of Technology, Guangzhou
510640, China.
b. Key Laboratory of Functional Molecular Engineering of Guangdong Province, School of Chemistry and
Chemical Engineering, South China University of Technology, Guangzhou 510640, China.
Fax: (+86) 20ꢀ87112906; Eꢀmail: cewuwq@scut.edu.cn, jianghf@scut.edu.cn
Abstract: A new transitionꢀmetalꢀfree version for the synthesis of πꢀconjugated
quinazolineꢀsubstituted ethene derivatives from readily available starting materials
has been developed. Quinazolineꢀsubstituted ethenes were obtained in moderate to
high yields with completely Zꢀselectivity, and the resulting quinazolineꢀsubstituted
ethenes show typical aggregationꢀinduced emission (AIE) properties.
INTRODUCTION
Conjugated organic πꢀsystems containing arenes and heteroarenes have gained
increasing interest owing to their potential utility in materials sciences.1 Due to the
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great value, the development of novel strategies for rapid synthesis of πꢀconjugated
organic molecules are critically important. In this respect, the common methods for
constructing πꢀconjugated compounds are transitionꢀmetalꢀcatalyzed reactions,2ꢀ6 such
as wellꢀknown Heck coupling reaction,7 Negishi coupling reaction,8 Sonogashira
coupling reaction9 and Suzuki coupling reaction.10 In recent years,
transitionꢀmetalꢀfree reactions are gradually recognized as an indispensable tool in
organic synthesis,11 which are not only less costly and more environmentally friendly
but also can avoid potential transition metal contamination in the heterocyclic
products. However, controlling chemoselectivity and regioselectivity in chemical
reactions under transitionꢀmetalꢀfree conditions still remains challenging, owing to the
intrinsic mechanistic limitation.11a From environmental and economic perspectives,
design and implementation of an efficient synthetic approach to construct
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πꢀconjugated molecules under transitionꢀmetalꢀfree conditions is still highly desirable.
Scheme 1. Different Reaction Pathways of Benzonitriles with 2ꢀEthynylanilines
More recently, we have reported a copperꢀcatalyzed process for the synthesis of
substituted quinazolines from benzonitriles and 2ꢀethynylanilines under O2
atmosphere (Scheme 1a).12 Inspired by this previous work and in continuation of our
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interest in the transformation of nitriles,13 we herein report a transitionꢀmetalꢀfree
catalytic route for chemoselective synthesis of πꢀconjugated quinazolineꢀsubstituted
ethenes from 2ꢀethynylanilines and benzonitriles (Scheme 1b), which exhibit typical
aggregationꢀinduced emission (AIE) properties14 with adjustable emission color.
RESULTS AND DISCUSSION
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Initially, 2ꢀ(phenylethynyl)aniline (1a) and 4ꢀchlorobenzonitrile (2a) were chosen
as the model substrates to optimize the reaction conditions (Table 1). Fortunately, the
desired product (Z)ꢀ1,2ꢀbis(2ꢀ(4ꢀchlorophenyl)quinazolinꢀ4ꢀyl)ꢀ1,2ꢀdiphenylethene
(3aa) was obtained in 7% yield with tꢀBuOK as base in toluene at 110 °C for 24 h
(entry 1). Subsequent investigation on the effect of the reaction temperature proved
that 120 °C was appropriate for this reaction (entries 1 vs 2ꢀ4). The initial substrate
ratio for this transformation was also investigated, and the reaction with 1a/2a (1:2)
gave the best result (entries 1 vs 5ꢀ6). Then, various bases were tested, and trace
amount of 3aa was detected when other bases such as tꢀBuONa and tꢀBuOLi were
employed (entries 7ꢀ8). No product was found with NEt3, NaOH, K2CO3 and K3PO4
as bases (entries 9ꢀ12), where tꢀBuOK turned out to be the most appropriate. Large
amount of unreacted starting material was recovered in all cases. Among the different
solvents that we screened (entries 13ꢀ17), when DMA was used as solvent, although
the yield was increased to 47% (entry 17), the intramolecular cyclization product
2ꢀphenylꢀ1Hꢀindole was also found. Gratifyingly, an improvement of the yield (73%)
and a shorter reaction time (2 h) were observed for conducting the reaction with the
combination of DMA and toluene (4:1) as solvent (entry 20). Further reduction of
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tꢀBuOK to 2 equiv led to a sharp decrease in yield to 27% (entry 22). Finally, we
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attempted the reaction under a N2 atmosphere, however, the corresponding product
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3aa could not be obtained (entry 23).
Table 1. Optimization of reaction conditionsa,b
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entrya
base (equiv)
solvent
temp (oC)
yield (%)b
1
2
tꢀBuOK (3)
tꢀBuOK (3)
tꢀBuOK (3)
tꢀBuOK (3)
tꢀBuOK (3)
tꢀBuOK (3)
tꢀBuONa (3)
tꢀBuOLi (3)
NEt3 (3)
toluene
toluene
toluene
toluene
toluene
toluene
toluene
toluene
toluene
toluene
toluene
toluene
1,4ꢀdioxane
MeCN
110
100
115
120
120
120
120
120
120
120
120
120
100
80
7
trace
9
3
4
13
5c
6d
7
6
8
trace
trace
ND
ND
ND
ND
ND
ND
21
8
9
10
11
12
13
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15
16
17
NaOH (3)
K2CO3 (3)
K3PO4 (3)
tꢀBuOK (3)
tꢀBuOK (3)
tꢀBuOK (3)
tꢀBuOK (3)
tꢀBuOK (3)
DMSO
DMF
120
120
120
32
DMA
47
18
19
20
21
22
23f
tꢀBuOK (3)
tꢀBuOK (3)
tꢀBuOK (3)
tꢀBuOK (3)
tꢀBuOK (2)
tꢀBuOK (3)
DMA/toluene (1/1)
DMA/toluene (2/1)
DMA/toluene (4/1)
DMA/toluene (5/1)
DMA/toluene (4/1)
DMA/toluene (4/1)
120
120
120
120
120
120
53
67
74 (73)e
52
27
ND
aReaction conditions: 1a (0.2 mmol), 2a (0.4 mmol), base (3 equiv) and solvent (1 mL), under air,
24 h. bIsolated yields. ND = not detected. c1a (0.4 mmol), 2a (0.2 mmol). d1a (0.2 mmol), 2a (0.2
mmol). e2 h. fUnder N2 atmosphere.
With the optimal reaction conditions in hand, we then started to examine the scope
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of quinazolineꢀsubstituted ethenes of this reaction (Scheme 2). It was observed that a
series of selected 2ꢀ(phenylethynyl)anilines and benzonitriles were applied to the
reaction, resulting in the generation of the desired products in moderate to good yields
with complete (Z)ꢀconfiguration. 2ꢀ(Phenylethynyl)anilines bearing electronꢀrich
substituents at para position of benzene ring, such as ꢀMe, ꢀEt, ꢀnꢀBu, ꢀtꢀBu and ꢀOMe
groups, transferred to the target products 3baꢀ3fb in 54ꢀ77% yields. The reactions of
substrates 1g, 1h and 1i possessing an electronꢀwithdrawing group at paraꢀposition of
aryl ring, including ꢀF, ꢀBr and ꢀCF3 groups, gave the desired products 3gaꢀ3ib in
42ꢀ61% yields. Obviously, 2ꢀ(phenylethynyl)anilines with an electronꢀdonating group
at the benzene ring furnished the desired products in higher yields than those bearing
electronꢀwithdrawing group. 2ꢀ(Phenylethynyl)aniline (1j) with a substituent at the
metaꢀposition reacted smoothly and converted to the products 3ja and 3jb in 42% and
49% yields. Delightfully, 2ꢀ(thiophenꢀ3ꢀylethynyl)aniline (1k) was also transferred to
the expected product 3kb in 31% yield. In addition, the 2ꢀ(phenylethynyl)anilines
bearing an electronꢀdonating group at R1 position, such as ꢀCH3, also provided the
desired products 3laꢀ3mb in high yields. Unfortunately, unsubstituted benzonitrile or
benzonitriles substituted with an electronꢀdonating group failed to transformed to the
corresponding products 3acꢀ3ae under the optimized conditions. Other benzonitriles
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presumably are not conducive to the formation of intermediate
Ⅱ (Scheme 4).
