Copper/β-diketone-catalysed N-arylation of carbazoles

Article abstract of DOI:10.1039/c5ra07690k

A copper-catalysed C-N bond-forming reaction of carbazoles with aryl iodides is described. Several commercially available ligands such as β-diketone and diamine, are tested in the N-arylation of carbazoles. The catalytic system generated in situ from an inexpensive copper salt, simple β-diketone and inorganic base efficiently N-arylated the carbazoles. A wide range of aryl iodides and carbazoles can be coupled to generate N-arylcarbazoles in the presence of various functional groups. However, the sterically hindered effect of aryl iodides is evident in this catalytic system. The selectivity of two iodine atoms on the aromatic ring of diiodobenzene is evaluated in the developed catalytic system. Results showed that the selectivity of diiodobenzene can be tuned by the reaction temperature.

Full text of DOI:10.1039/c5ra07690k

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DOI: 10.1039/C5RA07690K
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Copper/-Diketone-Catalysed N-Arylation of Carbazoles
Fei Chen,a Ning Liu,*a Enhui Jia and Bin Dai*a
Received 00th January 20xx,
Accepted 00th January 20xx
A copper-catalysed C–N bond-forming reaction of carbazoles with aryl iodides is described. Several commercially available
ligands such as -diketone and diamine, are tested in the N-arylation of carbazoles. The catalytic system generated in situ
from inexpensive copper salt, simple -diketone and inorganic base efficiently N-arylated the carbazoles. A wide range of
aryl iodides and carbazoles can be coupled to generate N-arylcarbazoles in the presence of various functional groups.
However, the sterically hindered effect of aryl iodides is evident in this catalytic system. The selectivity of two iodine
atoms on the aromatic ring of diiodobenzene is evaluated in the developed catalytic system. Results showed that the
DOI: 10.1039/x0xx00000x
www.rsc.org/
selectivity
of
diiodobenzene
can
be
tuned
by
the
reaction
temperature.
diamine-based ligands greatly accelerates copper-catalysed C–
N coupling reaction.19 Subsequently, Song et al. disclosed that
2,2,6,6-tetramethylheptane-3,5-dione was an efficient ligand
for copper-catalysed C–O coupling.20 Maligres et al also
recently reported a copper(II)/diketonate catalyst that showed
higher catalytic activity for C–N and C–O coupling.21 However,
few studies have reported on the copper-catalysed N-arylation
of carbazoles with aryl halides.
In this study, we report a simple and efficient method for the
synthesis of N-arylcarbazoles via copper-diketone catalyst. The
electronic and sterically hindered effect of aryl iodides and
carbazoles were investigated in the developed catalytic system.
A range of aryl iodides and carbazoles can be coupled to
generate N-arylcarbazoles, even bearing various functional
groups, such as halogen atom, that performed well under such
catalytic system. The halogenated carbazoles are of great use
and versatility in organic synthesis because they can be
converted into useful synthetic intermediates through
transition-metal-catalysed coupling.
Introduction
Carbazole is extensively applied as a building block in natural
products,1 pharmaceuticals,2 dye-sensitized solar cells,3 and
advanced material science4 because of its unique physical
properties. The absorption, light-emitting properties, and
electronic properties of carbazole can be tuned by introducing
substituents into its structure.5 The prevalence of substituted
carbazoles in organic chemistry drives the need for a new
approach to synthesize these compounds.6
Classical approaches to prepare N-arylcarbazoles include the
aromatic nucleophilic substitution reaction7 and copper-
catalysed Ullmann coupling reaction.8 These methods often
suffer from several drawbacks such as harsh reaction
conditions, the need to use stoichiometric quantities of copper,
and limited substrate scope.
Since the pioneering work of Buchwald9 and Hartwig,10
numerous studies on the palladium- and copper-catalysed C–N
bond-forming reaction have been published.11 Copper-
catalysed coupling reaction has attracted considerable interest
because copper is very inexpensive, and undergoes desirable
reactions for industrial applications. Different copper-fitted
ligands, including
diamines,14 diketone,15 imines,16 and others17 as well as
“ligand-free” systems,18 have emerged.
-Diketone and
Results and Discussion

-amino acids,12 phenanthrolines,13
The coupling reaction of iodobenzene and carbazole was
selected as the model reaction to optimize reaction conditions.
The effect of different ligands on the coupling reaction was
firstly investigated.
To prove the efficiency of ligands, we designed control
experiments by conducting the reaction in the presence of
Cu2O but in the absence of ligands. The results indicated that
the reaction was difficult to proceed with Cu2O in the absence
of ligands, and only 16% product yield was obtained. A wide

diamine derivatives are commercially available and efficient
ligands for the copper-catalysed N-arylation of aryl halides
with azoles. In 2001 Buchwald et al. found that the use of
range of
-diketone ligand was initially evaluated, and the
results showed that 2,2,6,6-tetramethylheptane-3,5-dione (L7
)
was the most efficient for iodobenzene conversion and
provided a 67% product yield. The potential catalytic efficiency
of four 1,2-ethanediamine derivatives was subsequently tested
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in the coupling of iodobenzene and carbazole. The results The nature of the base is an important factor thaVtiedweAtreticrlme Oinnleinse
DOI: 10.1039/C5RA07690K
(L14) was the efficiency of the copper-catalysed C–N bond formation
indicated that N,N'-dimethyl-1,2-ethanediamine
more catalytically active than other ethanediamine derivatives. reaction. Among potassium bases, potassium hydroxide was
L-Proline (L16) and trans-1,2-diaminocyclohexane (L17) were superior to a range of other potassium bases, with carbonate,
also examined, but poor results were obtained.
phosphate and alcoholate exhibiting lower conversion (Table 1,
entries 4 vs. 12, 13 and 14). Sodium hydroxide was superior to
other sodium salts (Table 1, entries 15 vs. 16-20). The strong
base of cesium carbonate showed lower conversion (Table 1,
entry 21).
Table 1. Optimization of Reaction Condition.[a]
Entry Solvent
Copper
Cu2O
Cu2O
Cu2O
Cu2O
CuI
Base
T (C)
90
90
90
90
90
90
90
90
90
90
90
90
90
90
90
90
90
90
90
90
90
110
130
Yield (%)[b]
trace
trace
16
1
DMA
NMP
DMSO
DMF
DMF
DMF
DMF
DMF
DMF
DMF
DMF
DMF
DMF
DMF
DMF
DMF
DMF
DMF
DMF
DMF
DMF
DMF
DMF
KOH
2
KOH
3
KOH
4
KOH
67
5
KOH
53
6
CuCl
KOH
48
7
CuSO4
Cu(OAc)2
Cu(NO3)2
CuO
KOH
20
8
KOH
39
9
KOH
30
10
11
12
13
14
15
16
17
18
19
20
21
22
23
KOH
none
24
Cu
KOH
Figure 1. Ligands for Copper-Catalysed Cross-Coupling.
Cu2O
Cu2O
Cu2O
Cu2O
Cu2O
Cu2O
Cu2O
Cu2O
Cu2O
Cu2O
Cu2O
Cu2O
K2CO3
K3PO43H2O
KtOBu
NaOH
Na2CO3
NaHCO3
NatOBu
CH3ONa
C6H5ONa
Cs2CO3
KOH
35
38
The cross-coupling of iodobenzene with carbazole was
selected as the model reaction to optimize the reaction
conditions using L7 as ligand, many solvent, copper sources,
bases and temperature were evaluated. The effect of different
solvents on the coupling between iodobenzene and carbazole
was initially examined (Table 1, entries 1-4). The results
showed that the solvent served a crucial function in the
coupling reaction. N,N-Dimethylformamide (DMF) was the
most efficient for the product formation (Table 1, entry 4).
