Facile Synthesis of 1,3,5-Triarylbenzenes and 4-Aryl-NH-1,2,3-Triazoles Using Mesoporous Pd-MCM-41 as Reusable Catalyst

Article abstract of DOI:10.1002/ejoc.201801290

We report mesoporous nano-Pd-MCM-41 catalyzed rapid and efficient synthesis of 1,3,5-triarylbenzenes via de-nitrative cyclotrimerization of β-nitrostyrenes. All the reactions were very fast and high yielding. The Pd-MCM-41 was also very effective in catalyzing de-nitrative [3+2] cycloaddition of β-nitrostyrenes with TMSN₃ to synthesize 4-aryl-NH-1,2,3-triazoles. The catalyst was reused at least up to eight times with minimum loss of catalytic activity.

Full text of DOI:10.1002/ejoc.201801290

A Journal of
Accepted Article
Title: Facile Synthesis of 1,3,5-Triarylbenzenes and 4-Aryl-NH-1,2,3-
Triazoles Using Mesoporous Pd-MCM-41 as Reusable Catalyst
Authors: Arijit Saha, Chia-Ming Wu, Ranjit T Koodali, and Subhash
Banerjee
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To be cited as: Eur. J. Org. Chem. 10.1002/ejoc.201801290
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10.1002/ejoc.201801290
European Journal of Organic Chemistry
FULL PAPER
Facile Synthesis of 1,3,5-Triarylbenzenes and 4-Aryl-NH-1,2,3-
Triazoles Using Mesoporous Pd-MCM-41 as Reusable Catalyst
Arijit Saha,[a] Chia-Ming Wu,[b] Rui Peng,[b] Ranjit Koodali,[b] and Subhash Banerjee[a],*
Abstract: We report mesoporous nano-Pd-MCM-41 catalyzed rapid
and efficient synthesis of 1,3,5-triarylbenzenes via de-nitrative
cyclotrimerization of -nitrostyrenes. All the reactions were very fast
and high yielding. The Pd-MCM-41 w as also very effective in
catalyzing de-nitrative [3+2] cycloaddition of -nitrostyrenes with
TMSN3 to synthesize 4-aryl-NH-1,2,3-triazoles. The catalyst was
reused at least up to eight times w ith minimum loss of catalytic
activity.
Introduction
The Pd-catalyzed coupling reaction is w ell recognized
indispensable and versatile tool for C-C bond formations to
construct highly functionalized polyaromatic hydrocarbons
(PAHs).[1] The -conjugated carbon- and heteroatom-based
polyaromatics have engrossed immense importance to the
organic as w ell as material chemists due to their w ide
applications in medicinal, chemical and material industries.[2]
Among them, 1,3,5-triarylbenzene analogous are classified as
the privileged PAHs because of their diverse utility as resist
materials,[3a-b] conductive polymers,[c-d] electroluminescent
materials for flat-panel displays,[3e-f] liquid crystals,[3g] laser
dyes,[3h] electronic and opto-electronic devices,[3i-j] molecular
w ires,[3k-l] organic light emitting diodes,[3m-n] and potential
Scheme 1. State-of -art of the synthesis of 1,3,5-triarylbenzenes.
chemosensors.[3o] These structural motifs are also exemplified as
the cutting-edge building blocks in pharmaceuticals and
biological applications.[4a-d] Additionally, they have been
frequently encountered in the fabrication of fullerene
fragments,[5a] bulky ligands,[5b-d] synthetic dendrimers,[5e] and
polycyclic aromatic hydrocarbons (PAHs).[5f-g] As a consequence,
enormous efforts have been made to access 1,3,5-
triarylbenzenesafter the discovery by Reppe et al.[6a] in 1948 via
transition metals catalyzed [2+2+2] cycloaddition of alkynes.
Later on, Pd-catalyzed coupling of 1,3,5-trihalobenzenes w ith
different organometallics w as adopted.[6b-k] As w ell, w ith the
contributions from numerous research groups over the past
decades, a number of straightforw ard methods have also been
developed for this purpose via cyclotrimerization of aryl ketones
[7a-b]
using Lew is/Bronsted acid catalysts
(Scheme 1a). Most of
the above mentioned protocols have suffered several limitations
such as (i) use of harsh reaction conditions and expensive
organometallic or strong acid as catalysts w hich are not
reusable and are toxic, (ii) narrow substrate scope and (iii) low
yields of products due to formation of undesirable side products.
Over the decades, few straightforw ard protocols have been
developed. For example, Wu et al.[8] have reported p-
toluenesulfonic acid catalyzed rearrangement of dienones to
1,3,5-triarlbenzenes. Besides, Ye et al.[9] have demonstrated
synthesis of these compounds via N-heterocyclic carbene
catalyzed [2+4] annulation of α-bromoenals and α-cyano-β-
methylenones (Scheme 1b). As w ell, Kim et al.[10] have prepared
PAHs from -nitrostyrenes using NaOAc in DMF at 90 oC.
Although, these protocols are selective but longer reaction time
(20 h), exploitation of non-reusable catalysts, easily not-
accessible starting compounds,[9] tw o-step process[9] and low
isolated yields (34-60 %)[10] restricted their practical applications
in terms of scope and sustainability. Till date, there is lack of a
mild, general and efficient protocol for synthesis of 1,3,5-
triarylbenzenes using reusable catalyst.