Scheme 2. Synthesis of QuinazolineꢀSubstituted Ethenes 3a,b
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aReaction conditions: 1 (0.2 mmol), 2 (0.4 mmol), tꢀBuOK (3 equiv) in 1 mL of DMA/toluene
(4/1), under air, 120 oC, 2 h. bIsolated yields. ND = not detected.
Scheme 3. Control Experiments
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O
O
N
O
CN
CF3
t-BuOK (3 equiv)
F
F
F
N
+
DMA/toluene (4/1), air
120 oC, 2 h
(a)
N
N
NH2
1m
2b
3mb
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CF3
with addition of TEMPO (2.0 equiv), 67%
with addition of BHT (2.0 equiv), 41%
O
O
CN
t-BuOK (3 equiv)
F
F
F
+
DMA/toluene (4/1), air
120 oC, 10 min
N
(b)
NH2
1m
N
F
F
2b
4mb, 17%
F
O
O
N
O
O
CF3
N
t-BuOK (3 equiv)
+
(c)
N
DMA/toluene (4/1
air, 120 oC, 2 h
N
N
N
N
F
F
N
4mb
F
F
F
F
4mb, >95%
CF3
3mb, trace
O
O
N
O
+
CN
CF3
t-BuOK (3 equiv)
F
F
+
4mb, 0%
F
N
+
4mb
(0.05mmol)
(d)
DMA/toluene (4/1)
air, 120 oC, 2 h
N
N
NH2
1m
2b
CF3
3mb, 84%
O
O
O
O
CN
CF3
F
F
t-BuOK (3 equiv)
+
+
(e)
N
N
DMA/toluene (4/1)
air, 120 oC, 2 h
NH2
F
N
N
NH2
0.4 mmol
2b
0.1 mmol
0.1 mmol
1c
1m
CF3
3cmb
ESI-MS analysis
[M+H]+= 813.2664
To gain more mechanistic insight into this transformation, some control
experiments were carried out (Scheme 3). When 2.0 equiv of the radical scavengers
such as TEMPO (2,2,6,6ꢀtetramethylꢀ1ꢀpiperidinyloxy) or BHT
(3,5ꢀdiꢀtertꢀbutylꢀ4ꢀhydroxytoluene) were added to this system under standard
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conditions, 67% and 41% yields of 3mb were smoothly obtained (Scheme 3a),
respectively, which suggested that this transformation might not undergo a radical
process. The reaction of 2ꢀ((4ꢀethoxyphenyl)ethynyl)ꢀ5ꢀmethylaniline (1m) with
4ꢀ(trifluoromethyl)benzonitrile (2b) under the standard conditions for 10 min gave
4mb in 17% yield (Scheme 3b). Subsequently, 4mb was subjected to the optimized
reaction conditions, and 3mb was detected in a trace yield with large amounts of
unreacted 4mb was found (Scheme 3c). When 0.05 mmol of 4mb was added to this
system under standard conditions, an 84% yield of 3mb was obtained and the species
4mb was not detected (Scheme 3d). These results demonstrated that 4mb should be
an intermediate in the current reaction. In addition, 3cmb ([M+H]+ = 813.2664) could
be detected in the reaction mixture by ESIꢀMS (Scheme 3e), suggesting that 3cmb
was formed through a crossꢀcoupling reaction between compounds Ⅴ and Ⅳ (see
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Scheme 4).
Scheme 4. Plausible Mechanism
Based on the above results and previous reports,12,15 we proposed a plausible
reaction mechanism for this transformation detailed in Scheme 4. The initial step is
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the deprotonation of 1 in the presence of tꢀBuOK to form anion intermediate І which
could selectively attack the cyano group to give the amidine intermediate . Then,
intramolecular cyclization of alkynes and amidine produces intermediate , which
would undergo protonation to generate intermediate . Further deprotonation of
gives carbanion and subsequent oxidation affords , followed by the attack of to
give species . Finally, elimination of one molecule of water leads to the desired
product 3. The benzene ring at the 2ꢀposition of quinazoline influences the
stereoselectivity of the reaction, leading to stereoregular product configuration.16
More encouragingly, all these products exhibited a marked solid luminescence
phenomenon. Obviously, the products with trifluoromethyl (ꢀCF3) substituents at the
benzene ring show better luminescence intensity than which possessed chloro (ꢀCl)
substituents on the benzene ring. To further evaluate the optical properties, 3bb, 3cb,
3fb, and 3gb were selected as the representatives, which were investigated by the
UVꢀvis absorption and PL spectra in dilute THF solution (1×10ꢀ5 mol/L) and thin
films. As shown in Table 2, all the selected compounds have the similar two
absorption peaks (Figure 1A), with the dominant one at 260 nm and a shoulder at 340
nm in pure THF solution, which should be attributed to the πꢀπ* transition of the
conjugated skeleton and the intramolecular charge transfer (ICT) between donor and
acceptor moieties. The molar absorptivities (ε) for 3bb, 3cb, 3fb, and 3gb were
determined to be 48900, 73700, 47500 and 38200 L·molꢀ1·cmꢀ1 at 340 nm,
respectively. The absorption capacity for the compounds featuring the
electronꢀdonating substituents at the phenyl ring was better than those of the
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electronꢀwithdrawing aryl substituted ones. This trend might be due to the increased
πꢀπ* transition. As can be seen from their PL spectra (Figure 1B), the emission
maximum for 3gb is located at 470 nm, while 3bb and 3fb show similar emission
bands at 493 nm. Compared to 3gb, the emission maximum of 3cb was redꢀshifted for
60 nm, indicating the stronger donorꢀacceptor interaction. These results show that
substituents with different electronic properties results in different intramolecular
charge transfer (ICT) effects. The fluorescence quantum yield (ΦF,film) values were
determined to be 16.1%, 52.3%, 9.7% and 5.4% for 3bb, 3cb, 3fb and 3gb in thin
films, respectively (Table 2). The quantum yields (ΦF,soln) of 3bb, 3cb, 3fb and 3gb in
THF solutions (1×10ꢀ5 mol/L) were also measured to be 1.4%, 3.4%, 3.6%, and 3.3%,
respectively. Therefore, the AIE factor (αAIE =ΦF,film/ΦF,soln) of 3bb, 3cb, 3fb and 3gb
were calculated to be 11.5, 15.4, 2.7, and 1.6, respectively. These data clearly showed
that 3bb, 3cb, 3fb and 3gb are AIE active molecules. Furthermore, the fluorescence
lifetimes (τfilm) were also investigated and they were 3.18 ns, 8.12 ns, 2.85 ns and 1.84
ns for 3bb, 3cb, 3fb, and 3gb, respectively. Obviously, the molecules bearing a strong
electronꢀdonating group at aryl ring, such as the ꢀOCH3 group, exhibited stronger AIE
effect than others.