Copper-catalysed cross-coupling is affected by the oxidation
state of the copper source. Therefore, different copper sources
[Cu(I), Cu(II) and Cu(0)] were evaluated. Cu(I) catalysts were
more catalytically active than the other copper sources. The
Cu(I) states showed moderate catalytic activity, and Cu2O
provided the best results (Table 1, entries 4 vs. 5 and 6).
Among Cu(II) sources, CuSO4, Cu(OAc)2 and Cu(NO3)2 showed
relatively higher catalytic activity than CuO (Table 1, entries 7,
8 and 9 vs. 10), and Cu(OAc)2 was superior to the other Cu(II)
sources (Table 1, entry 8 vs. 7, 9 and 10). Cu(0) powder yielded
much slower conversion (Table 1, entry 11).
33
40
21
18
25
34
30
25
89
KOH
80
[a] Reaction conditions: Iodobenzene (0.5 mmol), Carbazole (0.75 mmol),
Copper source (10 mol%), L7 (10 mol%), Base (1.0 mmol) in solvent (2 mL)
under N2. [b] Isolated yield.
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The effect of reaction temperature on cross-coupling was also
explored, and the results suggested that the product yield
increased with increasing temperature from 90 °C to 110 °C
(Table 1, entries 4 and 22). However, when temperature
reached to 130 °C, the product yield began to decrease (Table
1, entry 23). GC-MS analysis showed that small amounts of
deiodinated products were also observed. This result indicated
that an amount of iodobenzene consumption was responsible
for the decrease in efficiency. Thus, considering efficiency and
cost, 110 °C was selected as the optimized reaction
temperature and used in the following studies.
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DOI: 10.1039/C5RA07690K
The nature of the substituents bearing aryl iodides was initially
evaluated under optimized reaction conditions. The electronic
effect of para-substituents with the aromatic ring of aryl
iodides was observed. The aryl iodides containing electron-
neutral and electron-withdrawing groups such as 4-NO2, 4-F, 4-
Cl, and 4-Br, smoothly reacted with carbazole to afford the
corresponding products in good to excellent yields (Table 2,
1a-e). However, the aryl iodides containing electron-donating
group such as 4-OMe, 4-Me, and 4-OEt, were less reactive in
this system and resulted in moderate product yields (Table 2,
The scope and limitations of coupling of aryl iodides were
explored using Cu2O as catalyst, L7 as ligand, KOH as base and
DMF as solvent at 110 C (Table 2).
1f-h).
The electronic effect of meta-substituted aryl iodides
influenced the reaction rate. The reaction worked well with
aryl iodides bearing the electron-withdrawing group on the
meta-sites to afford the desired product in good yield (Table 2,
Table 2. Copper-Catalysed Coupling of Aryl Iodides.[a]
1i-k). However the aryl iodides bearing the electron-donating
group on the meta-sites, showed slightly slower conversion
(Table 2, 1l).
The coupling reaction of the aryl iodides bearing the sterically
hindered group was also examined, and the results showed
evident sterically hindered effect on the coupling reaction. The
aryl iodides bearing electron-withdrawing group on the ortho-
sites yielded a low conversion (Table 2, 1m-o), but the reaction
with those bearing electron-donating group was difficult to
trigger (Table 2, 1p).
The scope and limitations of the coupling of carbazoles were
also investigated under optimized reaction conditions (Table 3).
The electronic effect of substituents bearing the aromatic ring
of carbazoles was observed (Table 3, 2a-d). Iodobenzene
smoothly reacted with the carbazoles bearing electron-
donating 3,6-di-tert-butyl groups to give good product yields
(Table 3, 2a). However, carbazoles bearing electron-
withdrawing substituents such as 3-bromo, 3,6-dibromo and
2,7-dibromo groups, showed relatively lower reactivity in this
catalytic system (Table 3, 2b-d). Aryl iodides containing
electron-withdrawing group such as 4-Br, 4-Cl, and 4-F, reacted
with representative electron-poor, electron-neutral or
electron-rich carbazoles to provide the corresponding cross-
coupling products in moderate to good yields (Table 3, 2e-m).
Aryl iodides bearing electron-donating group showed high
reactivity with carbazoles containing electron-donating group
(Table 3, 2n and 2o), but exhibited lower reactivity with those
containing electron-withdrawing group (Table 3, 2p). In
addition, the electronic effect of meta-substituents bearing the
aromatic ring of aryl iodides was evaluated. The results
indicated that the reaction worked well with aryl iodides
bearing the electron-withdrawing group on meta-site and
carbazoles to afford the desired product in good yield (Table 3,
2q and 2r). Steric hindrance effects of aryl iodides significantly
influenced the outcome of the reaction, and the aryl iodides
bearing the steric hindrance group were difficult to react
(Table 3, 2s and 2t).
[a] Reaction conditions: Aryl iodides (0.5 mmol), Carbazole (0.75 mmol), Cu2O
(10 mol%), L7 (10 mol%), KOH (1.0 mmol) in DMF (2 mL) under N2, 110 C,
24 h. Isolated yield.
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Table 3. Copper-Catalysed Coupling of Carbazoles.[a]
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DOI: 10.1039/C5RA07690K
[a] Reaction conditions: Aryl iodides (0.5 mmol), Carbazoles (0.75 mmol), Cu2O (10 mol%), L7 (10 mol%), KOH (1.0 mmol) in DMF (2 mL) under N2, 130 C,
24 h. Isolated yield.
Optimized reaction conditions were also applied in the and 8). We inferred that high temperature was responsible for
coupling between diiodobenzene and carbazole, in which the the poor results. Therefore, the lower temperature of 90 °C
selectivity of two iodine atoms on the aromatic ring was was used to test the selectivity of diiodobenzenes. As expected,
evaluated (Table 4). The electronic effect of substituents the coupling of para-diiodobenzene or meta-diiodobenzene
bearing the aromatic ring of carbazoles was initially explored. with 3,6-di-tert-butyl carbazole proceeded smoothly and
Carbazoles bearing electron-donating group showed higher resulted in moderate product yield (Table 4, entries 6 and 9).
reactivity than those bearing electron-withdrawing or -neutral At
a
higher temperature, the coupling between 3-
group. For the carbazoles bearing electron-withdrawing or - bromocarbazole and meta-diiodobenzene was also prone to
neutral group, the selectivity for single coupling over double undergo double C–N coupling to give 78% yield of the
coupling was remarkably strong, and the product of single disubstituted product (Table 4, entry 10). Single coupling
coupling was obtained in good yield (Table 4, entries 1-4). resulted in 51% yield of product when the reaction
However, carbazoles bearing electron-donating group temperature was reduced to 90 °C (Table 4, entry 10). These
exhibited poor selectivity on either para-diiodobenzene or results indicated that the distribution of products was tuned
meta-diiodobenzene. NMR analysis showed varying amounts by the reaction temperature.
of disubstituted and deiodinated products (Table 4, entries 5
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Table 4. Copper-Catalysed Coupling of Diiodobenzene.[a]
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DOI: 10.1039/C5RA07690K
8
9
2a, 15%
Entry
Aryl iodides
Products
1
10
2
11
3
12
4
13
5
14
6
[a] Reaction conditions: Aryl iodides (0.5 mmol), Carbazole (0.75 mmol),
Cu2O (10 mol%), L7 (10 mol%), KOH (1.0 mmol) in DMF (2 mL) under N2,
130 C, 24 h. Isolated yield. [b] 90 C. [c] 110 C. [d] 3.0 equiv. Carbazole.
[e] without Cu2O.