[a]
[b]
Dr. Arijit Saha, Dr. Subhash Banerjee
Department of Chemistry
Guru Ghasidas Vishwavidyalaya
Koni, Bilaspur, C.G., 495009, India
E-mail: ocsb2009@yahoo.com
Chia-Ming Wu, Rui Peng,Prof. Ranjit Koodali
Department of Chemistry
Conversely, 4-aryl-NH-1,2,3-triazole compounds have also
fascinated chemists for over past few decades and they are still
a focus of interest because of their w ide range of applications in
medicinal, agrochemical, and material industries.[11] The
University of South Dakota
414E. Clark Street, Vermillion, SD 57069, USA
Supporting information for this article is given via a link at the end of
the document.((Please delete this text if not appropriate))
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10.1002/ejoc.201801290
European Journal of Organic Chemistry
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traditional methods are mainly restricted to the cycloaddition of
alkynes w ith trimethylsilyl azide (TMSN3) follow ed by
deprotection of the TMS group.[12] Recently, the persistent efforts
of synthetic chemists to develop proficient route for 1,3-dipolar
cycloaddition reactions have revived the accessibility of this vital
heterocycle.[13] How ever, some limitations still remain like, use of
toxic Lew is/Bronsted acids, non-reusable expensive Pd/Ru/Ir-
based catalysts, generation of unw anted side products and toxic
hydrazoic acids. Thus, the synthesis of 4-aryl-NH-1,2,3-triazoles
is still quite challenging in terms of selectivity, scope, and
desorption studies. The assigned diffraction peaks at 2θ = 2.52°,
4.36° and 5.02° in the pow der XRD pattern of Pd-MCM-41
(Figure 1a) correspond to the (100), (110) and (200) reflection
planes respectively w hich are consistent w ith MCM-41 type of
material.[14] Besides, the pow der XRD pattern of Pd-MCM-48
(Figure S1a, SI 2) is similar to cubic MCM-48 w ith the basal
diffraction peaks at 2θ = 2.7° and 3.1°, corresponding to (211)
and {220} diffractions of the Ia3d cubic structure.[14] As w ell, the
pow der XRD pattern of Pd-SBA-15 (Figure S1b, SI 2) show s
three w ell-defined diffraction peaks at 2θ = 0.4°, 1.4°, and 1.6°,
due to (100), (110) and (200) reflection planes respectively
which is w ell defined for hexagonal p6mm SBA-15 material.[14]
This clearly indicates that incorporation of Pd NPs does not
destroy the periodic mesoporous structures of MCM-41, MCM-
48 and SBA-15. The high-angle pow der XRD pattern (inset
Figure 1a) of Pd-MCM-41 designates a broad diffraction peak at
2θ near 25o for amorphous silica and no peaks corresponding to
Pd NPs w ere observed w hich could possibly due to high
dispersion and low loadings of Pd onto the mesoporous silica
matrices. The FE-SEM image (Figure 1b) reveals the existence
of spherical morphology in the Pd-MCM-41. Furthermore, the
TEM image (Figure 1c) of this material clearly exhibits the w ell-
ordered pore of the MCM-41, surrounded by highly dispersed
ultra-small Pd NPs (~ 2 nm). Besides, the Brunauer-Emmett-
Teller (BET) analysis demonstrates that Pd-MCM-41 (Figure 1d-
e), Pd-MCM-48 (Figure S1c-d, SI 2) and Pd-SBA-15 (Figure
S1e-f, SI 2) materials are having surface areas (SBET) of 1500,
1400, and 778 m2/g respectively w ith pore volumes (Dv) of 0.81,
0.74, and 1.04 cc/g respectively and pore diameters (Dp) of 22.0,
19.4, and 56.3 Å respectively (Table 1). The energy dispersive
X-ray spectroscopic (EDS) elemental mapping (Figure 1f-h)
indicates the high dispersion of the Pd NPs onto the
mesoporous MCM-41. Next, w e have investigated the catalytic
performance of the mesoporous Pd-catalysts in the de-nitrative
cyclotrimerization of the -nitrostyrenes.
sustainability. As
development of synthetic methodologies using transition metal
loaded mesoporous materials[14]
herein w e report, the
a part of our continuous interest in the
,
expeditious de-nitrative cycloaddition of -nitrostyrenes to afford
1,3,5-triarylbenzenes and 4-aryl-NH-1,2,3-triazoles using highly
ordered mesoporous Pd-MCM-41 as
a reusable catalyst
(Scheme 1c). It is notew orthy to mention that, the large surface
area and uniform pore size distributions of mesoporous siliceous
materials make them ideal supports for active catalysts like
Pd/Ru/Cu/Fe in organic transformations.[15]
Results and Discussion
At the outset, w e have synthesized mesoporous nano-Pd-
catalysts by follow ing our previously reported protocols.[14a-d]
Briefly, Pd-precursor w as impregnated onto pre-synthesized
mesoporous silica materials namely, MCM-41, MCM-48 and
SBA-15 (SI 2) follow ed by reduction w ith H2 gas. The amount of
Pd w as adjusted to ~ 2 w t % by taking appropriate amount of
Pd-precursor. The structural and physio-chemical and textural
properties of the three catalysts, that is, Pd-MCM-41, Pd-MCM-
48 and Pd-SBA-15 w ere determined by pow der X-ray diffraction
(XRD), field emission scanning electron microscope (FESEM),
transmission electron microscope (TEM) and N2 adsorption-
(a)
(b)
(c)
(d)
500
450
400
350
300
250
200
0.0
0.2
0.4
0.6
0.8
1.0
2
3
4
5
6
1 mm
Relative Pressure (P/P0)
2 (degree)
7
(e)
(f)
(g)
(h)
6
5
4
3
2
1
0
1 mm
1 mm
1 mm
0
25 50 75 100 125 150 175
Pore diameter (Å)
Figure 1. (a) Powder XRD pattern; (b) FE-SEM image; (c) TEM image; (d) nitrogen adsorption-desorption isotherm; (e) pore size distribution; and (f -h) Energy
Dispersive Spectroscopic (EDS) study of Pd-MCM-41.
