One-pot synthesis of benzoazoles via dehydrogenative coupling of aromatic 1,2-diamines/2-aminothiophenol and alcohols using Pd/Cu-MOF as a recyclable heterogeneous catalyst

Article abstract of DOI:10.1016/j.ica.2018.07.017

In this paper we report an efficient synthetic approach for the preparation of the widespread numbers of benzoazoles via dehydrogenative coupling of 1,2-phenylenediamine or 2-aminothiophenol and benzyl alcohols by Pd/Cu₂(BDC)₂(DABCO)-MOF as new heterogeneous catalyst under solvent-free condition. The catalyst recycled and reused for four times without loss of catalytic activity. The structures of benzoazoles were corroborated spectroscopically (¹H- and ¹³C NMR, and elemental analysis) and were confirmed by comparison with reference compounds. A plausible mechanism for this type of reaction is proposed.

Full text of DOI:10.1016/j.ica.2018.07.017

InorganicaChimicaActa482(2018)726–731
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Inorganica Chimica Acta
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Research paper
One-pot synthesis of benzoazoles via dehydrogenative coupling of aromatic
1,2-diamines/2-aminothiophenol and alcohols using Pd/Cu-MOF as a
recyclable heterogeneous catalyst
Javad Mokhtaria,⁎, Abolfazl Hasani Bozcheloeia
a
Department of Chemistry, Science and Research Branch, Islamic Azad University, P.O. Box 14515/775, Tehran, Iran
A R T I C L E I N F O
A B S T R A C T
Keywords:
Dehydrogenative coupling
Benzimidazoles
Benzothiazoles
Pd-NPs/MOF
Nanoporous compound
Cu2(BDC)2DABCO
Heterogeneous catalyst
In this paper we report an efficient synthetic approach for the preparation of the widespread numbers of ben-
zoazoles via dehydrogenative coupling of 1,2-phenylenediamine or 2-aminothiophenol and benzyl alcohols by
Pd/Cu2(BDC)2(DABCO)-MOF as new heterogeneous catalyst under solvent-free condition. The catalyst recycled
and reused for four times without loss of catalytic activity. The structures of benzoazoles were corroborated
spectroscopically (1H- and 13C NMR, and elemental analysis) and were confirmed by comparison with reference
compounds. A plausible mechanism for this type of reaction is proposed.
1. Introduction
attracted a considerable attention [17–19]. Metal–organic frameworks
(MOFs), as a new class of organic inorganic hybrid porous materials,
Benzoazoles and their derivatives are important building blocks
found in miscellaneous series of biologically active compounds, agri-
cultural chemicals, pharmaceutical chemicals, and organic materials
[1–5] Furthermore, they are the basis of special chemicals for industrial
applications such as pigments [6], optical brighteners for coatings [7]
and etc.
have attracted considerable attention for stabilization and support for
the metal nanoparticles due to their high surface areas, tunable pore
sizes, and thermal stability [20]. Encapsulation of metal nanoparticles
(NPs) in MOF structure generates new collaborative effects, by which
the catalytic activity, selectivity and stability of the metal NPs can be
enhanced effectively [21]. Recently, the application of MOFs as the
supports for Pd nanoparticle has attracted considerable interest [22].
For catalytic applications Pd NPs have been successfully deposited at
the outer surface of the MOF supports (Pd/MOFs) [23–28] or loaded
inside the cavities of the MOFs (Pd@MOFs) via various methods such as
impregnation and chemical vapor deposition [29–35].
We previously uncovered synthesis of Pd-NPs/Cu2(BDC)2DABCO-
MOF using via temperature controlling program and its role as reusable
heterogeneous catalyst in Suzuki cross coupling and oxidation of benzyl
alcohols [36], Herein, in continues of our work and importance of the
introduction and application of new catalysts in the synthesis of organic
compounds and drawback of the reported methods in the literature as
mentioned above, we report the development of this heterogeneous
catalyst that are effective for the selective synthesis of benzimidazoles
and benzothiazoles via a dehydrogenative coupling of 1,2-aryldiamines
or 2-aminothiophenols with alcohols under mild conditions (Scheme 1).