7
Furthermore, the selective coupling of poly-halogenated
benzene with carbazole was investigated in this copper/-
diketone catalytic system. The fluorine and iodine atoms on
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the benzene ring of 1-bromo-2-fluoro-4-iodobenzene showed mechanism;23 (3) radical mechanism.24 The first mechanism
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similar reactivity and provided disubstituted product (Table 4, has well explained the phenomena obsDerOvIe: 1d0.1in03o9/uCr5RrAe0a7c6t9io0nK
entry 13). Given that the formation of disubstituted product process. For example, the halogen displacement order of aryl
required 2.0 equiv. of carbazoles, a 3.0 equiv. of carbazoles halides is
 > Br > Cl, and aryl halides bearing electron-
was used to obtain higher product yield (Table 4, entry 13). To withdrawing group showed relatively high reactivity than
probe the main factors responsible for the selectivity of the those bearing electron-donating group. On the basis of
fluoride group bearing benzene ring, control experiments were oxidative addition/reductive elimination mechanism,
designed in the absence of Cu2O (Table 4, entry 14). The proposed mechanism for N-arylation of carbazole is depicted
control experiment revealed that the 1-bromo-2-fluoro-4- in Figure 3. The reaction proceeds via copper( ) complex
iodobenzene underwent highly selective coupling at the which is in situ generated through coordination of copper(
fluoride group with carbazole through nucleophilic oxide with -diketone. The subsequent oxidative addition of
substitution reaction in the copper-free condition. We copper( ) complex
a

I,

)


I
with Ph

occurs to form copper(
)
)
)
supposed that the bromide group at the position ortho to the complex II. And then transmetalation between copper(
fluoride group activated C–F bond through the effect of complex II and carbazole takes place to afford a copper(
electron-withdrawing, the effect was responsible for the complex III. At last, copper() complex III proceeds reductive
selectivity of fluoride group. elimination to provide the desired product IV while
Halogens, such as chlorine, bromine and iodine, on the simultaneously releasing active copper( ) complex
aromatic ring are well tolerated in the developed copper/

I.

-
diketone catalytic system. This characteristic provides an
opportunity to further functionalize the N-arylated carbazole
compounds and convert them into useful pharmaceutical, dye-
sensitized solar cells and advanced material intermediates. We
selected the obtained 9-(4-iodophenyl)-carbazole as model
substrate to explore its reactivity on a series of transition-
metal-catalysed cross-coupling reaction. Figure 2 illustrates
that 9-(4-iodophenyl)-carbazole was successfully converted
into valuable intermediates via classical transition-metal-
catalysed Suzuki coupling, Ullmann-type reaction, and
Sonogashira coupling.
Figure 3. Proposed mechanism for N-arylation of carbazole.
Experimental
General Experimental Methods. All reactions were performed in
Schlenk tubes under nitrogen atmosphere. DMF, DMSO, DMA, and
NMP were distilled from 4Å-molecular sieves. All solvents and
reagents were purchased from Alfa Aesar, Acros and Adamas-beta.
NMR spectra were recorded on a Varian Inova-400 or a Bruke
Avance III HD 400 spectrometer using TMS as internal standard (400
MHz for 1H NMR, 100 MHz for 13C NMR and 376 MHz for 19F NMR).
The Mass data of the compounds were collected on a Bruker
ultrafleXtreme mass spectrometer. All products were isolated by
short chromatography on a silica gel (200–300 mesh) column.
Figure 2. Functionalization of 9-(4-iodophenyl)-carbazole.
The mechanism for the copper-catalysed C–N bond-forming
reaction has been well summarized by Ma.12b Three studies
toward elucidation of the mechanism for the Ullmann-type
coupling reactions have been reported: (1) oxidative
General Procedure for N-Arylation of Carbazoles. A mixture of aryl
iodides (0.5 mmol), carbazoles (0.75 mmol), copper sources (0.05
mmol), ligand (0.05 mmol) and base (1.0 mmol) in solvent (2 mL)
was allowed to react under nitrogen atmosphere. The reaction
addition/reductive elimination mechanism;22 (2)
–complex
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mixture was heated to the specified temperature for 24 h. After MHz, CDCl3): δ 141.10, 137.39, 135.04, 130.49, 127.03, 125.88,
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reaction, the reaction mixture was added to brine (15 mL) and 123.27, 120.29, 119.75, 109.82, 21.28, ppm.DOI: 10.1039/C5RA07690K
extracted three times with dichloromethane (3×15 mL). The solvent
was concentrated under vacuum and the product was isolated by 9-(4-Ethoxyphenyl)-9H-carbazole (1h). Purification by flash
short chromatography on a silica gel (200–300 mesh) column.
chromatography (petroleum ether): a white solid (83 mg, 61%), mp
= 120 °C; H NMR (400 MHz, CDCl3): δ 8.14 (d, J = 7.6 Hz, 2H), 7.44-
1
9-Phenyl-9H-carbazole (1a).25 Purification by flash chromatography 7.38 (m, 4H), 7.33-7.25 (m, 4H), 7.09 (d, J = 8.4 Hz, 2H), 4.13 (q, J =
(petroleum ether): a white solid (108 mg, 89%), mp = 82-83 °C; H 6.8 Hz, 2H), 1.49 (t, J = 6.8 Hz, 2H), ppm; 13C NMR (100 MHz, CDCl3):
1
NMR (400 MHz, CDCl3): δ 8.19 (d, J = 8.0 Hz, 2H), 7.66-7.59 (m, 4H), δ 158.24, 141.37, 130.10, 128.53, 125.80, 123.07, 120.21, 119.58,
7.52-7.48 (m, 1H), 7.46-7.42 (m, 4H), 7.36-7.29 (m, 2H), ppm; 13C 115.55, 109.69, 63.82, 14.88, ppm.
NMR (100 MHz, CDCl3): δ 140.94, 137.76, 129.90, 127.48, 127.19,
125.96, 123.39, 120.34, 119.94, 109.81, ppm.
9-(3-Fluorophenyl)-9H-carbazole (1i). Purification by flash
chromatography (petroleum ether): a white solid (115 mg, 88%),
1
9-(4-Nitrophenyl)-9H-carbazole (1b).26 Purification by flash mp = 78-79 °C; H NMR (400 MHz, CDCl3): δ 8.18 (dt, J = 7.6 Hz, J =
chromatography (petroleum ether): a yellow solid (117 mg, 81%), 0.8 Hz, 2H), 7.63-7.58 (m, 1H), 7.50-7.41 (m, 5H), 7.38-7.32 (m, 3H),
1
mp = 172-173 °C; H NMR (400 MHz, CDCl3): δ 8.48 (d, J = 8.8 Hz, 7.21 (ddd, J = 8.4 Hz, J = 2.8 Hz, J = 1.2 Hz, 1H), ppm; 13C NMR (100
2H), 8.15 (d, J = 7.6 Hz, 2H), 7.80 (d, J = 8.8 Hz, 2H), 7.51-7.43 (m, MHz, CDCl3): δ 163.47 (d, JC-F = 246.6 Hz), 140.56, 139.34 (d, JC-F
=
4H), 7.35 (t, J = 7.2 Hz, 2H), ppm; 13C NMR (100 MHz, CDCl3): δ 9.8 Hz), 131.08 (d, JC-F = 9.2 Hz), 126.16, 123.59, 122.73 (d, JC-F = 3.2
144.78, 142.82, 138.81, 125.70, 125.44, 124.49, 123.13, 120.17, Hz), 120.44, 120.36, 114.52 (d, JC-F = 7.1 Hz), 114.30 (d, JC-F = 8.8 Hz),
119.59, 108.57, ppm.
109.73, ppm; 19F NMR (376 MHz, CDCl3): δ -110.46, ppm; HRMS
(MALDI): m/z calcd for C18H12FN [M]+ 261.0948, found 261.0947.
