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Synthesis, Regioselective Bromination, and Functionalization
ofCoronene TetracarboxydiimideTaifeng Liu,†,‡,§ Yongchao Ge,†,§
Baolai Sun,† Brandon Fowler,‡ Hexing Li,† Colin Nuckolls,†,‡
and Shengxiong Xiao*,†
†The Education Ministry Key Lab and International Joint Lab of
Resource Chemistry, Shanghai Key Laboratory of Rare EarthFunctional
Materials, Optoelectronic Nano Materials and Devices Institute,
Shanghai Normal University, Shanghai 200234, China‡Department of
Chemistry, Columbia University, New York, New York 10027, United
State
*S Supporting Information
ABSTRACT: A new method for the effective synthesis of
coronenetetracarboxydiimide (CDI) was developed by utilizing
inexpensiveand nontoxic potassium vinyltrifluoroborate.
Controllable bromi-nations of CDI were accomplished to yield CDI
mono-, di-, tri-, andtetra-bromides, which could be used as synthon
and functionalizedby aromatic nucleophilic substitution and the
Sonogashira couplingreaction.
■ INTRODUCTIONPerylene tetracarboxydiimide derivatives (PDIs),
initiallyutilized as industrial dyes and pigments,1,2 have
beenextensively investigated and found in a wide range
ofapplications in biochemical sensors,3−6 organic field
effecttransistors,7−11 light emitting diodes,12−14 organic
solarcells,15−19 and other optoelectronic devices.20−23 All of
thesepromising applications are attributed to the rigid backbone
ofextended π-conjugation of perylene tetracarboxydiimide.
Mucheffort has been devoted to the bay-extended
perylenetetracarboxydiimide systems, as the two representatives,
PDI-based nanoribbons and nonplanar polycyclic aromatic
hydro-carbon (PAHs), display efficient charge transfer,
broadabsorption in the visible light region, and desirable
morphologythrough self-assembly in organic electronics and
optoelectronicmaterials.24−26
The coronene tetracarboxydiimides (CDIs) are embeddedin many
PDI-based systems that have been applied in high-performance
optoelectronic materials, and, as such, they areimportant building
blocks to prepare.24,25 Scheme 1 containsrepresentative syntheses
of CDIs.27−36 In general, thesesyntheses suffer from numerous
reaction steps, low yields, orlack the ability to further fuse the
CDI subunits. Mullen andco-workers27,29 prepared
1,7-bisalkynyl-substituted perylenetetracarboxydiimide, which they
demonstrated could cyclize bytreatment with
1,8-diazabicyclo[5.4.0]undec-7-ene (DBU). Assuch, they prepared a
series of CDIs with high yields up to 95−100%. Bock and
co-workers30 obtained pyrene-based CDI by aDiels−Alder reaction
between maleic anhydride and pyrene atthe bay-position with a yield
of 2−10%, and this CDI systempossesses L-edges, not K-edges, at the
short molecular axis.37
In another study by Mullen and co-workers,33 they reported
atwo-step synthesis and PtCl2-catalyzed carbocyclization toyield
the first PDI-based CDI with hydrogens substituted inthe K region37
from 1,(6)7-diethinyl PDI in a yield of ∼38%.
More recently, Zhao and co-workers34,35 and, independently,Tian
and co-workers36 developed an ICl/IBr-mediated andlight-facilitated
cyclization procedure. They obtained CDIswith halogen and
trimethylsilyl groups that can be replaced byother halogen atoms.
However, these CDI derivatives stillpossess less versatility, such
as alkyl or trimethylsilyl groupsimpeding the coupling and aromatic
ring-fusion with otherbuilding blocks. The study described here
focused on a newroute to the CDI core. Moreover, we show that
thebromination is controllable and leads to further
functionaliza-tion for potential electronic materials using CDI as
thesubunits.
