Three-Component Synthesis of 2-Substituted Thiobenzoazoles Using Tetramethyl Thiuram Monosulfide (TMTM) as Thiocarbonyl Surrogate

Article abstract of DOI:10.1002/ejoc.202001214

A metal-free synthesis of 2-benzyl/allyl-substituted thiobenzoazoles was developed starting from tetramethyl thiuram monosulfide (TMTM) which served as thiocarbonyl surrogate. By using 2-aminophenols (or 2-aminothiophenols, or 1,2-phenylenediamines) and TMTM as starting materials, 2-mercaptobenzoazoles could be synthesized efficiently. The subsequent C–S bond formation with benzyl/allyl halides gave the final products (2-benzyl/allyl-substituted thiobenzoazoles) with good to excellent yields. The metal-free conditions, inexpensive and easily available starting materials, and broad substrate scope are the advantageous features of this protocol.

Full text of DOI:10.1002/ejoc.202001214

European Journal of Organic Chemistry
Accepted Article
Accepted Article
Title: Three-Component Synthesis of 2-Subsituted Thiobenzoazoles
using Tetramethyl Thiuram Monosulfide (TMTM) as Thiocarbonyl
Surrogate
Authors: Xi Wang, Chun-Yan Wu, Yue-Sheng Li, and Zhi-Bing Dong
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of the final Version of Record (VoR). This work is currently citable by
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To be cited as: Eur. J. Org. Chem. 10.1002/ejoc.202001214
Link to VoR: https://doi.org/10.1002/ejoc.202001214
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1/2020

European Journal of Organic Chemistry
10.1002/ejoc.202001214
FULL PAPER
A Chemoselective and Desulfurative Chan-Lam Coupling: C-N
Bond Formation between Benzimidazoline-2-Thiones and
Arylboronic Acids
[a]
[a]
[b],[c]
and Zhi-Bing Dong* [a],[b],[c],[d]
Jin-Quan Chen, Xing Liu, Jia Guo,
Abstract: An efficient method for the chemoselective and
desulfurative Chan-Lam cross-coupling based on benzimidazoline-2-
thiones was developed. By modulating the amount of the catalyst
and copper-catalyzed couplings of N-H substrates with NaBPh
4
(Scheme 1, e) are also optional pathways.[8] However, these
synthetic processes suffer from harsh reaction conditions such
as high reaction temperature, requirement of stoichiometric
amount of copper catalyst, or usage of toxic solvents and non-
commercially available ligands. Though N-arylations via cross-
coupling reactions between benzimidazoles and arylboronic
acids have been reported (Scheme 1, f),[9-10] the expanded
research based on classic Chan-Lam coupling is still desirable.
2 2
Cu(OAc) •H O, alkali, temperature and solvent, the desulfurizational
C-N bond formation product (N-arylbenzimidazoles) could be
selectively furnished smoothly. The features of this protocol are an
inexpensive and readily available catalyst, ligand-free conditions,
wide substrate scope, easy performance, and moderate to excellent
yields. It shows potential synthetic value for the preparation of a
diversity of arylbenzoheterocyclic compounds, which are potentially
active in pharmaceuticals and agrochemicals.
Introduction
Imidazole-based compounds are a class of very important and
versatile nitrogen-containing heterocyclic compounds due to
their numerous applications, such as drugs, pharmaceutical
intermediates, agrochemicals, antimicrobial agents, functional
materials, and biomimetic catalysts.[1] Among these, the N-
arylbenzimidazoles have attracted much attention since they are
key building blocks in a large number of pharmaceutical
molecules (Figure 1).[2] Besides, the N-arylbenzimidazoles also
have many comprehensive applications in other respects. For
instance, they can be applied in the synthesis of natural
products, and they are also fundamental materials for ionic
liquids, ligands for transition-metal catalysis, and versatile N-
heterocyclic carbene precursors.[3] Thus, the development of
simple and efficient approaches for the synthesis of N-
arylbenzimidazoles has attracted considerable attention in the
past decades.
Figure 1. Some biologically active N-arylbenzimidazoles.
Several strategies have been developed for the synthesis of N-
arylbenzimidazoles (Scheme 1). Synthetic protocols that afford
N-arylbenzimidazoles
catalyzed Ullmann-type
benzimidazoles and aryl halides (Scheme 1, a), intramolecular
cross coupling of aromatic o-diamines with CO
(Scheme 1, b),[5]
and H (Scheme
generally
involve
transition-metal-
cross-couplings
between
[
4]
2
or cyclization of aromatic o-diamines with CO
2
2
, c).[ In addition, N-arylation of azole compounds using
6]
1
reactive and selective TMP-iodonium(III) salts (Scheme 1, d),[7]
[
[
[
[
a]
b]
c]
d]
School of Chemistry and Environmental Engineering, Wuhan
Institute of Technology, Wuhan 430205, China.
Key Laboratory of Green Chemical Process, Ministry of Education,
Wuhan Institute of Technology, Wuhan 430205, China
Hubei Key Laboratory of Novel Reactor and Green Chemistry
Technology, Wuhan Institute of Technology, Wuhan 430205, China
Ministry-of-Education Key Laboratory for the Synthesis and
Application of Organic Functional Molecules, Hubei University,
Wuhan 430062, China.
Scheme 1. Existing Synthetic Strategies towards N-arylbenzimidazoles.
Recently, we disclosed an efficient chemoselective Chan–Lam
coupling reactions between benzimidazoline-2-thiones and
arylboronic acids,[11] and the coupling reactions could be
selectively directed to two different products (Scheme 2, S-
arylbenzimidazoles or N,S-diarylbenzimidazoles). On the other
Email: dzb04982@wit.edu.cn
https://cee.wit.edu.cn/info/1052/1538.htm
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European Journal of Organic Chemistry
10.1002/ejoc.202001214
FULL PAPER
hand, it is known that desulfurative couplings, such as the
Liebeskind reaction[12] or the Suzuki-Miyaura reaction,[13] are
generally performed under harsh reaction conditions, which
usually involve the use of expensive transition metal catalysts
and ligands, high temperature, as well as the use of inert
atmosphere for the construction of C-C bonds.[14] As part of our
longstanding interest in heterocyclic chemistry[12] and
organosulfur chemistry in the development of Chan-Lam
catalyst (entry 13). In addition, the screenings also showed that
the yields obtained from Cu(II) salts were slightly higher than the
ones obtained from Cu(I) salts. The catalyst loading (entries 20-
2 2
22) indicated that 0.1 equiv. of Cu(OAc) •H O was optimal (entry
21). To further optimize the reaction conditions, we screened the
substrate ratio, the temperature, and the solvent (entry 23-33),
while the yield of 3a could not be improved. Thus, the optimal
reaction conditions for desired product 3a were as follows: 1a:2a
couplings,[13] we herein disclose
a
chemoselective and
= 1:1.5, Cu(OAc)
(3 mL), 100 C, 8h (entry 21).
•H
O (10 mol%), NaHCO
(2.0 equiv), DMSO
2
2
3
o
desulfurative Chan–Lam coupling which affords C-N formation
products (N-arylbenzimidazoles, Scheme 2) starting from
benzimidazoline-2-thiones and arylboronic acids. The selectivity
Table 1. Optimization of Desulfurizational Chan–Lam Coupling for the
Synthesis of 3a.[
a]
2 2
can be controlled by modulating the amount of Cu(OAc) •H O,
base, temperature and solvent, which could provides attractive
and alternative approach to access these important compounds.
Entry
Base
Catalyst
Cu]
Ligand Solvent
Yield
[
3a
b]
(
%)[
0
1
2
3
4
5
6
7
8
9
--
Cu(OAc) .
2
2
H O(0.2eq.)
2
H O(0.2eq.)
2
H O(0.2eq.)
2
H O(0.2eq.)
2
H O(0.2eq.)
2
H O(0.2eq.)
2
H O(0.2eq.)
2
H O(0.2eq.)
2
H O(0.2eq.)
2
H O(0.2eq.)
2
H O(0.2eq.)