9-(4-Fluorophenyl)-9H-carbazole (1c).25 Purification by flash
chromatography (petroleum ether): a white solid (102 mg, 78%), 9-(3-Bromophenyl)-9H-carbazole (1j).27 Purification by flash
1
mp = 113-115 °C; H NMR (400 MHz, CDCl3): δ 8.15-8.13 (m, 2H), chromatography (petroleum ether): a colorless oil (135 mg, 84%);
7.54-7.49 (m, 2H), 7.43-7.39 (m, 2H), 7.33-7.24 (m, 6H), ppm; 13C 1H NMR (400 MHz, CDCl3): δ 8.09 (d, J = 7.6 Hz, 2H), 7.70 (s, 1H),
NMR (100 MHz, CDCl3): δ 161.60 (d, JC-F = 245.8 Hz), 141.07, 133.66 7.54 (d, J = 8.0 Hz, 1H), 7.46 (d, J = 7.6 Hz, 1H), 7.41-7.37 (m, 5H),
(d, JC-F = 2.9 Hz), 129.05 (d, JC-F = 8.5 Hz), 126.05, 123.32, 120.39, 7.28-7.25 (m, 2H), ppm; 13C NMR (100 MHz, CDCl3): δ 140.59,
120.04, 116.88 (d, JC-F = 22.6 Hz), 109.55, ppm; 19F NMR (376 MHz, 139.17, 131.16, 130.54, 130.17, 126.19, 125.75, 123.60, 123.28,
CDCl3): δ -113.66, ppm.
120.46, 120.41, 109.67, ppm.
9-(4-Chlorophenyl)-9H-carbazole (1d).25 Purification by flash 9-(3-Chlorophenyl)-9H-carbazole (1k).25 Purification by flash
chromatography (petroleum ether): a white solid (104 mg, 75%), chromatography (petroleum ether): a pale yellow oil (106 mg, 76%);
1
mp = 144-147 °C; H NMR (400 MHz, CDCl3): δ 8.13 (d, J = 8.0 Hz, 1H NMR (400 MHz, CDCl3): δ 8.09 (d, J = 7.6 Hz, 2H), 7.54 (t, J = 1.6
2H), 7.56 (d, J = 8.0 Hz, 2H), 7.49 (d, J = 8.0 Hz, 2H), 7.43-7.35 (m, Hz, 1H), 7.47-7.36 (m, 7H), 7.29-7.22 (m, 2H), ppm; 13C NMR (100
4H), 7.31-7.23 (m, 2H), ppm; 13C NMR (100 MHz, CDCl3): δ 140.68, MHz, CDCl3): δ 140.43, 138.88, 135.29, 130.75, 127.46, 127.12,
136.25, 133.01, 130.10, 128.39, 126.05, 123.44, 120.37, 120.17, 126.04, 125.10, 123.45, 120.31, 120.25, 109.54, ppm.
109.53, ppm.
9-(m-Tolyl)-9H-carbazole (1l). Purification by flash chromatography
1
9-(4-Bromophenyl)-9H-carbazole (1e).5c Purification by flash (petroleum ether): a yellow oil (85 mg, 66%); H NMR (400 MHz,
chromatography (petroleum ether): a pale yellow solid (153 mg, CDCl3): δ 8.22 (dt, J = 7.6 Hz, J = 0.8 Hz, 2H), 7.55 (t, J = 8.0 Hz, 1H),
95%), mp = 143-146 °C; 1H NMR (400 MHz, CDCl3): δ 8.12 (d, J = 8.0 7.51-7.43 (m, 6H), 7.39-7.33 (m, 3H), ppm; 13C NMR (100 MHz,
Hz, 2H), 7.69 (d, J = 8.0 Hz, 2H), 7.42-7.34 (m, 6H), 7.29-7.26 (m, 2H), CDCl3): δ 141.01, 139.94, 137.67, 129.68, 128.29, 127.73, 125.91,
ppm; 13C NMR (100 MHz, CDCl3): δ 139.57, 135.76, 132.07, 127.68, 124.21, 123.36, 120.32, 119.85, 109.90, 21.51, ppm; HRMS (MALDI):
125.04, 122.44, 119.85, 119.35, 119.17, 108.51, ppm.
m/z calcd for C19H15N [M]+ 257.1199, found 257.1201.
9-(4-Methoxyphenyl)-9H-carbazole (1f).25 Purification by flash 9-(2-Fluorophenyl)-9H-carbazole (1m). Purification by flash
1
chromatography (petroleum ether): a white solid (94 mg, 69%), mp chromatography (petroleum ether): a yellow oil (46 mg, 35%); H
1
= 139-140 °C; H NMR (400 MHz, CDCl3): δ 8.14 (d, J = 7.6 Hz, 2H), NMR (400 MHz, CDCl3): δ 8.18 (dt, J = 8.0 Hz, J = 0.8 Hz, 2H), 7.60 (td,
7.45-7.37 (m, 4H), 7.33-7.24 (m, 4H), 7.10 (d, J = 8.8 Hz, 2H), 3.90 (s, J = 8.0 Hz, J = 1.6 Hz, 1H), 7.55-7.50 (m, 1H), 747-7.37 (m, 4H), 7.35-
3H), ppm; 13C NMR (100 MHz, CDCl3): δ 158.83, 141.35, 130.28, 7.31 (m, 2H), 7.27 (dt, J = 8.0 Hz, J = 0.8 Hz, 2H), ppm; 13C NMR (100
128.55, 125.81, 123.08, 120.22, 119.61, 115.04, 109.67, 55.58, ppm. MHz, CDCl3): δ 158.36 (d, JC-F = 251.4 Hz), 140.85, 129.88 (d, JC-F
=
1.2 Hz), 129.61 (d, JC-F = 7.6 Hz), 126.05, 125.10 (d, JC-F = 3.9 Hz),
9-(p-Tolyl)-9H-carbazole
(1g).25
Purification
by
flash 123.55, 120.33, 120.18, 117.39 (d, JC-F = 19.6 Hz), 109.89 (d, JC-F =
chromatography (petroleum ether): a white solid (82 mg, 64%), mp 1.5 Hz), ppm; 19F NMR (376 MHz, CDCl3): δ -118.46, ppm; HRMS
= 105 °C; H NMR (400 MHz, CDCl3): δ 8.14 (d, J = 7.6 Hz, 2H), 7.45- (MALDI): m/z calcd for C18H12FN [M]+ 261.0948, found 261.0947.
1
7.36 (m, 8H), 7.29-7.25 (m, 2H), 2.49 (s, 3H), ppm; 13C NMR (100
This journal is © The Royal Society of Chemistry 20xx
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ARTICLE
Journal Name
9-(2-Chlorophenyl)-9H-carbazole (1n).28 Purification by flash 8.08 (d, J = 8.0 Hz, 1H), 7.74 (d, J = 8.0 Hz, 2H), 7.50V-i7ew.4A0rt(icmle,O4nHlin)e,
13
DOI: 10.1039/C5RA07690K
chromatography (petroleum ether): a pale yellow solid (38 mg, 7.36-7.29 (m, 2H), 7.23 (d, J = 8.0 Hz, 1H), ppm; C NMR (100 MHz,
27%), mp = 98-99 °C; 1H NMR (400 MHz, CDCl3): δ 8.13 (d, J = 7.6 Hz, CDCl3): δ 140.95, 139.30, 136.32, 133.25, 128.76, 128.64, 126.83,
2H), 7.66-7.64 (m, 1H), 7.49-7.42 (m, 3H), 7.38 (t, J = 8.0 Hz, 2H), 125.23, 123.15, 122.40, 121.31, 120.62, 120.57, 112.98, 111.03,
7.27 (t, J = 8.0 Hz, 2H), 7.08 (d, J = 8.4 Hz, 2H), ppm; 13C NMR (100 109.78, ppm.
