AgPd Nanoparticles Deposited on WO2.72 Nanorods as an Efficient Catalyst for One-Pot Conversion of Nitrophenol/Nitroacetophenone into Benzoxazole/Quinazoline

Article abstract of DOI:10.1021/jacs.7b01983

We report a seed-mediated growth of 2.3 nm AgPd nanoparticles (NPs) in the presence of 40 × 5 nm WO_2.72 nanorods (NRs) for the synthesis of AgPd/WO_2.72 composites. The strong interactions between AgPd NPs and WO_2.72 NRs make the composites, especially the Ag₄₈Pd₅₂/WO_2.72, catalytically active for dehydrogenation of formic acid (TOF = 1718 h^-1 and E_a = 31 kJ/mol) and one-pot reactions of formic acid, 2-nitrophenol, and aldehydes into benzoxazoles in near quantitative yields under mild conditions. The catalysis can also be extended to the one-pot reactions of ammonium formate, 2-nitroacetophenone, and aldehyde for high yield syntheses of quinazolines. Our studies demonstrate a new catalyst design to achieve a green chemistry approach to one-pot reactions for the syntheses of benzoxazoles and quinazolines.

Full text of DOI:10.1021/jacs.7b01983

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Communication
AgPd Nanoparticles Deposited on WO2.72 Nanorods as an
Efficient Catalyst for One-Pot Conversion of Nitrophenol/
Nitroacetophenone into Benzoxazole/Quinazoline
Chao Yu, Xuefeng Guo, Zheng Xi, Michelle Muzzio, Zhouyang
Yin, Bo Shen, Junrui Li, Christopher Seto, and Shouheng Sun
J. Am. Chem. Soc., Just Accepted Manuscript • DOI: 10.1021/jacs.7b01983 • Publication Date (Web): 12 Apr 2017
Downloaded from http://pubs.acs.org on April 12, 2017
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AgPd Nanoparticles Deposited on WO2.72 Nanorods as an Efficient
Catalyst for One-Pot Conversion of Nitrophenol/ Nitroacetophenone
into Benzoxazole/Quinazoline
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Chao Yu,† Xuefeng Guo,† Zheng Xi, Michelle Muzzio, Zhouyang Yin, Bo Shen, Junrui Li, Christopher
T. Seto* and Shouheng Sun*
†Department of Chemistry, Brown University, Providence, Rhode Island 02912, USA
.
Supporting Information Placeholder
dioxane/water (v/v 2/1), the Ag48Pd52/WO2.72 composite catalyzes
the dehydrogenation of FA, the hydrogenation of RNO2 to RNH2,
the condensation between RNH2 and aldehydes (RCHO) to form
Schiff base intermediates (RNH=CR), and the intra-molecular
nucleophilic addition within the Schiff base compounds followed
by the dehydrogenation into benzoxazoles. Each reaction step
gives nearly a quantitative yield of the related product. The
Ag48Pd52/WO2.72 catalysis can be readily extended to one-pot
reactions comprising the dehydrogenation of ammonium formate
(AF) and the conversion of 2-nitroacetophenone/aldehyde to
quinazolines. The catalyst offers a green chemistry approach to
high yield syntheses of benzoxazoles or quainazolines that are key
components found in large molecules prepared for natural product
and biomedical applications.23-28
ABSTRACT: We report a seed-mediated growth of 2.3 nm AgPd
nanoparticles (NPs) in the presence of 40 × 5 nm WO2.72 nanorods
(NRs) for the synthesis of AgPd/WO2.72 composites. The strong
interactions between AgPd NPs and WO2.72 NRs make the
composites, especially the Ag48Pd52/WO2.72, catalytically active
for dehydrogenation of formic acid (TOF = 1718 h-1 and Ea = 31
kJ/mol), and one-pot reactions of formic acid, 2-nitrophenol and
aldehydes into benzoxazoles in near quantitative yields under
mild conditions. The catalysis can also be extended to the one-pot
reactions of ammonium formate, 2-nitroacetophenone and
aldehyde for high yield syntheses of quinazolines. Our studies
demonstrate a new catalyst design to achieve a green chemistry
approach to one-pot reactions for the syntheses of benzoxazoles
and quinazolines.
Developing an efficient and reusable catalyst for multi-step
chemical reactions under environmentally benign conditions is a
hierarchic goal in catalytic sciences. This has stimulated
tremendous research efforts aiming to understand dimension- and
structure-dependent catalysis as well as synergistic effects that
can be employed within multiple catalyst systems to extend the
catalytic power from one reaction to another. Despite the progress
made in past computational and experimental studies, the catalysts
developed thus far are often effective for one specific reaction.