The classical methods for the synthesis of these skeletons are the
reaction between 1,2-phenylenediamines or 2-aminothiophenols and
carboxylic acid, formic acid and aldehydes [8–12], hence experiencing
disadvantages with regard to green chemistry points of view. Recently,
different strategies for these structures have been developed and men-
tioned in the literature. Among the methods used for the synthesis of
benzoazoles, [11–13] dehydrogenative coupling between alcohols and
1,2-phenylenediamine or 2-aminothiophenols are one of the most ef-
fective synthetic pathway by using homogeneous and heterogeneous
catalyst such as Ir(2.0 wt%)/CeO2, (PNNH)CoICl, Pt/TiO2, Pt/Al2O3,
Ru2Cl4(CO)6 and etc. [14] that require stoichiometric amounts of hy-
drogen acceptors, strong bases, high temperature, unsafe solvent and in
the case of homogeneous catalyst, failure to recover the catalyst
[14–16]. So, the development of novel heterogeneous catalysts that can
realize environmentally-benign synthesis of benzoazoles is an im-
portant topic. Application of supported palladium nanoparticles
(PdNPs/support) as green and efficient heterogeneous catalysts has
⁎
Corresponding author.
E-mail address: j.mokhtari@srbiau.ac.ir (J. Mokhtari).
https://doi.org/10.1016/j.ica.2018.07.017
Received 1 May 2018; Received in revised form 10 July 2018; Accepted 10 July 2018
0020-1693/©2018ElsevierB.V.Allrightsreserved.

J. Mokhtari, A. Hasani Bozcheloei
InorganicaChimicaActa482(2018)726–731
under vacuum at 130 °C for 12 h to yield 1.6 g of Cu2(BDC)2DABCO
(94%).
200 mg of the synthesized Cu2(BDC)2(DABCO) was dissolved in 2 cc
of DMF and then 5 mg of PdCl2 with purity of 99.9% were added to the
mixture. The solution was sonicated for 20 min, stirred at 80 °C for 20 h
and finally stirred at 130 °C with the purpose of reduction of Pd(II) to
Pd (0). The product (Pd-NPs/Cu2(BDC)2(DABCO) was centrifuged,
washed with DMF and methanol and dried in vacuum at 120 °C for 12 h.
Scheme 1. Synthesis of benzoazoles catalyzed by Pd/Cu-MOF.
Table 1
Optimization of reaction conditions.a
2.3. Catalyst usage for the dehydrogenative coupling
Typically, o-phenylenediamine (1.3 mmol) or 2-aminothiophenol
(1 mmol), benzyl alcohols (1 mmol), Na2CO3 (20 mol%), and Pd-NPs/
Cu2(BDC)2(DABCO) (20 mg, 0.01 mol%) were added to a round-bottom
flask. The reaction mixture was heated to 120 °C and stirred at for the
appropriate time in air (TLC monitoring). Ethyl acetate was added to
the reaction mixture and catalyst was filtered. For the purification of
impure products, chromatography on silica gel was performed
(EtOAc:Hep. (1:6)). The entire products characterized by melting point,
CHN, 1H NMR and13C-NMR spectroscopy.
Entry
Catalyst (mg)
Solvent
Base (20 mol%)
T (°C)
Yield (%)b
1
2
3
4
5
6
7
8
10
20
20
20
20
30
40
–
CH3CN
CH3CN
Toluene
DMF
–
–
–
–
–
–
–
Na2CO3
Na2CO3
Na2CO3
Na2CO3
Na2CO3
Na2CO3
Na2CO3
Na2CO3
–
80
80
20
30
60
65
88
86
84
0
110
120
120
120
120
120
120
120
120
3. Selected spectral data
3.1. 2-Phenyl-1H-benzo[d]imidazole (3a)
White crystals. mp 294–295 °C, 1H NMR (500 MHz, DMSO‑d6, ppm):
δ 12.91 (s, NH), 8.17 (d, 2H, 3J = 7.6 Hz, 2CH of Ar), 7.66 (bs, 2CH of
Ar), 7.47–7.56 (m, 4CH of Ar), 7.20 (bs, 2CH of Ar). 13C NMR
(125 MHz, DMSO‑d6, ppm): δ 151.2, 143.8, 134.9, 130.15, 129.8,
128.9, 126.4, 122.5, 121.6, 118.8, 111.3. Anal. Calcd. for C13H10N2
(194.24): C, 80.39; H, 5.19; N, 14.42. Found: C, 80.35; H, 5.16; N,
14.38.
