One-Pot Synthesis of Tetraphene and Construction of Expanded Conjugated Aromatics

Article abstract of DOI:10.1021/acs.joc.6b00890

Acene derivatives as a class of polycyclic aromatic hydrocarbons have attracted considerable interest because of their outstanding semiconductor properties. We developed a one-pot synthesis for fully conjugated tetraphene via a sequence of propargyl-allenyl isomerization, phosphine addition, intramolecular Wittig reactions, and Diels-Alder cyclization reactions. The derivative-conjugated aromatic compounds including carbazole or triphenylamine have been constructed via Pd-catalyzed coupling reaction with dibromotetraphene. These compounds show superior photophysical and electrochemical properties, which make them possible candidates for optoelectronic conjugated materials.

Full text of DOI:10.1021/acs.joc.6b00890

Note
pubs.acs.org/joc
One-Pot Synthesis of Tetraphene and Construction of Expanded
Conjugated Aromatics
Jianbo Wang,* Jinzhong Yao, Hailong Wang, Hao Chen, Jingcheng Dong, and Hongwei Zhou*
College of Biological, Chemical Sciences and Engineering, Jiaxing University, Jiaxing 314001, People’s Republic of China
*
S Supporting Information
ABSTRACT: Acene derivatives as a class of polycyclic aromatic hydrocarbons have attracted considerable interest because of
their outstanding semiconductor properties. We developed a one-pot synthesis for fully conjugated tetraphene via a sequence of
propargyl-allenyl isomerization, phosphine addition, intramolecular Wittig reactions, and Diels−Alder cyclization reactions. The
derivative-conjugated aromatic compounds including carbazole or triphenylamine have been constructed via Pd-catalyzed
coupling reaction with dibromotetraphene. These compounds show superior photophysical and electrochemical properties,
which make them possible candidates for optoelectronic conjugated materials.
ver the past two decades, polycyclic aromatic hydro-
carbons (PAHs) have attracted considerable interest as
Since Wittig olefination was reported in 1953, intramolecular
Wittig reactions have been applied in the synthesis of cyclic
compounds through the classic strategy, in which a carbonyl
group and suitable phosphorus ylide were constructed in the
O
organic electronic materials because of their photophysical and
electrochemical properties, and their applicability in organic
field-effect transistors (OFETs), photovoltaic (OPV) cells, and
10
same substrate. On the basis of our previous research, base-
catalyzed propargyl-allenyl isomerization could generate in situ-
1
organic light-emitting diodes (OLEDs). Among those
11
polycyclic systems, PAHs such as tetracene, pentacene, and
its derivatives play an important role in semiconducting
functionalized allene intermediates. We envisioned that the
allenylphosphonium including the carbonyl group might
produce a cyclic intermediate in the presence of phosphine
and then undergo the intramolecular Wittig reactions and
Diels−Alder cyclization reactions to give conjugated aromatic
compounds. Herein, we report the novel synthesis of
tetraphene by using simple propargylphosphonium salts as
starting materials.
2
materials for device applications. The extended conjugated
PAHs could exhibit good performance in devices; however,
these systems beyond five rings are susceptible to oxidation,
3
photodegradation, and Diels−Alder reactions. To improve the
stability of these higher acenes, some strategies, including the
4
incorporation of heteroatoms, the addition of protecting bulky
5
substituents, and the introduction of two-dimensional acene
Stimulated by this proposal, we chose propargylphospho-
nium salt (1a) as the starting material, which could be
synthesized readily via the treatment of 2-(3-bromoprop-1-yn-
1-yl)benzaldehyde with triphenylphosphine in toluene. We
initiated our reaction by using compound 1a and screened the
optimal conditions, such as base, solvent, and temperature. t-
BuOK was widely used as the base in Wittig reaction; thus, we
first examined the reaction with t-BuOK as the base and
6
analogues, were adopted in construction of these compounds,
which could lead to acene synthesis being more difficult and
could affect charge transport to some extent. On the othe7r
hand, PAHs with fewer than five rings such as pyrene,
8
9
chrysene, and tetraphene also have been reported and applied
as organic electronic materials. To the best of our knowledge,
the simple synthesis and modification of tetraphene have not
been well-documented; as a result, the application of tetraphene
is rarer than that of pyrene in organic functional materials.