Recent demonstrations on the dehydrogenation of ammonia
borane and hydrogenation of nitro- (RNO2) or cyano-compounds
(R-CN) to primary amines without using pure hydrogen provide
an exciting potential for using well-designed nanoparticles (NPs)
to catalyze tandem reactions.1-6 Compared to ammonia borane,
formic acid (FA) is environmentally greener and a less toxic
choice as a hydrogen source for hydrogenation reactions. Pd-
based NP catalysts have been the most attractive candidates
explored to promote FA dehydrogenation (HCOOH ꢀ H2 + CO2)
over dehydration pathway (HCOOH ꢀ CO + H2O).7-15 However,
these catalysts are rarely reported for other tandem reactions,
except for the two-step dehydrogenation of FA and hydrogenation
of RNO2 to RNH2.16-18
Scheme 1. Schematic illustration of one-pot FA dehydrogenation and
conversion of nitrophenol/aldehyde to benzoxazole catalyzed by
AgPd/WO2.72
.
We prepared the WO2.72 NRs by reacting WCl4 with oleic acid
(OA) and oleylamine (OAm) in 1-octadecene (ODE) at 280 °C for
10 h, as reported (supporting information, SI).29 Figure S1 shows
the transmission electron microscopy (TEM) image of the
representative NRs with an average length of 40 nm and diameter
of 5 nm. We also synthesized AgPd NPs by the co-reduction of
silver(I) acetate (AgOAc) and palladium(II) acetylacetonate
(Pd(acac)2) at 180°C as described previously.8 Figure S2 is the
representative TEM image of the as-synthesized 2.3 nm Ag48Pd42
NPs. We tested self-assembly of the AgPd NPs and the WO2.72
NRs but could only obtain a physical mixture of the two
components without evidence of them being in strong coupling.
To obtain the strongly coupled AgPd/WO2.72 nanocomposites, we
ran the same reaction leading to the synthesis of AgPd NPs but in
the presence of WO2.72 NRs (SI). The in-situ nucleation and
In this communication, we report a new catalyst design based
on AgPd alloy NPs and the defected perovskite-type WO2.72
nanorods (NRs) for efficient one-pot FA dehydrogenation and
conversion of nitrophenol/aldehyde to benzoxazole, as
summarized in Scheme 1. In this composite catalyst structure,
AgPd NPs act as the catalyst, which are then coupled strongly to
the acid-stable and oxygen-deficient WO2.72 NRs for strong
interactions with reactants.19-22 In the solvent mixture of
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growth of AgPd NPs along the WO2.72 NRs ensures strong
much less active than Ag48Pd52/WO2.72 (Figure S7). The high
activity of the Ag48Pd52/WO2.72 is induced most likely by the
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coupling between AgPd NPs and WO2.72 NRs.19,
The metal
1
content of the AgPd and the molar ratios of the AgPd/WO2.72 were
controlled by the molar ratios of metal precursors, and the
composition of the final products were determined by inductively
coupled plasma-atomic emission spectroscopy (ICP-AES). From
presence of WO2.72 and the strong binding between Ag48Pd52 and
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WO2.72 as the defected WO2.72 tends to absorb “H” to form
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HxWO2.72
,
which should facilitate AgPd catalysis for the FA
dehydrogenation reaction.
the controlled reaction, Ag78Pd22/WO2.72
, Ag57Pd43/WO2.72,
We tested the Ag48Pd52/WO2.72 catalyst for the hydrogenation
of R-NO2 to R-NH2 with FA as a hydrogen source at 50 °C.
Nitrobenzene was chosen as a model substrate to obtain the
optimum reaction conditions. After investigating the effects of
solvents, catalyst loadings and FA amounts on this reaction (Table
S1 and S2), we found that the reaction in the mixed solvent of
dioxane + water (v/v 2/1) could be completed within 30 mins and
the conversion yield (obtained by gas chromatography-mass
spectrometry (GC-MS)) to aniline reached 98%. Following this
reaction optimization, we studied the FA-induced hydrogenation
of five additional RNO2 molecules and summarize the results in
Table 1. The Ag48Pd52/WO2.72 catalyst is very effective in using
FA to hydrogenate RNO2 to RNH2 with nearly quantitative
conversion yield (by GC-MS) within 2 h.
Ag48Pd52/WO2.72, Ag39Pd61/WO2.72 and Ag20Pd80/WO2.72 were
obtained with the final metal/metal oxide molar ratio at 3:5 (SI)
and the Ag48Pd52/WO2.72 composition was further supported by
energy dispersive X-ray (EDX) spectroscopy (Figure S3). Figure
1 shows the representative TEM images of the Ag48Pd52/WO2.72
obtained from the synthesis (SI). The 2.3 nm Ag48Pd52 NPs attach
to WO2.72 NRs. High-resolution TEM (HRTEM) of a single
WO2.72 NR shown in Figure 1C indicates that the WO2.72 structure
has an interfringe distance of 0.38 nm that is close to 0.378 nm of
(010) interplanar distance of monoclinic WO2.72 (JCPDS No. 65-
1291). Ag48Pd52 NPs attached to the WO2.72 NR have an average
interfringe distance of 0.25 nm that is slightly larger than 0.23 nm
measured from the as-synthesized Ag48Pd52 NPs (Figure 1C
inset). X-ray diffraction (XRD) of the Ag48Pd52/WO2.72, Ag48Pd52
and WO2.72 structure (Figure S4) show a very weak diffraction
pattern of the fcc structured Ag48Pd52 NPs due to their small size.