MHz, CDCl3): δ 139.80, 133.98, 132.67, 129.96, 129.79, 128.71,
127.01, 124.87, 122.24, 119.26, 118.94, 108.90, ppm.
3,6-Dibromo-9-(4-bromophenyl)-9H-carbazole (2g).8a Purification
by flash chromatography (petroleum ether): a white solid (127 mg,
1
9-(2-Bromophenyl)-9H-carbazole (1o).29 Purification by flash 53%), mp = 217-218 °C; H NMR (400 MHz, CDCl3): δ 8.19 (s, 2H),
chromatography (petroleum ether): a white solid (66 mg, 41%), mp 7.74 (d, J = 8.0 Hz, 2H), 7.51 (d, J = 8.0 Hz, 2H), 7.38 (d, J = 8.0 Hz,
= 95-96 °C; 1H NMR (400 MHz, CDCl3): δ 8.14 (d, J = 8.0 Hz, 2H), 7.84 2H), 7.22 (d, J = 8.0 Hz, 2H), ppm; 13C NMR (100 MHz, CDCl3): δ
(dd, J = 8.0 Hz, J = 1.2 Hz, 1H), 7.52-7.43 (m, 2H), 7.39 (t, J = 8.0 Hz, 139.62, 135.85, 133.39, 129.56, 128.56, 124.06, 123.33, 121.72,
3H), 7.28 (t, J = 8.0 Hz, 2H), 7.06 (d, J = 8.0 Hz, 2H), ppm; 13C NMR 113.37, 111.28, ppm.
(100 MHz, CDCl3): δ 140.79, 136.69, 134.18, 131.09, 130.10, 128.77,
125.89, 123.79, 123.20, 120.31, 119.94, 109.98, ppm.
2,7-Dibromo-9-(4-bromophenyl)-9H-carbazole (2h).34 Purification
by flash chromatography (petroleum ether): a white solid (113 mg,
3,6-Di-tert-butyl-9-phenyl-9H-carbazole (2a).30 Purification by flash 47%), mp = 190-192 °C; 1H NMR (400 MHz, CDCl3): δ 7.94 (d, J = 8.0
chromatography (petroleum ether): a white solid (135 mg, 76%), Hz, 2H), 7.77 (d, J = 8.0 Hz, 2H), 7.46-7.38 (m, 6H), ppm; 13C NMR
1
mp = 155 °C; H NMR (400 MHz, CDCl3): δ 8.23 (d, J = 1.6 Hz, 2H), (100 MHz, CDCl3): δ 141.63, 135.48, 133.55, 128.72, 123.92, 122.07,
7.66-7.61 (m, 4H), 7.54-7.46 (m, 3H), 7.42 (d, J = 8.8 Hz, 2H), 1.54 (s, 121.80, 121.55, 120.13, 112.87, ppm.
18H), ppm; 13C NMR (100 MHz, CDCl3): δ 142.84, 139.33, 138.26,
129.79, 127.01, 126.83, 123.63, 123.39, 116.26, 109.25, ppm.
3-Bromo-9-(4-chlorophenyl)-9H-carbazole (2i). Purification by flash
chromatography (petroleum ether): a white solid (75 mg, 42%), mp
1
3-Bromo-9-phenyl-9H-carbazole (2b).31 Purification by flash = 131-133 °C; H NMR (400 MHz, CDCl3): δ 8.22 (s, 1H), 8.05 (d, J =
chromatography (petroleum ether): a white solid (87 mg, 54%), mp 8.0 Hz, 1H), 7.55 (d, J = 8.0 Hz, 2H), 7.47-7.40 (m, 4H), 7.33-7.27 (m,
= 75-76 °C; 1H NMR (400 MHz, CDCl3): δ 8.30 (d, J = 1.2 Hz, 1H), 8.13 2H), 7.19 (d, J = 8.0 Hz, 1H), ppm; 13C NMR (100 MHz, CDCl3): δ
(d, J = 8.0 Hz, 1H), 7.64 (t, J = 8.0 Hz, 2H), 7.57-7.51 (m, 4H), 7.48- 139.95, 138.29, 134.71, 132.34, 129.18, 127.68, 127.24, 125.75,
7.42 (m, 2H), 7.36-7.30 (m, 2H), ppm; 13C NMR (100 MHz, CDCl3): δ 124.13, 122.07, 121.30, 119.53, 119.51, 111.90, 109.95, 108.71,
141.25, 139.58, 137.28, 130.03, 128.63, 127.80, 127.07, 126.72, ppm; HRMS (MALDI): m/z calcd for C18H11BrClN [M]+ 354.9758,
125.14, 123.09, 122.32, 120.53, 120.37, 112.73, 111.30, 110.05, found 354.9751.
ppm.
3,6-Dibromo-9-(4-chlorophenyl)-9H-carbazole (2j).35 Purification by
3,6-Dibromo-9-phenyl-9H-carbazole (2c).32 Purification by flash flash chromatography (petroleum ether): a white solid (105 mg,
1
chromatography (petroleum ether): a white solid (66 mg, 33%), mp 48%), mp = 214-216 °C; H NMR (400 MHz, CDCl3): δ 8.19 (s, 2H),
= 164 °C; 1H NMR (400 MHz, CDCl3): δ 8.22 (s, 2H), 7.64 (t, J = 7.2 Hz, 7.59 (d, J = 8.0 Hz, 2H), 7.51 (d, J = 8.0 Hz, 2H), 7.44 (d, J = 8.0 Hz,
2H), 7.53-7.51 (m, 5H), 7.27 (d, J = 8.8 Hz, 2H), ppm; 13C NMR (100 2H), 7.21 (d, J = 8.0 Hz, 2H), ppm; 13C NMR (100 MHz, CDCl3): δ
MHz, CDCl3): δ 139.87, 136.79, 130.12, 129.38, 128.11, 126.96, 139.71, 135.32, 133.85, 130.40, 129.54, 128.26, 124.03, 123.32,
123.93, 123.21, 113.05, 111.51, ppm.
113.34, 111.28, ppm.
2,7-Dibromo-9-phenyl-9H-carbazole (2d).31 Purification by flash 2,7-Dibromo-9-(4-chlorophenyl)-9H-carbazole (2k). Purification by
chromatography (petroleum ether): a white solid (52 mg, 26%), mp flash chromatography (petroleum ether): a white solid (85 mg, 39%),
1
1
= 184-185 °C; H NMR (400 MHz, CDCl3): δ 7.97 (d, J = 8.4 Hz, 2H), mp = 166-168 °C; H NMR (400 MHz, CDCl3): δ 7.94 (d, J = 8.0 Hz,
7.69-7.64 (m, 2H), 7.57-7.51 (m, 5H), 7.42 (dd, J = 8.0 Hz, J = 1.6 Hz, 2H), 7.62 (d, J = 8.0 Hz, 2H), 7.46-7.40 (m, 6H), ppm; 13C NMR (100
2H), ppm; 13C NMR (100 MHz, CDCl3): δ 141.90, 136.44, 130.28, MHz, CDCl3): δ 141.71, 134.94, 134.18, 130.56, 128.43, 123.89,
128.39, 127.12, 123.62, 121.68, 121.47, 120.00, 113.04, ppm.
121.77, 121.55, 120.11, 112.87, ppm; HRMS (MALDI): m/z calcd for
C18H10Br2ClN [M]+ 432.8863, found 432.8859.