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Figure 1. (A) The absorption spectra of 3bb, 3cb, 3fb, and 3gb in THF solutions (10ꢀ5 M). (B)
The emission spectra of 3bb, 3cb, 3fb, and 3gb in thin films. (C) 3bb, 3cb, 3fb and 3gb taken
under the irradiation of 365 nm light.
Table 2. Photophysical properties of 3bb, 3cb, 3fb, and 3gb
comp.
λmax abs.a
(nm)
εa
λmax em.b
(nm)
a
b
c
ΦF,soln
ΦF,film
τfilmb (ns) αAIE
(M.cm)ꢀ1
3bb
3cb
3fb
3gb
261 342
261 341
260 340
261 341
48900
73700
47500
38200
493
530
493
470
1.4%
3.4%
3.6%
3.3%
16.1%
52.3%
9.7%
3.18
8.12
2.85
1.84
11.5
15.4
2.7
5.4%
1.6
aIn THF solutions (10ꢀ5 M). bIn thin films. cαAIE = ΦF,film/ΦF,soln
Density functional theory (DFT) calculation was carried out to help understand the
relationship between electronic structures and photophysical properties (Figure 2).
The lowest unoccupied molecular orbital (LUMO) of 3bb, 3cb, 3fb and 3gb exhibits
a strong electron clouds distribution at the quinazoline ring (see Supporting
Information for details). The electron distribution of the highest occupied molecular
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orbital (HOMO) of 3bb and 3fb are located mainly on the phenyl unit and vinyl core,
partly on the quinazoline ring. The electron density of the HOMO of 3gb is almost
spread to the whole molecule. In contrast to 3cb, the spatial distributions of the
HOMO and the LUMO are less overlapped, ascribed to the relatively strong ICT
effect. These results are consistent with their expected intramolecular charge transfer
process.
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Figure 2. The optimal structure and HOMO and LUMO distributions of 3bb, 3cb, 3fb and 3gb
To further verify the AIE character, the fluorescence properties of 3bb, 3cb, 3fb
and 3gb in water/THF mixtures of various ratios are shown in Figure 3. It is
noteworthy that the changing trends in luminescence of these compounds were similar.
As an example, the photoluminescence intensity of 3bb were almost continued to
decline until the water fraction (fw) reached 90%, and a red shift of about 110 nm to
490 nm was also observed. This can be attributed to an intramolecular chargeꢀtransfer
(ICT) process. Afterwards, with the increase of fw from 90% to 99%, a significantly
enhanced emission intensity could be detected, which should be associated with the
formation of nanoaggregates, since increasing water content will reduce the ability to
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dissolve, demonstrating AIE activity.
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Figure 3. Fluorescence spectra of (A) 3bb, (B) 3cb, (C) 3fb and (D) 3gb in THF/water mixtures
with different water content (10ꢀ5 mol/L).
To better explain and understand the AIE behaviors, single crystals of 3bb, 3cb, 3fb
and 3gb were grown through their slow crystallization in absolute alcohol and
analyzed by Xꢀray diffraction crystallography. Three kinds of aromatic ring in
compounds 3 are named as ϕ1, ϕ2 and ϕ3. The four molecules exhibited the folded
Zꢀisomer (Figure 4), and the dihedral angle between the two phenyl groups (ϕ1) in
3bb, 3cb, 3fb and 3gb were observed as 54.37o, 61.67o, 47.49o and 59.66o. The
dihedral angles between the two quinazoline moieties (ϕ2) were 70.04o, 69.55o, 62.60o
and 69.50o, respectively. Moreover, the quinazoline moieties (ϕ2) and the phenyl
groups (ϕ3) are located in an almost parallel manner. Thus, these molecules exhibited
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a highly twisted configuration, and no obvious intramolecular interactions occurred.
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Figure 4. (A, B, C and D) Basic unit structure of the 3bb, 3cb, 3fb and 3gb crystal.
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Figure 5. (A, B, C and D) CꢀH...π hydrogen bonds and πꢀπ interactions with indicated distances (Å)
between the adjacent molecules of 3bb, 3cb, 3fb and 3gb in the crystal state.
The intermolecular effects of crystals were also investigated. As shown in Figure 5,
similar modes of intermolecular interactions were observed in the four molecules.
Quinazoline moieties (ϕ2) from two neighboring molecules in 3bb, 3cb, 3fb and 3gb
are stacked in a roughly parallel manner and approximately half of their surfaces are
overlapped. The distance between two overlapped quinazoline planes were in the
range of 3.277ꢀ3.589 Å, indicating the presence of intermolecular πꢀπ stacking
interactions. In addition to πꢀπ stacking interactions, multiple CꢀH···π hydrogen
bonds from adjacent molecules were also found, and the shortest distances of these
CꢀH···π bonds were in the range of 2.988ꢀ3.263 Å. So the intermolecular CꢀH···π and
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πꢀπ stacking interactions together help to rigidify the molecular conformation and
lock the intramolecular rotations of the phenyl (ϕ1) and quinazoline rings (ϕ2) against
the vinyl core.
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CONCLUSION
In conclusion, we have successfully developed a flexible and rapid route to
synthesize a series of πꢀconjugated quinazolineꢀsubstituted ethene derivatives from
2ꢀethynylanilines and benzonitriles. The new reaction tolerated many functional
groups and obtained the corresponding products exhibiting typical AIE properties in
moderate to high yields. The relationship between structure and luminescence
properties of these compounds was investigated in detail.
EXPERIMENTAL SECTION
General Information: NMR spectra were obtained using a Bruker Avance 400
spectrometer (1H at 400 MHz, and 13 C at 101 MHz). Chemical shifts for H NMR
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spectra are reported in parts per million (ppm) from tetramethylsilane with the solvent
resonance as the internal standard (CDCl3: δ 7.26 ppm). Chemical shifts for 13C NMR
spectra are reported in parts per million (ppm) from tetramethylsilane with the solvent
as the internal standard (CDCl3: δ 77.0 ppm). IR spectra were obtained either as
potassium bromide pellets or as liquid films between two potassium bromide pellets
with a spectrometer. HRMS was obtained with a LCMSꢀITꢀTOF mass spectrometer.
Single crystal Xꢀray diffraction analyses were done on Bruker polycrystal Xꢀray
diffraction and Rigaku Oxford Diffraction Supernova Dual Source. UVꢀvis absorption
spectra were obtained using Shimadzu UVꢀ2600 spectrophotometer.
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Photoluminescence spectra were recorded on
a
Horiba Fluoromaxꢀ4
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spectrofluorometer. Solution and thin film fluorescence quantum yields were
measured using a Hamamatsu absolute PL quantum yield spectrometer C11347
QuantaurusꢀQY. Fluorescence lifetimes were determined with a Hamamatsu
C11367ꢀ11 QuantaurusꢀTau timeꢀresolved spectrometer. The groundꢀstate geometries
of 3bb, 3cb, 3fb and 3gb were optimized using the density function theory (DFT)
method with B3LYP hybrid functional at the basis set level of 6ꢀ31G (d, p). All the
calculations were performed using Gaussian 09 package. Benzonitriles were all
commercial available. Unless otherwise noted, materials obtained from commercial
suppliers were used without further purification.