BPy[c]
BPy
BPy
BPy
BPy
BPy
BPy
BPy
BPy
BPy
BPy
BPy
--
--
--
--
--
--
--
--
--
DMSO
DMSO
DMSO
DMSO
DMSO
DMSO
DMSO
DMSO
DMSO
DMSO
DMSO
DMSO
DMSO
DMSO
DMSO
DMSO
DMSO
DMSO
DMSO
DMSO
DMSO
DMSO
DMSO
DMSO
DMSO
DMSO
DMSO
DMSO
DMF
.
.
.
.
.
.
.
.
.
.
KOH(2eq.)
NaOH(2eq.)
Cu(OAc)
Cu(OAc)
Cu(OAc)
Cu(OAc)
Cu(OAc)
Cu(OAc)
Cu(OAc)
Cu(OAc)
Cu(OAc)
Cu(OAc)
2
2
2
2
2
2
2
2
2
2
62
71
64
65
47
88
K
Na
Cs
2
CO
CO
CO
NaHCO
pyridine(2eq.)
EtN (2eq.)
3
(2eq.)
(2eq.)
(2eq.)
(2eq.)
2
3
2
3
3
[d]
N.R.
3
trace
58
80
N.R.
86
72
52
75
77
82
68
82
92
79
79
92
N.R.
N.R.
44
10
NaHCO
NaHCO
NaHCO
3
(1eq.)
3
(3eq.)
3
(2eq.)
1
1
Scheme 2. Chan-Lam-type Coupling Reactions: (i) Previous Work:
Chemoselective C-S and C-N Bond Formations. (ii)This Work:
Desulfurizational C-N Coupling.
12
13
--
.
NaHCO (2eq.)
3
Cu(OAc)2
2
H O(0.2eq.)
14
15
16
17
18
19
20
NaHCO
NaHCO
NaHCO
NaHCO
NaHCO
NaHCO
NaHCO
3
(2eq.)
3
(2eq.)
3
(2eq.)
3
(2eq.)
3
(2eq.)
3
(2eq.)
3
(2eq.)
CuSO
CuCl .
2H
CuBr (0.2eq.)
4
(0.2eq.)
2
2
O(0.2eq.)
2
CuI(0.2eq.)
CuCl(0.2eq.)
Results and Discussion
Cu(OTf)
2
(0.2eq.)
Thus, the reaction condition survey for the chemoselective and
desulfurative Chan–Lam coupling reaction of benzimidazoline-2-
thione (1a) with phenylboronic acid (2a) are summarized in
Table 1. Initially, the reaction of benzimidazoline-2-thione (1a)
and phenylboronic acid (2a) was examined in DMSO at 100 °C
Cu(OAc) .
2
H
2
O(0.05eq.)
.
21
22
NaHCO (2eq.)
3
Cu(OAc) H O(0.1eq.)
2
2
.
NaHCO
NaHCO
NaHCO
NaHCO
NaHCO
NaHCO
NaHCO
NaHCO
NaHCO
NaHCO
NaHCO
NaHCO
3
(2eq.)
3
(2eq.)
3
(2eq.)
3
(2eq.)
3
(2eq.)
3
(2eq.)
3
(2eq.)
3
(2eq.)
3
(2eq.)
3
(2eq.)
3
(2eq.)
3
(2eq.)
Cu(OAc)
Cu(OAc)
Cu(OAc)
Cu(OAc)
Cu(OAc)
Cu(OAc)
Cu(OAc)
Cu(OAc)
Cu(OAc)
Cu(OAc)
Cu(OAc)
Cu(OAc)
2
2
2
2
2
2
2
2
2
2
2
2
H
H
H
H
H
H
H
H
H
H
H
H
2
2
2
2
2
2
2
2
2
2
2
2
O(1.0eq.)
--
--
--
--
--
--
--
--
[
e]
.
.
.
.
.
.
.
.
.
.
.
2
2
3
O(0.1eq.)
O(0.1eq.)
O(0.1eq.)
O(0.1eq.)
O(0.1eq.)
O(0.1eq.)
O(0.1eq.)
O(0.1eq.)
O(0.1eq.)
O(0.1eq.)
O(0.1eq.)
[
f]
4
[g]
25
in the presence of Cu(OAc)
2
•H
2
O (0.2 eq.) and 2,2'-bipyridine
[h]
[i]
26
(
Bpy; 0.2 equiv). A mixture of S-arylbenzimidazole and N,S-
2
7
28
29
[
j]
diarylbenzimidazole were detected simultaneously (entry 1)
without the addition of base. To our delight, the N-arylation
product 3a was obtained with 62% yield as the single product
when KOH (2.0 eq.) was added (entry 2), which demonstrated
that base was crucial to afford the desulfurative N-arylation
product. Encouraged by this result, various bases were
74
75
65
N.R.
N.R.
N.R.
30
31
32
33
--
DMAc
--
2
H O
--
--
PhCH
1,4-
3
dioxane
screened (entry 2-9), revealing that NaHCO
other bases, providing the desired product 3a in 88% yield (entry
). Next, the amount of NaHCO was surveyed (entry 10-11),
and it was found that 2 equiv. of NaHCO was the optimal. The
control experiment for copper catalyst Cu(OAc) •H O and ligand
3
was superior to
[a] Reaction conditions: 1a (0.5 mmol), 2a (0.75 mmol), base (2.0 equiv.),
solvent (3 mL), temperature : 100 oC, stirred for 6-8 h. [b] Isolated yield based
on 1a. [c] Bpy = 2,2'-bipyridine (0.2 equiv.). [d] No Reaction. [e] 1a : 2a = 1:1.
7
3
o
o
[
f] 1a : 2a = 1:2. [g] temperature: 25 C. [h] temperature: 60 C. [i] temperature:
o
o
3
80 C. [j] temperature: 120 C.
2
2
Bpy revealed that copper catalyst was crucial for the reaction
while ligand was not necessary (entry 12). Based on these
results, several copper catalysts were screened (entry 13-19)
With the optimal conditions established, we next explored the
scope of this desulfurative Chan–Lam coupling by employing
structurally diverse arylboronic acids and benzimidazoline-2-
thiones, and the results are summarized in Table 2. It was
2 2
and it showed that Cu(OAc) •H O was the most effective
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European Journal of Organic Chemistry
10.1002/ejoc.202001214
FULL PAPER
satisfying that a serious of substituted phenylboronic acids could
couple with benzimidazoline-2-thione in moderate to excellent
yields. Phenylboronic acids bearing electron-withdrawing groups
Subsquently, we continued to explore the substrate scope either
for benzimidazoline-2-thiones or for arylboronic acids, and the
results are listed in Table 3. It was gratifying to find that whether
the electron-donating or the electron-withdrawing groups
attaching to the substituted benzimidazoline-2-thiones reacted
with a variety of substituted arylboronic acids in moderate to
good yields, showing good substrate compatibility of this
protocol. The substrates surveyed also revealed that
(
F, Cl, Br, CN) successfully coupled with benzimidazoline-2-
thione, providing the desired products (3b-3g, 3r) in moderate to
good yields (49%-79%), and electron-donating groups on the
phenylboronic acids gave the corresponding products (3h-3p)
with moderate to excellent yields (51%-98%). The investigation
results indicated that the electronic nature of the substituent
somehow effected the reaction. The electron donating
arylboronic acids were more reactive than the electron
withdrawing ones. The steric effect on this transformation was
also studied. Thus, disubstituted arylboronic acids (with ortho-,
meta- and para- groups) were employed, giving the
corresponding products N-arylbenzimidazoles (3i-3k) with 51%-
benzimidazoline-2-thiones
bearing
electron-withdrawing
substituents were more reactive than the electron-donating ones
(3ze vs 3u, 3zf vs 3zb), and arylboronic acids bearing electron
donating groups showed higher yields than the ones with
electron withdrawing groups (3zb vs 3v, 3zf vs 3zh, 3zk vs 3zm).
Table 3. Substrate Scope for the Desulfurative Chan-Lam Reaction of
Substituted Arylboronic Acids with Benzimidazoline-2-thiones.[
a]
8
4
2% yields, which showed a certain steric effect. To our delight,
-(methoxycabonyl)phenylboronic acid was also suitable for this
transformation, giving the intended product 3q in 70% yield.