■ RESULTS AND DISCUSSIONIn general,
1,(6)7-dibromoperylene-3,4,9,10-tetracarboxylicdiimide is the
starting material for most core-extended PDIderivatives.38 In our
studies, 1,(6)7-divinyl perylene tetracar-boxydiimide was obtained
by Suzuki coupling between a 4:1mixture of 1,7- and
1,6-dibromoperylene tetracarboxydiimide139 and potassium
vinyltrifluoroborate (Scheme 2). However,1,(6)7-divinyl perylene
tetracarboxydiimide is unstable anddifficult to be isolated on
silica gel under light. After flashcolumn chromatography and
recrystallization from acetonitrileand dichloromethane protected
from light, the 1H NMRspectrum revealed that very pure 1,7-divinyl
perylenetetracarboxydiimide 2 was obtained with a high yield up
to60%, and the other isomer 1,6-divinyl perylene
tetracarbox-ydiimide could not be isolated by flash column
chromatog-raphy and recrystallization (Figures S1 and S2).Then, the
next step is the photocyclization reaction of
intermediate molecule 2 (Scheme 2). A similar photo-cyclization
reaction was performed to yield 4,5,9,10-tetrahy-
Received: December 8, 2018Published: February 8, 2019
Article
pubs.acs.org/jocCite This: J. Org. Chem. 2019, 84, 2713−2720
© 2019 American Chemical Society 2713 DOI:
10.1021/acs.joc.8b03129J. Org. Chem. 2019, 84, 2713−2720
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dropyrene as the main product from 2,2′-diethenyl-1,1′-biphenyl
by Laarhoven et al. and Padwa et al.40,41 Thisreaction was carried
out under ultraviolet light from a 450-WHanovia lamp, and no I2 was
used. Then, dehydrogenation of
4,5,9,10-tetrahydropyrene with DDQ in benzene afforded
thecorresponding pyrene with a high yield up to 98%.42 Themodified
photocyclization between a PDI core and an ethyleneat the
bay-position in toluene with I2 as the catalyst under
Scheme 1. Previous Works on the Synthesis of the CDI Core
Reported until Now
Scheme 2. Suzuki-Coupling Reaction between a 4:1 Mixture of 1,7-
and 1,6-Dibromoperylene-3,4,9,10-tetracarboxylic Diimideand
Potassium Vinyltrifluoroborate and the CDI Synthesisa
aMethod A: Photocyclization for at least 48 h.
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ultraviolet light from a 450-W Hanovia lamp gives
adehydrogenated product with high yields.25 Accordingly,
thephotocyclization of molecule 2 was carried out by adding
3.0equiv of I2 and purging with air under irradiation of a
450-WHanovia medium pressure mercury lamp. This one-step
routecyclizes molecule 2 and yields the CDI core 3 (Scheme 2,method
A). After 48 h under the photocyclization, pure targetproduct 3 was
obtained by silica gel column chromatographyand characterized by
NMR (Figures S3 and S4) and MALDI-TOF mass spectrometry, with a
yield up to 80%.Interestingly, when we terminated the reaction
under the
same photocyclization condition after 12 h, no starting
materialwas detected, but the target product 3 and intermediates 4
and5 with a ratio between 3, 4, and 5 of 60:10:20 (Scheme 3,method
B) in the reaction mixture were obtained. Compounds4 (Figure S5)
and 5 (Figure S6) could be identified andseparated by silica gel
preparative thin layer chromatography(TLC) and characterized by 1H
NMR spectra. When thereaction time was prolonged, 4 and 5 gradually
disappearedcompletely and converted into target product 3 in 48 h;
thesame as what has been described in method A. Meanwhile,even
without separation and purification, intermediates 4 and 5underwent
dehydrogenation and transformed into 3 byrefluxing the reaction
mixture in toluene for 3−4 h underthe oxidation of
2,3-dicyano-5,6-dichlorobenzoquinone(DDQ), with a total yield of
about 76% starting from 2.As depicted in Scheme 3, the target CDI
chromophore could
be synthesized with high yields and good atom economy. Butthis
parent CDI core still suffers from difficulty to couple withother
chromophores. In general, bromination is very useful toform
aromatic bromides that can be used as coupling partnersin the
Suzuki−Miyaura coupling, Migita−Kosugi−Stillecoupling,
Mizoroki−Heck coupling, Sonogashira coupling,and other coupling
reactions.Bromine is inexpensive and readily available. Being
stirred at
room temperature or refluxed with a large excess of bromine
indichloromethane have proven to be effective for thebromination of
PDI-based systems.43 Table 1 shows thebrominations of CDI at
different conditions. First, the usualcondition without any
catalyst, following the bromination ofthe PDI bay-position,25 was
adopted to brominate the CDIcore at the K-edge (Scheme 4). After 24
h of being stirred inrefluxing dichloromethane, the CDI remained
almost un-changed, and only 2% of CDI-monobromide 6 was
obtained(entry 1). Next, we tried to brominate the CDI in refluxing
1,2-dichloroethane for 24 h, but we only got 10% of CDI-monobromide
6 (entry 2). At last, an FeCl3 catalyst was usedto activate the
K-region of the CDI at 60 °C in 1,2-
dichloroethane, and the reaction process was monitored byTLC.