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General Procedure for the Preparation of Compound 3: A mixture of
2ꢀethynylanilines 1 (0.2 mmol), nitriles 2 (0.4 mmol), tꢀBuOK (3 equiv) were added
to 1 mL DMA/toluene (4:1, v/v). The mixture was stirred in a tube under open air at
o
120 C for 2 h and monitored periodically by TLC. Upon completion, the reaction
mixture was diluted with water (30 mL) and extracted with ethyl acetate (3 × 30 mL).
The combined organic layers were washed with water and brine, dried over Na2SO4
and filtered. The solvent was removed under vacuum. The residue was purified by
flash column chromatography to afford quinazolineꢀsubstituted ethenes 3.
General Procedure for the Preparation of Compound 1: a mixture of
2ꢀiodoanilines (2 mmol), CuI (2 mol %), PdCl2(PPh3)2 (1mol %), and Et3N (5 mL)
were added successively under N2 and then alkynes (2.4 mmol) were added via
syringe. The mixture was stirred at room temperature for 5 h and monitored
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periodically by TLC. Upon completion, the reaction mixture was diluted with water
(30 mL) and extracted with ethyl acetate (3 × 30 mL). The combined organic layers
were washed with water and brine, dried over Na2SO4 and filtered. The solvent was
removed under vacuum. The residue was purified by chromatography on silica gel
(petroleum ether/ethyl acetate 10/1 v/v).
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General Procedure for the Preparation of Compound 4mb: A mixture of
2ꢀethynylaniline 1m (0.2 mmol), nitrile 2b (0.4 mmol), tꢀBuOK (3 equiv) were added
to 1 mL DMA/toluene (4:1, v/v). The mixture was stirred in a tube under open air at
120 oC for 10 min, the reaction mixture was diluted with water (30 mL) and extracted
with ethyl acetate (3 × 30 mL). The combined organic layers were washed with water
and brine, dried over Na2SO4 and filtered. The solvent was removed under vacuum.
The residue was purified by flash column chromatography to afford 4mb.
(Z)ꢀ1,2ꢀBis(2ꢀ(4ꢀchlorophenyl)quinazolinꢀ4ꢀyl)ꢀ1,2ꢀdiphenylethene (3aa): Purified
via flash column chromatography with 40% ethyl acetate/petroleum ether, yielding
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73% (47.8 mg) as a white solid: 210ꢀ212 C. H NMR (400 MHz, CDCl3, δ ppm)
8.22ꢀ8.15 (m, 2H), 7.89ꢀ7.80 (m, 6H), 7.76ꢀ7.71 (m, 2H), 7.50ꢀ7.43 (m, 2H),
7.42ꢀ7.35 (m, 4H), 7.28ꢀ7.22 (m, 6H), 7.20ꢀ7.12 (m, 4H); 13C NMR (101 MHz,
CDCl3, δ ppm) 169.8, 158.8, 151.2, 141.9, 138.8, 136.3, 136.2, 133.4, 130.3, 129.5,
128.9, 128.6, 128.4, 128.3, 127.3, 126.9, 122.9. IR (KBr, cm–1): 2930, 1722, 1539,
1337, 1038, 759. HRMS (ESI) m/z: calcd for C42H26Cl2N4Na [M + Na]+ 679.1427;
found 679.1433.
(Z)ꢀ1,2ꢀBis(2ꢀ(4ꢀchlorophenyl)quinazolinꢀ4ꢀyl)ꢀ1,2ꢀdiꢀpꢀtolylethene
(3ba):
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Purified via flash column chromatography with 40% ethyl acetate/petroleum ether,
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yielding 69% (47.1 mg) as a white solid: 282ꢀ284 C. 1H NMR (400 MHz, CDCl3, δ
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(m, 2H), 7.23 (d, J = 8.1 Hz, 4H), 7.16ꢀ7.11 (m, 4H), 7.04 (d, J = 8.0 Hz, 4H), 2.31 (s,
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6H); C NMR (101 MHz, CDCl3, δ ppm) 170.2, 158.8, 151.1, 141.5, 138.1, 136.2,
136.1, 136.0, 133.3, 130.2, 129.5, 129.3, 128.9, 128.3, 127.4, 126.9, 123.0, 21.4. IR
(KBr, cm–1): 2928, 1723, 1543, 1345, 1038, 850. HRMS (ESI) m/z: calcd for
C44H30Cl2N4Na [M + Na]+ 707.1740; found 707.1743.
(Z)ꢀ1,2ꢀBis(2ꢀ(4ꢀchlorophenyl)quinazolinꢀ4ꢀyl)ꢀ1,2ꢀbis(4ꢀmethoxyphenyl)ethene
(3ca): Purified via flash column chromatography with 40% ethyl acetate/petroleum
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ether, yielding 66% (47.2 mg) as a white solid: 304ꢀ306 C. H NMR (400 MHz,
CDCl3, δ ppm) 8.12 (d, J = 8.2 Hz, 2H), 7.85 (d, J = 8.5 Hz, 2H), 7.74 (dd, J = 13.4,
8.0 Hz, 6H), 7.46 (t, J = 7.5 Hz, 2H), 7.28ꢀ7.24 (m, 4H), 7.12 (d, J = 8.4 Hz, 4H),
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6.77 (d, J = 8.6 Hz, 4H), 3.78 (s, 6H); C NMR (101 MHz, CDCl3, δ ppm) 170.4,
159.3, 158.8, 151.1, 140.8, 136.2, 133.3, 131.6, 131.5, 129.4, 128.9, 128.3, 127.4,
126.9, 123.1, 114.1, 55.2. IR (KBr, cm–1): 2924, 1726, 1539, 1386, 1026, 756. HRMS
(ESI) m/z: calcd for C44H31Cl2N4O2 [M + H]+ 717.1819; found 717.1824.
(Z)ꢀ1,2ꢀBis(2ꢀ(4ꢀchlorophenyl)quinazolinꢀ4ꢀyl)ꢀ1,2ꢀbis(4ꢀethylphenyl)ethene
(3da): Purified via flash column chromatography with 40% ethyl acetate/petroleum
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ether, yielding 62% (44.1 mg) as a white solid: 262ꢀ264 C. H NMR (400 MHz,
CDCl3, δ ppm) 8.16 (d, J = 8.3 Hz, 2H), 7.84ꢀ7.70 (m, 8H), 7.46 (t, J = 7.6 Hz, 2H),
7.25 (d, J = 7.6 Hz, 4H), 7.14 (d, J = 8.5 Hz, 4H), 7.05 (d, J = 8.0 Hz, 4H), 2.62 (q, J
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= 7.6 Hz, 4H), 1.21 (t, J = 7.6 Hz, 6H); C NMR (101 MHz, CDCl3, δ ppm) 170.2,
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128.0, 127.5, 126.8, 123.0, 28.6, 15.1. IR (KBr, cm–1): 2923, 1729, 1539, 1386, 1082,
757. HRMS (ESI) m/z: calcd for C46H35Cl2N4 [M + H]+ 713.2233; found 713.2239.
(Z)ꢀ1,2ꢀBis(4ꢀbutylphenyl)ꢀ1,2ꢀbis(2ꢀ(4ꢀchlorophenyl)quinazolinꢀ4ꢀyl)ethene
(3ea): Purified via flash column chromatography with 40% ethyl acetate/petroleum
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ether, yielding 71% (54.5 mg) as a white solid: 238ꢀ239 C. H NMR (400 MHz,
CDCl3, δ ppm) 8.53 (d, J = 8.3 Hz, 4H), 8.26 (d, J = 8.3 Hz, 2H), 8.02 (d, J = 8.4 Hz,
2H), 7.78 (t, J = 7.5 Hz, 2H), 7.48 (t, J = 8.0 Hz, 6H), 7.07 (d, J = 7.8 Hz, 4H), 6.72
(d, J = 8.0 Hz, 4H), 2.30 (t, J = 7.6 Hz, 4H), 1.32ꢀ1.26 (m, 4H), 1.08ꢀ0.99 (m, 4H),
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0.73 (t, J = 7.3 Hz, 6H); C NMR (101 MHz, CDCl3, δ ppm) 170.1, 159.2, 151.3,
142.5, 140.6, 136.7, 133.7, 130.0, 129.1. 128.8, 128.7, 128.1, 127.4, 126.7, 122.6,
35.1, 33.0, 22.0, 13.8. IR (KBr, cm–1): 2929, 1722, 1538, 1343, 1037, 754. HRMS
(ESI) m/z: calcd for C50H42Cl2N4Na [M + Na]+ 791.2679; found 791.2681.