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10.1002/ejoc.201801290
European Journal of Organic Chemistry
FULL PAPER
Table 1. Physiochemical parameters of the mesoporous Pd-materials
Table 2. Optimization for 1,3,5-triarylbenzene (2a) synthesisa
Entry
Pd-catalyst
Pd-MCM-41
Pd-MCM-48
Pd-SBA-15
SBET (m2/g)
1500
1400
778
Dv (cc/g)
0.81
0.74
Dp (Å)
22.0
19.4
1
2
3
1.04
56.3
Entry
1
2
Catalyst
Base
Solvent
DMF
DMF
DMF
DMF
DMF
DMF
DMF
DMF
Yield (%)
99
84
80
63
00
00
65
82
TON
13.34
11.33
10.75
08.46
-
Pd-MCM-41
Pd-MCM-48
Pd-SBA-15
Pd-SiO2 NPs
Pd-MCM-41
No catalyst
Pd-MCM-41
Pd-MCM-41
Pd-MCM-41
Pd-MCM-41
Pd-MCM-41
K2CO3
K2CO3
K2CO3
K2CO3
No base
K2CO3
K2CO3
Na2CO3
Cs2CO3
K2CO3
K2CO3
To our delight, w hen, 1 mmol of -nitrostyrene (1a) w as heated
in presence of 2 equivalents of K2CO3 and 40 mg of Pd-MCM-41
in DMF at 120 oC, excellent yield (99%) of 1,3,5-
triphenylbenzene (2a) w as produced w ithin just 10 minutes
(entry 1, Table 2). Besides, Pd-MCM-48 and Pd-SBA-15 also
selectively produced 2a; albeit w ith low er yields as compared to
Pd-MCM-41(entry 2-3, Table 2). Interestingly, amorphous Pd-
SiO2 NPs (SI 3) as catalyst ended up the reaction w ith moderate
yield (63%, entry 4, Table 2). The low er yield of product using
Pd-SiO2 could possibly due to low er surface area (352 m2/g)
and lack of ordered and uniform pores in amorphous SiO2.[16]
3
4
5b
6b
-
7b,c
8b
08.76
11.05
09.43
05.53
06.74
9b
DMF
DMSO
PhMe
70
41
50
10b
11b
a-nitrostyrene (1.0 mmol), base (2.0 equiv.), catalyst (40 mg), solvent (3 mL),
120 oC, 10 min., unless otherwise stated. b60 min. reaction time. c1.0 equiv.
base was used. dTurnover number (TON) is moles of 2a formed per mole of
palladium.
Table 3. Substrate scope of meso-Pd-MCM-41catalyzed synthesis of 1,3,5-tri(aryl/heteroaryl)benzenesa
a-nitrostyrene 1 (1.0 mmol), K2CO3 (2.0 equiv.), Pd-MCM-41 (40 mg), DMF (3.0 mL), 120 oC, unless otherwise stated.
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10.1002/ejoc.201801290
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The higher activity of the MCM-41 based catalysts suggests that
the uniform and periodic pore structure and favorable textural
properties provide effective molecular trafficking of the reactants
and products and result in higher yields. These results highlight
the significant driving effect of the ordered pore structure in
MCM-41 mesoporous materials for catalytic reactions.
Conversely, the reaction in DMSO or PhMe proceeded
sluggishly, w hich suggests that DMF might be the solvent of
choice (entry 9-10, Table 2). Finally, the combination of Pd-
MCM-41 (40 mg) and K2CO3 (2 equiv.) in DMF w as proven to be
the efficient catalyst system to access this PAHs.
Scheme 2. Large scale production of 2a and 3a.
demonstrated by investigating the feasibility of the formation of
1,3,5-tri(heteroaryl)benzenes. Interestingly, Pd-MCM-41
efficiently catalyzed the denitrative cyclotrimerization of
heteroaromatic (e.g. furan, thiophene etc.) ring substituted -
nitrostyrenes under the standard reaction conditions affording 2s
and 2t w ith excellent yield and selectivity.
Furthermore, this excellent outcome motivated us to explore the
pow erful catalytic activity of the Pd-MCM-41 for the construction
of 4-aryl-NH-1,2,3-triazoles (3). To our delight, a variety of
substituted -nitrostyrenes w ere smoothly coupled w ith TMSN3
via de-nitrative [3+2] cycloaddition under the standard reaction
conditions (SI 5) affording 3a-l w ith excellent yields (93-99%)
and selectivity w ithin just 10 minutes. It is notew orthy to mention
that, further step or any additive (e.g. MeOH, TBAF etc.) for
TMS-deprotection is not required in this method. Besides, no
such pronounced electronic or steric effects w ere observed. The
scope of this reaction is presented in Table 4.
Under the standard reaction conditions (SI 5), w e further
achieved the de-nitrative cyclotrimerization of -nitrostyrenes
(1a-t) affording the functionalized 1,3,5-triarylbenzenes (2a-t)
w ith excellent yields (88-99%) w ithin just 15-30 min. A variety of
electron donating (e.g. -Me, -OMe, -Cl, -Br, -O-CH2-O- etc.) and
electron w ithdraw ing groups (e.g. -CN, -F, -CF3 etc.) containing
-nitrostyrenes smoothly underw ent the coupling reactions w ith
excellent efficiency. The results are presented in Table 3.
Notably, the presence of electron donating groups on -
nitrostyrene led to higher yields to some extent as compared to
electron w ithdraw ing groups. How ever, no significant steric
effect w as accounted for mono-/di-/tri-substitution at the aryl ring
of 1a. Conversely, different aromatic hydrocarbons like, 1-
naphthyl, 9-anthracenyl etc. substituted -nitrostyrenes furnished
the reactions w ith excellent productivity w ithin short reaction
time (12-15 min.). These aromatic hydrocarbon substituted
triarylbenzenes (2p, 2q) provided extended -conjugation and
may be better materials for electronics and opto-electronic
applications. Further, the diversity of this protocol has been
The catalytic system is also effective for large scale production
of 2 and 3 and good yields (88% for 2a and 90% for 3a) w ere
obtained even after 10 fold scaled-up under the standard
reaction conditions (Scheme 2).
Further, a plausible mechanism for mesoporous Pd-MCM-41
catalyzed de-nitrative cyclotrimerization of -nitrostyrenes
leading to 1,3,5-triarylbenzenes has been outlined in Scheme 3.
The reaction is proceeding via entrapment of -nitrostyrenes into
the mesopores of MCM-41 follow ed by cyclotrimerization under
the influence of interfacial Pd0 and finally the elimination of
nitrous acid[17] sequences. As, the reactions are typically very
fast, the intermediates w ere not detected during the course of
Table 4. Substrate scope of 4-aryl-NH-1,2,3-triazolesa
the reaction. Thus,
a clear understanding of the reaction
mechanism is still obscure.