Therefore, the development of efficient synthesis routes for
four-ring aromatics remains interesting and challenging for
chemists.
CH CN as the solvent. Fortunately, the desired product 2a was
3
Received: April 20, 2016
©
XXXX American Chemical Society
A
DOI: 10.1021/acs.joc.6b00890
J. Org. Chem. XXXX, XXX, XXX−XXX

The Journal of Organic Chemistry
Note
obtained in 23% yield (Table 1, entry 1), which was confirmed
by NMR and MS spectra. Replacing t-BuOK with NaH
routes and exhibited excellent OFET characteristics in the
4d
previous report. Furthermore, 3,10-dibromotetraphene (2g)
was afforded and unequivocally confirmed by the X-ray single-
a
12
Table 1. Optimization of the Reaction Conditions
crystal analysis (Figure S1).
On the basis of the result described above, we propose a
possible reaction pathway as shown in Scheme 1. The starting
materials 1, via the propargyl−allenyl isomerization in the
13
presence of NaH, form phosphonium salts A attacked by
14
trace nucleophiles PPh to afford B. Then, intermediate B
3
experiences its first intramolecular Wittig reaction, producing
C, which undergoes Diels−Alder reaction with another
15
entry
base
solvent
T (°C)
yield (%)
molecule of 1 to offer intermediate D. The second Wittig
reaction gives intermediate E, which undergoes the retro-
Diels−Alder reaction to offer the final compound 2. The
1
2
3
4
5
6
7
8
t-BuOK
CH CN
40
40
40
40
40
40
rt
23
63
8
3
NaH
CH CN
3
Et N
3
CH CN
ethynephosphonium salts may release PPh in the presence of
3
3
DBU
NaH
NaH
NaH
NaH
CH CN
6
NaH, which recycles the reaction.
3
toluene
THF
11
45
48
40
Bromo-modified acenes have attracted a great deal of
attention in the organic electronics community for designing
and constructing novel organic semiconducting functional
CH CN
3
7
,8
CH CN
60
materials. Therefore, with intermediate 2g in hand, the
expended conjugated aromatic compounds could be synthe-
sized via Pd-catalyzed coupling reaction. As shown in Scheme 2,
Buchwald coupling of 2g with carbazole afforded compound 3a
in 46% yield, and Suzuki coupling of 2g with 4-
3
a
The reaction was conducted using 1a (0.5 mmol), base (0.6 mmol),
and triphenylphosphine (5 μmol) in solvent (3 mL) under Ar.
produced the best result as the yield was improved to 63%,
while an organic base (Et N and DBU) produced low yields.
Subsequent screening showed that the use of other common
solvents such as toluene and THF did not improve the yield
entries 5 and 6).
(
diphenylamino)phenylboronic acid gave compound 3b in
3
62% yield.
The absorption and fluorescence spectra of 3a and 3b in
dichloromethane are shown in Figure 2, and the data are listed
in Table 3. Compounds 3a and 3b display absorption peaks at
(
With the optimal condition in hand, the scope of this
3
45 and 368 nm, respectively, which are attributed to the
reaction was further investigated. As shown in Table 2, this
reaction was successfully used to construct the disubstituted
tetraphene compounds in one pot. Among those compounds,
naphthobisbenzo[b]thiophene (2i) was easily synthesized with
our method, which was obtained using multistep synthetic
HOMO−LUMO transition of these molecules. These peaks
reflect the extent of conjugation between the tetraphene core
and the electron donor (carbazole or triphenylamine). As
shown in Figure 1 and Table 3, compound 3a in dichloro-
methane shows the maximal emission peaks at 434 nm and
gives a sky blue color under an UV lamp. Because of the large
extent of conjugation compared with that of 3a, compound 3b
displays emission peaks around at 488 nm with an obvious red-
shift, which can be observed as green color. The fluorescence
quantum yields of 3a and 3b in dichloromethane have been
measured to be 0.71 and 0.82, respectively, using quinine
Table 2. Synthesis of Disubstituted Tetraphene and
a
Naphthobisbenzo[b]thiophenes
16
sulfate (Φ = 0.546 in 1 N H SO ) as a reference.