Furthermore, 1-naphthylboronic acid and 2-naphthylboronic acid
successfully coupled with benzimidazoline-2-thione, giving the
target products 3s and 3t in good yields (62% and 71%),
respectively.
Table 2. Substrate Scope for the Desulfurizational Chan-Lam Reaction of
Substituted Arylboronic Acids with Benzimidazoline-2-thione.[a]
[a]Reaction conditions: 1 (0.5 mmol), 2 (0.75 mmol), Cu(OAc)
NaHCO
(2.0 equiv.), DMSO (3 mL), 100 oC, open air for 8-24 h; Isolated yield
based on 1.
2 2
•H O (10 mol%),
3
To further explore the mechanism of this desulfurative C-N
coupling, the following control experiments were performed
(
Scheme 3). Firstly, benzimidazoline-2-thione was treated with
NaHCO
3
in DMSO at 100 oC for 20 h. In the reaction, the
starting material benzimidazoline-2-thione was remained a lot
and the desulfurative product benzimidazole was detected
[a]Reaction conditions: 1 (0.5 mmol), 2 (0.75 mmol), Cu(OAc)
NaHCO
(2.0 equiv.), DMSO (3 mL), 100 oC, open air for 8-24 h; Isolated yield
based on 1.
2
2
•H O (10 mol%),
(
isolation yield: 30%). The yield of benzimidazole could not be
3
improved when the reaction time was prolonged to 48 h.
Sequently, arylboronic acid (1.5 equiv.) and Cu(OAc) •H O (10
2
2
mol%) were added to the hybrid system, and the mixture
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European Journal of Organic Chemistry
10.1002/ejoc.202001214
FULL PAPER
(
benzimidazoline-2-thione and benzimidazole) were transformed
diarylbenzimidazoles starting from benzimidazoline-2-thiones
and arylboronic acids, by modulating the amount of
to N-arylbenzimidazole smoothly (isolation yield: 92%), which
might be due to the driving force of Chan-Lam C-N coupling. To
further confirm the fact of this desulfurative Chan-Lam coupling,
Cu(OAc)
2 2
•H O, base, temperature, and solvent. The protocol
features good selectivity, broad functional group tolerance, easy
product 3g was characterized by X-ray crystallography (Figure 2, performance and moderate to excellent yields. This protocol
CCDC 1953877), and it was identified with our speculated
reaction pathway.
showed potential application value for the preparation of a
diversity of N-aryl benzoheterocyclic compounds, which are
potentially active in pharmaceuticals and agrochemicals.
Experimental Section
Scheme 3. Control Experiments
Flash column chromatography was operated on silica gel with petroleum
ether-EtOAc (PE-EA) as the eluent. Thin layer Chromatography was
adopted and visualized under UV light. The RY-1G instrument was
adopted to determine melting points of target compounds. The HRMS
(
high-resolution mass spectra) was recorded from a Finnigan MAT 95Q
mass instrument (ESI). A Bruker AM400 NMR instrument was operated
in CDCl to record NMR spectra.
3
Figure 2. X-ray Crystallography of Product 3g from the Desulfurizational
Chan-Lam Coupling.
According to the above experimental results and previous
[
17]
Typical procedure for the synthesis of N-arylbenzimidazoles 3a (TP).
literature reports, we proposed a possible mechanism for this
reaction (Scheme 4). Firstly, the benzimidazoline-2-thione was
transformed to 2-mercaptobenzimidazole via isomerization (it is
a dynamic equilibrium), followed by desulfuration under the
Benzimidazoline-2-thione 1a (0.5 mmol) and phenylboronic acid 2a (0.75
mmol), Cu(OAc) •H O (0.05 mmol), NaHCO (1.0 mmol) were added to a
2 2 3
dried tube (open to air) equipped with a magnetic stirring bar, DMSO (3.0
mL) was then added. The mixture was stirred at 100 oC and checked by
action of base (NaHCO
3
), giving benzimidazole (a dynamic
equilibrium as well). Secondly, the arylboronic acid reacted with
the copper catalyst (A) to form complex B, which could be
TLC. The reaction was quenched with sat. NH
extracted with ethyl acetate. The preliminary solution was dried over
Na SO and evaporated. The crude material was further purified by
4
Cl solution and then
oxidized by O
transmetalation with readily available desulfurative intermediate
benzimidazole) gave intermediate C. Intermediate C easily
2
to give Cu(III) species, and the subsequent
2
4
(
column chromatography to get the intended product 3a.
provided the desired C-N coupling product D along with Cu(I)
species (E) by reductive elimination. E was then oxidized by
oxygen to regenerate Cu(II) catalyst A.
Analytical data of the products
Scheme 4. Proposed Reaction Mechanism.
[
5]
1-phenyl-1H-benzo[d]imidazole (3a)
Based on THE ABOVE MENTIONED PROCEDURE, the crude material
was isolated by column (PE/EA = 2:1) to give the intended compound 3a
1
as a colorless oil (90 mg, yield = 92%). H NMR (400 MHz, CDCl
3
, TMS):
δ (ppm) 8.00 (s, 1H), 7.76-7.78 (m, 1H), 7.30-7.45 (m, 6H), 7.18-7.23 (m,
2
1
H). 13C NMR (100 MHz, CDCl
, TMS): δ (ppm) 142.8, 141.2, 135.2,
3
32.6, 128.9, 126.9, 122.9, 122.6, 121.7, 119.4, 109.4. HRMS (ESI) m/z
+
[M+H] Calcd for C13
H N
11 2
(195.0917), found: 195.0915.
1
-(4-fluorophenyl)-1H-benzo[d]imidazole (3b) [9e]
Based on THE ABOVE MENTIONED PROCEDURE, the crude material
was isolated by column (PE/EA = 2:1) to give the intended compound 3b
as a white soild (78 mg, yield = 74%). mp: 112-116 oC. 1H NMR (400
MHz, CDCl
H), 7.24-7.28 (m, 2H), 7.16-7.20 (m, 2H). 13C NMR (100 MHz, CDCl
TMS): δ (ppm) 160.9 (d, J = 247.0 Hz), 142.8, 141.2, 132.8, 131.3 (d, J =
3
, TMS): δ (ppm) 7.98 (s, 1H), 7.78-7.81 (m, 1H), 7.36-7.41 (m,
3
3
,
Conclusions
3
1
2
.0 Hz), 125.0 (d, J = 8.0 Hz), 122.8, 121.8, 119.6, 116.0 (d, J = 23.0 Hz),
09.1. HRMS (ESI) m/z [M+H]+ Calcd for C13
13.0826.
2
H10FN (213.0823), found:
In summary, we reported herein a chemoselective, desulfurative
Chan-Lam coupling by using inexpensive and commercially
available arylboronic acids and benzimidazoline-2-thiones. This
expanded research together with our previous work[11] affords a
useful protocol for the chemoselective formation of N-
arylbenzimidazoles, S-arylbenzimidazoles, as well as N,S-
1-(4-chlorophenyl)-1H-benzo[d]imidazole (3c) [9a]
Based on THE ABOVE MENTIONED PROCEDURE, the crude material
was isolated by column (PE/EA = 2:1) to give the intended compound 3c
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European Journal of Organic Chemistry
10.1002/ejoc.202001214
FULL PAPER
as a white soild (56 mg, yield = 49%). mp: 108-110 oC. 1H NMR (400
1-(3,5-dimethylphenyl)-1H-benzo[d]imidazole (3i) [18c]
MHz, CDCl
H), 7.36-7.42 (m, 3H), 7.24-7.29 (m, 2H). 13C NMR (100 MHz, CDCl
TMS): δ (ppm) 142.9, 141.0, 133.8, 132.8, 132.5, 129.2, 124.2, 122.9,
22.0, 119.7, 109.1. HRMS (ESI) m/z [M+H]+ Calcd for C13
229.0527), found: 229.0521.