Mesoporous
Pd--MCM-41
a-nitrostyrene derivative (1.0 mmol), TMSN3 (1.2 mmol), K2CO3 (2.0 equiv.),
Pd-MCM-41 (20 mg), DMF (3 mL), 80 oC, unless otherwise stated.
Scheme 3. Plausible reaction mechanism.
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99
100
90
80
70
60
50
40
30
20
10
0
100
90
80
70
60
50
40
30
20
10
0
97
96
96
(a)
85
(b)
(c)
93
91
90
20
15
15
12
12
12
10
10
1
2
3
4
5
6
7
8
2
3
4
5
6
2 (degree)
Run
Figure 2.(a) Reusability of Pd-MCM-41 for the synthesis of triphenylbenzene (1a); (b) Powder XRD pattern; and (c) TEM image of eight times reused Pd-MCM-41.
To probe the reusability of the studied catalyst in the synthesis
Conclusion
of 2a, Pd-MCM-41 w as recovered from the reaction system by
centrifugation, w ashed w ith w ater follow ed by acetone and then
dried w ell prior to reuse. The catalyst exhibited high reusability
(Figure 2a) and could be reused at least eight times w ithout
compromising its catalytic efficiency and stability (Figure 2b-c).
How ever, the slight change in product yield could be due to
changes in the structural integrity of the hexagonal mesophase,
agglomeration of Pd on the mesoporous support, and small loss
of catalyst during separation. The TEM image of the recycled
catalyst is presented in Figure 2c.
In order to investigate the heterogeneity of the as prepared
mesoporous Pd-MCM-41, leaching study w as performed by in
situ filtration technique. Here, 40 mg of Pd-MCM-41 w as stirred
in 3 mL of DMF for 24 h at 120 °C, subsequently; it w as filtered
in a 10 mL round bottom flask. Then, 1 mmol of -nitrostyrene
(1a) and 2 equivalents of K2CO3 w ere added in the same pot
follow ed by stirred at 120 °C. How ever, no desired product (2a)
was found even after 1 h, suggesting that Pd NPs are not being
leached out from the mesoporous MCM-41 support during the
course of the reaction. Further, this result w as also validated by
Atomic Absorption Spectrophotometric (AAS) analysis of the
filtrate w hich revealed the absence of Pd ions in the liquid phase.
In summary, w e have developed a rapid and efficient method for
the synthesis of functionalized 1,3,5-triarylbenzenes via
mesoporous Pd-MCM-41 catalyzed dentrative cyclotrimerization
of -nitrostyrenes. We have also compared the catalytic activity
of Pd-MCM-41 w ith Pd-MCM-48/Pd-SBA-15 but Pd-MCM-41
was proven to be the best due to the relatively high reactive
surface area and uniform pore diameter. Our results suggest the
importance of the periodicity of the silica support in enhancing
the catalytic activity due to efficient molecular trafficking and
effective dispersion of Pd nanopartciles, thus indicating the
effectiveness of active species present in a confined space.[32]
The catalyst w as also very effective in the de-nitrative [3+2]
cycloaddition of -nitrostyrenes w ith TMSN3to construct of 4-
aryl-NH-1,2,3-triazoles. All the reactions are typically very fast
and furnished w ithin 30 minutes affording excellent yields of
desired benzenes/triazoles. Remarkably, the compatibility of
w ide range of substituent offers further transformation
possibilities to synthesize useful functionalized molecules. The
catalyst exhibited high stability and reusability at least up to eight
times. Due to the mild conditions, easy availability of the
substrates, and high reusability of the catalyst, the present
method could potentially provide a practical approach to access
these benzene as w ell as triazole framew orks.
Finally,
a comparative study for the synthesis of 1,3,5-
triarylbenzenes, presented in Table 5, clearly indicates that the
present method using mesoporous Pd-MCM-41 is a better
alternative to the existing protocols[10] in terms of product yields,
reaction time and selectivity.
Experimental Section
Table 5. Comparative study of present methodology vs. previously reported
protocols for the synthesis of 1,3,5-triarylbenzenes from nitrostyrenes
Preparation
of
Mesoporous
Pd-MCM-41:
1.5
g
of
cetyltrimethylammonium bromide (CTAB) was added to 30 mL of
deionized water under vigorous stirring until completely dissolved. 35 mL
of aqueous NH3 and 45.6 mL of ethanol were added to the surfactant
solution. Afterwards, 3mL of tetraethylorthosilicate (TEOS) was added to
this solution. The stirring speed was kept at 500 rpm for 3 h and then
adjusted to 300 rpm for 12 h. The powder was recovered by filtration,
washed with distilled water, and dried in an oven at 80 - 90 oC overnight.
The dried powder was then ground finely and calcined at 550 oC for 5 h
at a heating rate of 1 oC min-1 to remove the template.
Pd-MCM-41 was synthesized by post-impregnation method as noted
below. The preparation of MCM-41 and MCM-48 is conducted in a highly
basic medium, while the preparation of SBA-15 is conducted in a highly
acidic medium. In order to ensure consistency and uniformity in the
loading of Pd, a post-impregnation method was used. 1 g of preformed
Entry
Catalyst;
Time
Yield
(%)
Product
scope
Catalyst
Reaction
reusability
conditions
Pd-MCM-41;
DMF; 120 oC
DMF-DMA; DMF;
80-90 oC
1[a]
15-30
min.
88-99
20-40
34-66
20
05
07
Yes
No
2[10a]
3[10b]
20 h
NaOAc; DMF; 80- 20 h
90 o
aRefers to present work.
No
C
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10.1002/ejoc.201801290
European Journal of Organic Chemistry
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Si-MCM-41 was dispersed in 20 mL of ethanol. Next, 0.056 g of
Na2PdCl4 was dissolved in 5 mL of aqueous ethanol and added drop
wise with continuous stirring. The dispersion was then dried at room
temperature. Finally, the dried sample was collected and calcined at 550
oC for 6 hours at a heating rate of 3 oC min-1. The calcined Pd-MCM-41
may contain Pd in the +2 oxidation state. Hence they were reduced in
hydrogen flow (20 mL/ min.) at 300 oC for 2 h in a tubular furnace.