F
2
4
The electrochemical characteristics of 3a and 3b were
investigated by cyclic voltammetry using a standard three-
electrode cell in an electrolyte solution of 0.1 M tetrabuty-
lammonium hexafluorophosphate (TBAPF ) dissolved in
6
dichloromethane. The working electrode is glassy carbon; the
counter electrode is a platinum wire, and the reference
electrode is a Ag/AgCl electrode. As shown in Figure 2,
compounds 3a and 3b show two oxidation peaks and one
oxidation peak, respectively, which are well-defined reversible
oxidation waves. The half-wave oxidation potentials (E1/2) for
3
a and 3b are 0.55 and 0.47 V, respectively, which were
+
measured relative to Fc /Fc used as an internal standard. The
oxidation potential decreases show that 3a with triphenylamine
increases the level of conjugation more than 3b does. On the
basis of the half-wave oxidation potentials, the highest occupied
molecular orbital (HOMO) energy levels of 3a and 3b are
−
5.35 and −5.27 eV, respectively (HOMO = E1 + 4.8 eV),
/2
a
and the lowest unoccupied molecular orbital (LUMO) energy
Condition: 1 (0.5 mmol) and NaH (0.6 mmol) in CH CN (3 mL) at
0 °C for 12 h under Ar. Compound 2i was obtained by using 2-
3
b
levels are −2.35 and −2.49 eV, respectively, estimated from the
HOMO and energy band gap (E ) based on the absorption
4
carbaldehydebenzo[b]thiophene-3-propargylphosphonium salt as the
g
starting material.
thresholds from absorption spectra.
B
DOI: 10.1021/acs.joc.6b00890
J. Org. Chem. XXXX, XXX, XXX−XXX

The Journal of Organic Chemistry
Note
Scheme 1. Proposed Pathway
Scheme 2. Synthetic Route of Compounds 3a and 3b
Table 3. Photophysical and Electrochemical Properties of 3a
and 3b
on the tetraphene cores at the LUMO level. This electron
density is redistributed, which indicates that an intramolecular
charge transfer process from the electron donor to the
tetraphene core occurs.
a
b
c
λem
E1/2
HOMO/LUMO
(eV)
a
compd
λabs (nm)
(nm)
ΦF
(V)
d
3
3
a
345 (2.34 )
434
488
0.71
0.82
0. 55
0.47
−5.35/−2.35
In summary, we have developed a simple and efficient
method for fully accessing conjugated tetraphene derivatives
through a sequence of propargyl−allenyl isomerization,
phosphine addition, intramolecular Wittig reactions, and
Diels−Alder reactions. This reaction brings about the breaking
of synthesis of four-fused ring aromatic compounds. On the
basis of the key intermediate 3,10-dibromotetraphene, the
extended conjugated aromatics including carbazole or triphe-
nylamine have been constructed. These aromatics display high
fluorescence quantum yields and excellent electrochemical
properties, which could greatly enhance their application as
optoelectronic conjugated materials.
d
b
368 (5.3 )
−5.27/−2.49
a
b
+
CH Cl2 solution. Half-wave oxidation potentials vs Fc /Fc.
2
c
HOMO values calculated on the basis of the oxidation of the
d
ferrocene reference in vacuum (4.8 eV): LUMO = HOMO + E . The
values in parentheses are molar extinction coefficients (10 M cm ).
g
4
−1
−1
To determine the electronic structures and the frontier
orbitals, density functional theory (DFT) calculations of 3a and
3b were conducted at the B3LYP/6-31G(d) level (Table 3).
