Synthesis, Regioselective Bromination, and Functionalization of

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Synthesis, regioselective bromination and functionalization of coronene tetracarboxydiimide Taifeng Liu, Yongchao Ge, Baolai Sun, Brandon Fowler, Hexing Li, Colin Nuckolls, and Shengxiong Xiao J. Org. Chem., Just Accepted Manuscript • DOI: 10.1021/acs.joc.8b03129 • Publication Date (Web): 08 Feb 2019 Downloaded from http://pubs.acs.org on February 8, 2019

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The Journal of Organic Chemistry

Synthesis, Regioselective Bromination and Functionalization of Coronene Tetracarboxydiimide Taifeng Liu , Yongchao Ge , Baolai Sun , Brandon Fowler , Hexing Li , Colin †,‡ ,#

†,#

†

‡

†

Nuckolls , Shengxiong Xiao †,‡

*†

The Education Ministry Key Lab and International Joint Lab of Resource Chemistry,

†

Shanghai Key Laboratory of Rare Earth Functional Materials, Optoelectronic Nano Materials and Devices Institute, Shanghai Normal University, Shanghai 200234, China. E-mail: [email protected] ‡

Department of Chemistry, Columbia University, New York, New York 10027, United

State #

These authors contributed equally to this work.

ABSTRACT A new method for the effective synthesis of coronene tetracarboxydiimide (CDI) was developed by utilizing inexpensive and non-toxic potassium vinyltrifluoroborate. Controllable brominations of CDI were accomplished to yield CDI mono-, di-, triand tetra- bromides, which could be used as synthon and functionalized by aromatic nucleophilic substitution and Sonogashira Coupling reaction.

INTRODUCTION Perylene tetracarboxydiimide derivatives (PDIs), initially utilized as industrial dyes and pigments, have been extensively investigated and found wide range 1,2

of applications in biochemical sensors, organic field effect transistors, 3-6

emitting diodes,

12-14

organic solar cells

15-19

7-11

and other optoelectronic devices.

light

20-23

All

these promising applications are attributed to the rigid backbone of extended p-conjugation of perylene tetracarboxydiimide. Much effort has been devoted

ACS Paragon Plus Environment

The Journal of Organic Chemistry 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

to

the

bay-extended

perylene

Page 2 of 20

tetracarboxydiimide

systems,

as

two

representatives of which, PDI-based nanoribbons and non-planar polycyclic aromatic hydrocarbon (PAHs) displays efficient charge transfer, broad absorption in visible light region and desirable morphology through self-assembly in organic electronics and optoelectronic materials.

24-26

O

R N

Previous Works: O

Alkyl Alkyl

Alkyl Alkyl

yield: 95-100% K. Mullen et al.[27, 29] N R

O

O

O 1) chloranil, maleic anhydride, o 140 C,4 days Alkyl N 2) alkylamine, reflux, overnight O yield: 2-10% H. Bock et al. [30]

O

R N

N R

O

O

O N Alkyl O L region R N

O

Si

O

DBU, toluene, 100 oC, 12 h

O

R N

O

O

PtCl2, Ar,

K region

90 oC, 48 h yield: 38%

Si

K. Mullen et al. [33] O

O

N R R N

O

yield: 28-60% N R

O

R N

O

O

1) IBr or ICl, CH2Cl2, (Cl)Br -78 oC, 1 h; 2) hv, r.t., 24 h

Si

N R

O

Si

O

O

O

Si

Si

Zhao et al. [34, 35] Tian et al. [36]

Br(Cl)

O

N R

O

Scheme 1. Previous works on the synthesis of CDI core reported until now.

The coronene tetracarboxydiimides (CDIs) are embedded in many PDI-based systems that have been applied in high performance optoelectronic materials and as such are important building blocks to prepare.

24,25


Scheme 1 contains

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representative syntheses of CDIs.