The ICP-AAS study indicates the presence of 1.974 wt% of Pd in the
material.
7.65-7.62 (m, 6H), 7.17 (t, J = 8.4 Hz, 6H); 13C NMR (100 MHz,
CDCl3):163.9, 161.5, 141.5, 137.03, 137.0, 128.95, 128.87, 124.9,
115.9, 115.7.
4,4''-bis(trifluoromethyl)-5'-(4-(trifluoromethyl)phenyl)-1,1':3',1''-
terphenyl (2g, Table 3)[19]: White solid (146.31 mg, 86%); 1H NMR (400
MHz, CDCl3):7.82 (s, 3H), 7.80 (d, J = 8.4 Hz, 6H), 7.76 (d, J = 8.4 Hz,
6H); 13C NMR (100 MHz, CDCl3):144, 141.5, 130.2, 129.9, 127.7,
126.1, 126.0, 125.99, 125.96, 125.92, 125.5, 122.8.
2,2''-dichloro-5'-(2-chlorophenyl)-1,1':3',1''-terphenyl (2h, Table 3)[18]
:
White solid (132.48 mg, 97%); 1H NMR (500 MHz, CDCl3):7.60 (s, 3H),
7.48-7.45 (m, 6H), 7.35-7.25 (m, 6H); 13C NMR (125 MHz,
CDCl3):139.9, 138.9, 132.6, 131.6, 130.1, 129.8, 128.8, 126.9.
Representative Procedure for the Preparation of  -Nitrostyrene
derivatives[13c]
: In an oven dried 100 mL round bottom flask,
benzaldehyde (10.0 mmol), nitromethane (12.0 mmol) and ammonium
acetate (6.0 mmol) were added to 7 mL of glacial acetic acid. The
resulting solution was then refluxed for 2 h. After the completion of the
reaction, the reaction mixture was poured into ice cooled water. Then,
the yellow solid was collected by filtration followed by purified by column
chromatography on 100-200 mesh silica gel using ethyl acetate and
hexanes as eluent to afford -nitrostyrene (1a) as a yellow solid (1.12 g,
75%). 1H NMR (400 MHz, CDCl3): 7.98 (d, J = 14.0 Hz, 1H), 7.42-7.59
(m, 6H); 13C NMR(100 MHz, CDCl3):139.1, 137.1, 132.2, 130.1, 129.4,
129.2; HRMS: m/z [M+H]+ calcd. for C8H7NO2: 150.0550; found:
150.0542.
3,3''-dimethoxy-5'-(3-methoxyphenyl)-1,1':3',1''-terphenyl (2i, Table
3)[20]: White solid (129.52 mg, 98%); 1H NMR (400 MHz, CDCl3):7.77
(s, 3H), 7.39 (t, J = 8.0 Hz, 3H), 7.27 (d, J = 8.0 Hz, 3H), 7.21 (s, 3H),
6.93 (dd, J = 8.0, 1.6 Hz, 3H); 13C NMR (100 MHz, CDCl3):158.8,
141.4, 141.0, 128.7, 124.2, 118.7, 111.9, 111.8, 54.2.
5'-(2,4-dimethylphenyl)-2,2'',4,4''-tetramethyl-1,1':3',1''-terphenyl (2j,
Table 3): White solid (126.28 mg, 97%);1H NMR (400 MHz,
CDCl3):7.24 (s, 3H), 7.22 (d, J = 8.0 Hz, 3H), 7.11 (s, 3H), 7.06 (d, J =
7.6 Hz, 3H), 2.36 (s, 9H), 2.34 (s, 9H); 13C NMR (100 MHz,
CDCl3):141.3, 139.0, 136.9, 135.2, 131.2, 129.9, 128.5, 126.5, 21.1,
20.6; HRMS: m/z [M+H]+ calcd. for C24H18: 391.2420; found: 391.2416.
The above procedure was followed to prepare the other -nitrostyrene
derivatives from different aryl/heteroaryl aldehydes.
3,3'',4,4''-tetrachloro-5'-(3,4-dichlorophenyl)-1,1':3',1''-terphenyl (2k,
Table 3)[21]
:
White solid (167.60 mg, 98%);1H NMR (500 MHz,
Representative
procedure
for
the
synthesis
of
1,3,5-
CDCl3):7.79 (s,3H), 7.70 (d, J = 9.0 Hz, 3H), 7.48 (t, J = 9.0 Hz, 3H),
7.39 (t, J = 9.0 Hz, 3H); 13C NMR (125 MHz, CDCl3):142.4, 141.2,
128.9, 127.6, 127.4, 125.2.
triphenylbenzene derivative, 5'-phenyl-1,1':3',1''-terphenyl (2a, Table
3): In a 20 mL pre-dried screw-capped sealed tube, a suspension of -
nitrostyrene 1a (149.15 mg, 1.0 mmol), potassium carbonate (276.5 mg,
2.0 mmol) and Pd-MCM-41 (40 mg) in dry DMF (3 ml) was stirred at
120o C in an pre-heated oil bath for 10 minutes. After the completion of
the reaction, the reaction mixture was diluted with EtOAc (10 mL), filtered
through a short pad of silica gel and washed with EtOAc (30 mL). The
EtOAc layer was washed with saturated NH4Cl solution (2 x 10 mL) and
then brine (2 x 10 mL). The organic phase was dried over anhydrous
Na2SO4 and concentrated under reduced pressure. The crude product
was purified by column chromatography on 100-200 mesh silica gel with
n-hexane as an eluent to afford 1,3,5-triphenylbenzene (2a, Table 2) as a
white solid (101.11 mg, 99%). 1H NMR (400 MHz, CDCl3): 7.79 (s, 3H),
7.71 (d, J = 8.4 Hz, 6H), 7.48 (t, J = 8.0 Hz, 6H), 7.39 (t, J = 8.0 Hz, 3H);
13C NMR (100 MHz, CDCl3): 142.5, 141.3, 129.0, 127.7, 127.5, 125.3;
5'-(2,4-difluorophenyl)-2,2'',4,4''-tetrafluoro-1,1':3',1''-terphenyl
(2l,
Table 3)[22]
:
White solid (121.54 mg, 88%);1H NMR (500 MHz,
CDCl3):7.63 (s, 3H), 7.51-7.46 (m, 3H), 7.01-6.92 (m, 6H); 13C NMR
(125 MHz, CDCl3):135.6, 131.6, 128.8, 124.7, 111.8, 111.6, 104.5,
104.3.