After 5 and 12 h, the ratio between 3, 6, 7, and 8 reached5:60:35:0
and 2:25:68:5, respectively (entries 3 and 4). CDI-monobromide 6
and -dibromide 7 were separated by silica gelcolumn chromatography
with hexane and dichloromethane asthe eluent. The structure of
CDI-monobromide 6 (Figures S7and S8) was characterized by NMR and
mass spectrometry.CDI-dibromides 7 were identified as regioisomers,
consistingof 4,11- and 5,11-dibromide at the K-region (Figures S9
andS10), which cannot be separated by silica gel
columnchromatography. As the reaction time was extended,
CDI-tribromide 8 (Figures S11 and S12) and -tetrabromide 9(Figures
S13 and S14) were enriched at 85 °C in 1,2-dichloroethane. The
reaction was terminated after 48 h, andCDI-tri/tetrabromide were
separated easily by a silica gelcolumn with yields of 60 and 20%,
respectively (entry 5).While the CDI core was heated at 130 °C in
chlorobenzene for24 h with 5% FeCl3, the bromination was not
successful, andthe starting material decomposed (entry 6). When
catalyzed by3 equiv of iron powder in 1,2-dichloroethane under
reflux, thebromination of 3 results in 9 with a high yield up to
90%(entry 7).The functionalizations of CDI-tetrabromide 9 were
further
investigated in order to obtain potential CDI-based materialsby
using CDI as a synthon (Scheme 5). We found that CDI-tetrabromide 9
underwent aromatic nucleophilic substitutionreactions with phenol
and thiophenol or the Sonogashiracoupling reaction. Ten equivalents
of phenol reacted with 9 at110 °C for 48 h in 1,4-dioxane under
potassium carbonate,resulting in CDI-tetraphenyl ether 10 with a
yield of 50%.43−45
Similarly, CDI-tetrathiophenyl sulfide 11 was obtained with
ayield of 82% by using thiophenol as the nucleophile and
Scheme 3. CDI Synthesisa
aMethod B: Photocyclization for 12 h, then followed by oxidation
by DDQ.
Table 1. Controllable Brominations of CDI 3 by Tuning
theSolvents, with/without FeCl3/Iron Powder Catalysts;Reaction
Temperature; and Reaction Time
entry solventa catalysttemp(°C)
time(h)
ratio of3:6:7:8:9
1 DCM reflux 24 98:2:-:-:-2 DCE 85 24 90:10:-:-:-3 DCE 5% FeCl3
60 5 5:60:35:-:-4 DCE 5% FeCl3 60 12 2:25:68:5:-5 DCE 5% FeCl3 85
48 -:-:20:60:206 chlorobenzene 5% FeCl3 130 24 decomposed7 DCE 3
equiv iron
powder85 12 0:0:0:0:90b
aSolvent: DCM, dichloromethane; DCE, 1,2-dichloroethane. b90%
isthe isolated yield of 9.
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triethylamine as the acid-binding agent at 80 °C in
1,4-dioxane.46−48 Additionally, the Pd−Cu-catalyzed
Sonogashiracoupling gave the CDI-tetraacetylene 12 with a high
yield upto 80%.The absorption spectra of the CDI core have been
previously reported (Figure 1),33 with the typical vibrionicfine
structure in the range of 360−450 nm and S0−S1transitions
absorption peaks at 450−500 nm.35 The stepwisered-shift in the
absorption spectra of about 4 nm was observedas the bromine
addition was increased at the K-region of theCDI core (Table 2).
The absorption and emission spectra(Figures 2 and 3) were
investigated and compared betweenparent CDI and CDI derivatives.
CDI derivatives 10, 11, and12 kept the vibrionic fine structure but
exhibited an obviousred-shift compared with CDI 3 and
CDI-tetrabromide 9. Theabsorption of 11 is broader compared to 10
and 12, which isalso observed in other multisulfur molecules.38 The
band gapsof 3, 10, 11, and 12 measured from the absorption maxima
are2.51, 2.36, 2.38, and 2.31 eV, respectively (Table 2).
Thefluorescence spectra also demonstrated defined structures
andStokes shifts. CDI derivatives 9, 10, 11, and 12 showed a
Scheme 4. Controllable Brominations of CDI 3 by Tuning Reaction
Temperature and Time with FeCl3 Catalyst
Scheme 5. Aromatic Nucleophilic Substitution andSonogashira
Coupling of CDI Tetrabromide
Figure 1. UV−vis absorption spectra of CDI 3, CDI-monobromide
6,-dibromide 7, -tribromide 8, and -tetrabromide 9 in
dichloromethaneat room temperature (solution concentrations are 1 ×
10−5 mol/L).