27-36

In general these syntheses suffer from

numerous reaction steps, low yields, or lack the ability to further fuse the CDI subunits. Mullen and coworkers

27,29

prepared 1,7-bisalkynyl substituted perylene

tetracarboxydiimide, which they demonstrated could cyclize by treatment with 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU). As such, they prepared a series of CDIs with high yield up to 95-100%. Bock and coworkers obtained 30

pyrene-based CDI by a Diels-Alder reaction between maleic anhydride and pyrene at the bay-position with yield 2-10%, and this CDI system possesses L-edges not K-edges at the short molecular axis. In another study by Mullen 37

and coworkers,

33

they reported a two-step synthesis and PtCl catalyzed 2

carbocyclization to yield the first PDI-based CDI with hydrogens substituting the K region from 1,(6)7-diethinyl PDI in a yield of ~38%. More recently, 37

Zhao and coworkers

34,35

and independently Tian and coworkers developed an 36

ICl/IBr-mediated and light-facilitated cyclization procedure. They obtained CDIs with halogen and trimethylsilyl groups that can be replaced by other halogen atoms. However, these CDI derivatives still possess less versatility, such as alkyl or trimethylsilyl groups impede the coupling and aromatic ring-fusion with other building blocks. The study described here focused on a new route to CDI core. Moreover, we show that the bromination is controllable and leads to further functionalization for potential electronic materials using CDI as the subunits.

RESULTS AND DISCUTION In general, 1,(6)7-dibromoperylene-3,4,9,10-tetracarboxylic diimide is the starting material for most core-extended PDI derivatives. In our studies, 38

1,(6)7-divinyl perylene tetracarboxydiimide was obtained by Suzuki coupling between a 4:1 mixture of 1,7- and 1,6-dibromoperylene tetracarboxydiimide 1

39

and potassium vinyltrifluoroborate (Scheme 2). However, 1,(6)7-divinyl perylene tetracarboxydiimide are unstable and difficult to be isolated on silica gel under light. After flash column chromatography and recrystallization from



Page 4 of 20

acetonitrile and dichloromethane protected from light, the H NMR spectrum 1

revealed that very pure 1,7-divinyl perylene tetracarboxydiimide 2 was obtained with high yield up to 60% and the other isomer 1,6-divinyl perylene tetracarboxydiimide could not be isolated by flash column chromatography and recrystallization (Figure S1, S2, ESI†). C5H11 O

C5H11

C5H11 N

O

O

N

C5H11

C5H11

O

O

N

O

O

N

C5H11

C5H11

C5H11 O

BF3K Br

R2 R1

Pd(PPh3)4

hv, O2, I2, Toluene 48 h, 80%

K2CO3, Toluene/EtOH/ H2O, 85 oC, 5-6 h, 60%

Method A O C5H11

N

O

O

C5H11

C5H11

1 4:1 mixture of 1,7-dibromo PDI (R1=Br, R2=H) and 1,6-dibromo PDI (R1=H, R2=Br)

Scheme

2.

Suzuki-Coupling

N

3

2

reaction

between

O C5H11

a

4:1

mixture

of

1,7-

and

1,6-dibromoperylene-3,4,9,10-tetracarboxylic diimide and potassium vinyltrifluoroborate, and the CDI synthesis. Method A: photocyclization for at least 48 h.

Then the next step is the photocyclization reaction of intermediate molecule 2 (Scheme 2). A similar photocyclization reaction was performed to yield 4,5,9,10-tetrahydropyrene as the main product from 2,2'-diethenyl-1,1'-biphenyl by Laarhoven et al. and Padwa et al.

40,41

. This reaction was carried out under

ultraviolet light from a 450-W Hanovia lamp and no I was used. Then 2

dehydrogenation of 4,5,9,10-tetrahydropyrene with DDQ in benzene afforded the corresponding pyrene with high yield up to 98%.

42

The modified

photocyclization between a PDI core and an ethylene at the bay-position in toluene with I as catalyst under ultraviolet light from a 450-W Hanovia lamp 2

gives

dehydrogenated

product

with

high

yields.

25

Accordingly,

the

photocyclization of molecule 2 was carried out by adding 3.0 eq. of I and 2

purging with air under irradiation of a 450 W Hanovia medium pressure mercury lamp. This one-step route cyclizes molecule 2 and yields the CDI core 3 (Scheme 2, Method A). After 48 h under the photocyclization, pure target product 3 was obtained by silica gel column chromatography, and characterized