Charge distributions are listed in Table 4. At the HOMO level,
electrons are fully delocalized over the whole aromatics,
including the electron donor (carbazole or triphenylamine)
and tetraphene cores, whereas they are located most prevalently
C
DOI: 10.1021/acs.joc.6b00890
J. Org. Chem. XXXX, XXX, XXX−XXX

The Journal of Organic Chemistry
Note
counter electrode was a Pt wire, and the reference electrode was a Ag/
AgCl electrode. Tetrabutylammonium hexafluorophosphate (TBAPF6,
0
.1 M) was used as the supporting electrolyte, with ferrocene/
+
ferrocenium (Fc/Fc ) as an external reference. The scan rate used was
1
−1
00 mV s .
Typical Procedure for the Synthesis of 2a. To a solution of 1a
243 mg, 0.5 mmol) and triphenylphosphine (1.3 mg, 5 μmol) in dry
17
(
CH CN (3.0 mL) at room temperature was added NaH (24 mg, 0.6
3
mmol, 60%) in 3.0 mL under N . The reaction mixture was stirred at
2
4
0 °C for 12 h. Upon completion, the reaction was quenched with a
saturated aqueous NH Cl solution, and the mixture was extracted with
4
ethyl acetate and dried over anhydrous Na SO . After evaporation,
2
4
chromatography on silica gel (50:1 petroleum ether/ethyl acetate) of
the reaction mixture afforded 2a as a white solid (36 mg, 63%).
18a
Tetraphene (2a). White solid (36 mg, 63%): mp 158−159 °C;
1
H NMR (400 MHz, CDCl ) δ 9.18 (s, 1H), 8.84 (d, J = 8.4 Hz, 1H),
3
8
.38 (s, 1H), 8.13 (d, J = 6.0 Hz, 1H), 8.05 (d, J = 8.0 Hz, 1H), 7.85
(
d, J = 8.0 Hz, 1H), 7.80 (d, J = 9.2 Hz, 1H), 7.66−7.69 (m, 1H),
13
Figure 1. Absorption spectra (empty) (5.0 μM) and normalized
fluorescence emission spectra (filled) of compounds 3a (squares) and
7.60−7.63 (m, 2H), 7.55−7.58 (m, 2H); C NMR (100 MHz,
CDCl ) δ 131.9, 128.6, 128.4, 127.7, 127.3, 127.1, 126.8, 126.7, 125.7,
3
3
b (triangles) in dichloromethane solutions.
122.9, 121.5; HRMS (EI-TOF) calcd for C H 228.0939, found
18
12
2
28.0938.
,10-Dimethoxytetraphene (2b).
18b
3
White amorphous solid (35
1
mg, 48%): mp 178−179 °C; H NMR (400 MHz, CDCl ) δ 9.18 (s,
3
1
7
1
3
1
1
H), 8.71 (d, J = 8.8 Hz, 1H), 8.27 (s, 1H), 7.91 (d, J = 9.2 Hz, 1H),
.76 (d, J = 8.8 Hz, 1H), 7.53 (d, J = 8.8 Hz, 1H), 7.34 (d, J = 2.0 Hz,
H), 7.26−7.29 (m, 2H), 7.20 (dd, J = 8.2, 2.4 Hz, 1H), 4.00 (s, 3H),
.98 (s, 3H); 13C NMR (100 MHz, CDCl ) δ 158.7, 157.5, 133.6,
3
33.2, 129.4, 128.4, 128.0, 127.6, 126.8, 125.8, 124.5, 124.2, 119.7,
19.0, 116.1, 109.6, 104.6, 55.4, 55.3; HRMS (EI-TOF) calcd for
C H O 288.1150, found 288.1153.