3
, TMS): δ (ppm) 8.00 (s, 1H), 7.79-7.81 (m, 1H), 7.46-7.48 (m,
2
3
,
Based on THE ABOVE MENTIONED PROCEDURE, the crude material
was isolated by column (PE/EA = 2:1) to give the intended compound 3i
1
(
H10ClN
2
1
as a yellow oil (75 mg, yield = 68%). H NMR (400 MHz, CDCl
3
, TMS): δ
(
2
ppm) 8.00 (s, 1H), 7.77-7.79 (m, 1H), 7.43-7.46 (m, 1H), 7.21-7.25 (m,
H), 7.02 (d, J=12 Hz, 3H), 2.33 (s, 6H). 13C NMR (100 MHz, CDCl
,
3
1
-(4-bromophenyl)-1H-benzo[d]imidazole (3d) [9a]
TMS): δ (ppm) 142.9, 141.3, 138.9, 135.1, 132.7, 128.6, 122.4, 121.6,
20.6, 119.4, 109.6, 20.2. HRMS (ESI) m/z [M+H]+ Calcd for C15
223.1230), found: 223.1235.
1
15 2
H N
(
Based on THE ABOVE MENTIONED PROCEDURE, the crude material
was isolated by column (PE/EA = 2:1) to give the intended compound 3d
as a white soild (99 mg, yield = 79%). mp: 100-104 oC. 1H NMR (400
1-(2,4-dimethylphenyl)-1H-benzo[d]imidazole (3j)
MHz, CDCl
H), 7.38-7.41 (m, 1H), 7.22-7.31 (m, 4H). 13C NMR (100 MHz, CDCl
TMS): δ (ppm) 142.9, 140.9, 134.3, 132.3, 132.2, 124.4, 122.9, 122.0,
20.5, 119.7, 109.1. HRMS (ESI) m/z [M+H]+ Calcd for C13
273.0022), found: 273.0027.
3
, TMS): δ (ppm) 7.98 (s, 1H), 7.77-7.81 (m, 1H), 7.58-7.62 (m,
2
3
,
Based on THE ABOVE MENTIONED PROCEDURE, the crude material
was isolated by column (PE/EA = 2:1) to give the intended compound 3j
1
(
H10BrN
2
1
as a yellow oil (57 mg, yield = 51%). H NMR (400 MHz, CDCl
3
, TMS): δ
(
1
ppm) 7.86 (s, 1H), 7.79-7.86 (m, 1H), 7.04-7.26 (m, 6H), 2,35 (s, 3H),
.97 (s, 3H). 13C NMR (100 MHz, CDCl
, TMS): δ (ppm) 142.2, 142.1,
138.3, 134.0, 133.8, 131.0, 126.7, 126.4, 122.4, 121.3, 119.2, 109.5,
0.1, 16.4. HRMS (ESI) m/z [M+H]+ Calcd for C15
(223.1230),
found: 223.1236.
3
1
-(3-bromophenyl)-1H-benzo[d]imidazole (3e) [18a]
2
15 2
H N
Based on THE ABOVE MENTIONED PROCEDURE, the crude material
was isolated by column (PE/EA = 2:1) to give the intended compound 3e
o
1
1-(3,4-dimethylphenyl)-1H-benzo[d]imidazole (3k) [18b]
as a white soild (94 mg, yield = 69%). mp: 98-100 C. H NMR (400 MHz,
CDCl , TMS): δ (ppm) 8.00 (s, 1H), 7.76-7.81 (m, 1H), 7.59-7.60 (m, 1H),
.48-7.51 (m, 1H), 7.41-7.45 (m, 1H), 7.32-7.38 (m, 2H), 7.23-7.28 (m,
H). 13C NMR (100 MHz, CDCl
, TMS): δ (ppm) 142.9, 140.9, 136.4,
32.2, 130.3, 130.0, 125.9, 123.0, 122.4, 122.0, 121.4, 119.7, 109.2.
(273.0022), found:
3
7
2
1
Based on THE ABOVE MENTIONED PROCEDURE, the crude material
3
was isolated by column (PE/EA = 2:1) to give the intended compound 3k
1
as a yellow oil (91 mg, yield = 82%). H NMR (400 MHz, CDCl
3
, TMS): δ
HRMS (ESI) m/z [M+H]+ Calcd for C13
H10BrN
2
(
5
ppm) 7.99 (s, 1H), 7.76-7.80 (m, 1H), 7.41-7.45 (m, 1H), 7.71-7.26 (m,
273.0025.
H), 2.27 (s, 6H). 13C NMR (100 MHz, CDCl
3
, TMS): δ (ppm) 142.8,
1
41.3, 137.5, 135.7, 132.9, 132.8, 129.9, 124.1, 122.4, 120.3, 119.4,
1-(3,5-difluorophenyl)-1H-benzo[d]imidazole (3f)
109.5, 18.8, 18.4. HRMS (ESI) m/z [M+H]+ Calcd for
15 15
C H N
2
(223.1230), found: 223.1234.
Based on THE ABOVE MENTIONED PROCEDURE, the crude material
was isolated by column (PE/EA = 2:1) to give the intended compound 3f
1-(4-ethylphenyl)-1H-benzo[d]imidazole (3l) [18e]
o
1
as a white soild (86 mg, yield = 75%). mp: 84-86 C. H NMR (400 MHz,
CDCl , TMS): δ (ppm) 8.01 (s, 1H), 7.77-7.81 (m, 1H), 7.47-7.51 (m, 1H),
.26-7.30 (m, 2H), 6.98-7.05 (m, 2H), 6.80-6.86 (m, 1H). 13C NMR (100
MHz, CDCl , TMS): δ (ppm) 162.7 (dd, J = 250.0 Hz, J = 14.0 Hz), 143.1,
40.6, 137.4 (t, J = 12.0 Hz), 131.9, 123.3, 122.4, 119.9, 109.2, 106.1 (d,
J = 28.0 Hz), 102.4 (t, J = 25.0 Hz). HRMS (ESI) m/z [M+H]+ Calcd for
(271.0728), found: 231.0729.
3
Based on THE ABOVE MENTIONED PROCEDURE, the crude material
7
was isolated by column (PE/EA = 2:1) to give the intended compound 3l
3
1
as a yellow oil (87 mg, yield = 78%). H NMR (400 MHz, CDCl
3
, TMS): δ
1
(
4
ppm) 8.00 (s, 1H), 7.76-7.80 (m, 1H), 7.40-7.43 (m, 1H), 7.27-7.32 (m,
H), 7.20-7.25 (m, 2H), 2.62-2.68 (m, 2H), 1.21 (t, J = 8.0 Hz, 3H). 13
C
13 9 2 2
C H F N
NMR (100 MHz, CDCl
28.3, 123.0, 122.5, 121.6, 119.4, 27.4, 14.4. HRMS (ESI) m/z [M+H]
Calcd for C15 (223.1230), found: 223.1236.
3
, TMS): δ (ppm) 143.3, 142.8, 141.3, 132.8, 132.8,
+
1
1-(3,5-dichlorophenyl)-1H-benzo[d]imidazole (3g)
15 2
H N
Based on THE ABOVE MENTIONED PROCEDURE, the crude material
was isolated by column (PE/EA = 2:1) to give the intended compound 3g
as a white soild (65 mg, yield = 50%). mp: 162-164 oC. 1H NMR (400
1-(4-isopropylphenyl)-1H-benzo[d]imidazole (3m)
Based on THE ABOVE MENTIONED PROCEDURE, the crude material
MHz, CDCl
H), 7.36-7.37 (m, 3H), 7.25-7.30 (m, 2H). 13C NMR (100 MHz, CDCl
TMS): δ (ppm) 143.0, 140.6, 137.0, 135.4, 131.9, 127.0, 123.2, 122.3,
19.9, 109.1. HRMS (ESI) m/z [M+H]+ Calcd for C13
Cl (263.0173),
found: 263.0177.
3
, TMS): δ (ppm) 7.99 (s, 1H), 7.78-7.80 (m, 1H), 7.43-7.46 (m,
was isolated by column (PE/EA = 2:1) to give the intended compound 3m
1
3
,
1
as a yellow oil (110 mg, yield = 93%). H NMR (400 MHz, CDCl
3
, TMS):
δ (ppm) 7.98 (s, 1H), 7.76-7.79 (m, 1H), 7.42-7.43 (m, 1H), 7.30 (s, 4H),
.19-7.22 (m, 2H), 2.87-2.96 (m, 1H), 1.21 (d, J = 8.0 Hz, 6H). 13C NMR
1
H
9
2 2
N
7
(
100 MHz, CDCl , TMS): δ (ppm) 147.8, 142.8, 141.3, 132.8, 132.7,
3
1
26.9, 122.9, 122.4, 121.5, 119.4, 109.4, 32.7, 22.9. HRMS (ESI) m/z
-(o-tolyl)-1H-benzo[d]imidazole (3h) [9e]
[M+H] Calcd for C16
+
H N
16 2
(236.1313), found: 236.1311.