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by NMR (Figure S3, S4, ESI†) and MALDI-TOF mass spectrometry, with yield up to 80%. Interestingly, when we terminated the reaction under the same photocyclization condition after 12 h, no starting material was detected. But target product 3, intermediates 4 and 5 with the ratio between 3, 4 and 5 of 60:10:20 (Scheme 3, method B) in the reaction mixture was obtained. Compounds 4 (Figure S5, ESI†) and 5 (Figure S6, ESI†) could be identified and separated by silica gel preparative thin layer chromatography (TLC) and characterized by H NMR 1

spectra. When the reaction time was prolonged, 4 and 5 gradually disappeared completely and converted into target product 3 in 48 h, the same as what has been described in Method A. Meanwhile, even without separation and purification, intermediates 4 and 5 underwent dehydrogenation and transformed into 3 by refluxing the reaction mixture in toluene for 3-4 h under the 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. But this parent CDI core still suffers from difficulty to couple with other chromophores. In general, bromination is very useful to form aromatic bromides that can be used as coupling partners in the Suzuki-Miyaura coupling, Migita-Kosugi-Stille coupling, Mizoroki-Heck coupling, Sonogashira coupling and other coupling reactions. C5H11 O

N

C5H11

C5H11

O

O

N

C5H11

C5H11

O

O

hv, O2, I2,

N

C5H11

C5H11

O

O

+

N

C5H11

C5H11

O

O

N

O

N

O

O

N

C5H11

C5H11

2

O

DDQ, toluene,

+

reflux, 3-4 h, 84%

toluene,12 h, 90%

C5H11

C5H11

O

O

C5H11

C5H11

N

3

O

O

C5H11

C5H11

N

4

O

O

C5H11

C5H11

N

5

O C5H11

3

Method B, the total yield of compund 3 in two steps is 76%

Scheme 3. CDI synthesis Method B: photocyclization for 12 h then followed by oxidation by DDQ.



C5H11 O

N

C5H11

C5H11

O

O

N

C5H11

C5H11

O

O

solvent

O

N

C5H11

O

O

Br

O

O

C5H11

C5H11

3

C5H11

Br

Br2, FeCl3 or Fe(cat.)

C5H11

N

N

6

O

O

C5H11

C5H11

N

R1

Br

R2

Br

Page 6 of 20

N

C5H11

C5H11

O

O

Br

O

O

C5H11

C5H11

7 5,11-dibromo CDI (R1=Br, R2=H) 4,11-dibromo CDI (R1=H, R2=Br)

N

8

C5H11 N

O

Br

Br

Br

Br

O

O

C5H11

C5H11

N

O C5H11

9

Scheme 4. Controllable brominations of CDI 3 by tuning reaction temperature and time with FeCl catalyst. 3

Bromine is inexpensive and readily available. Stirring at room temperature or reflux with large excess of bromine in dichloromethane have proved effective for the bromination of PDI-based systems. Table 1 shows the brominations of 43

CDI at different conditions. Firstly, the usual condition without any catalyst, following the bromination of PDI bay-position, was adopted to brominate CDI 25

core at K edge (Scheme 4). After 24 h stirring in refluxing dichloromethane, the CDI remained almost unchanged 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 only got 10% of CDI monobromide 6 (entry 2). At last, FeCl catalyst was used to activate the K region of the CDI at 60 °C in 3

1,2-dichloroethane and the reaction process was monitored by TLC. After 5 h and 12 h, the ratio between 3, 6, 7 and 8 reached 5:60:35:0 and 2:25:68:5, respectively (entry 3, 4). CDI monobromide 6 and dibromide 7 were separated by silica gel column chromatography with hexane and dichloromethane as eluent. The structure of CDI monobromide 6 (Figure S7, S8 ESI†) was characterized by NMR and mass spectrometry. CDI dibromides 7 were identified as regioisomers, consist of 4,11- and 5,11- dibromide at the K region (Figure S9, S10, ESI†), which can’t be separated by silica gel column chromatography. As reaction time was extended, CDI tribromide 8 (Figure S11, S12, ESI†) and tetrabromide 9 (Figure S13, S14, ESI†) enriched at 85 °C in 1,2-dichloroethane. The reaction was terminated after 48 h and CDI tri-/tetrabromide were separated easily by silica gel column with yields of 60%