2,2''-dibromo-5'-(2-bromo-5-fluorophenyl)-5,5''-difluoro-1,1':3',1''-
terphenyl (2m, Table 3): White solid (179.12 mg, 90%);1H NMR (400
MHz, CDCl3):8.28 (d, J = 8.8 Hz, 3H), 8.12 (s, 3H), 7.76-7.65 (m, 3H),
7.17-7.00 (m, 3H); 13C NMR (100 MHz, CDCl3):163.1, 134.6, 134.5,
129.9, 129.8, 129.6, 127.1, 121.5, 121.4, 118.6, 118.4, 116.8, 116.6,
116.4, 110.9, 110.7; HRMS: m/z [M+H]+ calcd. for C24H18: 594.8514;
found: 594.8515.
HRMS: m/z [M+H]+ calcd. for C24H : 307.1481; found: 307.1483.[18]
18
2,2''-dibromo-5'-(2-bromo-4-methylphenyl)-4,4''-dimethyl-1,1':3',1''-
terphenyl (2n, Table 3): White solid (183.35 mg, 94%);1H NMR (400
MHz, CDCl3):7.51 (s, 3H), 7.46 (s, 3H), 7.33 (d, J = 7.6 Hz, 3H), 7.17
(d, J = 7.6 Hz, 3H), 2.7 (s, 9H); 13C NMR (100 MHz, CDCl3): 140.2,
139.1, 139.0, 133.6, 131.3, 129.6, 128.3, 122.3, 20.7; HRMS: m/z [M+H]+
calcd. for C24H18: 582.9266; found: 582.9258.
The above procedure was followed to prepare the other 1,3,5-
triphenylbenzene derivatives 2b-2t from their respective starting
materials.
4,4''-dimethoxy-5'-(4-methoxyphenyl)-1,1':3',1''-terphenyl (2b, Table
3)[18]: White solid (130.84 mg, 99%); 1H NMR (400 MHz, CDCl3):7.65
(s, 3H),7.61 (d, J = 8.8 Hz, 6H), 7.00 (d, J = 8.0 Hz, 6H), 3.84 (s, 9H);
13CNMR (100 MHz, CDCl3):159.3, 141.9, 133.9, 128.4, 123.9, 114.3,
55.4.
1,3,5-tris(benzo[d][1,3]dioxol-5-yl)benzene (2o, Table 3): White solid
(143.22 mg, 98%);1H NMR (400 MHz, CDCl3):7.57 (s, 3H), 7.13 (d, J =
6.8 Hz, 6H), 6.89 (d, J = 8.4 Hz, 3H), 6.00 (s, 6H); 13C NMR (100 MHz,
CDCl3):148.2, 147.3, 142.0, 135.4, 124.3, 120.8, 108.6, 107.8, 101.2;
4,4''-dimethyl-5'-(p-tolyl)-1,1':3',1''-terphenyl (2c, Table 3)[18]: White
solid (113.84 mg, 98%); 1H NMR (500 MHz, CDCl3):7.73 (s, 3H), 7.59
(d, J = 8.0 Hz, 6H), 7.28 (d, J = 8.0 Hz, 6H), 1.54 (s, 9H); 13C NMR (125
MHz, CDCl3):142.3, 138.6, 137.4, 129.7, 127.3, 124.7, 21.3.
HRMS: m/z [M+H]+ calcd. for C24H : 439.1176; found: 439.1174.
18
1,3,5-tri(naphthalen-1-yl)benzene (2p, Table 3)[23]: White solid (147.63
mg, 97%);1H NMR (400 MHz, CDCl3):9.26 (d, J = 8.4 Hz, 3H), 8.11 (d,
J = 8.4 Hz, 3H), 8.01-7.92 (m, 9H), 7.72-7.60 (m, 9H); 13C NMR (100
MHz, CDCl3):136.7, 135.3, 131.4, 131.1, 130.6, 129.1, 128.5, 128.1,
128.0, 127.0, 125.0, 124.9.
1,3,5-tri(anthracen-9-yl)benzene (2q, Table 3)[24]: White solid (194.16
mg, 96%);1H NMR (400 MHz, CDCl3):8.49 (s, 3H), 8.28 (d, J = 7.2 Hz,
6H), 7.96 (d, J = 8.4 Hz, 6H), 7.74 (s, 3H), 7.65 (t, J = 7.2 Hz, 6H), 7.52
(t,J = 8.0 Hz,6H); 13C NMR (100 MHz, CDCl3):136.8, 135.7, 133.8,
132.8, 130.9, 130.6, 128.8, 127.3, 126.4, 125.3.
4,4''-dichloro-5'-(4-chlorophenyl)-1,1':3',1''-terphenyl (2d, Table 3)[18]
:
White solid (135.21 mg, 99%); 1H NMR (400 MHz, CDCl3):7.69 (s, 3H),
7.60 (d, J = 8.4 Hz, 6H), 7.45 (d, J = 8.4, 6H); 13C NMR (100 MHz,
CDCl3):141.5, 139.2, 133.9, 129.1, 128.6, 125.0.
4,4''-dibromo-5'-(4-bromophenyl)-1,1':3',1''-terphenyl (2e, Table 3)[18]
:
White solid (177.41 mg, 98%); 1H NMR (500 MHz, CDCl3):7.69 (s, 3H),
7.61 (d, J = 8.0 Hz, 6H), 7.53 (d, J = 8.5 Hz, 6H); 13C NMR (125 MHz,
CDCl3):141.5, 139.6, 132.1, 128.90, 125.0, 122.1.