9-(4-Bromophenyl)-3,6-di-tert-butyl-9H-carbazole
(2e).33
Purification by flash chromatography (petroleum ether): a white 3,6-Di-tert-butyl-9-(4-fluorophenyl)-9H-carbazole (2l). Purification
1
solid (165 mg, 76%), mp = 158-159 °C; H NMR (400 MHz, CDCl3): δ by flash chromatography (petroleum ether): a pale yellow solid (99
8.13 (d, J = 2.0 Hz, 2H), 7.71 (dt, J = 8.8 Hz, J = 2.8 Hz, 2H), 7.48-7.42 mg, 53%), mp = 192-193 °C; 1H NMR (400 MHz, CDCl3): δ 8.15 (dd, J
(m, 4H), 7.32 (dt, J = 8.4 Hz, J = 0.4 Hz, 2H), 1.47 (s, 18H), ppm; 13C = 1.6 Hz, J = 0.4 Hz, 2H), 7.53-7.49 (m, 2H), 7.47 (dd, J = 8.4 Hz, J =
NMR (100 MHz, CDCl3): δ 143.15, 138.93, 137.27, 132.95, 128.28, 2.0 Hz, 2H), 7.30-7.25 (m, 4H), 1.47 (s, 18H), ppm; 13C NMR (100
123.71, 123.46, 120.24, 116.30, 108.96, 34.73, 31.98, ppm.
MHz, CDCl3): δ 161.29 (d, JC-F = 245.5 Hz), 142.86, 139.36, 134.05 (d,
JC-F = 2.9 Hz), 128.56 (d, JC-F = 8.4 Hz), 123.60, 123.20, 116.65 (d, JC-F
3-Bromo-9-(4-bromophenyl)-9H-carbazole (2f).29 Purification by = 22.6 Hz), 116.22, 108.86, 34.69, 31.96, ppm; 19F NMR (376 MHz,
flash chromatography (petroleum ether): a white solid (130 mg, CDCl3): δ -36.65 – -36.72 (m), ppm; HRMS (MALDI): m/z calcd for
1
65%), mp = 138-139 °C; H NMR (400 MHz, CDCl3): δ 8.24 (s, 1H), C26H28FN [M]+ 373.2200, found 373.2199.
8 | J. Name., 2012, 00, 1-3
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RSC Advances
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Journal Name
3,6-Dibromo-9-(4-fluorophenyl)-9H-carbazole (2m). Purification by 9-(2-Bromophenyl)-3,6-di-tert-butyl-9H-carbazole
ARTICLE
(2s).39
View Article Online
DOI: 10.1039/C5RA07690K
flash chromatography (petroleum ether): a white solid (124 mg, Purification by flash chromatography (petroleum ether): a white
1
1
59%), mp = 164-166 °C; H NMR (400 MHz, CDCl3): δ 8.19 (dd, J = solid (137 mg, 63%), mp = 173-174 °C; H NMR (400 MHz, CDCl3): δ
2.0 Hz, J = 0.4 Hz, 2H), 7.51 (dd, J = 8.8 Hz, J = 2.0 Hz, 2H), 7.48-7.45 8.20 (d, J = 2.0 Hz, 2H), 7.89 (dd, J = 8.0 Hz, J = 2.0 Hz, 1H), 7.55-7.38
(m, 2H), 7.33-7.29 (m, 2H), 7.17 (dd, J = 8.4 Hz, J = 0.4 Hz, 2H), ppm; (m, 5H), 7.03 (d, J = 8.4 Hz, 2H), 1.51 (s, 18H), ppm.
13C NMR (100 MHz, CDCl3): δ 161.95 (d, JC-F = 247.4 Hz), 140.01,
132.67 (d, JC-F = 3.2 Hz), 129.46, 128.91 (d, JC-F = 8.7 Hz), 123.86, 9-(4-Iodophenyl)-9H-carbazole (3a).40 Purification by flash
123.25, 117.14 (d, JC-F = 22.8 Hz), 113.16, 111.24, ppm; 19F NMR chromatography (petroleum ether): a white solid (98 mg, 53%), mp
1
(376 MHz, CDCl3): δ -34.72 – -34.79 (m), ppm; HRMS (MALDI): m/z = 133-135 °C; H NMR (400 MHz, CDCl3): δ 8.13 (dt, J = 8.0 Hz, J =
calcd for C18H10Br2FN [M]+ 416.9159, found 416.9159.
1.2 Hz, 2H), 7.95-7.91 (m, 2H), 7.44-7.37 (m, 4H), 7.35-7.28 (m, 4H),
ppm; 13C NMR (100 MHz, CDCl3): δ 140.50, 139.07, 137.50, 128.92,
3,6-Di-tert-butyl-9-(p-tolyl)-9H-carbazole (2n).36 Purification by 126.06, 123.50, 120.37, 120.21, 109.55, 92.02, ppm.
flash chromatography (petroleum ether): a yellow oil (148 mg,
80%); 1H NMR (400 MHz, CDCl3): δ 8.22 (d, J = 1.2 Hz, 2H), 7.53-7.47 3-Bromo-9-(4-iodophenyl)-9H-carbazole (3b). Purification by flash
(m, 4H), 7.43 (d, J = 8.0 Hz, 2H), 7.38 (d, J = 8.0 Hz, 2H), 2.53 (s, 3H), chromatography (petroleum ether): a white solid (105 mg, 47%),
1.54 (s, 18H), ppm; 13C NMR (100 MHz, CDCl3): δ 142.64, 139.51, mp = 171-172 °C; 1H NMR (400 MHz, CDCl3): δ 8.23 (s, 1H), 8.07 (d, J
136.86, 135.55, 130.40, 126.71, 123.56, 123.27, 116.23, 109.26, = 8.0 Hz, 1H), 7.92 (d, J = 8.0 Hz, 2H), 7.49-7.41 (m, 2H), 7.36-7.22
34.79, 32.12, 21.28, ppm.
(m, 5H), ppm; 13C NMR (100 MHz, CDCl3): δ 140.84, 139.20, 137.01,
128.81, 128.74, 126.81, 125.24, 123.13, 122.41, 120.62, 120.56,
(2o).37 112.99, 111.03, 109.78, 92.47, ppm; HRMS (MALDI): m/z calcd for
3,6-Di-tert-butyl-9-(4-methoxyphenyl)-9H-carbazole
Purification by flash chromatography (petroleum ether): a white C18H11BrIN [M]+ 446.9114, found 446.9112.
solid (176 mg, 91%), mp = 160 °C; 1H NMR (400 MHz, CDCl3): δ 8.17
(dd, J = 2.0 Hz, J = 0.8 Hz, 2H), 7.49-7.45 (m, 4H), 7.29 (d, J = 8.8 Hz, 3,6-Dibromo-9-(4-iodophenyl)-9H-carbazole (3c).40 Purification by
2H), 7.14-7.10 (m, 2H), 3.94 (s, 3H), 1.50 (s, 18H), ppm; 13C NMR flash chromatography (petroleum ether): a white solid 142 mg,
1
(100 MHz, CDCl3): δ 158.54, 142.49, 139.77, 130.83, 128.27, 123.49, 54%), mp = 188-190 °C; H NMR (400 MHz, CDCl3): δ 8.19 (s, 2H),
123.04, 116.17, 114.95, 109.07, 55.59, 34.73, 32.06, ppm.