(Z)ꢀ1,2ꢀBis(4ꢀ(tertꢀbutyl)phenyl)ꢀ1,2ꢀbis(2ꢀ(4ꢀchlorophenyl)quinazolinꢀ4ꢀyl)ethe
ne (3fa): Purified via flash column chromatography with 40% ethyl acetate/petroleum
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ether, yielding 66% (50.6 mg) as a white solid: 278ꢀ280 C. H NMR (400 MHz,
CDCl3, δ ppm) 8.24 (d, J = 7.8 Hz, 2H), 7.90ꢀ7.82 (m, 6H), 7.73 (ddd, J = 8.4, 6.9,
1.3 Hz, 2H), 7.51ꢀ7.46 (m, 2H), 7.36ꢀ7.30 (m, 4H), 7.29ꢀ7.25 (m, 4H), 7.22ꢀ7.17 (m,
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4H), 1.32 (s, 18H); C NMR (101 MHz, CDCl3, δ ppm) 170.0, 158.7, 151.2, 151.1,
141.0, 136.3, 136.2, 135.7, 133.2, 129.8, 129.5, 128.8, 128.3, 127.5, 126.7, 125.3,
122.9, 34.6, 31.2. IR (KBr, cm–1): 2956, 1720, 1539, 1392, 1088, 757. HRMS (ESI)
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m/z: calcd for C50H42Cl2N4Na [M + Na]+ 791.2679; found 791.2673.
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(3ga): Purified via flash column chromatography with 40% ethyl acetate/petroleum
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ether, yielding 54% (37.4 mg) as a white solid: 234ꢀ236 C. H NMR (400 MHz,
CDCl3, δ ppm) 8.12 (d, J = 8.3 Hz, 2H), 7.84 (t, J = 9.4 Hz, 6H), 7.78ꢀ7.69 (m, 2H),
7.50ꢀ7.46 (m, 2H), 7.39ꢀ7.29 (m, 4H), 7.17 (d, J = 8.6 Hz, 4H), 6.97 (t, J = 8.6 Hz,
4H); 13C NMR (101 MHz, CDCl3, δ ppm) 169.3, 162.7 (d, J = 248.4 Hz), 158.8,
151.3, 141.0, 136.5, 136.1, 134.5(d, J = 3.5 Hz), 133.6, 132.1 (d, J = 8.2 Hz), 1295,
129.1, 128.4, 127.0 (d, J = 28.5 Hz), 122.6, 116.0, 115.8. IR (KBr, cm–1): 2930, 1723,
1596, 1388, 1038, 767. HRMS (ESI) m/z: calcd for C42H24Cl2F2N4Na [M + Na]+
715.1238; found 715.1233.
(Z)ꢀ1,2ꢀBis(4ꢀbromophenyl)ꢀ1,2ꢀbis(2ꢀ(4ꢀchlorophenyl)quinazolinꢀ4ꢀyl)ethene
(3ha): Purified via flash column chromatography with 40% ethyl acetate/petroleum
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ether, yielding 58% (47.2 mg) as a white solid: 308ꢀ309 C. H NMR (400 MHz,
CDCl3, δ ppm) 8.09 (d, J = 8.2 Hz, 2H), 7.83 (dd, J = 12.4, 8.6 Hz, 6H), 7.75 (t, J =
7.2 Hz, 2H), 7.48 (t, J = 7.5 Hz, 2H), 7.41 (d, J = 8.4 Hz, 4H), 7.23 (d, J = 8.5 Hz,
4H), 7.17 (d, J = 8.6 Hz, 4H); 13C NMR (101 MHz, CDCl3, δ ppm) 168.9, 158.8,
151.3, 141.3, 137.3, 136.5, 136.0, 133.7, 132.1, 131.8, 129.5, 129.1, 128.4, 127.1,
126.9, 122.9, 122.5. IR (KBr, cm–1): 2932, 1725, 1537, 1349, 1040, 752. HRMS
(ESI) m/z: calcd for C42H24Cl2Br2N4Na [M + Na]+ 834.9637; found 834.9652.
(Z)ꢀ1,2ꢀBis(3ꢀchlorophenyl)ꢀ1,2ꢀbis(2ꢀ(4ꢀchlorophenyl)quinazolinꢀ4ꢀyl)ethene
(3ja): Purified via flash column chromatography with 40% ethyl acetate/petroleum
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ether, yielding 49% (35.5 mg) as a white solid: 224ꢀ226 C. H NMR (400 MHz,
CDCl3, δ ppm) 8.17 (d, J = 8.3 Hz, 2H), 7.89 (t, J = 8.5 Hz, 6H), 7.82ꢀ7.74 (m, 2H),
7.53 (t, J = 7.6 Hz, 2H), 7.37 (d, J = 1.7 Hz, 2H), 7.33ꢀ7.29 (m, 4H), 7.28ꢀ7.19 (m,
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6H); C NMR (101 MHz, CDCl3, δ ppm) 168.5, 158.8, 151.3, 141.3, 139.9, 136.6,
136.0, 134.7, 133.7, 130.0, 129.9, 129.5, 129.1, 128.8, 128.4, 128.3, 127.2, 126.9,
122.4. IR (KBr, cm–1): 2925, 1719, 1540, 1399, 1037, 757. HRMS (ESI) m/z: calcd
for C42H24Cl4N4Na [M + Na]+ 747.0647; found 747.0652.
(Z)ꢀ1,2ꢀBis(4ꢀ(tertꢀbutyl)phenyl)ꢀ1,2ꢀbis(2ꢀ(4ꢀchlorophenyl)ꢀ7ꢀmethylquinazolin
ꢀ4ꢀyl)ethene (3la): Purified via flash column chromatography with 40% ethyl
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acetate/petroleum ether, yielding 72% (57.3 mg) as a white solid: 283ꢀ285 C. H
NMR (400 MHz, CDCl3, δ ppm) 8.00ꢀ7.94 (m, 6H), 7.66 (d, J = 8.6 Hz, 2H), 7.48
(dd, J = 8.6, 1.8 Hz, 2H), 7.31 (d, J = 8.4 Hz, 4H), 7.24ꢀ7.18 (m, 8H), 2.42 (s, 6H),
1.28 (s, 18H); 13C NMR (101 MHz, CDCl3, δ ppm) 169.0, 158.0, 151.1, 149.7, 140.1,
136.8, 136.6, 136.1, 135.6, 129.8, 129.5, 128.3, 126.3, 125.2, 122.6, 34.6, 31.3, 21.9.