1
Based on THE ABOVE MENTIONED PROCEDURE, the crude material
1-(4-methoxyphenyl)-1H-benzo[d]imidazole (3n) [9e]
was isolated by column (PE/EA = 2:1) to give the intended compound 3h
1
as a yellow oil (72 mg, yield = 69%). H NMR (400 MHz, CDCl
3
, TMS): δ
Based on THE ABOVE MENTIONED PROCEDURE, the crude material
(
4
ppm) 7.88 (s, 1H), 7.79-7.81 (m, 1H), 7.32-7.37 (m, 2H), 7.17-7.29 (m,
was isolated by column (PE/EA = 2:1) to give the intended compound 3n
H), 7.03-7.06 (m, 1H), 2.01 (s, 3H). 13C NMR (100 MHz, CDCl
3
, TMS): δ
1
as a yellow oil (98 mg, yield = 88%). H NMR (400 MHz, CDCl
3
, TMS): δ
(
1
ppm) 142.2, 141.9, 134.3, 133.7, 133.6, 130.4, 128.3, 126.6, 126.1,
22.4, 121.4, 119.3, 109.4, 16.5. HRMS (ESI) m/z [M+H]+ Calcd for
(209.1073), found: 209.1074.
(
2
ppm) 8.05 (s, 1H), 7.86-7.88 (m, 1H), 7.39-7.46 (m, 3H), 7.28-7.35 (m,
H), 7.05-7.08 (m, 2H) 3.88 (m, 3H). 13C NMR (100 MHz, CDCl
3
, TMS): δ
14 13 2
C H N
This article is protected by copyright. All rights reserved.

European Journal of Organic Chemistry
10.1002/ejoc.202001214
FULL PAPER
(
1
(
ppm) 159.3, 143.8, 142.5, 134.2, 129.1, 125.7, 123.5, 122.6, 120.4,
15.1, 110.3, 55.6. HRMS (ESI) m/z [M+H]+ Calcd for C14
225.1022), found: 225.1027.
Based on THE ABOVE MENTIONED PROCEDURE, the crude material
13 2
H N O
was isolated by column (PE/EA = 2:1) to give the intended compound 3t
1
as a yellow oil (87 mg, yield = 71%). H NMR (400 MHz, CDCl
3
, TMS): δ
(
(
ppm) 8.20 (s, 1H), 8.03 (d, J = 8.0 Hz, 1H), 7.89-7.94 (m, 4H), 7.55-7.62
m, 4H), 7.32-7.38 (m, 2H). 13C NMR (100 MHz, CDCl
3
, TMS): δ (ppm)
1
-(4-ethoxyphenyl)-1H-benzo[d]imidazole (3o)
1
44.1, 142.4, 133.9, 133.7, 133.6, 132.4, 130.2, 127.9, 127.9, 127.3,
+
126.8, 123.7, 122.9, 122.2, 122.1, 120.6, 110.5. HRMS (ESI) m/z [M+H]
Based on THE ABOVE MENTIONED PROCEDURE, the crude material
was isolated by column (PE/EA = 2:1) to give the intended compound 3o
as a yellow oil (106 mg, yield = 89%). H NMR (400 MHz, CDCl
δ (ppm) 8.04 (s, 1H), 7.84-7.89 (m, 1H), 7.43-7.46 (m, 1H), 7.37-7.39 (m,
Calcd for C17
13 2
H N (245.1073), found: 245.1075.
1
3
, TMS):
5
,6-dimethyl-1-phenyl-1H-benzo[d]imidazole (3u) [18d]
2
=
1
H), 7.29-7.32 (m, 2H), 7.03-7.07 (m, 2H), 4.07-4.12 (m, 2H) 1.46 (t, J
8.0 Hz, 3H). 13C NMR (100 MHz, CDCl
, TMS): δ (ppm) 158.7, 143.8,
42.5, 134.2, 128.9, 125.7, 123.5, 122.5, 120.4, 115.6, 110.3, 63.9, 14.7.
3
Based on THE ABOVE MENTIONED PROCEDURE, the crude material
was isolated by column (PE/EA = 2:1) to give the intended compound 3u
HRMS (ESI) m/z [M+H]+ Calcd for C15H15N2O (239.1179), found:
as a yellow oil (82 mg, yield = 74%). H NMR (400 MHz, CDCl
1
3
, TMS): δ
2
39.1172.
(ppm) 8.01 (s, 1H), 7.63 (s, 1H), 7.53-7.57 (m, 2H), 7.41-7.50 (m, 3H),
.30-7.38 (s, 1H), 2.36 (t, J = 12.0 Hz, 6H). 13C NMR (100 MHz, CDCl
TMS): δ (ppm) 142.5, 141.5, 136.6, 132.9, 132.1, 131.7, 129.9, 127.7,
23.8, 120.4, 110.5, 20.5, 20.2. HRMS (ESI) m/z [M+H]+ Calcd for
(223.1230), found: 223.1233.
7
3
,
1-(benzo[d][1,3]dioxol-5-yl)-1H-benzo[d]imidazole (3p)
1
15 15 2
C H N
Based on THE ABOVE MENTIONED PROCEDURE, the crude material
was isolated by column (PE/EA = 2:1) to give the intended compound 3p
1
1-(4-fluorophenyl)-5,6-dimethyl-1H-benzo[d]imidazole (3v)
as a yellow oil (117 mg, yield = 98%). H NMR (400 MHz, CDCl
3
, TMS):
δ (ppm) 8.03 (s, 1H), 7.85-7.87 (m, 1H), 7.45-7.47 (m, 1H), 7.29-7.34 (m,
H), 6.93-6.96 (m, 3H), 6.07 (s, 2H). 13C NMR (100 MHz, CDCl
, TMS): δ
ppm) 148.7, 147.5, 143.7, 142.4, 143.0, 130.1, 123.6, 122.7, 120.5,
17.8, 110.3, 108.8, 105.7, 102.0. HRMS (ESI) m/z [M+H]+ Calcd for
(239.0815), found: 239.0818.
2
(
1
C
3
Based on THE ABOVE MENTIONED PROCEDURE, the crude material
was isolated by column (PE/EA = 2:1) to give the intended compound 3v
1
as a yellow oil (67 mg, yield = 56%). H NMR (400 MHz, CDCl
3
, TMS): δ
H N O
14 11 2 2
(ppm) 7.95 (s, 1H), 7.62 (s, 1H), 7.44-7.47 (m, 2H), 7.22-7.27 (m, 3H),
.38 (d, J = 8.0 Hz, 6H). 13C NMR (100 MHz, CDCl
, TMS): δ (ppm)
161.8 (d, J = 247.0 Hz）, 142.4, 141.4, 133.1, 132.7 (d, J = 3.0 Hz),
2
3
methyl 4-(1H-benzo[d]imidazol-1-yl)benzoate (3q) [18d]
1
2
32.4, 131.8, 125.8 (d , J = 9.0 Hz), 120.5, 116.9 (d, J = 23.0 Hz), 110.2,
0.5, 20.2. HRMS (ESI) m/z [M+H]+ Calcd for C15
(241.1136),
H14FN
2
Based on THE ABOVE MENTIONED PROCEDURE, the crude material
was isolated by column (PE/EA = 2:1) to give the intended compound 3q
as a white soild (89 mg, yield = 70%). mp: 100-104 oC. 1H NMR (400
found: 241.1138.