Table 2. Absorption Spectra Properties of CDI 3, CDI-Monobromide
6, -Dibromide 7, -Tribromide 8, and-Tetrabromide 9 in
Dichloromethane at RoomTemperaturea
entryλmax
(nm)bε
(M−1cm−1)c absorption band (nm)Egap(eV)
3 494 7400 375, 396, 419, 462, 494 2.516 498 7000 376, 397, 421,
465, 498 2.497 502 6600 377, 398, 423, 469, 502 2.478 504 5100 379,
401, 425, 471, 504 2.469 506 4900 381, 403, 427, 473, 506 2.4510
525 8035 342, 379, 402, 428, 488, 525 2.3611 520 10 060 348, 487,
522 2.3812 537 22 685 352, 370, 392, 412, 438, 500, 536 2.31
aSolution concentrations are 1 × 10−5 mol/L. bThe
longestabsorption maxima. cMolar absorption coefficient at the
longestabsorption wavelength. Egap was calculated by the equation
Egap =1240/λmax (eV).
Figure 2. UV−vis absorption spectra of CDI 3, CDI-tetrabromide
9,CDI-tetraphenyl ether 10, CDI-tetrathiophenyl sulfide 11, and
CDI-tetraacetylene 12 in chloroform at room temperature
(solutionconcentrations are 1 × 10−5 mol/L).
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similar red-shift in the fluorescence spectra relative to the
CDIcore 3. CDI-tetrabromide 9 and CDI-tetrathiophenol ether
11manifested a significantly lower fluorescence compared with 3,10,
and 12. Notably, the fluorescence of 11 was quenchedalmost
completely due to the strong charge-transfer interactionbetween the
electron-rich sulfur atom and electron-deficientCDI core.49
The electrochemistry properties of 3, 10, 11, and 12
wereinvestigated by cyclic voltammetry (CV) in chloroformsolution
with Bu4NPF6 as the supporting electrolyte and theFc/Fc+ redox
couple as an internal standard (Figure 4). CDI 3
and CDI derivatives 10, 11, and 12 all display two
reversiblereduction processes. Calculated from half-wave
potentials, theLUMO energy levels of 3, 10, 11, and 12 are −3.31,
−3.44,−3.47, and 3.50 eV, respectively (Figures S21−24 and
TableS1). HOMO energy levels of 3, 10, 11, and 12 are
calculatedfrom different values between optical band gaps (Table
2), andthe LUMO energy levels are −5.82, 5.80, −5.85, and 5.81
eV,respectively.
■ CONCLUSIONSIn summary, a new method for the synthesis of the
CDI corechromophore was developed with a cheap and nontoxicreagent
and photocyclization reaction with 48% yield for twosteps. The
brominations of the CDI core were investigatedunder the catalyst of
FeCl3 and iron powder. CDI-tetrabromide was obtained with a high
yield up to 90%. Thefunctionalizations of CDI-tetrabromide were
further studied inorder to obtain potential CDI-based materials by
using CDI asa synthon. CDI derivatives were obtained by
aromatic
nucleophilic substitution and the Sonogashira couplingreaction.
Photophysical and electrochemical properties ofCDI derivatives were
discussed by absorption, emission, andCV spectra.
■ EXPERIMENTAL SECTIONGeneral Information. Unless otherwise
noted, all materials and
reagents, including dry solvents, were obtained from
commercialsuppliers and used without further purification.
1,(6)7-Dibromoper-ylene tetracarboxydiimide was prepared according
to the proceduresreported in the literature.39 Unless otherwise
noted, all workupprocessing and purification procedures were
carried out with reagent-grade solvents in air.
1H and 13C NMR spectra were obtained from a Bruker DRX300(300
MHz), Bruker DRX400 (400 MHz), or a Bruker DMX500 (500MHz)
spectrometer. High-resolution mass spectrometry (HRMS)data were
obtained at the Columbia University Mass Spectrometryfacility using
a Waters XEVO G2XS instrument equipped with a 9UPC2 SFC inlet,
electrospray (ESI) and atmospheric pressurechemical (APCI)
ionization, and a QTOF mass spectrometer.Absorption spectra were
obtained on a Shimadzu UV 1800 UV−visspectrophotometer.