IR (KBr, cm–1): 2925, 1723, 1539, 1402, 1036, 834. HRMS (ESI) m/z: calcd for
C52H46Cl2N4Na [M + Na]+ 819.2992; found 819.2994.
(Z)ꢀ1,2ꢀDiꢀpꢀtolylꢀ1,2ꢀbis(2ꢀ(4ꢀ(trifluoromethyl)phenyl)quinazolinꢀ4ꢀyl)ethene
(3bb): Purified via flash column chromatography with 40% ethyl acetate/petroleum
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ether, yielding 54% (40.6 mg) as a yellow solid: 270ꢀ271 C. H NMR (400 MHz,
CDCl3, δ ppm) δ 8.05 (d, J = 8.3 Hz, 2H), 7.75 (dd, J = 18.3, 8.3 Hz, 6H), 7.63 (t, J =
7.6 Hz, 2H), 7.38 (t, J = 7.6 Hz, 2H), 7.27 (d, J = 8.3 Hz, 4H), 7.11 (d, J = 7.7 Hz,
13
4H), 6.92 (d, J = 7.9 Hz, 4H), 2.18 (s, 9H); C NMR (101 MHz, CDCl3, δ ppm) δ
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170.4, 158.4, 151.1, 141.5, 138.3, 135.9, 133.5, 131.6 (q, J = 32.0 Hz), 130.2, 129.4,
129.1, 128.3, 127.4, 127,3, 125.01 (q, J = 3.7 Hz), 123.8 (q, J = 270.6 Hz), 123.3,
21.4. IR (KBr, cm–1): 2922, 1729, 1538, 1321, 1078, 756. HRMS (ESI) m/z: calcd for
C46H31F6N4 [M + H]+ 753.2447; found 753.2451.
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(Z)ꢀ1,2ꢀBis(4ꢀmethoxyphenyl)ꢀ1,2ꢀbis(2ꢀ(4ꢀ(trifluoromethyl)phenyl)quinazolinꢀ
4ꢀyl)ethene (3cb): Purified via flash column chromatography with 40% ethyl
acetate/petroleum ether, yielding 72% (56.4 mg) as a white solid: 272ꢀ274 oC. 1H NMR
(400 MHz, CDCl3, δ ppm) 8.16 (d, J = 8.2 Hz, 2H), 7.88 (t, J = 6.8 Hz, 6H), 7.79 (t, J =
7.6 Hz, 2H), 7.52 (t, J = 7.5 Hz, 2H), 7.39 (d, J = 8.2 Hz, 4H), 7.27 (d, J = 8.9 Hz, 4H),
6.78 (d, J = 8.7 Hz, 4H), 3.79 (s, 6H); 13C NMR (101 MHz, CDCl3, δ ppm) 170., 159.4,
158.4, 151.1, 141.0, 140.9, 133.5, 133.2 (q, J = 32.0 Hz ), 131.9, 131.4, 129.0, 128.3,
127.4, 127.3, 125.2 (q, J = 270.7 Hz), 123.3, 122.8 (q, J = 3.5 Hz), 114.1, 55.2. IR
(KBr, cm–1): 2922, 1733, 1507, 1320, 1067, 758. HRMS (ESI) m/z: calcd for
C46H30F6N4NaO2 [M + Na]+ 807.2165; found 807.2166.
(Z)ꢀ1,2ꢀBis(4ꢀethylphenyl)ꢀ1,2ꢀbis(2ꢀ(4ꢀ(trifluoromethyl)phenyl)quinazolinꢀ4ꢀyl
)ethene (3db): Purified via flash column chromatography with 40% ethyl
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acetate/petroleum ether, yielding 69% (53.8 mg) as a white solid: 236ꢀ238 C. H
NMR (400 MHz, CDCl3, δ ppm) 8.21 (d, J = 8.3 Hz, 2H), 7.93 (d, J = 8.2 Hz, 4H),
7.86 (d, J = 8.4 Hz, 2H), 7.77 (t, J = 7.6 Hz, 2H), 7.52 (t, J = 7.6 Hz, 2H), 7.42 (d, J =
8.3 Hz, 4H), 7.27 (d, J = 8.1 Hz, 4H), 7.07 (d, J = 8.0 Hz, 4H), 2.63 (q, J = 7.6 Hz,
4H), 1.22 (t, J = 7.6 Hz, 6H); 13C NMR (101 MHz, CDCl3, δ ppm) 170.3, 158.3,
151.1, 144.4, 141.4, 141.0, 136.0, 133.4, 131.5(q, J = 32.1 Hz), 130.2, 129.0, 128.3,
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128.0, 127.4, 127.3, 125.0 (q, J = 3.5 Hz), 124.0 (q, J = 268.3 Hz), 123.2, 28.5, 15.0.
IR (KBr, cm–1): 2925, 1726, 1540, 1321, 1068, 761. HRMS (ESI) m/z: calcd for
C48H35F6N4 [M + H]+ 781.2760; found 781.2762.
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(Z)ꢀ1,2ꢀBis(4ꢀbutylphenyl)ꢀ1,2ꢀbis(2ꢀ(4ꢀ(trifluoromethyl)phenyl)quinazolinꢀ4ꢀyl
)ethene (3eb): Purified via flash column chromatography with 40% ethyl
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acetate/petroleum ether, yielding 77% (64.4 mg) as a white solid: 136ꢀ138 C. H
NMR (400 MHz, CDCl3, δ ppm) 8.20 (d, J = 8.2 Hz, 2H), 7.94 (d, J = 8.1 Hz, 4H),
7.87 (d, J = 8.4 Hz, 2H), 7.76 (t, J = 7.3 Hz, 2H), 7.51 (t, J = 7.5 Hz, 2H), 7.42 (d, J =
8.2 Hz, 4H), 7.27ꢀ7.23 (m, 4H), 7.05 (d, J = 8.0 Hz, 4H), 2.63ꢀ2.52 (m, 4H),
1.64ꢀ1.52 (m, 4H), 1.38ꢀ1.28 (m, 4H), 0.92 (t, J = 7.3 Hz, 6H); 13C NMR (101 MHz,
CDCl3, δ ppm) 170.3, 158.3, 151.1, 143.2, 141.5, 141.0, 136.1, 133.5, 131.6 (q, J =
31.9 Hz), 130.1, 129.0, 128.6, 128.4, 127.4, 127.3, 125.01 (q, J = 3.8 Hz), 123.3,
122.8 (q, J = 270.5 Hz), 35.4, 33.2, 22.3, 14.0. IR (KBr, cm–1): 2975, 1666, 1542,
1320, 1068, 758. HRMS (ESI) m/z: calcd for C52H43F6N4 [M + H]+ 837.3386; found
837.3393.