1
-(4-chlorophenyl)-5,6-dimethyl-1H-benzo[d]imidazole (3w) [18d]
MHz, CDCl
.90 (m, 1H), 7.58-7.63 (m, 3H), 7.35-7.38 (m, 2H), 3.98 (s, 3H). 13C
NMR (100 MHz, CDCl , TMS): δ (ppm) 166.0, 144.2, 141.9, 140.1, 133.1,
31.6, 129.4, 124.1, 123.2, 123.2, 120.8, 110.4, 52.4. HRMS (ESI) m/z
3
, TMS): δ (ppm) 8.26 (d, J = 8.0 Hz, 2H), 8.17 (s, 1H), 7.88-
7
3
Based on THE ABOVE MENTIONED PROCEDURE, the crude material
was isolated by column (PE/EA = 2:1) to give the intended compound 3w
as a yellow solid (58 mg, yield = 45%). mp: 116-118 oC. 1H NMR (400
1
+
13 2 2
[M+H] Calcd for C15H N O (253.0972), found: 253.0978.
MHz, CDCl
2H), 7.44 (d, J = 8.0 Hz, 2H), 7.26 (s, 1H), 2.39 (d, J = 12.0 Hz, 6H). 13C
NMR (100 MHz, CDCl , TMS): δ (ppm) 142.6, 141.2, 135.2, 133.5, 133.2,
32.0, 132.0, 130.2, 125.1, 120.6, 110.3, 20.6, 20.2. HRMS (ESI) m/z
3
, TMS): δ (ppm) 7.79 (s, 1H), 7.63 (s, 1H), 7.53 (d, J = 8.0 Hz,
-(1H-benzo[d]imidazol-1-yl)benzonitrile (3r) [10a]
4
3
1
Based on THE ABOVE MENTIONED PROCEDURE, the crude material
was isolated by column (PE/EA = 2:1) to give the intended compound 3r
as a white soild (87 mg, yield = 79%). mp: 112-114 oC. 1H NMR (400
+
2
[M+H] Calcd for C15H14ClN (257.0840), found: 257.0846.
1
-(3,5-dichlorophenyl)-5,6-dimethyl-1H-benzo[d]imidazole (3x)
MHz, CDCl
H), 7.57-7.60 (m, 1H), 7.38-7.40 (m, 2H). 13C NMR (100 MHz, CDCl
TMS): δ (ppm) 144.3, 141.6, 140.1, 134.2, 133.0, 132.8, 129.1, 124.5,
23.9, 123.6, 121.0, 117.8, 111.5, 110.2. HRMS (ESI) m/z [M+H]+ Calcd
for C14 (220.0869), found: 220.0866.
3
, TMS): δ (ppm) 8.18 (s, 1H), 7.89-7.91 (m, 3H), 7.68-7.70 (m,
2
3
,
Based on THE ABOVE MENTIONED PROCEDURE, the crude material
was isolated by column (PE/EA = 2:1) to give the intended compound 3x
as a yellow solid (76 mg, yield = 52%). mp: 99-102 oC. 1H NMR (400
1
10 3
H N
MHz, CDCl
3
, TMS): δ (ppm) 7.91 (s, 1H), 7.53 (s, 1H), 7.36 (s, 3H), 7.21
, TMS): δ (ppm) 206.1,
41.3, 139.8, 137.3, 135.3, 132.7, 131.5, 126.7, 121.0, 119.6, 109.2,
9.6, 19.2. HRMS (ESI) m/z [M+H]+ Calcd for C15
(290.0378),
(t, J = 12.0 Hz, 1H). 13C NMR (100 MHz, CDCl
1
1
-(naphthalen-1-yl)-1H-benzo[d]imidazole (3s) [9e]
3
1
2 2
H12Cl N
Based on THE ABOVE MENTIONED PROCEDURE, the crude material
found: 259.0377.
was isolated by column (PE/EA = 2:1) to give the intended compound 3s
1
as a colorless oil (76 mg, yield = 62%). H NMR (400 MHz, CDCl
3
, TMS):
1
-(3,5-difluorophenyl)-5,6-dimethyl-1H-benzo[d]imidazole (3y)
δ (ppm) 8.12 (s, 1H), 7.94-8.04 (m, 3H), 7.53-7.62 (m, 3H), 7.40-7.46 (m,
H), 7.33-7.37 (m, 1H), 7.22-7.26 (m, 1H), 7.09 (d, J = 8.0 Hz, 1H). 13C
NMR (100 MHz, CDCl , TMS): δ (ppm) 143.7, 143.3, 134.4, 129.6, 128.4,
27.5, 120.7, 125.4, 124.9, 123.6, 122.7, 122.5, 120.4, 110.8. HRMS
2
3
Based on THE ABOVE MENTIONED PROCEDURE, the crude material
was isolated by column (PE/EA = 2:1) to give the intended compound 3y
as a yellow solid (58 mg, yield = 45%). mp: 110-114 oC. 1H NMR (400
1
+
13 2
(ESI) m/z [M+H] Calcd for C17H N (245.1073), found: 245.1079.
MHz, CDCl
(d, J = 12.0 Hz, 2H), 6.79-6.84 (m, 1H), 2.32 (s, 6H). 13C NMR (100 MHz,
CDCl , TMS): δ (ppm) 162.6 (dd, J = 249.0 Hz, J = 14.0 Hz), 141.6,
39.8, 137.7 (t, J = 12.0 Hz), 132.6, 131.4, 130.3, 119.8, 109.3, 105.8 (d,
3
, TMS): δ (ppm) 7.91 (s, 1H), 7.54 (s,1H), 7.26 (s, 1H), 7.01
-(naphthalen-2-yl)-1H-benzo[d]imidazole (3t) [9n]
1
3
1
This article is protected by copyright. All rights reserved.

European Journal of Organic Chemistry
10.1002/ejoc.202001214
FULL PAPER
J = 28.0 Hz), 102.0 (t, J = 26.0 Hz), 19.6, 19.2. HRMS (ESI) m/z [M+H]+
Based on THE ABOVE MENTIONED PROCEDURE, the crude material
Calcd for C15
H
13
F
2
N
2
(259.1041), found: 259.1042.
was isolated by column (PE/EA = 2:1) to give the intended compound
o
1
3
ze as a yellow solid (94 mg, yield = 82%). mp: 78-80 C. H NMR (400
MHz, CDCl , TMS): δ (ppm) 8.03 (s, 1H), 7.48-7.55 (m, 3H), 7.36-7.43 (m,
H), 7.18-7.23 (m, 1H). 13C NMR (100 MHz, CDCl
, TMS): δ (ppm) 156.1,
47.8 (dd, J = 243.0 Hz, J = 16.0 Hz), 147.1 (dd, J = 240.0 Hz, J = 16.0
3
5,6-dimethyl-1-(o-tolyl)-1H-benzo[d]imidazole (3z)
3
1
3
Based on THE ABOVE MENTIONED PROCEDURE, the crude material
was isolated by column (PE/EA = 2:1) to give the intended compound 3z
as a yellow oil (53 mg, yield = 45%). H NMR (400 MHz, CDCl
Hz), 142.5 (d, J = 2.0 Hz), 138.0 (d. J = 12.0 Hz), 134.6, 129.2, 127.6,
1
22.8, 118.6, 114.6, 106.7 (d, J = 20.0 Hz), 97.5 (d, J = 23.0 Hz). HRMS
1
3
, TMS): δ
+
(ESI) m/z [M+H] Calcd for C13
9 2
H F N
2
(231.0728), found: 231.0723.
(ppm) 7.78 (s, 1H), 7.56 (s, 1H), 7.33-7.35 (m, 2H), 7.26-7.30 (m, 1H),
7
3
1
1
.20 (t, J = 8.0 Hz, 1H), 6.82 (s, 1H), 2.32 (s, 3H), 2.25 (s, 3H), 2.02 (s,
H). 13C NMR (100 MHz, CDCl
5,6-difluoro-1-(4-isopropylphenyl)-1H-benzo[d]imidazole (3zf)
3
, TMS): δ (ppm) 141.1, 140.8, 134.3,
34.0, 132.2, 131.7, 130.4, 130.4, 128.1, 126.4, 126.0, 119.2, 109.5,
+
9.4, 19.2, 16.6. HRMS (ESI) m/z [M+H] Calcd for C16
H N
17 2
(237.1386),
Based on THE ABOVE MENTIONED PROCEDURE, the crude material
was isolated by column (PE/EA = 2:1) to give the intended compound 3zf
as a white solid (94 mg, yield = 85%). mp: 136-138 oC. 1H NMR (400
found: 237.1385.