9
10
11
20
20
Cu-MOF
25
82
25
Et3N
Na2CO3
a
Isolated yields.
b
Reaction Conditions: benzene-1,2-diamine (1.3 mmol), benzyl alcohol
(1.0 mmol), catalyst (20 mg), base (1.0 mmol).
2. Experimental section
3.2. 2-Phenylbenzo[d]thiazole (3g)
2.1. Materials and instruments
White solid. m.p. = 113–114 °C. 1H NMR (500 MHz, CDCl3) δ
8.07–8.12 (m, 3CH of Ar), 7.91 (d, 3J = 8.0 Hz, CH of Ar), 7.48–7.52
(m, 4CH of Ar), 7.26–7.42 (m, CH of Ar); 13C NMR (125 MHz, CDCl3) δ
167.9, 154.0, 134.9, 133.5, 130.8, 128.9, 127.4, 126.2, 125.0, 123.1,
121.5. Anal. Calcd. for C13H10N2 (211.28): C, 73.90; H, 4.29; N, 6.63.
Found: C, 73.86; H, 4.28; N, 6.61.
All reagents including organic linker H2BDC, metal salt Cu
(OAc)2·H2O, 1,4-benzenedicarboxylate (BDC, 99%), 1,4-diazabicyclo
[2.2.2]octane (DABCO), Palladium (II) chloride (PdCl2), 1,2-pheneyle-
nediamines, 2-aminothiophenol, benzyl alcohols, sodium carbonate
(Na2CO3) and ethyl acetate were obtained from commercially available
sources such as Sigma–Aldrich and Merck without any purification. X-
ray powder diffraction (XRD) measurements were performed using an
X’pert MPD. Philips diffractometer with Cu radiation source
(λ = 1.54050 Å) at 40 Kv voltage and 40 mA current. Transmission
electron microscopy (TEM) was carried out using an EM10C-100 kV
series microscope from the Zeiss Company, Germany and the actual
loading of palladium was determined by Inductively Coupled Plasma
(ICP) analysis on sequential plasma spectrometer, Shimadzu (ICPS-
7000 ver. 2). BET (Brunauer-Emmett-Teller) surface area of the samples
was determined from N2 adsorption–desorption isotherms using a mi-
cromeritics ASAP 2020 analyzer. 1H NMR and 13C NMR spectra were
measured (CDCl3) with a Bruker DRX-500 AVANCE spectrometer at
500.13 and 125 MHz. Melting points were measured on an
Electrothermal 9100 apparatus.
4. Result and discussion
Pd/Cu2(BDC)2(DABCO) was synthesized and characterized in the
manner previously reported in our previous work [36]. The XRD pat-
tern of Pd@Cu2(BDC)2DABCO shows that the crystalline structure of
Cu2(BDC)2DABCO is maintained after deposition of Pd NPs. The ab-
sence of a Pd diffraction pattern relates to the low Pd contents in the
materials [36] (Fig. S1). Nitrogen adsorption-desorption and surface
areas of Pd-NPs@Cu2(BDC)2(DABCO) samples were noticeably reduced
compared to Cu2(BDC)2(DABCO), indicating that the cavities of
Cu2(BDC)2(DABCO) may be occupied by highly dispersed Pd nano-
particles (Fig. S2). TEM micrograph (Fig. 2), confirmed that a crystal-
line and nano-scaled material was produced. It is also to emphasize that
Pd nanoparticle has resulted in producing uniformly distributed nano-
scale and with a mean particle diameter of 6.5
0.2 nm as estimated
2.2. Supporting of palladium nanoparticle in MOF (Pd-NPs/
Cu2(BDC)2(DABCO))
from particle size distribution (Fig. 2). The actual loading of Pd (0) was
characterized by ICP analysis and found to be 0.9%.