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and 20%, respectively (entry 5). While CDI core was heated at 130 °C in chlorobenzene for 24 h with 5% FeCl , the bromination was not successful and 3

the starting material decomposed (entry 6). When catalyzed by 3 eq. of iron powder in 1,2-dichloroethane under reflux, the bromination of 3 results into 9 with high yield, up to 90% (entry 7). Table 1 Controllable brominations of CDI 3 by tuning the solvents, with/without FeCl / 3

iron powder catalysts, reaction temperature and reaction time

Entry Solvent

Catalyst

a

a

Temp./°C Time/h

Ratio of 3:6:7:8:9

1

DCM

--

reflux

24

98:2:-:-:-

2

DCE

--

85

24

90:10:-:-:-

3

DCE

5% FeCl

60

5

5:60:35:-:-

4

DCE

5% FeCl

60

12

2:25:68:5:-

5

DCE

5% FeCl

85

48

-:-:20:60:20

6

Chlorobenzene 5% FeCl

130

24

Decomposed

7

DCE

12

0:0:0:0:90

3

3

3

3

3eq iron powder 85

b

Solvent: DCM dichloromethane, DCE 1,2-dichloroethane, 90% is isolated yield of 9. b

The functionalizations of CDI tetrabromide 9 were further investigated in order to obtain potential CDI-based materials by using CDI as a synthon (Scheme 5). We

found

that

CDI

tetrabromide

9

underwent

aromatic

nucleophilic substitution reactions with phenol, thiophenol or Sonogashira Coupling reaction. 10 equivalents of phenol reacted with 9 at 110 °C for 48 h in 1,4-dioxane under potassium carbonate, resulted into CDI tetraphenyl ether 10 with yield of 50%.

43-45

Similarly, CDI tetrathiophenyl sulfide 11 was obtained

with yield of 82% by using thiophenol as nucleophile and triethylamine as acid-binding agent at 80 °C in 1, 4-dioxane.

46-48

Additionally, Pd-Cu catalyzed

Sonogashira Coupling gave the CDI tetraacetylene 12, with high yield up to 80%.



C5H11 O

N

Page 8 of 20

C5H11

C5H11

O

O

OH (10 eq)

Br

Br

Br

Br

K2CO3, 1,4-dioxane, 110 oC

48 h

C5H11 N

O

O

O

O

O

50% O

N

C5H11

O

O

C5H11

C5H11

O

N

O C5H11

10

9 C5H11

N

C5H11

C5H11

O

O

SH

Br

Br

Br

Br

(10 eq)

Et3N, 1,4-dioxane, 80 oC

24 h

C5H11 N

O

S

S

S

S

82% O

N

C5H11

O

O

C5H11

C5H11

9 C5H11 O

N

C5H11

C5H11

O

O

Br

Br

Br

Br

(10 eq)

Et3N, THF, 90 oC

24 h 80%

O

N

O C5H11

11

Si

C5H11

N

C5H11 N

O

Si

Si

Si

Si

O

O

C5H11

C5H11

9

N

O C5H11

12

Scheme 5. Aromatic nucleophilic substitution and Sonogashira Coupling of CDI tetrabromide.

Figure 1. Uv-vis absorption spectra of CDI 3, CDI-monobromide 6, dibromide 7, tribromide 8 and tetrabromide 9 in dichloromethane at room temperature (Solution concentrations are 1x10 mol/L) -5

Table 2. Absorption spectra properties of CDI 3, CDI-monobromide 6, dibromide 7, tribromide 8 and tetrabromide 9 in dichloromethane at room temperature (solution concentrations are 1x10 mol/L) -5


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Entry

λ (nm)

3

494

7400

375, 396, 419, 462, 494

2.51

6

498

7000

376, 397, 421, 465, 498

2.49

7

502

6600

377, 398, 423, 469, 502

2.47

8

504

5100

379, 401, 425, 471, 504

2.46

9

506

4900

381, 403, 427, 473, 506

2.45

10

525

8035

342, 379, 402, 428, 488, 525

2.36

11

520

10060

348, 487, 522

2.38

12

537

22685

352,370,392,412,438,500,536

2.31

a

max

a

ε(M cm ) -1

-1

b

Absorption Band (nm)

E (eV) gap

The longest absorption maxima. Molar absorption coefficient at the longest absorption b

wavelength. E was calculated by the equation E = 1240/λ (eV). gap

gap

max

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 (Solution concentrations are 1x10 mol/L) -5

Figure 3. Fluorescence spectra of CDI 3, CDI-tetrabromide 9, CDI tetraphenyl ether 10,



Page 10 of 20

CDI tetrathiophenyl sulfide 11 and CDI tetraacetylene 12 in chloroform at room temperature (Solution concentrations are 1x10 mol/L) -5