MHz, CDCl
3
, TMS): δ (ppm) 8.00 (s, 1H), 7.51-7.55 (m, 1H), 7.35 (d, J =
.0 Hz, 2H), 7.29 (d, J = 8.0 Hz, 2H), 7.19-7.23 (m, 1H), 2.90-2.97 (m,
H), 1.24 (d, J = 8.0 Hz, 6H). 13C NMR (100 MHz, CDCl
, TMS): δ (ppm)
48.6, 147.7 (dd, J = 243.0Hz, J = 15.0 Hz), 147.1 (dd, J = 241.0Hz, J =
1-(3,5-dimethylphenyl)-5,6-dimethyl-1H-benzo[d]imidazole (3za)
8
1
1
3
Based on THE ABOVE MENTIONED PROCEDURE, the crude material
was isolated by column (PE/EA = 2:1) to give the intended compound
za as a yellow oil (73 mg, yield = 58%). 1H NMR (400 MHz, CDCl
15.0 Hz),142.6, 138.0 (d, J = 10.0 Hz), 132.3, 128.3 (d, J = 10.0 Hz),
27.1, 122.9, 106.6(d, J = 20.0 Hz), 97.5 (d, J = 24.0 Hz), 32.8, 22.8.
HRMS (ESI) m/z [M+H]+ Calcd for
(273.1198), found:
3
3
,
1
TMS): δ (ppm) 7.90 (s, 1H), 7.53 (s, 1H), 7.21 (s, 1H), 7.00(d, J = 12.0
Hz, 3H), 2.31 (t, J = 8.0 Hz, 12H). 13C NMR (100 MHz, CDCl
, TMS): δ
ppm) 141.4, 140.6, 138.8, 135.4, 131.6, 130.5, 128.3, 120.5, 119.3,
16 15 2 2
C H F N
3
273.1193.
(
1
09.6, 20.3, 19.5, 19.2. HRMS (ESI) m/z [M+H]+ Calcd for C17
H N
19 2
5,6-difluoro-1-(4-methoxyphenyl)-1H-benzo[d]imidazole (3zg)
(251.1543), found: 251.1545.
Based on THE ABOVE MENTIONED PROCEDURE, the crude material
1-(4-isopropylphenyl)-5,6-dimethyl-1H-benzo[d]imidazole (3zb)
was isolated by column (PE/EA = 2:1) to give the intended compound
o
1
3
zg as a white solid (78 mg, yield = 60%). mp: 130-132 C. H NMR (400
MHz, CDCl , TMS): δ (ppm) 7.96 (s, 1H), 7.50-7.55 (m, 1H), 7.28 (d, J =
8.0 Hz, 2H), 7.10-7.15 (m, 1H), 7.00 (d, J = 12.0 Hz, 2H), 3.81 (s, 3H).
13C NMR (100 MHz, CDCl
, TMS): δ (ppm) 158.6, 147.7 (dd, J = 243.0
Hz, J = 16.0 Hz), 147.0 (dd, J = 240.0 Hz, J = 15.0 Hz), 142.8, 137.8 (d, J
10.0 Hz), 128.6 (d, J = 11.0 Hz), 127.4, 124.6, 114.2, 106.6 (d, J = 19.0
Hz), 97.3 (d, J = 23.0 Hz), 54.6. HRMS (ESI) m/z [M+H]+ Calcd for
O (261.0834), found: 261.0838.
Based on THE ABOVE MENTIONED PROCEDURE, the crude material
3
was isolated by column (PE/EA = 2:1) to give the intended compound
zb as a yellow oil (73 mg, yield = 55%). 1H NMR (400 MHz, CDCl
3
3
,
3
TMS): δ (ppm) 7.89 (s, 1H), 7.54 (s, 1H), 7.32 (s, 4H), 7.22 (s, 1H), 2.89-
.95 (m, 1H), 2.30 (d, J = 12.0 Hz, 6H), 1.23 (d, J = 8.0 Hz, 6H). 13C
NMR (100 MHz, CDCl , TMS): δ (ppm) 147.6, 141.5, 140.5, 133.2, 131.7,
31.3, 130.5, 126.8, 122.8, 119.3, 109.6, 32.8, 22.9, 19.5, 19.2. HRMS
2
=
3
1
14 11 2 2
C H F N
+
(ESI) m/z [M+H] Calcd for C18
21 2
H N (265.1699), found: 265.1696.
1-(3,5-difluorophenyl)-5,6-difluoro-1H-benzo[d]imidazole (3zh)
1-(4-methoxyphenyl)-5,6-dimethyl-1H-benzo[d]imidazole (3zc)
Based on THE ABOVE MENTIONED PROCEDURE, the crude material
Based on THE ABOVE MENTIONED PROCEDURE, the crude material
was isolated by column (PE/EA = 2:1) to give the intended compound
was isolated by column (PE/EA = 2:1) to give the intended compound
o
1
zc as a yellow oil (66 mg, yield = 53%). 1H NMR (400 MHz, CDCl
3zh as a white solid (98 mg, yield = 74%). mp: 156-158 C. H NMR (400
MHz, CDCl , TMS): δ (ppm) 8.04 (s, 1H), 7.54-7.58 (m, 1H), 7.26-7.30 (m,
H), 6.98-7.01 (m, 2H), 6.86-6.92 (m, 1H). 13C NMR (100 MHz, CDCl
TMS): δ (ppm) 168.2 (dd, J = 250.0 Hz, J = 15.0 Hz), 148.1 (dd, J =
3
3
,
3
TMS): δ (ppm) 7.86 (s. 1H), 7.53 (s, 1H), 7.31 (d, J = 12.0 Hz, 2H), 7.14
1
3
,
(
s, 1H), 6.98 (d, J = 12.0 Hz, 2H), 3.80 (s, 3H), 2.29 (d, J = 16.0 Hz, 6H).
1
3C NMR (100 MHz, CDCl
3
, TMS): δ (ppm) 158.1, 141.3, 140.7, 131.7,
245.0 Hz, J = 14.0 Hz), 147.4 (dd, J = 242.0 Hz, J = 15.0 Hz), 141.9 (d, J
= 3.0 Hz), 138.3 (d, J = 10.0 Hz), 136.7 (t, J = 13.0 Hz), 127.3 (d, J =
11.0 Hz), 107.3 (d, J = 19.0 Hz), 106.2 (d, J = 29.0 Hz), 103.1 (t, J = 25.0
1
31.7, 130.4, 128.4, 124.5, 119.3, 114.0, 109.4, 54.6, 19.5, 19.2. HRMS
+
(ESI) m/z [M+H] Calcd for C16
17 2
H N O (253.1335), found: 253.1335.
Hz), 97.5 (d, J = 24.0 Hz). HRMS (ESI) m/z [M+H]+ Calcd for C13
267.0540), found: 267.0541.
7 4 2
H F N
5,6-dimethyl-1-(naphthalen-1-yl)-1H-benzo[d]imidazole (3zd)
(
Based on THE ABOVE MENTIONED PROCEDURE, the crude material
5
,6-difluoro-1-(naphthalen-1-yl)-1H-benzo[d]imidazole (3zi)
was isolated by column (PE/EA = 2:1) to give the intended compound
3
zd as a yellow oil (50 mg, yield = 36%). 1H NMR (400 MHz, CDCl
,
3
Based on THE ABOVE MENTIONED PROCEDURE, the crude material
was isolated by column (PE/EA = 2:1) to give the intended compound 3zi
as a yellow solid (91 mg, yield = 65%). mp: 144-146 oC. 1H NMR (400
TMS): δ (ppm) 7,89-7.94 (m, 3H), 7.61 (s, 1H), 7.43-7.54 (m, 3H), 7.36 (d,
J = 4.0 Hz, 2H), 6.79 (s, 1H), 2.32 (s, 3H), 2.18 (s, 3H). 13C NMR (100
MHz, CDCl
3
, TMS): δ (ppm) 142.0, 140.8, 133.7, 133.3, 131.8, 131.6,
30.6, 128.8, 128.4, 127.3, 126.4, 125.9, 124.4, 123.8, 121.6, 119.3,,
09.8, 19.4, 19.2. HRMS (ESI) m/z [M+H]+ Calcd for
C H N
19 17 2
MHz, CDCl
3
, TMS): δ (ppm) 8.10 (s, 1H), 7.95 (d, J = 12.0 Hz, 1H), 7.79-
1
1
7
.86 (m, 3H), 7.43-7.57 (m, 4H), 7.23-7.27 (m, 1H). 13C NMR (100 MHz,
3
CDCl , TMS): δ (ppm) 147.8 (dd, J = 243.0 Hz, J = 16.0 Hz), 147.1 (dd, J
(273.1386), found: 273.1389.