7.94 (d, J = 8.0 Hz, 2H), 7.51 (d, J = 8.0 Hz, 2H), 7.22 (d, J = 8.0 Hz,
4H), ppm; 13C NMR (100 MHz, CDCl3): δ 139.53, 139.36, 136.56,
3-Bromo-9-(p-tolyl)-9H-carbazole (2p).38 Purification by flash 129.55, 128.74, 124.09, 123.32, 113.38, 111.29, 92.93, ppm.
chromatography (petroleum ether): a white solid (69 mg, 41%), mp
1
= 152-153 °C; H NMR (400 MHz, CDCl3): δ 8.27 (d, J = 1.6 Hz, 1H), 2,7-Dibromo-9-(4-iodophenyl)-9H-carbazole (3d).41 Purification by
8.11 (d, J = 7.6 Hz, 1H), 7.51-7.38 (m, 7H), 7.33-7.25 (m, 2H), 2.52 (s, flash chromatography (petroleum ether): a white solid (145 mg,
1
3H), ppm; 13C NMR (100 MHz, CDCl3): δ 141.40, 139.74, 137.76, 55%), mp = 207-208 °C; H NMR (400 MHz, CDCl3): δ 7.98-7.92 (m,
134.54, 130.59, 128.52, 126.91, 126.59, 124.98, 122.99, 122.17, 4H), 7.46 (s, 2H), 7.41 (d, J = 8.0 Hz, 2H), 7.26 (d, J = 8.0 Hz, 2H),
120.44, 120.15, 21.17, ppm.
ppm; 13C NMR (100 MHz, CDCl3): δ 141.54, 139.52, 136.19, 128.89,
123.93, 121.83, 121.55, 120.13, 112.88, 93.32, ppm.
3-Bromo-9-(3-bromophenyl)-9H-carbazole (2q).29 Purification by
flash chromatography (petroleum ether/EtOAc = 40:1): a white solid 1,4-Bis(3,6-di-tert-butyl-9H-carbazol-9-yl)benzene
(3e).42
(124 mg, 62%), mp = 80-82 °C; 1H NMR (400 MHz, CDCl3): δ 8.24 (s, Purification by flash chromatography (petroleum ether): a white
1
1H), 8.07 (d, J = 8.0 Hz, 1H), 7.70 (s, 1H), 7.63-7.59 (m, 1H), 7.50- solid (184 mg, 58%), mp = 297-298 °C; H NMR (400 MHz, CDCl3): δ
7.25 (m, 7H), ppm; 13C NMR (100 MHz, CDCl3): δ 140.87, 139.22, 8.22 (s, 4H), 7.81 (s, 4H), 7.58-7.51 (m, 8H), 1.53 (s, 36H), ppm; 13C
138.61, 131.22, 130.86, 130.07, 128.78, 126.85, 125.64, 125.25, NMR (100 MHz, CDCl3): δ 143.16, 139.18, 136.73, 127.84, 123.77,
123.32, 123.13, 122.41, 120.71, 120.55, 113.08, 111.09, 109.82, 123.54, 116.36, 109.24, 34.80, 32.06, ppm;
ppm.
3,6-di-tert-butyl-9-(4-iodophenyl)-9H-carbazole (3f).5d Purification
3,6-Di-tert-butyl-9-(3-fluorophenyl)-9H-carbazole (2r). Purification by flash chromatography (petroleum ether): a white solid (113 mg,
by flash chromatography (petroleum ether): a white solid (140 mg, 47%), mp = 177 °C; 1H NMR (400 MHz, CDCl3): δ 8.15 (dd, J = 2.0 Hz,
75%), mp = 143-145 °C; 1H NMR (400 MHz, CDCl3): δ 8.16 (d, J = 2.0 J = 0.4 Hz, 2H), 7.94-7.90 (m, 2H), 7.48 (dd, J = 8.4 Hz, J = 1.6 Hz, 2H),
Hz, 2H), 7.59-7.53 (m, 1H), 7.50 (dd, J = 4.8 Hz, J = 2.0 Hz, 2H), 7.42- 7.36-7.33 (m, 4H), 1.49 (s, 18h), ppm; 13C NMR (100 MHz, CDCl3): δ
7.38 (m, 3H), 7.33 (dt, J = 7.6 Hz, J = 0.8 Hz, 2H), 7.42-7.38 (m, 3H), 143.20, 138,94, 138.85, 138.01, 128.53, 123.73, 123.52, 116.33,
7.18-7.13 (m, 1H), 1.50 (s, 18H), ppm; 13C NMR (100 MHz, CDCl3): δ 109.01, 99.99, 91.34, 34.76, 32.00, ppm.
163.36 (d, JC-F = 246.5 Hz), 143.22, 139.75 (d, JC-F = 9.9 Hz), 138.81,
130.84 (d, JC-F = 9.3 Hz), 123.72, 123.50, 122.18 (d, JC-F = 3.2 Hz), 9-(3-Iodophenyl)-9H-carbazole (3g).43 Purification by flash
116.27, 113.91, 113.69 (d, JC-F = 2.3 Hz), 109.10, 34.71, 31.96, ppm; chromatography (petroleum ether): a white solid (61 mg, 33%), mp
1
19F NMR (376 MHz, CDCl3): δ -33.09 – -33.15 (m), ppm; HRMS = 111-112 °C; H NMR (400 MHz, CDCl3): δ 8.12 (d, J = 7.6 Hz, 2H),
(MALDI): m/z calcd for C26H28FN [M]+ 373.2200, found 373.2198.
7.93 (s, 1H), 7.79 (d, J = 8.0 Hz, 1H), 7.54 (d, J = 8.0 Hz, 1H), 7.40 (q, J
= 8.0 Hz, 4H), 7.30 (q, J = 8.0 Hz, 3H), ppm; 13C NMR (100 MHz,
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ARTICLE
Journal Name
CDCl3): δ 140.57, 138.98, 136.46, 136.00, 131.25, 126.44, 126.11, 120.56, 120.54, 120.37, 110.00, 109.48, ppm; HRMSV(ieMwAArLtDiclIe):Omnlin/ez
+
DOI: 10.1039/C5RA07690K
123.51, 120.38, 120.31, 109.61, 94.58, ppm.
calcd for C30H19BrN2 [M] 486.0726, found 486.0726.
3,6-di-tert-butyl-9-(3-iodophenyl)-9H-carbazole (3h). Purification 9-(2-Bromo-5-iodophenyl)-9H-carbazole (3m). Purification by flash
by flash chromatography (petroleum ether): a white solid (106 mg, chromatography (petroleum ether): a white solid (114 mg, 51%),
1
44%), mp = 170-171 °C; 1H NMR (400 MHz, CDCl3): δ 8.19 (d, J = 2.0 mp = 138 °C; H NMR (400 MHz, CDCl3): δ 8.18 (d, J = 7.6 Hz, 2H),
Hz, 2H), 7.98 (t, J = 2.0 Hz, 1H), 7.81-7.79 (m, 1H), 7.61-7.58 (m, 1H), 7.85 (d, J = 2.0 Hz, 1H), 7.75 (dd, J = 8.4 Hz, J = 2.4 Hz, 1H), 7.61 (d, J
7.52 (dd, J = 8.4 Hz, J = 1.6 Hz, 2H), 7.40-7.32 (m, 3H), 1.52 (s, 18H), = 8.4 Hz, 1H), 7.48-7.44 (m, 2H), 7.37-7.33 (m, 2H), 7.12 (d, J = 8.0
ppm; 13C NMR (100 MHz, CDCl3): δ 143.30, 139.50, 138.93, 135.94, Hz, 2H), ppm; 13C NMR (100 MHz, CDCl3): δ 140.59, 139.90, 139.14,
135.60, 131.18, 126.00, 123.80, 123.56, 116.35, 109.09, 99.99, 138.23, 135.54, 126.13, 123.95, 123.42, 120.47, 120.38, 110.00,
94.56, 34.79, 32.04, ppm.
92.40, ppm; HRMS (MALDI): m/z calcd for C18H11BrIN [M]+ 446.9120,
found 446.9119.