20
16
2
3
,10-Dichlorotetraphene (2c). White amorphous solid (53 mg,
1
7
8
2%): mp 192−193 °C; H NMR (400 MHz, CDCl ) δ 8.94 (s, 1H),
.66 (d, J = 8.8 Hz, 1H), 8.31 (s, 1H), 8.06 (s, 1H), 7.95 (d, J = 9.2
3
Hz, 1H), 7.76−7.81 (m, 2H), 7.61 (dd, J = 8.8, 2.0 Hz, 1H), 7.53 (d, J
9.2 Hz, 1H), 7.47 (dd, J = 8.8, 2.0 Hz, 1H); 13C NMR (100 MHz,
CDCl ) δ 133.2, 133.1, 132.3, 131.7, 130.4, 130.1, 129.4, 129.0, 128.5,
=
3
1
28.4, 127.7, 127.3, 127.1, 126.7, 126.2, 124.5, 120.6; HRMS (EI-
TOF) calcd for C H Cl 296.0160, found 296.0164.
18
10
2
3
,10-Difluorotetraphene (2d). White amorphous solid (38 mg,
1
Figure 2. Cyclic voltammetry of 3a and 3b in dichloromethane.
57%): mp 196−197 °C; H NMR (400 MHz, CDCl ) δ 8.98 (s, 1H),
.76 (dd, J = 8.8, 5.2 Hz, 1H), 8.35 (s, 1H), 8.03 (dd, J = 8.8, 5.6 Hz,
H), 7.80 (d, J = 9.2 Hz, 1H), 7. 68 (dd, J = 9.6, 1.2 Hz, 1H), 7.55 (d, J
9.2 Hz, 1H), 7. 49 (dd, J = 9.2, 2.4 Hz, 1H), 7.35−7.41 (m, 2H);
NMR (100 MHz, CDCl ) δ 161.8 (d, J
JC−F = 246.1 Hz), 133.7, 132.5, 130.5, 129.5, 129.2, 128.9, 128.5,
3
8
1
=
Table 4. Frontier Molecular Orbitals of 3a and 3b Calculated
at the B3LYP/6-31G(d) Level
1
3
C
1
= 246.2 Hz), 160.6 (d,
3
C−F
1
1
27.3, 126.5, 126.1, 125.2, 120.4, 117.1, 115.2, 113.2, 110.4; HRMS
(EI-TOF) calcd for C H F 264.0751, found 264.0749.
18
10 2
2
,9-Dichlorotetraphene (2e). White amorphous solid (50 mg,
1
6
8
8%): mp 181−182 °C; H NMR (400 MHz, CDCl ) δ 9.04 (s, 1H),
.74 (d, J = 1.6 Hz, 1H), 8.26 (s, 1H), 8.06 (d, J = 8.8 Hz, 1H), 8.02
3
(
d, J = 1.6 Hz, 1H), 7.76−7.79 (m, 2H), 7.63 (s, 1H), 7.56−7.60 (m,
1
1
1
H), 7.50 (dd, J = 8.8, 2.0 Hz, 1H); 13C NMR (100 MHz, CDCl ) δ
3
33.0, 132.5, 132.0, 131.6, 131.2, 130.2, 130.1, 129.9, 129.9, 127.9,
27.6, 127.3, 127.1, 126.9, 126.1, 126.0, 122.7, 121.9; HRMS (EI-
TOF) calcd for C H Cl 296.0160, found 296.0161.
18
10
2
2
,9-Dimethyltetraphene (2f). White amorphous solid (38 mg,
EXPERIMENTAL SECTION
General. THF and toluene were dried with sodium and distilled
1
■
60%): mp 165−166 °C; H NMR (400 MHz, CDCl ) δ 9.10 (s, 1H),
3
8.60 (s, 1H), 8.23 (s, 1H), 8.02 (d, J = 8.8 Hz, 1H), 7.78 (s, 1H), 7.71
(t, J = 8.8 Hz, 2H), 7.58 (d, J = 9.2 Hz, 1H), 7.37−7.43 (m, 2H), 2.65
freshly before being used. CH CN was dried with CaH and distilled
3
2
(s, 3H), 2.58 (s, 3H); 13C NMR (100 MHz, CDCl ) δ 136.5, 135.4,
freshly before being used. Other materials and solvents were purchased
3
from commercial suppliers and used without additional purification.
132.2, 130.9, 130.6, 130.3, 129.6, 128.4, 128.3, 128.3, 128.2, 128.1,
126.8, 126.4, 126.2, 125.8, 122.8, 121.2, 22.1, 21.9; HRMS (EI-TOF)
calcd for C H 256.1252, found 256.1254.