After
full
characterization
of
the
synthetic
PdNPs/
Pd/Cu2(BDC)2DABCO was synthesized and characterized in the
manner previously reported in our previous work [36]. A mixture of Cu
(OAc)2·H2O (0.6 mmol), H2BDC (0.6 mmol) and DABCO (0.3 mmol)
with molar ratio of 2:2:1 were ball-milled at 28 Hz at room temperature
for 2 h. The obtained green powder was washed with DMF (3 × 10 mL),
and then with methanol (3 × 10 mL). Resulting green powder dried
Cu2(BDC)2DABCO, it was employed as a heterogeneous catalyst in the
dehydrogenative coupling of 1,2-phenylenediamine and benzyl alco-
hols as model reaction. For this purpose, 1,2-phenylenediamine
(1.0 equiv), benzyl alcohol (1.0 equiv), Na2CO3 (20 mol%) and catalyst
(20 mg, 0.01 mol %) in CH3CN under open air atmosphere were used as
starting parameters. A yield of 30% within 24 h at a temperature of
727

J. Mokhtari, A. Hasani Bozcheloei
InorganicaChimicaActa482(2018)726–731
Table 2
Synthesis of benzimidazoles and benzothiazoles via dehydrogenative of alcohols.
Entry
1
Benzyl alcohols
X
Productsa
Yield (%)b
88
mp (°C) [ref.]
NH
294–295 [37]
3a
2
3
NH
NH
84
86
275–276 [37]
226–227 [37]
3b
3c
4
5
NH
NH
85
81
290–291 [37]
324–326 [38]
3d
3e
6
NH
80
151–153 [39]
3f
7
8
9
S
S
S
86
79
76
113–114 [40]
78–81 [40]
3g
3h
123–124 [40]
3i
10
11
S
S
78
80
115–116 [41]
227–228 [40]
3j
3k
12
S
74
155–158 [40]
3l
a
Reaction Conditions: benzene-1,2-diamine (1.3 mmol) or 2-aminothiophenol (1.0 mmol), alcohol (1.0 mmol), Catalyst (20 mg), Na2CO3 (20 mol%).
Isolated yields.
b
80 °C was observed. To investigate the effect of temperature and solvent
also was performed under solvent-free condition in 120 °C and inter-
estingly, it was observed that the yield was very good and without the
formation of impurities (Table 1, Entry 5). In order to prevent dialky-
lation of the diamine, the diamine to alcohol ratio was changed and an
excess of diamine (1.3 eq) was used and as a result yield increased to
88%.
on the yield, above reaction was examined in different solvent in-
cluding toluene and DMF in reflux condition. The result summarized in
Table 1. As shown in Table 1, from the acetonitrile to the DMF, the yield
increased with increasing of temperature. On the other hand, and
considering our experience in the oxidation of benzyl alcohol to alde-
hyde with this catalyst under solvent-free condition, [36] the reaction
For the optimization of catalyst loading, 10, 20, 30 and 40 mg
728

J. Mokhtari, A. Hasani Bozcheloei
InorganicaChimicaActa482(2018)726–731
For the study of reusability of Pd/Cu-MOF after completion of the
reaction, ethyl acetate was added to the reaction mixture and catalyst
filtered and washed by methanol and dried and activated under vacuum
at 120 °C. The resulting recycled catalyst was used for dehydrogenative
coupling of 1,2-phenylenediamines and benzyl alcohol. The reaction
was completed after 12 h and isolated yield was 86%. This reusability
experiment was repeated for more four times and the results summar-
ized in Fig. 1. ICP analysis of the recycled Pd@Cu-MOF showed an
overall loss of 1 wt% Pd after 4 runs.
As shown in Fig. 1, the yield decreased after 4 runs. The reason is
probably due to the leaching of Pd nanoparticle and agglomeration.
TEM Image of recycled catalyst confirmed crystalline structure of the
palladium nanoparticles and a very small accumulation of palladium
nanoparticles.
90
85
80
75
70
65
1
2
3
4
Run
Fig. 1. Reusability test of the catalyst for the four times.