=
1
1
241.0 Hz, J = 15.0 Hz), 142.7, 138.2 (d, J = 11.0 Hz), 132.5, 132.0,
31.6, 129.4, 128.2 (d, J = 10.0 Hz), 126.9 (d, J = 10.0 Hz), 126.5, 126.1,
21.1, 120.7, 106.8 (d, J = 19.0 Hz), 97.7, 97.4. HRMS (ESI) m/z [M+H]
5,6-difluoro-1-phenyl-1H-benzo[d]imidazole (3ze)
+
11 2 2
Calcd for C17H F N (281.0885), found: 281.0883.
This article is protected by copyright. All rights reserved.

European Journal of Organic Chemistry
10.1002/ejoc.202001214
FULL PAPER
5
,6-dichloro-1-phenyl-1H-benzo[d]imidazole (3zj)
Laboratory for the Synthesis and Application of Organic
Functional Molecules, Hubei University (KLSAOFM1810),
Science and Technology Department of Hubei Province
Based on THE ABOVE MENTIONED PROCEDURE, the crude material
was isolated by column (PE/EA = 2:1) to give the intended compound 3zj
as a white solid (130 mg, yield = 98%). mp: 120-124 oC. 1H NMR (400
(
2019CFB596), Key Laboratory of Hubei Province for Coal
Conversion and New Carbon Materials (WKDM202003) are all
greatly appreciated. J.-Q. C. thanks the support of Postgraduate
Innovation Foundation from Wuhan Institute of Technology
3
MHz, CDCl , TMS): δ (ppm) 8.03 (s, 1H), 7.85 (s, 1H), 7.51 (t, J = 8.0 Hz,
3
1
H), 7.37-7.43 (m, 3H). 13C NMR (100 MHz, CDCl
, TMS): δ (ppm) 134.4,
3
29.2, 127.6, 126.8, 125.9, 122.9, 120.6, 110.9. HRMS (ESI) m/z [M+H]+
(
CX2019170).
9 2 2
Calcd for C13H Cl N (263.0173), found: 263.0175.
,6-dichloro-1-(4-ethylphenyl)-1H-benzo[d]imidazole (3zk) [18e]
Keywords: Chemoselective
Coupling • C-N Bond
•
Desulfurative
•
Chan-Lam
5
Based on THE ABOVE MENTIONED PROCEDURE, the crude material
was isolated by column (PE/EA = 2:1) to give the intended compound
References
o
1
3
zk as a white solid (84 mg, yield = 58%). mp: 120-122 C. H NMR (400
MHz, CDCl , TMS): δ (ppm) 8.01 (s, 1H), 7.86 (s, 1H), 7.52 (s, 1H), 7.28-
.34 (m, 4H), 2.65-2.71 (m, 2H), 1.23 (t, J = 8.0 Hz, 3H). 13C NMR (100
MHz, CDCl , TMS): δ (ppm) 144.1, 143.1, 142.1, 132.1, 132.0, 128.6,
26.7, 125.8, 123.0, 120.6, 110.9, 27.5, 14.4. HRMS (ESI) m/z [M+H]+
Calcd for C15 (291.0540), found: 291.0545.
3
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Based on THE ABOVE MENTIONED PROCEDURE, the crude material
was isolated by column (PE/EA = 2:1) to give the intended compound 3zl
as a white solid (63 mg, yield = 41%). mp: 138-140 oC. 1H NMR (400
MHz, CDCl
d, J = 8.0 Hz, 2H), 6.98-7.00 (m, 2H), 4.01-4.06 (m, 2H). 13C NMR (100
MHz, CDCl , TMS): δ (ppm) 158.1, 143.3, 141.9, 132.5, 126.9, 126.7,
25.7, 124.6, 120.5, 114.8, 110.8, 62.9, 13.7. HRMS (ESI) m/z [M+H]+
Calcd for C15 O (307.0399), found: 307.0396.
3
, TMS): δ (ppm) 7.97 (s, 1H), 7.85 (s, 1H), 7.45 (s, 1H), 7.23
(
3
1
[2]
2 2
H13Cl N
5,6-dichloro-1-(4-fluorophenyl)-1H-benzo[d]imidazole (3zm)
Based on THE ABOVE MENTIONED PROCEDURE, the crude material
(f) J. M. Smallheer, R. S. Alexander, J. M. Wang, Bioorg. Med. Chem.
was isolated by column (PE/EA = 2:1) to give the intended compound
Lett. 2004, 14, 5263–5267.
3
zm as a white solid (63 mg, yield = 45%). mp: 210-214 oC. 1H NMR
[
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(
7
400 MHz, CDCl
3
, TMS): δ (ppm) 8.00 (s, 1H), 7.88 (s, 1H), 7.47 (s, 1H),
.37-7.41 (m, 2H), 7.19-7.25 (m, 2H). 13C NMR (100 MHz, CDCl
3
, TMS):
δ (ppm) 161.3 (d, J = 249.0 Hz), 142.9, 142.0, 132.1, 130.4, 127.1, 126.1,
125.1 (d, J = 8.0 Hz), 120.8, 116.3 (d, J = 23.0 Hz), 110.6. HRMS (ESI)
+
m/z [M+H] Calcd for C13
8
H Cl
2
FN
2
(281.0043), found: 281.0048.
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5,6-dichloro-1-(naphthalen-1-yl)-1H-benzo[d]imidazole (3zn)
[
4]
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Based on THE ABOVE MENTIONED PROCEDURE, the crude material
was isolated by column (PE/EA = 2:1) to give the intended compound
3
zn as a colorless oil (69 mg, yield = 44%). 1H NMR (400 MHz, CDCl
,
3
TMS): δ (ppm) 8.05 (s, 1H), 7.99 (d, J = 8.0 Hz, 1H), 7,94 (d, J = 4.0 Hz,
H), 7.51-7.57 (m, 2H), 7.39-7.47 (m, 2H), 7.25 (d, J = 8.0 Hz, 1H), 7.12
s, 1H). 13C NMR (100 MHz, CDCl
, TMS): δ (ppm) 144.4, 141.6, 133.7,
2
(
3
1
1
33.4, 130.3, 129.2, 128.4, 127.6, 126.9, 126.9, 126.2, 126.0, 124.4,
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2
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This article is protected by copyright. All rights reserved.

European Journal of Organic Chemistry
10.1002/ejoc.202001214
FULL PAPER
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European Journal of Organic Chemistry
10.1002/ejoc.202001214
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Key Topic*: Chan-Lam Coupling
Jin-Quan Chen, Xing Liu, Jia Guo, and
Zhi-Bing Dong *
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A Chemoselective and Desulfurative
Chan-Lam Coupling: C-N Bond
Formation between Benzimidazoline-
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2-Thiones and Arylboronic Acids
*one or two words that highlight the emphasis of the paper or the field of the study
An efficient method for the chemoselective and desulfurative Chan-Lam cross-coupling was developed. By modulating the
amount of the catalyst Cu(OAc) •H O, alkali, temperature and solvent, the desulfurative C-N bond formation product (N-
2
2
arylbenzimidazoles) could be selectively furnished smoothly. The features of this protocol are the use of inexpensive and
readily available catalyst, ligand-free condition, wide substrate scope, easy performance, giving the C-N cross-coupling
products in moderate to excellent yields. It shows potential synthetic value for the preparation of a diversity of
arylbenzoheterocyclic compounds which are potentially active in pharmaceuticals and agrochemicals.
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