Synthesis and Characterization of Compound 2. Nitrogen
wasbubbled through a mixed solution of toluene (10 mL), EtOH (2
mL),and water (2 mL) for 30 min, and to this solution were
addedcompound 1 (a 4:1 mixture of 1,7- and
1,6-dibromoperylenetetracarboxydiimide) (0.86 g, 1.00 mmol),
Pd(PPh3)4 (0.11 g, 0.10mmol), K2CO3 (0.55 g, 4.00 mmol), and
potassium vinyltrifluor-oborate (0.40 g, 3.00 mmol). The mixture
was heated at 85 °C for 5−6 h. Then, the mixture was poured into
water and extracted withCH2Cl2. The organic layer was dried over
anhydrous Na2SO4 andfiltered, and the solvent was removed by a
rotary evaporator. Theproduct was purified by flash silica gel
column chromatography(dichloromethane:petroleum ether = 1:2, Rf =
0.4) and thenrecrystallized from acetonitrile and dichloromethane
to give pureproduct 2 (0.45 g) as a purple solid in 60% yield. 1H
NMR (400MHz, CDCl3, δ): 8.87 (s, 2H), 8.65 (s, 2H), 8.53−8.51 (d,
2H),7.33−7.26 (m, 2H), 6.33−6.29 (d, 2H), 5.79−5.76 (d, 2H),
5.23−5.20 (m, 2H), 2.29−2.26 (m, 4H), 1.88−1.86 (m, 4H),
1.29−1.28(m, 24H), 0.85−0.82 (t, 12H). 13C{1H} NMR (101 MHz, CDCl3,
δ):164.9, 163.9, 137.9, 136.8, 134.5, 133.0, 132.2, 130.2, 129.6,
128.5,127.9, 123.1, 122.4, 120.0, 54.9, 32.5, 31.9, 26.8, 22.7,
14.2. HRMS(ESI+) (m/z): [M + H]+ Calculated for C50H59N2O4
+, 751.4475;found,, 751.4470.
Synthesis and Characterization of Compound 3. Method A. In
aquartz photo reactor, compound 2 (1.00 g, 1.34 mmol) was
dissolvedin 500 mL of toluene, and then iodine (1.02 g, 4.02 mmol)
was added.The resultant purple solution was photoirradiated using a
450 Wmedium-pressure mercury lamp for 48 h. Toluene was removed
byrotator evaporation. The residue was purified by silica gel
columnchromatography (1:1 = dichloromethane:petroleum ether, Rf =
0.2)to afford compound 3 as a brown solid in 80% yield.
Method B. In a quartz photo reactor, compound 2 (1.00 g,
1.34mmol) was dissolved in 500 mL of toluene, and then iodine (1.02
g,4.02 mmol) was added. The resultant purple solution
wasphotoirradiated using a 450 W medium-pressure mercury lamp for12
h. The solvent was removed under reduced pressure, and the
solidprecipitate was collected. A portion of the reaction mixture
wassubjected to silica gel preparative thin layer chromatography
(TLC),and brown intermediates 4 and 5 were identified by 1H NMR
spectra.DDQ (0.55 g, 2.40 mmol) was added to the rest of this
reactionmixture in toluene (100 mL) and was heated to 115 °C for 4
h beforeit was quenched by saturated NaHCO3 solution (20 mL).
Thesolution was extracted by CH2Cl2 twice (100 mL × 2). The
combinedextracts were washed with brine and dried over MgSO4. After
removalof solvent in vacuum, the crude material was purified by
silica gelcolumn chromatography (1:1 = dichloromethane:petroleum
ether, Rf= 0.2) to afford compound 3 as a brown solid (0.76 g) in a
total yieldof 76% starting from compound 2.
Figure 3. Fluorescence spectra of CDI 3, CDI-tetrabromide 9,
CDI-tetraphenyl ether 10, CDI-tetrathiophenyl sulfide 11, and
CDI-tetraacetylene 12 in chloroform at room temperature
(solutionconcentrations are 1 × 10−5 mol/L).
Figure 4. Cyclic voltammetry of 3, 10, 11, and 12 (0.1 M
n-Bu4NPF6in chloroform) at a scan rate of 100 mV s−1.
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3: 1H NMR (400 MHz, CDCl3, δ): 9.42 (s, 4H), 8.57 (s,
4H),5.52−5.49 (m, 2H), 2.56−2.54 (m, 4H), 2.18−2.16 (m, 4H),
1.52−1.39 (m, 24H), 0.95−0.91 (t, 12H). 13C{1H} NMR (101 MHz,CDCl3,
δ): 165.2, 129.9, 129.3, 128.3, 128.0, 122.0, 121.4, 118.6,
55.2,32.6, 31.9, 27.0, 22.8, 14.2. HRMS (ESI+) (m/z): [M + H]+
Calculated for C50H55N2O4+, 747.4162; found,, 747.4164.