The absorption and emission spectra (Figure 2 and 3) were investigated and compared between parent CDI and CDI derivatives. The absorption spectra of CDI core has been previously reported (Figure 1), with the typical vibrionic 33

fine structure in the range from 360-450 nm and S -S transitions absorption 0

1

peaks at 450-500 nm. The stepwise red-shift in the absorption spectra of about 35

4 nm was observed as increasing bromine addition at K region of CDI core (Table 2). CDI derivatives 10, 11 and 12 kept the vibrionic fine structure but exhibited obvious red-shift compared with CDI 3 and CDI tetrabromide 9. The absorption of 11 is broader compared to 10 and 12, which is also observed in other multi-sulfur molecules. Band gaps of 3, 10, 11 and 12 measured from 38

absorption maxima are 2.51 eV, 2.36 eV, 2.38 eV and 2.31 eV, respectively (Table 2). The fluorescence spectra also demonstrated defined structures and Stokes shifts. CDI derivatives 9, 10, 11 and 12 showed similar red-shift in the fluorescence spectra relative to CDI core 3. CDI tetrabromide 9 and CDI tetrathiophenol ether 11 manifested significant lower fluorescence compared with 3, 10 and 12. Notably, the fluorescence of 11 was quenched almost completely due to the strong charge-transfer interaction between electron-rich sulfur atom and electron-deficient CDI core.

49

Figure 4. Cyclic voltammetry of 3, 10, 11 and 12 (0.1 M n-Bu NPF in chloroform) at a scan rate 4

of 100 mV s . −1


6

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The electrochemistry properties of 3, 10, 11 and 12 were investigated by cyclic voltammetry (CV) in chloroform solution with Bu NPF as supporting electrolyte and 4

6

the Fc/Fc redox couple as an internal standard (Figure 4). CDI 3 and CDI derivatives +

10, 11, 12 all display two reversible reduction processes. Calculated from half-wave potentials, LUMO energy levels of 3, 10, 11 and 12 are -3.31 eV, -3.44 eV, -3.47 eV and 3.50 eV, respectively (Figure S21-24 and Table S1). HOMO energy levels of 3, 10, 11 and 12 calculated from difference values between optical band gaps (Table 2) and LUMO energy levels are -5.82 eV, 5.80 eV, -5.85 eV and 5.81 eV, respectively.

CONCLUSIONS In summary, a new method for the synthesis of CDI core chromophore was developed with cheap and nontoxic reagent and photocyclization reaction with 48% yield for two steps. The brominations of CDI core were investigated under the catalyst of FeCl and iron powder. CDI tetrabromide was obtained with high 3

yield up to 90%. The functionalizations of CDI tetrabromide were further studied in order to obtain potential CDI-based materials by using CDI as a synthon. CDI derivatives were obtained by aromatic nucleophilic substitution and Sonogashira Coupling reaction. Photophysical and electrochemical properties of CDI derivatives were discussed by absorption, emission and cyclic voltammetry spectra.

EXPERIMENTAL SECTION General Informaitons Unless otherwise noted, all materials and reagent including dry solvents were obtained from commercial suppliers and used without further purification. 1,(6)7-dibromoperylene tetracarboxydiimide were prepared according to the procedures reported in the literature. Unless otherwise noted, all work-up processing 39

and purification procedures were carried out with reagent-grade solvents in air. 1

H, and C NMR spectra were obtained from a Bruker DRX300 (300 MHz), Bruker 13

DRX400 (400 MHz) or a Bruker DMX500 (500 MHz) spectrometer. High-Resolution Mass Spectrometry (HRMS) data were obtained at the Columbia University Mass



Page 12 of 20

Spectrometry facility using a Waters XEVO G2XS instrument equipped with a 9 UPC2 SFC inlet, electrospray (ESI) and atmospheric pressure chemical (APCI) ionization, and a QTOF mass spectrometer. Absorption spectra were obtained on Shimadzu UV 1800 UV-Vis spectrophotometer. Synthesis and Characterization of Compound 2 Nitrogen was bubbled through a mixed solution of toluene (10 mL), EtOH (2 mL) and water (2 mL) for 30 min, and to this solution was added compound 1 (a 4:1 mixture of1,7- and 1,6-dibromoperylene tetracarboxydiimide) (0.86 g, 1.00 mmol), Pd(PPh )