(Z)ꢀ1,2ꢀBis(4ꢀ(tertꢀbutyl)phenyl)ꢀ1,2ꢀbis(2ꢀ(4ꢀ(trifluoromethyl)phenyl)quinazoli
nꢀ4ꢀyl)ethene (3fb): Purified via flash column chromatography with 40% ethyl
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acetate/petroleum ether, yielding 72% (60.2 mg) as a white solid: 231ꢀ233 C. H
NMR (400 MHz, CDCl3, δ ppm) 8.26 (d, J = 8.2 Hz, 2H), 8.00 (d, J = 8.1 Hz, 4H),
7.87 (d, J = 8.4 Hz, 2H), 7.76 (t, J = 7.6 Hz, 2H), 7.53 (t, J = 7.6 Hz, 2H), 7.46 (d, J =
8.1 Hz, 4H), 7.29 (dd, J = 19.4, 8.3 Hz, 8H), 1.31 (s, 18H); 13C NMR (101 MHz,
CDCl3, δ ppm) 170.3, 158.4, 151.4, 151.1, 141.1, 135.7, 133.5, 131.6 (q, J = 31.9 Hz),
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129.9, 129.0, 128.4, 127.6, 127.3, 125.4, 125.0 (d, J = 3.7 Hz), 123.2, 122.8 (q, J =
270.5 Hz), 34.7, 31.3. IR (KBr, cm–1): 2958, 1727, 1541, 1320, 1067, 759. HRMS
(ESI) m/z: calcd for C52H42F6N4Na [M + Na]+ 859.3206; found 859.3218.
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(Z)ꢀ1,2ꢀBis(4ꢀfluorophenyl)ꢀ1,2ꢀbis(2ꢀ(4ꢀ(trifluoromethyl)phenyl)quinazolinꢀ4ꢀ
yl)ethene (3gb): Purified via flash column chromatography with 40% ethyl
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acetate/petroleum ether, yielding 52% (39.5 mg) as a white solid: 216ꢀ218 C. H
NMR (400 MHz, CDCl3, δ ppm) 8.16 (d, J = 8.2 Hz, 2H), 7.97 (d, J = 8.2 Hz, 4H),
7.89 (d, J = 8.4 Hz, 2H), 7.83ꢀ7.76 (m, 2H), 7.54 (t, J = 7.4 Hz, 2H), 7.44 (d, J = 8.3
Hz, 4H), 7.36 (dd, J = 8.7, 5.3 Hz, 4H), 6.98 (t, J = 8.6 Hz, 4H); 13C NMR (101 MHz,
CDCl3, δ ppm) 169.4, 162.5 (d, J = 258.4 Hz), 158.4, 151.2, 141.1, 140.8, 134.5 (d, J
= 3.5 Hz), 133.7, 132.0 (d, J = 9.3 Hz), 131.8 (q, J = 32.0 Hz), 129.3, 128.3, 127.5,
127.0, 125.2 (q, J = 3.6 Hz), 124.3 (q, J = 270..6 Hz), 122.8, 116.0 (d, J = 2.2 Hz). IR
(KBr, cm–1): 2924, 1604, 1543, 1320, 1067, 760. HRMS (ESI) m/z: calcd for
C44H25F8N4 [M + H]+ 761.1946; found 761.1954.
(Z)ꢀ1,2ꢀBis(4ꢀbromophenyl)ꢀ1,2ꢀbis(2ꢀ(4ꢀ(trifluoromethyl)phenyl)quinazolinꢀ4ꢀ
yl)ethene (3hb): Purified via flash column chromatography with 40% ethyl
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acetate/petroleum ether, yielding 61% (53.7 mg) as a white solid: 247ꢀ249 C. H
NMR (400 MHz, CDCl3, δ ppm) δ 8.01 (d, J = 8.3 Hz, 2H), 7.85 (d, J = 8.1 Hz, 4H),
7.78 (d, J = 8.4 Hz, 2H), 7.69 (t, J = 7.4 Hz, 2H), 7.43 (t, J = 7.5 Hz, 2H), 7.3ꢀ7.2 (m,
13
8H), 7.13 (t, J = 6.5 Hz, 4H); C NMR (101 MHz, CDCl3, δ ppm) δ 169.1, 158.4,
151.3, 141.4, 140.7, 137.2, 133.8, 132.2, 131.9 (q, J = 32.1 Hz), 131.7, 129.3, 128.3,
127.6, 126.9, 125.5 (q, J = 3.6 Hz), 124.4 (q, J = 270.0 Hz),123.0, 122.8. IR (KBr,
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cm–1): 2923, 1726, 1541, 1320, 1068, 760. HRMS (ESI) m/z: calcd for
C44H25Br2F6N4 [M + H]+ 881.0345; found 881.0345.
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nazolinꢀ4ꢀyl)ethene (3ib): Purified via flash column chromatography with 40% ethyl
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acetate/petroleum ether, yielding 42% (36.1 mg) as a white solid: 212ꢀ214 C. H
NMR (400 MHz, CDCl3, δ ppm) δ 8.15 (d, J = 8.3 Hz, 2H), 8.05 (d, J = 8.1 Hz, 4H),
7.91 (d, J = 8.4 Hz, 2H), 7.81 (t, J = 7.7 Hz, 2H), 7.60ꢀ7.44 (m, 14H); 13C NMR (101
MHz, CDCl3, δ ppm) δ 168.5, 158.4, 151.3, 141.9, 141.5, 140.6, 134.0, 131.9 (q, J
=32.1 Hz), 130.9 (q, J =33.0 Hz),130.5, 129.4, 128.4, 127.8, 126.7, 125.9 (q, J = 3.7
Hz), 125.1 (q, J = 3.7 Hz), 124.0 (q, J =270.5 Hz), 123.3 (q, J =206.1 Hz), 122.5. IR
(KBr, cm–1): 2926, 1724, 1540, 1321, 1067, 758. HRMS (ESI) m/z: calcd for
C46H24F12N4Na [M + Na]+ 883.1702; found 883.1710.
(Z)ꢀ1,2ꢀBis(3ꢀchlorophenyl)ꢀ1,2ꢀbis(2ꢀ(4ꢀ(trifluoromethyl)phenyl)quinazolinꢀ4ꢀ
yl)ethene (3jb): Purified via flash column chromatography with 40% ethyl
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acetate/petroleum ether, yielding 42% (33.2 mg) as a white solid: 259ꢀ261 C. H
NMR (400 MHz, CDCl3, δ ppm) 8.09 (d, J = 8.3 Hz, 2H), 7.93 (d, J = 8.2 Hz, 4H),
7.81 (d, J = 8.4 Hz, 2H), 7.71 (t, J = 7.3 Hz, 4H), 7.47 (t, J = 7.5 Hz, 2H), 7.37 (d, J =
13
8.3 Hz, 4H), 7.26 (s, 2H), 7.21ꢀ712 (m, 6H); C NMR (101 MHz, CDCl3, δ ppm)
167.7, 157.4, 150.2, 140.4, 139.7, 138.8, 133.7, 132.9, 130.7 (q, J = 32.1), 129.0,
128.9, 128.2, 127.9, 127.3, 126.6, 125.8, 124.0 (q, J = 3.8 Hz), 123,7 (q, J = 270.0
Hz), 121.7. IR (KBr, cm–1): 2922, 1722, 1543, 1320, 1069, 755. HRMS (ESI) m/z:
calcd for C44H25Cl2F6N4 [M + H]+ 793.1355; found 793.1351.