Intermediate 4 was obtained as a brown solid by a silica gel
plate(2:3 = dichloromethane:petroleum ether, Rf = 0.3) and
characterizedby 1H NMR spectrum. 1H NMR (400 MHz, CDCl3, δ):
8.43−8.38(d, 4H), 5.21−5.18 (m, 2H), 3.38 (s, 8H), 2.26−2.23 (m,
4H), 1.83(m, 4H), 1.29−1.25 (m, 24H), 0.84−0.81(t,
12H).Intermediate 5 was obtained as a brown solid by a silica gel
plate
(1:2 = dichloromethane:petroleum ether, Rf = 0.3) and
characterizedby 1H NMR spectrum. 1H NMR (400 MHz, CDCl3, δ):
9.37−9.33(d, 2H), 8.90−8.86 (d, 2H), 8.73 (s, 2H), 5.33−5.30 (m,
2H), 3.77(s, 4H), 2.36−2.34 (m, 4H), 1.96−1.92 (m, 4H), 1.31−1.25
(m,24H), 0.83−0.81 (t, 12H).Synthesis and Characterization of
Compound 6. Compound 3
(2.60 g, 3.45 mmol) was dissolved in 50 mL of dichloroethane.
Excessbromine (3 mL, 58.5 mmol) was added, followed by a few
crystals ofFeCl3 (5 mol %). The solution was stirred at 60 °C. The
reaction wasmonitored by TLC and was terminated after 5 h. Bromine
wasquenched with saturated NaHSO3 solution (300 mL) and
extractedwith CH2Cl2. The combined organic layer was dried over
anhydrousmagnesium sulfate and concentrated under reduced pressure.
Theproduct was purified by silica gel column chromatography (1:2
=dichloromethane:petroleum ether, Rf = 0.7) to afford compound 6
asa brown solid (1.71 g, 60% yield). 1H NMR (400 MHz, CDCl3,
δ):9.55−9.45 (d, 3H), 9.12−9.07 (d, 1H), 8.78−8.72 (d, 2H), 8.54
(s,1H), 5.51−5.41 (m, 2H), 2.53−2.49 (m, 4H), 2.23−2.17 (m,
4H),1.59−1.39 (m, 24H), 0.95−0.92 (t, 12H). 13C{1H} NMR (101
MHz,CDCl3, δ): 164.9, 163.9, 130.9, 128.8, 128.8, 128.8, 128.7,
128.3,127.0, 123.6, 122.2, 122.2, 121.0, 121.3, 121.0, 120.2,
118.5, 118.4,55.5, 32.8, 32.1, 27.3, 27.2, 22.9, 14.3. HRMS (ESI+)
(m/z): [M +H]+ Calculated for C50H54BrN2O4
+, 825.3267; found, 825.3262.Synthesis and Characterization of
Compound 7. Compound 3
(1.30 g, 1.73 mmol) was dissolved in 40 mL of dichloroethane.
Excessbromine (2 mL, 39 mmol) was added, followed by a few crystals
ofFeCl3. The solution was capped with a rubber septum and stirred
at60 °C for 12 h. The reaction was monitored by TLC and
terminatedwhen dibromide dominated. Then, the mixture was cooled to
roomtemperature. Bromine was quenched with saturated NaHSO3
solution(300 mL), and the mixture was extracted with 200 mL of
CH2Cl2.The combined organic layer was dried over anhydrous
magnesiumsulfate and concentrated under reduced pressure. The
product waspurified by silica gel column chromatography (1:2 =
dichlorometha-ne:petroleum ether, Rf = 0.8) to afford regioisomeric
dibromidecompound 7 as a brown solid (1.06 g, 68% yield). 1H NMR
(500MHz, CDCl3, δ): 9.82 (s, 1H), 9.69 (s, 1H), 9.41 (d, 2H),
8.94−8.92(d, 2H), 5.46−5.43 (m, 2H), 2.52 (m, 4H), 2.19 (m, 4H),
1.51−1.38(m, 24H), 0.94−0.92 (t, 12H). 13C{1H} NMR (101 MHz, CDCl3,
δ):164.8, 163.7, 131.9, 131.8, 129.9, 129.1, 128.0, 127.7, 124.5,
122.7,122.5, 122.4, 120.9, 120.4, 118.9, 118.8, 118.6, 55.7, 32.7,
32.1, 27.2,22.9, 14.3. HRMS (ESI+) (m/z): [M + H]+ Calculated
forC50H53Br2N2O4
+, 903.2372; found, 903.2375.Synthesis and Characterization of
Compound 8 and 9. Method
A. Following the procedure for the synthesis of compound
7,compound 3 (1.30 g, 1.73 mmol) was dissolved in 40 mL
ofdichloroethane. Excess bromine (2 mL, 39 mmol) was added,followed
by FeCl3 powder (14 mg, 0.085 mmol). The reactionmixture was
refluxed in 1,2-dichloroethane and monitored by TLC.After 48 h,
bromine was quenched by NaHSO3, and the mixture wasextracted with
200 mL of CH2Cl2. The combined organic layer wasdried over
anhydrous magnesium sulfate and concentrated underreduced pressure.