1
13
H and C NMR spectra were recorded in CDCl at 400 and 100
3
MHz, respectively, and chemical shifts are reported in parts per million
using tetramethylsilane (TMS) as an internal standard. Mass
spectroscopy data of the products were collected with an HRMS-
TOF instrument. UV−vis absorption and fluorescence emission
spectra were recorded at room temperature. Cyclic voltammetry was
performed at room temperature using an Electrochemical Work-
station. The working electrode was a glassy carbon electrode. The
20
16
3,10-Dibromotetraphene (2g). White amorphous solid (65 mg,
1
67%): mp 172−173 °C; H NMR (400 MHz, CDCl ) δ 8.95 (s, 1H),
3
8.59 (d, J = 8.8 Hz, 1H), 8.30 (s, 1H), 8.26 (s, 1H), 7.97 (d, J = 2.0
Hz, 1H), 7.89 (d, J = 8.8 Hz, 1H), 7.75−7.78 (m, 2H), 7.60 (dd, J =
8.8, 2.0 Hz, 1H), 7.53 (d, J = 8.8 Hz, 1H); 13C NMR (100 MHz,
CDCl ) δ 133.6, 132.8 130.9, 130.5, 130.2, 130.1, 129.9, 129.5, 129.4,
3
D
DOI: 10.1021/acs.joc.6b00890
J. Org. Chem. XXXX, XXX, XXX−XXX

The Journal of Organic Chemistry
Note
29.0, 128.9, 128.4, 127.2, 126.2, 124.7, 121.4, 120.6, 120.0; HRMS
*E-mail: zhouhw@zju.edu.cn.
18
10
2
Notes
Tetrapheno[2,3-d:9,10-d′]bis([1,3]dioxole) (2h). White amorphous
1
The authors declare no competing financial interest.
3
.74 (s, 1H), 8.15 (s, 1H), 8.13 (s, 1H), 7.66 (d, J = 9.2 Hz, 1H), 7.50
(
2
1
1
d, J = 8.8 Hz, 1H), 7.32 (s, 1H), 7.25 (s, 1H), 7.21 (s, H), 6.12 (s,
ACKNOWLEDGMENTS
H), 6.08 (s, 2H); 13C NMR (100 MHz, CDCl ) δ 155.8, 153.7,
■
3
This work was supported by the National Natural Science
Foundation of China (Project 20972134) and the Zhejiang
Provincial Natural Science Foundation of China (Grants
LQ15B060005 and LY14B020008).
47.9, 131.1, 129.5, 125.9, 125.6, 125.3, 119.8, 106.3, 103.1, 102.5,
01.4, 101.3, 101.1; HRMS (EI-TOF) calcd for C H O 316.0736,
20
12
4
found 316.0740.
4
d
Naphthobisbenzo[b]thiophenes (2i). White amorphous solid
1
(46 mg, 54%): mp 224−225 °C; H NMR (400 MHz, CDCl ) δ 9.43
(s, 1H), 8.93 (d, J = 8.4 Hz, 1H), 8.75 (s, 1H), 8.29−8.31 (m, 1H),
3
REFERENCES
■
8
7
1
1
.02−8.07 (m, 2H), 7.88−7.93 (m, 2H), 7.65−7.68 (m, 1H), 7.50−
.55 (m, 3H); 13C NMR (100 MHz, CDCl ) δ 139.4, 138.9, 136.6,
(1) (a) Mu
̈
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llen, K.; Scherf, U.