3 4

(0.11 g, 0.10 mmol), K CO (0.55 g, 4.00 mmol) and potassium vinyltrifluoroborate 2

3

(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 with CH Cl . The organic layer was dried over 2

2

anhydrous Na SO , filtered and the solvent was removed by rotary evaporator. The 2

product

4

was

purified

by

flash

silica

gel

column

chromatography

(dichloromethane:petroleum ether = 1:2, R = 0.4) then recrystallized from acetonitrile f

and dichloromethane to give pure product 2 (0.45 g) as purple solid in 60% yield. H 1

NMR (400 MHz, CDCl ) δ 8.87 (s, 2H), 8.65 (s, 2H), 8.53-8.51 (d, 2H), 7.33-7.26 (m, 3

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). C{ H} NMR (101 MHz, 13

1

CDCl ) δ 164.9, 163.9, 137.9, 136.8, 134.5, 133.0, 132.2, 130.2, 129.6, 128.5, 127.9, 3

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 C H N O 751.4475; found 751.4470. 50

59

2

+ 4

Synthesis and Characterization of Compound 3 Method A: In a quartz photo reactor, compound 2 (1.00 g, 1.34 mmol) was dissolved in 500 mL of toluene, then iodine (1.02 g, 4.02 mmol) was added. The resultant purple solution was photo-irradiated using a 450 W medium-pressure mercury lamp for 48 hours. Toluene was removed by rotator evaporation. The residue was purified by silica gel column chromatograph (1:1 = dichloromethane: petroleum ether, R = 0.2) to f

afford compound 3 as brown solid in 80% yield. Method B: In a quartz photo reactor, compound 2 (1.00 g, 1.34 mmol) was dissolved in 500 mL of toluene, then iodine (1.02 g, 4.02 mmol) was added. The resultant purple


Page 13 of 20 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


solution was photo-irradiated using a 450 W medium-pressure mercury lamp for 12 hours. The solvent was removed under reduced pressure and the solid precipitate was collected. A portion of the reaction mixture was subjected to silica gel preparative thin layer chromatography (TLC), and brown intermediates 4 and 5 were identified by 1

H-NMR spectra. DDQ (0.55 g, 2.40 mmol) was added to the rest of this reaction

mixture in toluene (100 mL) and was heated to 115 °C for 4 h before it was quenched by saturated NaHCO solution (20 mL). The solution was extracted by CH Cl twice 3

2

2

(100 mL x 2). The combined extracts were washed with brine, and dried over MgSO . 4

After removal of solvent in vacuum, the crude material was purified by silica gel column chromatograph (1:1 = dichloromethane: petroleum ether, R = 0.2) to afford f

compound 3 as brown solid (0.76 g) in a total yield of 76% starting from compound 2. 3: H NMR (400 MHz, CDCl ) δ 9.42 (s, 4H), 8.57 (s, 4H), 5.52-5.49 (m, 2H), 1

3

2.56-2.54 (m, 4H), 2.18-2.16 (m, 4H), 1.52-1.39 (m, 24H), 0.95-0.91 (t, 12H). C{ H} 13

1

NMR (101 MHz, CDCl ) δ 165.2, 129.9, 129.3, 128.3, 128.0, 122.0, 121.4, 118.6, 3

55.2, 32.6, 31.9, 27.0, 22.8, 14.2. HRMS (ESI+) : m/z [M+H] Calculated for +

C H N O 747.4162; Found 747.4164. 50

55

2

+ 4

Intermediate 4 was obtained as brown solid by silica gel plate (2:3 = dichloromethane: petroleum ether, R = 0.3) and characterized by HNMR spectrum. H NMR (400 MHz, 1

f

1

CDCl ) 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 3

(m, 4H), 1.29-1.25 (m, 24H), 0.84-0.81(t, 12H). Intermediate 5 was obtained as brown solid by silica gel plate (1:2 = dichloromethane: petroleum ether, R = 0.3) and characterized by HNMR spectrum. H NMR (400 MHz, 1

1

f

CDCl ) 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, 3

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. Excess bromine (3 mL, 58.5 mmol) was added, followed by a few crystals of FeCl (5 mol%). 3

The solution was stirred at 60 °C. The reaction was monitored by TLC and was terminated after 5 hours. Bromine was quenched with saturated NaHSO solution (300 3

mL) and extracted with CH Cl . The combined organic layer was dried over anhydrous 2