3-Bromo-9-(3-iodophenyl)-9H-carbazole (3ia).43 Purification by
flash chromatography (petroleum ether): a colorless oil (114 mg, 9-(4'-fluoro-[1,1'-biphenyl]-4-yl)-9H-carbazole (4a). Purification by
51%); 1H NMR (400 MHz, CDCl3): δ 8.26 (d, J = 2.0 Hz, 1H), 8.10 (d, J flash chromatography (petroleum ether): a white solid (74 mg, 44%),
1
= 8.0 Hz, 1H), 7.92 (d, J = 2.0 Hz, 1H), 7.86-7.83 (m, 1H), 7.54-7.45 mp = 205-206 °C; H NMR (400 MHz, CDCl3): δ 8.20 (d, J = 7.6 Hz,
(m, 3H), 7.41-7.26 (m, 4H), ppm; 13C NMR (100 MHz, CDCl3): δ 2H), 7.80 (d, J = 8.4 Hz, 2H), 7.70-7.66 (m, 4H), 7.51-7.44 (m, 4H),
140.90, 139.24, 138.50, 136.81, 135.90, 131.40, 128.82, 126.91, 7.34 (t, J = 8.0 Hz, 2H), 7.23 (t, J = 8.4 Hz, 2H), ppm; 13C NMR (100
126.35, 125.27, 123.18, 122.43, 120.76, 120.61, 113.13, 111.13, MHz, CDCl3): δ 162.69 (d, JC-F = 245.4 Hz), 140.85, 139.32, 136.91,
109.88, 94.76, ppm.
136.42 (d, JC-F = 3.2 Hz), 128.74 (d, JC-F = 8.0 Hz), 128.40, 127.41,
126.01, 123.47, 120.37, 120.04, 115.89 (d, JC-F = 21.3 Hz), 109.81,
1,3-Bis(3-bromo-9H-carbazol-9-yl)benzene (3ib).44 Purification by ppm; 19F NMR (376 MHz, CDCl3): δ -115.04, ppm; HRMS (MALDI):
flash chromatography (petroleum ether): a white solid (221 mg, m/z calcd for C24H16FN [M]+ 337.1261, found 337.1263.
1
78%), mp = 119 °C; H NMR (400 MHz, CDCl3): δ 8.28 (d, J = 2.0 Hz,
2H), 8.12 (d, J = 7.6 Hz, 2H), 7.89 (t, J = 8.0 Hz, 1H), 7.77 (t, J = 2.0 Hz, 9-(4-(1H-pyrrol-1-yl)phenyl)-9H-carbazole (4b). Purification by flash
1H), 7.71 (dd, J = 8.0 Hz, J = 2.0 Hz, 2H), 7.56-7.47 (m, 6H), 7.41 (d, J chromatography (petroleum ether): a white solid (113 mg, 73%),
1
= 8.8 Hz, 2H), 7.37-7.33 (m, 2H), ppm; 13C NMR (100 MHz, CDCl3): δ mp = 208-209 °C; H NMR (400 MHz, CDCl3): δ 8.20 (d, J = 8.0 Hz,
140.90, 139.24, 139.05, 131.49, 128.86, 126.95, 126.07, 125.39, 2H), 7.65 (s, 4H), 7.50-7.44 (m, 4H), 7.37-7.33 (m, 2H), 7.23-7.22 (s,
125.17, 123.26, 122.55, 120.82, 120.69, 113.18, 111.10, 109.84, 2H), 6.47-6.46 (m, 2H), ppm; 13C NMR (100 MHz, CDCl3): δ 140.93,
ppm.
139.76, 135.05, 128.35, 126.09, 123.45, 121.66, 120.44, 120.13,
119.40, 111.00, 109.70, ppm; HRMS (MALDI): m/z calcd for C22H16N2
2,7-Dibromo-9-(3-iodophenyl)-9H-carbazole (3j). Purification by [M]+ 308.1308, found 308.1306.
flash chromatography (petroleum ether): a white solid (142 mg,
54%), mp = 200 °C; 1H NMR (400 MHz, CDCl3): δ 7.96 (s, 1H), 7.94 (s, 9-(4-(m-tolylethynyl)phenyl)-9H-carbazole (4c). Purification by
1H), 7.91-7.87 (m, 2H), 7.52-7.37 (m, 6H), ppm; 13C NMR (100 MHz, flash chromatography (petroleum ether): a white solid (109 mg,
1
CDCl3): δ 141.68, 137.64, 137.60, 136.08, 131.64, 126.65, 124.00, 61%), mp = 114 °C; H NMR (400 MHz, CDCl3): δ 8.18 (d, J = 8.0 Hz,
121.77, 121.55, 120.16, 112.90, 94.95, ppm; Anal. Calcd. for 2H), 7.81-7.77 (m, 2H), 7.62-7.59 (m, 2H), 7.50-7.42 (m, 6H), 7.36-
C18H10Br2IN: C, 41.02; H, 1.91; N, 2.66. Found: C, 41.22; H, 1.99; N, 7.29 (m, 3H), 7.22 (d, J = 7.6 Hz, 1H), 2.42 (s, 3H), ppm; 13C NMR
2.69.
(100 MHz, CDCl3): δ 140.61, 138.18, 137.53, 133.14, 132.31, 129.48,
128.84, 128.40, 126.88, 126.12, 123.61, 122.90, 122.43, 120.43,
3,6-Dibromo-9-(3-iodophenyl)-9H-carbazole (3k). Purification by 120.27, 109.81, 90.61, 88.42, 21.34, ppm; HRMS (MALDI): m/z calcd
flash chromatography (petroleum ether): a white solid (87 mg, 33%), for C27H19N [M]+ 357.1512, found 357.1513.
1
mp = 180-181 °C; H NMR (400 MHz, CDCl3): δ 8.21 (d, J = 2.0 Hz,
2H), 7.89-7.85 (m, 2H), 7.56-7.50 (m, 3H), 7.37 (t, J = 8.0 Hz, 1H),
7.26 (d, J = 8.8 Hz, 2H), ppm; 13C NMR (100 MHz, CDCl3): δ 139.59,
138.03, 137.17, 135.85, 131.49, 129.60, 126.29, 124.07, 123.32,
113.47, 111.36, 94.78, pmm; Anal. Calcd. for C18H10Br2IN: C, 41.02;
H, 1.91; N, 2.66. Found: C, 41.97; H, 2.28; N, 2.61.
Conclusions
We have developed a copper/-diketone-catalysed method for
C–N bond-forming reaction of carbazoles with aryl iodides.
Aryl iodides bearing electron-withdrawing group showed
slightly higher reactivity than those bearing electron-donating
group in this catalytic system. Aryl iodides bearing sterically
hindered group were difficult to react with carbazoles.
Reaction temperature significantly affected the site-selectivity
of diiodobenzene. At high reaction temperature, carbazoles
bearing electron-withdrawing group were prone to undergo
single coupling with diiodobenzene with high selectivity.
However, carbazoles bearing electron-donating group
underwent double coupling and formed disubstituted or
9,9'-(4-Bromo-1,3-phenylene)bis(9H-carbazole) (3l). Purification by
flash chromatography (petroleum ether): a white solid (185 mg,
1
76%), mp = 226 °C; H NMR (400 MHz, CDCl3): δ 8.21-8.12 (m, 5H),
7.79 (d, J = 2.4 Hz, 1H), 7.73 (dd, J = 8.4 Hz, J = 2.3 Hz, 1H), 7.55-7.45
(m, 6H), 7.35 (q, J = 8.0 Hz, 4H), 7.27 (d, J = 8.0 Hz, 2H), ppm; 13C
NMR (100 MHz, CDCl3): δ 140.66, 140.23, 138.51, 138.38, 135.50,
129.17, 128.32, 126.33, 126.19, 123.76, 123.50, 121.89, 120.69,
10 | J. Name., 2012, 00, 1-3
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Acknowledgements
The authors thank the financial support from the National
Natural Science Foundation of China (grant number 21466033).
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