3
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22
12 2
Synthesis of 3a. A mixture of 2g (78 mg, 0.2 mmol), carbazole
2
(
2
4
(
84 mg, 0.5 mmol), Pd(dba) (8 mg, 0.014 mmol), t-Bu P·HBF (4
2
3
4
mg, 0.014 mmol), and t-BuONa (58 mg, 0.6 mmol) in dry toluene (8
mL) was stirred at 100 °C for 4 h under Ar. After completion of the
reaction, it was quenched with a saturated aqueous NH Cl solution,
4
(
and the mixture was extracted with ethyl acetate. The organic layers
were dried Na SO , filtered, and evaporated. The residue was purified
by silica gel column chromatography (10:1 petroleum ether/ethyl
2
4
acetate) to give compound 3a (52 mg, 46%) as a pale white solid: mp
(3) (a) Ehrlich, S.; Bettinger, H. F.; Grimme, S. Angew. Chem., Int. Ed.
2013, 52, 10892. (b) Einholz, R.; Bettinger, H. F. Angew. Chem., Int.
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Dokmeci, M. R.; Pramanik, C.; McGruer, N. E.; Miller, G. P. J. Am.
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Katagiri, C.; Yamaguchi, Y.; Kuzuhara, D.; Aratani, N.; Nakayama, K.;
Yamada, H. J. Mater. Chem. C 2015, 3, 5995. (b) Yue, W.; Suraru, S.
1
1
8
8
7
90−191 °C; H NMR (400 MHz, CDCl ) δ 9.28 (s, 1H), 9.05 (d, J =
3
.8 Hz, 1H), 8.56 (s, 1H), 8.37 (s, 1H), 8.31 (d, J = 8.8 Hz, 1H),
.20−8.23 (m, 4H), 8.09 (d, J = 2.0 Hz, 1H), 7.96 (d, J = 9.2 Hz, 1H),
.90 (dd, J = 8.8, 2.0 Hz, 1H), 7.79 (dd, J = 8.8, 2.0 Hz, 1H), 7.74 (d, J
=
9.2 Hz, 1H), 7.55−7.60 (m, 4H), 7.44−7.49 (m, 4H), 7.33−7.38 (m,
4
1
1
1
H); 13C NMR (100 MHz, CDCl ) δ 140.9, 140.9, 136.8, 135.3,
3
33.4, 132.5, 131.0, 130.9, 129.9, 129.2, 129.2, 128.4, 127.4, 127.0,
26.2, 126.1, 126.0, 125.7, 125.6, 125.4, 124.9, 123.6, 123.5, 121.7,
20.4, 120.4, 120.2, 120.1, 109.9, 109.8; HRMS (EI-TOF) calcd for
C H N 558.2096, found 558.2092.
̈ ̈
L.; Bialas, D.; Muller, M.; Wurthner, F. Angew. Chem., Int. Ed. 2014,
42
26
2
Synthesis of 3b. A mixture of 2g (78 mg, 0.2 mmol), 4-
53, 6159. (c) Bunz, U. H. F.; Engelhart, J. U.; Lindner, B. D.;
Schaffroth, M. Angew. Chem., Int. Ed. 2013, 52, 3810. (d) Yamamoto,
K.; Katagiri, H.; Tairabune, H.; Yamaguchi, Y.; Pu, Y. J.; Nakayama, K.;
Ohba, Y. Tetrahedron Lett. 2012, 53, 1786.
(
(
diphenylamino)phenylboronic acid (146 mg, 0.5 mmol), Pd(PPh3)4
23 mg, 0.02 mmol), and K CO (84 mg, 0.6 mmol) in a toluene (8
2
3
mL)/water (1 mL) solvent was stirred at 90 °C for 10 h under Ar.
After completion of the reaction, it was quenched with a saturated
(5) (a) Xiao, J.; Duong, H.; Liu, Y.; Shi, W.; Ji, L.; Li, G.; Li, S.; Liu,
X.; Ma, J.; Wudl, F.; Zhang, Q. Angew. Chem., Int. Ed. 2012, 51, 6094.