After attaching to WO2.72, the (111) diffraction peak of the
Ag48Pd52 NPs shift to a lower diffraction angle, while the WO2.72
NRs in the composite structure show no obvious diffraction peak
change. The (111) peak shift of the AgPd NPs is similar to what
was reported.8 These HRTEM and XRD studies indicate that in
the composite AgPd/WO2.72 structure, AgPd NPs are in the alloy
form and interactions between AgPd and WO2.72 lead to more
obvious changes to AgPd (lattice expansion) than to WO2.72.
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Table 1. The Ag48Pd52/WO2.72-catalyzed hydrogenation of Ar-NO2 in the
presence of FA. Reaction conditions: R-NO2 (1 mmol), Ag48Pd52/WO2.72
(3 mol%), dioxane (6 mL), H2O (3 mL), FA (3 mmol), 50 °C.
Next, we studied the Ag48Pd52/WO2.72 catalyzed hydrogenation
of RNO2 and condensation of the resulting RNH2 with RCHO.
Under similar reaction conditions with addition of 1.2 mmol
benzaldehyde, 1.5 h of reaction at 50 °C led to the formation of
the Schiff base, diphenylmethanimine (conversion yield 98%).
We further studied the combined hydrogenation of 2-
nitrophenol and subsequent condensation/cyclization with
benzaldehyde to give benzoxazoles. Benzoxazoles are commonly
synthesized by condensation of 2-substituted aminoaromatics with
aldehydes or by coupling 2-substituted aminoaromatics with
carboxylic acid derivatives.42-47 Both methods are complicated by
strongly acidic conditions, long reaction times, multiple reaction
steps, and tedious work-up procedures. We studied the reaction in
the presence of different Ag, Pd, and AgPd catalysts with
different supports (Table S3) and reaction conditions (Table S4)
and found Ag48Pd52/WO2.72 to be the best catalyst, and 80 °C to be
the optimal reaction temperature for the synthesis of 2-
Figure 1. (A-B) TEM image of the Ag48Pd52/WO2.72 nanocomposite in
different scale bar; (C) HRTEM image of the Ag48Pd52/WO2.72. Inset is the
HRTEM image of the Ag48Pd52 NPs synthesized in the absence of WO2.72
.
We first studied catalytic properties of the AgPd/WO2.72 for FA
dehydrogenation reactions, similar to what was reported in the
study of the AgPd/C systems.8 From the FA dehydrogenation
kinetics studied at 50°C (Figure S5), we concluded that our
AgPd/WO2.72 is generally more active than AgPd/C for the
reaction. The most active catalyst in the AgPd/C system is
Ag42Pd58/C while in the current WO2.72-supported AgPd system,
Ag48Pd52/WO2.72 is the most active one (Figure S5&S6). With an
initial TOF of 1718 h-1 and an activation energy of Ea = 31
phenylbenzoxazole (99
%
conversion yield). Using the
Ag48Pd52/WO2.72 catalyzed one-pot reactions, we prepared several
different benzoxazoles as listed in Table 2. The nearly
quantitative yields of the purified products indicate that the
tandem reactions are insensitive to the electron-donating or
election-withdrawing nature of the substitutes. The results from
the one-pot reactions and two control experiments (Figure S8)
show that the one-pot reactions follow the known reaction
mechanisms,48, 49 but the presence of Ag48Pd52/WO2.72 makes the
reactions proceed (Scheme S1) in much milder reaction
conditions. Overall, compared with previous syntheses of
benzoxazoles, the unique part of the current catalyst is that it
kJ/mol, this Ag48Pd52/WO2.72 is one of the most active
11, 13, 31-35
heterogeneous catalysts ever reported.10,
We also
deposited the Ag48Pd52 NPs on C and found Ag48Pd52/C to be
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catalyzes one-pot reactions into the benzoxazole products without
no obvious loss in activity and the yield remained >92% (Figure
S13). We characterized again the catalyst after the 5th reaction
cycle for the synthesis of 2-phenylbenzoxazole and found that the
catalyst had neither morphology nor structure change (Figure
S14).
