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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.

The Journal of Organic Chemistry Article

DOI: 10.1021/acs.joc.8b03129J. Org. Chem. 2019, 84, 2713−2720

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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.



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■ 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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