(b) Kang, M. J.; Doi, I.; Mori, H.; Miyazaki, E.; Takimiya, K.; Ikeda,
M.; Kuwabara, H. Adv. Mater. 2011, 23, 1222. (c) Kaur, I.; Jazdzyk, M.;
Stein, N. N.; Prusevich, P.; Miller, G. P. J. Am. Chem. Soc. 2010, 132,
1261.
aqueous NH Cl solution, and the mixture was extracted with ethyl
4
acetate. The organic layers were dried with Na SO , filtered, and
evaporated. The residue was purified by silica gel column
chromatography (10:1 petroleum ether/ethyl acetate) to give
2
4
compound 3b (89 mg, 62%) as a pale yellow solid: mp 170−171
1
°
C; H NMR (400 MHz, CDCl ) δ 9.18 (s, 1H), 8.86 (d, J = 8.8 Hz,
(6) (a) Zhang, L.; Cao, Y.; Colella, N. S.; Liang, Y.; Bred
Houk, K. N.; Briseno, A. L. Acc. Chem. Res. 2015, 48, 500. (b) Per
D.; Pena, D.; Guitian, E. Eur. J. Org. Chem. 2013, 2013, 5981.
́
as, J. L.;
3
1
1
2
7
1
1
1
H), 8.36 (s, 1H), 8.30 (s, 1H), 8.09 (d, J = 8.8 Hz, 1H), 8.03 (d, J =
.6 Hz, 1H), 7.91 (dd, J = 8.8, 2.0 Hz, 1H), 7.81 (dd, J = 8.8, 2.0 Hz,
H), 7.66−7.71 (m, 5H), 7.28−7.33 (m, 8H), 7.17−7.24 (m, 12H),
́
ez,
̃
́
(7) (a) Mallesham, G.; Swetha, C.; Niveditha, S.; Mohanty, M. E.;
Babu, N. J.; Kumar, A.; Bhanuprakash, K.; Rao, V. J. J. Mater. Chem. C
2015, 3, 1208. (b) Wang, Z. Q.; Liu, C. L.; Zheng, C. J.; Wang, W. Z.;
Xu, C.; Zhu, M.; Ji, B. M.; Li, F.; Zhang, X. H. Org. Electron. 2015, 23,
179. (c) Liu, F.; Lai, W. Y.; Tang, C.; Wu, H. B.; Chen, Q. Q.; Peng,
B.; Wei, W.; Huang, W.; Cao, Y. Macromol. Rapid Commun. 2008, 29,
13
.05−7.09 (m, 4H); C NMR (100 MHz, CDCl ) δ 147.6, 147.4,
3
47.3, 139.2, 137.7, 134.8, 134.5, 132.4, 132.3, 130.9, 130.6, 129.3,
29.1, 129.1, 129.0, 128.3, 128.0, 127.9, 127.7, 127.2, 126.6, 126.1,
25.5, 125.1, 124.5, 124.4, 123.9, 123.9, 123.5, 123.0, 123.0, 121.6;
HRMS (EI-TOF) calcd for C H N 714.3035, found 714.3032.
54
38
2
6
59.
ASSOCIATED CONTENT
Supporting Information
(8) (a) Chung, Y. H.; Sheng, L.; Xing, X.; Zheng, L.; Bian, M.; Chen,
■
Z.; Xiao, L.; Gong, Q. J. Mater. Chem. C 2015, 3, 1794. (b) Guo, B.;
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L.; Chou, H. H.; Huang, P. Y.; Cheng, C. H.; Liu, R. S. J. Org. Chem.
*
S
The Supporting Information is available free of charge on the
ACS Publications website at DOI: 10.1021/acs.joc.6b00890.
2
014, 79, 267.
1H and 13C NMR spectra of all new compounds and
crystal structure of 2g (PDF)
Crystallographic data of 2g (CIF)
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AUTHOR INFORMATION
Corresponding Authors
E-mail: wjb4207@mail.ustc.edu.cn.
■
S.; Parameswaran, P. S.; Tilve, S. G. Helv. Chim. Acta 2008, 91, 1500.
(d) Tale, N. P.; Shelke, A. V.; Tiwari, G. B.; Thorat, P. B.; Karade, N.
N. Helv. Chim. Acta 2012, 95, 852.
*
E
DOI: 10.1021/acs.joc.6b00890
J. Org. Chem. XXXX, XXX, XXX−XXX

The Journal of Organic Chemistry
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(
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characterization.
(
3
(
(
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6
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