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(Z)ꢀ1,2ꢀDi(thiophenꢀ3ꢀyl)ꢀ1,2ꢀbis(2ꢀ(4ꢀ(trifluoromethyl)phenyl)quinazolinꢀ4ꢀyl)
ethene (3kb): Purified via flash column chromatography with 40% ethyl
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acetate/petroleum ether, yielding 31% (22.8 mg) as a white solid: 224ꢀ226 C. H
NMR (400 MHz, CDCl3, δ ppm) 8.12 (d, J = 8.3 Hz, 2H), 7.96ꢀ7.87 (m, 6H), 7.80 (t,
J = 7.7 Hz, 2H), 7.54 (t, J = 7.6 Hz, 2H), 7.42 (d, J = 8.0 Hz, 4H), 7.31 (s, 2H), 7.18
(s, 2H), 7.07 (d, J = 4.9 Hz, 2H); 13C NMR (101 MHz, CDCl3, δ ppm) δ 169.5, 158.4,
151.1, 140.8, 139.3, 136.4, 133.7, 131.7 (q, J = 32.0 Hz) , 129.1, 128.4, 128.3, 127.4,
127.1, 127.0, 125.9, 125.1 (q, J = 3.4 Hz), 124.2 (q, J = 271.3 Hz), 123.1. IR (KBr,
cm–1): 2922, 1729, 1541, 1320, 1068, 756. HRMS (ESI) m/z: calcd for
C40H22F6N4NaS2 [M + H]+ 759.1082; found 759.1073.
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(Z)ꢀ1,2ꢀBis(4ꢀ(tertꢀbutyl)phenyl)ꢀ1,2ꢀbis(7ꢀmethylꢀ2ꢀ(4ꢀ(trifluoromethyl)phenyl)
quinazolinꢀ4ꢀyl)ethene (3lb): Purified via flash column chromatography with 40%
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ethyl acetate/petroleum ether, yielding 70% (60.5 mg) as a white solid: 266ꢀ268 C.
1H NMR (400 MHz, CDCl3, δ ppm) 8.13 (d, J = 8.2 Hz, 4H), 8.01 (s, 2H), 7.71 (d, J
= 8.6 Hz, 2H), 7.55 – 7.48 (m, 6H), 7.33 (d, J = 8.5 Hz, 4H), 7.25 (d, J = 8.6 Hz, 4H),
2.45 (s, 6H), 1.30 (s, 18H); 13C NMR (101 MHz, CDCl3, δ ppm) 169.1, 157.6, 151.2,
149.7, 140.2, 137.3, 135.7, 135.6, 132.0 (q, J = 32.0 Hz), 129.8, 128.5, 128.3,
126.2,125.2, 125.0 (q, J = 3.7 Hz), 124.3 (q, J = 270.5 Hz), 122.8, 34.6, 31.2, 21.9. IR
(KBr, cm–1): 2957, 1687, 1543, 1319, 1067, 755. HRMS (ESI) m/z: calcd for
C54H47F6N4 [M + H]+ 865.3699; found 865.3707.
(Z)ꢀ1,2ꢀBis(4ꢀethoxyphenyl)ꢀ1,2ꢀbis(7ꢀmethylꢀ2ꢀ(4ꢀ(trifluoromethyl)phenyl)qui
nazolinꢀ4ꢀyl)ethene (3mb): Purified via flash column chromatography with 40%
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ethyl acetate/petroleum ether, yielding 74% (62.2 mg) as a white solid: 135ꢀ136 C.
1H NMR (400 MHz, CDCl3, δ ppm) 8.01 (d, J = 8.1 Hz, 4H), 7.96 (s, 2H), 7.74 (d, J
= 8.6 Hz, 2H), 7.56 (d, J = 8.6 Hz, 2H), 7.44 (d, J = 8.2 Hz, 4H), 7.28 (d, J = 8.5 Hz,
4H), 6.77 (d, J = 8.5 Hz, 4H), 4.01 (q, J = 6.9 Hz, 4H), 2.46 (s, 6H), 1.40 (t, J = 6.9
Hz, 6H); 13C NMR (101 MHz, CDCl3, δ ppm) 169.6, 158.7, 157.7, 149.7, 141.3,
134.0, 137.4, 135.7, 131.6, 131.2, 131.0 (q, J = 32.4 Hz), 128.6, 128.3, 126.1, 125.5,
124.9 (q, J = 3.6 Hz), 124.2 (q, J = 270.7 Hz), 123.0, 114.5, 21.9, 14.8. IR (KBr,
cm–1): 2923, 1723, 1545, 1319, 1029, 755. HRMS (ESI) m/z: calcd for
C50H38F6N4NaO2 [M + Na]+ 863.2791; found 863.2805.
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(Z)ꢀ4ꢀ(1ꢀ(4ꢀethoxyphenyl)ꢀ2ꢀ(4ꢀmethoxyphenyl)ꢀ2ꢀ(2ꢀ(4ꢀ(trifluoromethyl)pheny
l)quinazolinꢀ4ꢀyl)vinyl)ꢀ7ꢀmethylꢀ2ꢀ(4ꢀ(trifluoromethyl)phenyl)quinazoline
(3cmb): HRMS (ESI) m/z: calcd for C48H35F6N4O2 [M + H]+ 813.2659; found
813.2664.
4ꢀ(4ꢀEthoxybenzyl)ꢀ6ꢀmethylꢀ2ꢀ(4ꢀ(trifluoromethyl)phenyl)quinazoline (4mb):
Purified via flash column chromatography with 40% ethyl acetate/petroleum ether,
yielding 17% (14.3 mg) as a yellow solid: 107ꢀ109 oC. 1H NMR (400 MHz, CDCl3, δ
ppm) 8.72 (d, J = 8.2 Hz, 2H), 7.96 (d, J = 8.6 Hz, 1H), 7.89 (s, 1H), 7.74 (d, J = 8.3
Hz, 2H), 7.65 (dd, J = 8.6, 1.7 Hz, 1H), 7.26 (d, J = 8.6 Hz, 2H), 6.82 (d, J = 8.6 Hz,
2H), 4.57 (s, 2H), 3.97 (d, J = 7.0 Hz, 2H), 2.52 (s, 3H), 1.36 (t, J = 7.0 Hz, 3H); 13C
NMR (101 MHz, CDCl3, δ ppm) 169.1, 158.1, 157.8, 149.6, 141.7, 137.7, 135.9,
131.8 (q, J = 31.7. Hz), 129.9, 129.7, 129.2, 128.7, 125.3 (q, J = 3.8. Hz), 124.3 (q, J
= 270.5 Hz), 123.9, 122.7, 114.7, 63.4, 40.4, 22.0, 14.8. IR (KBr, cm–1): 2928, 1719,
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1508, 1321, 1121, 828. HRMS (ESI) m/z: calcd for C25H22F3N2O [M + H]+ 423.1679;
found 423.1683.
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ASSOCIATED CONTENT
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Supporting Information
Copies of NMR spectra for all compounds, Xꢀray crystallographic data for 3bb, 3cb,
3fb and 3gb, and computational details. This material is available free of charge via
the Internet at http://pubs.acs.org.
AUTHOR INFORMATION
Corresponding Authors
cewuwq@scut.edu.cn; jianghf@scut.edu.cn
Notes
The authors declare no competing financial interest.
ACKNOWLEDGMENT
The authors thank the National Program on Key Research Project (2016YFA0602900),
the National Natural Science Foundation of China (21490572 and 21420102003), and
Pearl River S&T Nova Program of Guangzhou (201610010160) for financial support.
REFERENCES
(1) (a) Hoeben, F. J. M.; Jonkheijm, P.; Meijer, E. W.; Schenning, A. P. H. J. About
Supramolecular Assemblies of πꢀConjugated Systems. Chem. Rev. 2005, 105,
1491ꢀ1546. (b) Br é das, J.ꢀL.; Beljonne, D.; Coropceanu, V.; Cornil, J.
ChargeꢀTransfer and EnergyꢀTransfer Processes in πꢀConjugated Oligomers and
Polymers: A Molecular Picture. Chem. Rev. 2004, 104, 4971ꢀ5003. (c) Segura, J.;
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