A comparison with other catalytic systems in the dehydrogenative
coupling of diamines and alcohols was shown in Table 3. As shown in
Table 3 the most of the catalyst needed harsh conditions such as diffi-
cult work up, homogenous catalyst and consequently the non-reusa-
bility of the catalyst, using of unsafe solvent such as toluene and ex-
pensive base including tBuOK. While, our present Pd@Cu-MOF catalyst
exhibited a heterogeneous system, simple work up, solvent-free con-
dition and reusability of the catalyst. To study the role of palladium in
this reaction, under the same reaction conditions, three experiments
with Cu2(BDC)2DABCO and CuO NPs were examined. The results
shown in Table 3 indicate the importance of the presence of palladium
NPs in this reaction.
catalyst was used. The results in Table 1 shown that 20 mg (0.01 mol%
base on Pd) (Entry 5) of catalyst is the best value and the increase over
this amount does not have a noticeable effect on the yield (Entry 6, 7).
On the other hand, when the reaction was examined without the cat-
alyst, no product was formed (Table 1, Entry 8). To study the role of Pd
nanoparticle in this reaction, a reaction with Cu-MOF alone was ex-
amined, the result shown that yield decreased significantly (Entry 11)
and palladium plays an undeniable role in this reaction. The base,
which accelerates the alcohol oxidation and mediates the condensation
step, was optimized towards an efficient benzimidazole formation. Two
different type of base such as Na2CO3 and Et3N was used, results shown
that both base led to good yield, however, due to the availability and
easy work up of the product, sodium carbonate was used as base. In the
absence of base, a yield of only 25% of 3a was observed. We next in-
vestigated the scope of the synthesis of benzimidazoles and ben-
zothiazoles derivatives (Table 2). The results summarized in Table 2
and shown that all benzylic alcohol with both electrons-withdrawing
and electron-donating groups gave excellent conversions. Encouraged
by this success, in the next step, we investigated the scope of the
synthesis of benzothiazoles derivatives in the same manner as shown in
Table 2.
The proposed reaction mechanism is shown in the scheme 2. At the
first benzyl alcohol oxidized to benzaldehyde in presence of Pd (0) and
O
2 [33]. In the next step, condensation of aldehyde and amine function
of 1,2-phenylenediamine or 2-aminothiophenol led to intermediate 4.
In the next step Cu-MOF as a Lewis acid accelerated cyclization and
formation of compound 6. In the last step, hydrogen peroxide, which is
obtained from the oxidation of benzyl alcohol in first step or O2, leads
to the oxidation of the compound 6 and the formation of compound 3.
5. Conclusion
Since the synthesized compounds are known compounds, therefore
the structures of all products were elucidated from the comparison of
melting point of them by literature reports (Table 2) and structure of
some of them also characterized by 1H NMR and CHN analysis (please
see the supporting information).
In conclusion, dehydrogenative coupling of aromatic 1,2-diamines
or 2-aminothiophenol and benzyl alcohols for the formation of benzi-
midazoles and benzothiazoles under solvent-free conditions by a reu-
sable heterogeneous Pd-NPs@Cu-MOF catalyst was discovered. The
Fig. 2. TEM image of as-synthesized Pd@Cu2(BDC)2DABCO (left) TEM image of recycled Pd/Cu2(BDC)2DABCO (right).
729

J. Mokhtari, A. Hasani Bozcheloei
InorganicaChimicaActa482(2018)726–731
Table 3
Comparison of different catalytic systems in the dehydrogenative coupling of o-phenylenediamines and benzyl alcohol.
Entry
catalyst
Reaction condition
Yield
Ref No.
1
2
3
4
5
6
7
8
Ir(2.0 wt%)/TiO2 – 500
TAP-Cu 2 mol%
10 mg Pt(0.2)@TiO2
[IrCl(cod)]2 (1.4 mol%)
Co3O4@Al2O3/SiO2 (5 mol %)
Cu2(BDC)2DABCO
Mesitylene, 120 °C, 18 h, Ar atmosphere
Toluene, reflux, tBuOK, 24 h
Ethanol, 80 °C, 303 k, 4 h, N2 atmosphere
Diglyme, 110 °C, 24 h
91%
92%
89%
85%
92%
31%
15%
88%
[37]
[38]
[39]
[40]
Solvent-free, 120 °C, 6 h, Air
[41]
Solvent-free/Na2CO3/120 °C, Air
Solvent-free/Na2CO3/120 °C, Air
Solvent-free/Na2CO3/120 °C, Air
Present work
Present work
Present work
CuO NPs
Pd@Cu2(BDC)2DABCO (0.01 mol%)
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