2



Page 14 of 20

magnesium sulfate and concentrated under reduced pressure. The product was purified by silica gel column chromatography (1:2 = dichloromethane: petroleum ether, R = 0.7) to afford compound 6 as brown solid (1.71 g, 60% yield). H NMR 1

f

(400 MHz, CDCl ) δ 9.55-9.45 (d, 3H), 9.12-9.07 (d, 1H), 8.78-8.72 (d, 2H), 8.54 (s, 3

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). C{ H} NMR (101 MHz, CDCl ) δ 164.9, 163.9, 130.9, 128.8, 13

1

3

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 C H BrN O 825.3267; Found 825.3262. 50

54

2

+ 4

Synthesis and Characterization of Compound 7 Compound 3 (1.30 g, 1.73 mmol) was dissolved in 40 mL of dichloroethane. Excess bromine (2 mL, 39 mmol) was added, followed by few crystals of FeCl . The solution 3

was capped with a rubber septum and stirred at 60 °C for 12 h. The reaction was monitored by TLC and terminated when dibromide dominated. Then the mixture was cooled to room temperature. Bromine was quenched with saturated NaHSO solution 3

(300 mL) and the mixture was extracted with 200 mL of CH Cl . The combined 2

2

organic layer was dried over anhydrous magnesium sulfate and concentrated under reduced pressure. The product was purified by silica gel column chromatography (1:2 = dichloromethane: petroleum ether, R = 0.8) to afford regioisomeric dibromide f

compound 7 as brown solid (1.06 g, 68% yield). H NMR (500 MHz, CDCl ) δ 9.82 (s, 1

3

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). C{ H} NMR (101 MHz, CDCl ) 13

1

3

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 for C H Br N O 903.2372; Found 903.2375. +

50

53

2

2

4

+

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 of dichloroethane. Excess bromine (2 mL, 39 mmol) was added, followed by FeCl powder (14 mg, 0.085 mmol). The reaction 3

mixture was refluxed in 1,2-dichloroethane and monitored by TLC. After 48 h, bromine was quenched by NaHSO , and the mixture was extracted with 200 mL of 3

CH Cl . The combined organic layer was dried over anhydrous magnesium sulfate and 2

2


Page 15 of 20 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


concentrated under reduced pressure. CDI tribromide 8 and tetrabromide 9 were separated by silica gel chromatography column (chloroform: petroleum ether =1:2, R

f

= 0.8) as both brown solid, the yield is 60% and 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 eq.) was added dropwise at room temperature. The mixture was stirred at 85 °C for 12 h, then poured into ice/water. The organic phase was extracted with dichloromethane (20 mLx2), then dried with anhydrous magnesium sulfate and purified by flash silica gel column chromatography eluted with dichloromethane. The filtrate was concentrated and 9 (95 mg, yield 90%) was obtained as brown solid. 8: H NMR (400 MHz, CDCl ) δ 9.63 (s, 1H), 9.52 (s, 1H), 9.40 (s, 1H), 9.33 (s, 1H), 1

3

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). C{ H} NMR (101 MHz, CDCl ) δ 163.2, 131.9, 129.9, 13

1

3

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 C H Br N O 980.1399; -

50

51

3

2

4

Found 980.1429. 9: H NMR (400 MHz, CDCl ) δ 9.81 (s, 4H), 5.42-5.39 (m, 2H), 2.52-2.49 (m, 4H), 1

3

2.25-2.22 (m, 4H), 1.53-1.41 (m, 24H), 0.95-0.91 (t, 12H). C{ H} NMR (101 MHz, 13

1

CDCl ) 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, 3

22.9, 14.3. HRMS (MALDI-TOF, dithranol matrix): m/z [M] Calculated for -

C H Br N O 1058.0499; Found 1058.0495. 50

50

4

2

4

Synthesis and Characterization of Compound 10 Under N atmosphere, a 2 mL of anhydrous 1,4-dioxane solution of CDI tetrabromide 2

9 (106 mg, 0.1 mmol), phenol (94 mg, 1 mmol), K CO (276 mg, 2 mmol) was stirred 2