3,3'',4,4'',5,5''-hexamethoxy-5'-(3,4,5-trimethoxyphenyl)-1,1':3',1''-
4,4''-difluoro-5'-(4-fluorophenyl)-1,1':3',1''-terphenyl (2f, Table 3)[18]
White solid (110.51 mg, 92%); 1H NMR (400 MHz, CDCl3):7.66 (s, 3H),
:
terphenyl (2r, Table 3)[25]: White solid (188.37 mg, 98%); 1H NMR (400
MHz, CDCl3):7.31 (s, 3H), 6.87 (s, 6H), 3.91 (s, 18H), 3.88 (s, 9H); 13
C
This article is protected by copyright. All rights reserved.

10.1002/ejoc.201801290
European Journal of Organic Chemistry
FULL PAPER
NMR (100 MHz, CDCl3):153.6. 152.9, 125.1, 119.0, 109.4, 106.8, 56.4,
4-(3,4,5-trimethoxyphenyl)-1H-1,2,3-triazole (2 i, Table 4)[30]: Off-white
solid (230.54 mg, 98%); 1H NMR (400 MHz, CDCl3+DMSO-d6):14.74
(bs, 1H), 8.02 (s, 1H), 7.07 (s, 2H), 3.83 (s, 6H), 3.72 (s, 3H); 13C NMR
(100 MHz, CDCl3):152.9, 146.0, 137.1, 129.9, 126.0, 102.4, 59.7, 55.4.
1,4-di(1H-1,2,3-triazol-4-yl)benzene (2j, Table 4)[31]: Off-white solid
(210.09 mg, 99%); 1H NMR (400 MHz, CDCl3+DMSO-d6):14.91 (bs,
1H), 8.10 (s, 2H), 7.92 (s, 4H); 13C NMR (100 MHz, CDCl3):146.1,
135.8, 130.4, 126.3.
56.2.
1,3,5-tri(furan-2-yl)benzene (2s, Table 3)[26]: White solid (90.25 mg,
98%); 1H NMR (500 MHz, CDCl3):7.86 (s, 3H), 7.50 (d, J = 2.0 Hz, 3H),
6.76 (d, J = 4.0 Hz, 3H), 6.50 (dd, J = 4.0, 2.0 Hz, 3H); 13C NMR (125
MHz, CDCl3):153.5, 142.3, 131.7, 118.0, 111.8, 105.8.
1,3,5-tri(thiophen-2-yl)benzene (2t, Table 3)[19]: White solid (106.0 mg,
98%);1H NMR (400 MHz, CDCl3):7.74 (s, 3H), 7.40 (d, J = 2.8 Hz, 3H),
7.33 (d, J = 4.8 Hz, 3H), 7.12 (t, J = 4.4 Hz, 3H); 13C NMR (100 MHz,
CDCl3):143.5, 135.7, 128.1, 125.4, 123.9, 122.8.
4-(1-ferrocenyl)-1H-1,2,3-triazole (2b, Table 4): Yellow solid (277.49
mg, 98%); 1H NMR (400 MHz, CDCl3+DMSO-d6):14.50 (bs, 1H), 7.68
(s, 1H), 4.67 (s, 2H), 4.25 (s, 2H), 3.98 (s, 5H); 13C NMR (100 MHz,
CDCl3):130.0, 119.3, 75.2, 74.6, 69.0, 68.2, 66.2; HRMS: m/z [M+H]+
calcd. for C8H7N3: 254.0375; found: 254.0385.
Representative procedure for the synthesis of 4-aryl-NH-1,2,3-
triazole derivative,4-phenyl-1H-1,2,3-triazole (3a, Table 4): In a 20 mL
pre-dried screw-capped sealed tube, a suspension of -nitrostyrene 1a
(149.15 mg, 1.0 mmol), trimethylsilyl azide (138.25 mg, 1.2 mmol),
potassium carbonate (276.5 mg, 2.0 mmol) and Pd-MCM-41 (40 mg) in
dry DMF (3 ml) was stirred at 80o C in an pre-heated oil bath for 5
minutes. After the complition of the reaction, the reaction mixture was
diluted with EtOAc (10 mL), filtered through a short pad of silica gel and
washed with EtOAc (30 mL). The EtOAc layer was washed with
saturated NH4Cl solution (2 x 10 mL) and then brine (2 x 10 mL). The
organic phase was dried over anhydrous Na2SO4 and concentrated
under reduced pressure. The crude product was purified by column
chromatography on 100-200 mesh silica gel with n-hexane-EtOAc as an
eluent to afford 4-phenyl-NH-1,2,3-triazole derivative (3a, Table 3) as a
off-white solid (143.71 mg, 99%). 1H NMR (500 MHz, CDCl3): 14.47 (bs,
1H), 7.92 (s, 1H), 7.83 (d, J = 8.0 Hz, 2H), 7.43 (t, J = 10.0 Hz, 2H), 7.34
(t, J = 9.0 Hz, 1H); 13C NMR (125 MHz, CDCl3): 147.2, 129.0, 128.8,
127.6, 126.7, 126.1; HRMS: m/z [M+H]+ calcd. for C8H7N3: 146.0713;
found: 146.0719.[13c]
4-(thiophen-2-yl)-1H-1,2,3-triazole (2l, Table 4)[13c]
: Brown solid
(148.17 mg, 98%); 1H NMR (400 MHz, CDCl3+DMSO-d6):14.86 (bs,
1H), 7.89 (s, 1H), 7.36 (s, 1H), 7.30 (s, 1H), 7.01 (s, 1H); 13C NMR (100
MHz, CDCl3):141.4, 132.6, 129.6, 127.3, 124.9, 124.1.
Acknowledgements
We are pleased to acknow ledge funding agency CCOST, Raipur
(ENDT No 2096/CCOST/MRP/2017). Special thanks to Prof. R.