CDI-tribromide 8 and -tetrabromide 9 wereseparated by silica gel
chromatography column (chloroform:petro-leum ether = 1:2, Rf = 0.8)
as both brown solids, the yields were 60and 20%,
respectively.Method B. To a mixture of 3 (76.3 mg, 0.1 mmol) and
iron powder
(16.8 mg, 0.3 mmol) in 2 mL of anhydrous 1,2-dichloroethane,
bromine (0.1 mL, 20 equiv) was added dropwise at
roomtemperature. The mixture was stirred at 85 °C for 12 h and
thenpoured into ice/water. The organic phase was extracted
withdichloromethane (20 mL × 2), then dried with anhydrous
magnesiumsulfate, and purified by flash silica gel column
chromatography elutedwith dichloromethane. The filtrate was
concentrated, and 9 (95 mg,yield 90%) was obtained as a brown
solid.
8: 1H NMR (400 MHz, CDCl3, δ): 9.63 (s, 1H), 9.52 (s, 1H),
9.40(s, 1H), 9.33 (s, 1H), 8.91 (s, 1H), 5.43−5.34 (m, 2H),
2.52−2.48(m, 4H), 2.26−2.22 (m, 4H), 1.54−1.43 (m, 24H), 0.98−0.94
(t,12H). 13C{1H} NMR (101 MHz, CDCl3, δ): 163.2, 131.9,
129.9,128.9, 128.5, 128.0, 128.0, 127.9, 127.8, 127.6, 124.8,
122.2, 121.6,120.5, 120.1, 119.7, 118.0, 117.8, 55.9, 32.8, 32.2,
32.1, 27.4, 27.3,22.9, 22.9, 14.4, 14.4. HRMS (MALDI-TOF, dithranol
matrix) (m/z): [M]− Calculated for C50H51Br3N2O4, 980.1399; found,
980.1429.
9: 1H NMR (400 MHz, CDCl3, δ): 9.81 (s, 4H), 5.42−5.39 (m,2H),
2.52−2.49 (m, 4H), 2.25−2.22 (m, 4H), 1.53−1.41 (m, 24H),0.95−0.91
(t, 12H). 13C{1H} NMR (101 MHz, CDCl3, δ): 163.1,131.5, 128.8,
128.7, 122.9, 122.7, 121.0, 118.6, 56.0, 32.7, 32.1, 27.3,22.9,
14.3. HRMS (MALDI-TOF, dithranol matrix) (m/z): [M]−
Calculated for C50H50Br4N2O4, 1058.0499; found,
1058.0495.Synthesis and Characterization of Compound 10. Under an
N2
atmosphere, 2 mL of an anhydrous 1,4-dioxane solution of
CDI-tetrabromide 9 (106 mg, 0.1 mmol), phenol (94 mg, 1 mmol),
andK2CO3 (276 mg, 2 mmol) was stirred for 48 h at 110 °C in a
pressuretube. After being cooled to room temperature, the reaction
mixturewas evaporated and separated by a silica gel chromatography
column(dichloromethane:petroleum ether = 2:3, Rf = 0.2). Compound
10was obtained as a brown solid, 56 mg (yield 50%). 1H NMR (400MHz,
CDCl3, δ): 10.25 (s, 4H), 7.30−7.26 (t, 8H), 7.13−7.10 (t,4H),
6.88−6.86 (d, 8H), 5.44−5.36 (m, 2H), 2.43, 2.42−2.34 (m,4H),
1.99−1.91(m, 4H), 1.41−1.21(m, 24H), 0.83−0.78 (t, 12H).13C{1H} NMR
(126 MHz, CDCl3, δ): 165.6, 164.5, 158.2, 143.0,129.6, 127.3,
126.3, 125.5, 123.4, 123.1, 122.4, 122.0, 121.2, 116.5,116.5,
116.0, 55.3, 32.5, 31.8, 26.7, 22.6, 14.0. HRMS (ESI+) (m/z):[M +
H]+ Calculated for C74H71N2O8
+, 1115.5244; found, 1115.5219.Synthesis and Characterization of
Compound 11. Under an N2
atmosphere, 2 mL of an anhydrous 1,4-dioxane solution of
CDI-tetrabromide 9 (106 mg, 0.1 mmol), thiophenol (94 mg, 1
mmol),and triethylamine (0.5 mL) was stirred for 24 h at 80 °C in a
pressuretube. After being cooled to room temperature, the reaction
mixturewas evaporated and separated by a silica gel chromatography