3

for 48 h at 110 C in pressure tube. After cooled to room temperature, the reaction o

mixture was evaporated and separated by silica gel chromatography column (Dichloromethane: petroleum ether = 2:3, R = 0.2). Compound 10 was obtained as f

brown solid, 56 mg (yield 50%). H NMR (400 MHz, CDCl ) δ 10.25 (s, 4H), 1

3

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). C{ H} 13


1


Page 16 of 20

NMR (126 MHz, CDCl ) δ 165.6, 164.5, 158.2, 143.0, 129.6, 127.3, 126.3, 125.5, 3

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 C H N O 1115.5244; Found +

74

71

2

+ 8

1115.5219. Synthesis and Characterization of Compound 11 Under N atmosphere, a 2 mL of anhydrous 1,4-dioxane solution of CDI tetrabromide 2

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 pressure tube. After cooled to room temperature, the o

reaction mixture was evaporated and separated by silica gel chromatography column (Dichloromethane: petroleum ether = 2:3, R = 0.3). Compound 11 was obtained as f

brown solid, 97 mg (yield 82%). H NMR (400 MHz, CDCl ) δ 10.77 (s, 4H), 1

3

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). C{ H} NMR (101 MHz, 13

1

CDCl ) δ 165.2, 164.1, 142.0, 137.9, 132.5, 132.3, 131.8, 130.2, 129.3, 128.4, 126.32, 3

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 C H N O S 1179.4297; Found 1179.4298. +

74

71

2

4

4

+

Synthesis and Characterization of Compound 12 Under N atmosphere, a 2 mL of anhydrous tetrahydrofuran solution of CDI 2

tetrabromide 9 (106 mg, 0.1 mmol), CuI (0.4 mg, 0.002 mmol), Pd(PPh ) Cl (3.5 mg, 3 2

2

0.005 mmol), trimethylsilylacetylene (282 uL, 2 mmol) and triethylamine (0.5 mL) was stirred for 24 h at 90 C in pressure tube. When cooled to room temperature, the o

reaction mixture was evaporated, then separated by silica gel chromatography column (Dichloromethane: petroleum ether = 1:2, R = 0.3). Compound 12 was obtained as f

brown solid, 90 mg (yield 80%). H NMR (400 MHz, CDCl ) δ10.35 (s, 4H), 1

3

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). C{ H} NMR (126 MHz, CDCl ) δ 165.5, 13

1

3

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 +

for C H N O Si 1131.5743; Found 1131.5731. 70

87

2

4

4

+

ASSOCIATED CONTENT Supporting Information Available


Page 17 of 20 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


The Supporting Information is available free of charge on the ACS Publications website. NMR spectra for all compounds.

AUTHOR INFORMATION Corresponding Author * E-mail: [email protected] Shengxiong Xiao: 0000-0002-9151-9558 Notes The authors declare no competing financial interest.

ACKNOWLEDGES We acknowledge financial support from National Natural Science Foundation of China (No. 21473113, 21772123 and 51502173), Program of Shanghai Academic/Technology Research Leader (No. 16XD1402700), Program for Professor of Special Appointment (Eastern Scholar) at Shanghai Institutions of Higher Learning (No. 2013-57), “Shuguang Program” supported by Shanghai Education Development Foundation and Shanghai Municipal Education Commission (14SG40), Ministry of Education of China(PCSIRT_16R49), Supported by the Programme of Introducing Talents of Discipline to Universities and International Joint Laboratory of Resource Chemistry (IJLRC). NOTES AND REFERENCES (1) Nagao, Y.; Misono, T. Synthesis and properties of N-alkyl-N ′ -aryl-3,4:9,10-perylenebis(dicarboximide). Dyes Pigments 1984, 5, 171. (2) Christie, R. M. Pigments, dyes and fluorescent brightening agents for plastics: An overview. Polym. Int. 1994, 34, 351. (3) Ma, Y.; Marszalek, T.; Yuan, Z.; Stangenberg, R.; Pisula, W.; Chen, L.; Müllen, K. A Crown Ether Decorated Dibenzocoronene Tetracarboxdiimide Chromophore: Synthesis, Sensing, and Self-Organization. Chem. - Asian J. 2015, 10, 139. (4) Takada, T.; Ido, M.; Ashida, A.; Nakamura, M.; Yamana, K. DNA-Templated Synthesis of Perylenediimide Stacks Utilizing Abasic Sites as Binding Pockets and Reactive Sites. ChemBioChem 2016, 17, 2230.



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Synthesis, Regioselective Bromination, and Functionalization of

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