Balamurugan and his research group and UGC Netw orking
Resource Centre, School of Chemistry, University of Hyderabad
for analytical facilities. We are also thankful to NSF-CHE-
0722632, NSF-CHE-0840507, NSF-EPS-0903804, and SD
NASA-EPSCOR NNX12AB17G for financial support.
The above procedure was followed to prepare the other 4-aryl-NH-1,2,3-
Keywords: 1,3,5-triarylbenzene • 4-aryl-NH-1,2,3-triazole •
cycloaddition • mesoporous materials • palladium
triazole derivatives3b-3lfrom their respective starting materials.
4-(4-methoxyphenyl)-1H-1,2,3-triazole (2b, Table 4)[13c]: Off-white solid
(173.44 mg, 99%); 1H NMR (500 MHz, CDCl3+DMSO-d6):14.41 (bs,
1H), 7.85 (s, 1H), 7.74 (d, J = 5.5 Hz, 2H), 6.96 (d, J = 10.5 Hz, 2H), 3.83
(s, 3H); 13C NMR (125 MHz, CDCl3):159.6, 129.7, 127.2, 123.4, 114.2,
113.5, 55.2.
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4-(4-chlorophenyl)-1H-1,2,3-triazole (2c, Table 4)[13c]: Off-white solid
(176.02 mg, 98%); 1H NMR (500 MHz, CDCl3+DMSO-d6):15.0 (bs, 1H),
8.13 (s, 1H), 7.84 (d, J = 8.0 Hz, 2H), 7.43 (d, J = 8.8 Hz, 2H); 13C NMR
(125 MHz, CDCl3):132.8, 129.2, 128.6, 128.2, 126.9.
4-(1H-1,2,3-triazol-4-yl)benzonitrile (2d, Table 4)[13c]
: Yellow solid
(163.36 mg, 96%); 1H NMR (400 MHz, CDCl3+DMSO-d6):15.18 (bs,
1H), 8.22 (s, 1H), 8.03 (d, J = 7.6 Hz, 2H), 7.78 (d, J = 7.2 Hz, 2H); 13
NMR (100 MHz, CDCl3):144.3, 134.6, 132.9, 126.5, 118.8, 110.5.
C
4-(4-(trifluoromethyl)phenyl)-1H-1,2,3-triazole (2e, Table 4)[27]: Off-
white solid (198.24 mg, 93%); 1H NMR (400 MHz, CDCl3+DMSO-
d6):14.39 (bs, 1H), 7.48 (s, 1H), 7.21 (d, J = 7.6 Hz, 2H), 6.87 (d, J =
8.0 Hz, 2H); 13C NMR (100 MHz, CDCl3):144.4, 134.2, 128.4, 128.1,
127.7, 127.2, 126.8, 125.6, 125.2, 125.17, 125.1, 125.06, 122.4.
4-(3-methoxyphenyl)-1H-1,2,3-triazole (2f, Table 4)[28]: Off-white solid
(171.69 mg, 98%); 1H NMR (400 MHz, CDCl3+DMSO-d6):15.13 (bs,
1H), 8.35 (s, 1H), 7.44 (d, J = 9.2 Hz, 2H), 7.36 (t, J = 8.0 Hz, 1H), 6.92
(d, J = 8.0 Hz, 1H), 3.81 (s, 3H); 13C NMR (100 MHz, CDCl3):160.1,
145.1, 131.0, 130.2, 126.2, 117.7, 113.1, 111.1, 55.7.
4-(2,4-difluorophenyl)-1H-1,2,3-triazole (2g, Table 4)[29]: Off-white solid
(170.27 mg, 94%); 1H NMR (400 MHz, CDCl3+DMSO-d6):14.30 (bs,
1H), 7.22 (s, 1H), 7.16 (s, 1H), 6.18 (d, J = 8.8 Hz, 2H); 13C NMR (100
MHz, CDCl3):163.0, 162.9, 160.5, 160.4, 160.1, 157.7, 139.5, 132.1,
131.7, 131.6, 131.3, 128.7, 114.8, 111.6, 111.55, 111.3, 104.0, 103.8,
103.5.
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4-(3,4-dichlorophenyl)-1H-1,2,3-triazole (2h, Table 4)[27]
: Off-white
solid (207.63 mg, 97%); 1H NMR (400 MHz, CDCl3+DMSO-d6):15.31
(bs, 1H), 8.49 (s, 1H), 8.11 (s, 1H), 7.86 (d, J = 8.4 Hz, 1H), 7.70 (d, J =
8.4 Hz, 1H).
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10.1002/ejoc.201801290
European Journal of Organic Chemistry
FULL PAPER
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This article is protected by copyright. All rights reserved.

10.1002/ejoc.201801290
European Journal of Organic Chemistry
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Mesoporous Pd-MCM-41 catalyzed
expeditious synthesis of 1,3,5-
De-nitrative Cycloaddition*
Arijit Saha,[a] Chia-Ming Wu,[b] Rui
Peng,[b] Ranjit Koodali,[b] and Subhash
Banerjee[a],*
triarylbenzenes and 4-aryl-NH-1,2,3-
triazoles have been developed via de-
nitrative cyclo-trimerization of -
nitrostyrenes and de-nitrative [3+2]
cycloaddition of -nitrostyrenes w ith
TMSN3 respectively. The catalyst w as
Page No. – Page No.
Mesoporous
Pd--MCM-41
Facile Synthesis of 1,3,5-
Triarylbenzenes and 4-Aryl-NH-1,2,3-
Triazoles Using Mesoporous Pd-
MCM-41 as reusable Catalyst
reused at least up to eight times w ith
minimum loss of catalytic activity.
12 examples
20 examples
High yielding protocol with high selectivity
 High functional groups compatibility
Broad substrate scope
*one or two words that highlight the emphasis of the paper or the field of the study
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Key Topic*
Author(s), Corresponding Author(s)*
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Title
Text for Table of Contents
*one or two words that highlight the emphasis of the paper or the field of the study
This article is protected by copyright. All rights reserved.