column(dichloromethane:petroleum ether = 2:3, Rf = 0.3). Compound
11was obtained as a brown solid, 97 mg (yield 82%).1H NMR (400MHz,
CDCl3, δ): 10.77 (s, 4H), 7.20−7.19 (d, 8H), 7.15−7.07 10.77(m,
12H), 5.40−5.32 (s, 2H), 2.41−2.31 (m, 4H), 2.00−1.93 (m,4H),
1.41−1.21 (m, 24H), 0.83−0.79 (s, 12H). 13C{1H} NMR (101MHz, CDCl3,
δ): 165.2, 164.1, 142.0, 137.9, 132.5, 132.3, 131.8,130.2, 129.3,
128.4, 126.32, 125.1, 124.5, 123.4, 122.6, 121.4, 55.3,32.4, 31.7,
26.7, 22.6, 14.0. HRMS (ESI+) (m/z): [M + H]+
Calculated for C74H71N2O4S4+, 1179.4297; found, 1179.4298.
Synthesis and Characterization of Compound 12. Under an
N2atmosphere, 2 mL of an anhydrous tetrahydrofuran solution of
CDI-tetrabromide 9 (106 mg, 0.1 mmol), CuI (0.4 mg, 0.002
mmol),Pd(PPh3)2Cl2 (3.5 mg, 0.005 mmol), trimethylsilylacetylene
(282 uL,2 mmol), and triethylamine (0.5 mL) was stirred for 24 h at
90 °C ina pressure tube. When cooled to room temperature, the
reactionmixture was evaporated and then separated by a silica
gelchromatography column (dichloromethane:petroleum ether = 1:2,Rf
= 0.3). Compound 12 was obtained as a brown solid, 90 mg
(yield80%). 1H NMR (400 MHz, CDCl3, δ): 10.35 (s, 4H), 5.47−5.44
(m,2H), 2.47−2.43 (m, 4H), 2.09−2.06 (m, 4H), 1.40−1.26 (m,
24H),0.87, 0.87−0.84 (t, 12H), 0.61−0.59 (s, 18H). 13C{1H} NMR
(126MHz, CDCl3, δ): 165.5, 164.2, 130.6, 129.9, 129.7, 126.2,
126.0,124.5, 123.5, 123.0, 122.6, 120.7, 109.2, 100.9, 55.5, 32.6,
32.0, 27.0,22.6, 14.1, 0.2. HRMS (ESI+) (m/z): [M + H]+ Calculated
forC70H87N2O4Si4
+, 1131.5743; found, 1131.5731.
The Journal of Organic Chemistry Article
DOI: 10.1021/acs.joc.8b03129J. Org. Chem. 2019, 84,
2713−2720
2718
http://dx.doi.org/10.1021/acs.joc.8b03129
-
■ ASSOCIATED CONTENT*S Supporting InformationThe Supporting
Information is available free of charge on theACS Publications
website at DOI: 10.1021/acs.joc.8b03129.
NMR spectra for all compounds and cyclic voltammetryof 3, 10,
11, and 12 (PDF)
■ AUTHOR INFORMATIONCorresponding Author*E-mail:
[email protected] Li: 0000-0002-3558-5227Colin
Nuckolls: 0000-0002-0384-5493Shengxiong Xiao:
0000-0002-9151-9558Author Contributions§T.L. and Y.G. contributed
equally to this work.
NotesThe authors declare no competing financial interest.
■ ACKNOWLEDGMENTSWe acknowledge financial support from the
National NaturalScience Foundation of China (21473113, 21772123,
and51502173), Program of Shanghai Academic/TechnologyResearch
Leader (16XD1402700), Program for Professor ofSpecial Appointment
(Eastern Scholar) at Shanghai Institu-tions of Higher Learning
(2013-57), “Shuguang Program”supported by Shanghai Education
Development Foundationand Shanghai Municipal Education Commission
(14SG40),Shanghai Government (18DZ2254200) and Ministry ofEducation
of China (PCSIRT_16R49) supported by theProgramme of Introducing
Talents of Discipline to Uni-versities and International Joint
Laboratory of ResourceChemistry (IJLRC).
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