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the use of pure hydrogen and in environmentally benign
conditions. Compared to any other catalyst reported,48-54
Ag48Pd52/WO2.72 is much more active and selective towards the
formation of benzoxazole products due likely to the synergistic
role of WO2.72 in enriching the O-containing precursors around
each AgPd NP and in facilitating AgPd-catalyzed
dehydrogenation reactions via the HxWO2.72 intermediates.
Detailed mechanistic studies are on the way.
In conclusion, we report a convenient seed-mediated approach
to synthesize the composite AgPd/WO2.72. In this seed-mediated
growth process, the in-situ nucleation/growth of AgPd NPs in the
presence of WO2.72 NRs stabilizes the AgPd NPs and enhances
their interactions with the WO2.72 NRs. The resultant lattice
expansion of the AgPd NPs coupled with the synergistic effect
from WO2.72 make the composite, especially Ag48Pd52/WO2.72, an
excellent catalyst to promote one-pot reactions of formic acid, 2-
nitrophenol and RCHO into benzoxazoles in near quantitative
yields under mild conditions. In this one-pot high-yield synthesis
of benzoxazole, the Ag48Pd52/WO2.72 composite shows a unique
capability to catalyze two dehydrogenations, one hydrogenation,
one condensation and one cyclization reaction. The hydrogenation
reaction proceeds without the use of pure hydrogen in
dioxane/water (v/v 2/1) at temperatures below 80 °C. The
Ag48Pd52/WO2.72 catalysis can be further extended to one-pot
reactions of ammonium formate, 2-nitroacetophenone and
aldehyde for high-yield syntheses of quinazolines under 60 °C.
Our studies demonstrate the design of a new catalyst to achieve a
green chemistry approach to one-pot reactions for the syntheses of
benzoxazoles or quinazolines that can be important for natural
product and pharmaceutical applications in the future.
Table 2. Ag48Pd52/WO2.72-catalyzed one-pot aromatization of 2-
nitrophenol and various benzaldehydes. Reaction conditions: 2-
nitrophenol (1 mmol), aromatic or aliphatic aldehyde (1.2 mmol),
Ag48Pd52/WO2.72 (3 mol%), dioxane (6 mL), water (3 mL) and formic acid
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(4 mmol), 8 h
.
The Ag48Pd52/WO2.72 composite can also catalyze the
dehydrogenation of ammonium formate (AF) for the one-pot
synthesis of quinazolines. The Ag48Pd52/WO2.72 catalyzed
decomposition of AF (Figure S9&S10) provides the desired
source of hydrogen and ammonia for next-step reactions. Using
the formation of 4-methyl-2-phenylquinazoline as an example, we
screened reaction conditions (Table S5) and chose 60 °C as the
optimal reaction temperature. We investigated the aromatization
of 2-nitroacetophenone with several representative aromatic or
aliphatic aldehydes in the Ag48Pd52/WO2.72 catalyzed one-pot
reactions and list the results in Table 3. The one-pot reactions lead
to the high yield formation of the corresponding quinazoline
products. Furthermore, control experiments (Figure S11)
ASSOCIATED CONTENT
Materials and experimental methods, and supplementary figures
and tables. This material is available free of charge via the
Internet at http://pubs.acs.org.
AUTHOR INFORMATION
Corresponding Author
ssun@brown.edu
christopher_seto@brown.edu
corroborate what has been reported in the related organic
56
reactions,55,
and indicate that the formation of quinazoline
follows a similar reaction mechanism as outlined in Scheme S3.
Author Contributions
†These authors contributed equally to this study.
Table 3. Ag48Pd52/WO2.72-catalyzed one-pot aromatization of 2-
nitroacetophenone with various aldehydes. Reaction conditions: 2-
nitroacetophenone (1 mmol), aromatic or aliphatic aldehyde (1.2 mmol),
Ag48Pd52/WO2.72 (4 mol%), dioxane (6 ml), water (3 ml) and ammonium
Notes
The authors declare no competing financial interest.
formate (3 mmol), 6 h
.
ACKNOWLEDGMENT
The work was supported in part by the U.S. Army Research
Laboratory and the U.S. Army Research Office under grant
W911NF-15-1-0147, and by Strem Chemicals. M.M. is supported
by the National Science Foundation Graduate Research
Fellowship, under Grant No. 1644760. We also thank
Professor Qing Li of Huazhong University of Science and
Technology (China) for his help in characterizing the catalyst
after the stability test.
Finally, we studied the stability of the Ag48Pd52/WO2.72 catalyst
in the one-pot reactions. Once the reaction was over, we
precipitated the catalyst by adding a small amount of ethyl acetate
for better catalyst isolation and purification (Figure S12). We
separated and washed the catalyst with water/methanol, and re-
used it in the one-pot reactions for the formation of 2-
phenylbenzoxazole or 4-methyl-2-phenylquinazoline. In each
case, after the 5th reaction-purification cycle, the catalyst showed
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