Xiumin
Ma
,
Yinxi
Zhou
,
Jicheng
Zhang
,
Anlian
Zhu
,
Tao
Jiang
* and
Buxing
Han
*
Beijing National Laboratory for Molecular Sciences, Institute of Chemistry, Chinese Academy of Sciences, Beijing, 100080, China. E-mail: Jiangt@iccas.ac.cn; Hanbx@iccas.ac.cn; Fax: +86-10-62562821
First published on 19th October 2007
Heck arylation of olefins with aryl halides was carried out in solvent-free conditions with a Pd catalyst supported on 1,1,3,3-tetramethylguanidinium (TMG)-modified molecular sieve SBA-15 (designated as SBA-TMG-Pd). SBA-TMG-Pd was much more active and stable than a Pd catalyst supported on pristine SBA-15 (designated as SBA-Pd). The catalysts were characterized by Fourier transform infrared spectroscopy (FT-IR), X-ray photoelectron spectroscopy (XPS), and transmission electron microscopy (TEM), and the reasons for the excellent performance of catalyst SBA-TMG-Pd were also discussed.
Mesoporous SiO2 are attractive supports due to their advantageous properties, such as excellent chemical and thermal stability, high porosity, large surface area, and high surface concentration of silanols. Ying et al.11d reported Pd-grafted molecular sieves MCM-41 that effectively catalyzed heterogeneous Heck reactions. More recently, Crudden et al.11c demonstrated that thiol-modified mesoporous materials (SBA-15-SH) are excellent scavengers for Pd and the Mizoroki–Heck reaction was successfully catalyzed without leaching Pd into the solution.
In recent years, ionic liquids (ILs) have attracted much attention due to their special properties, such as negligible vapor pressure, wide liquid range, excellent chemical stability, high thermal stability, and the strong solvent power for a wide range of organic, inorganic, and polymeric molecules. Many reactions have been carried out in ILs,14 including the Heck reaction in 1,1,3,3-tetramethylguanidinium IL, without using additional base.14c Recently, ILs immobilized onto solid supports have been used to prepare catalysts. For example, 1-butyl-3-methylimidazolium hexafluorophosphate ([bmim][PF6]) and 1-butyl-3-methylimidazolium tetrafluoroborate ([bmim][BF4]) dispersed on silica gel can provide a solvent environment for a Rh complex, resulting in the excellent catalytic activity and stability for hydrogenation.15 Some functional ILs exhibit a strong ability to stabilize nanoparticles. By immobilizing Pd and Ru nanoparticles on different supports with the assistance of 1,1,3,3-tetramethylguanidinium-based IL, different catalysts have been prepared, which also showed outstanding catalytic performance for the hydrogenation of benzene and olefins.16 More recently, a series of very effective supported catalysts for different organic reactions have been prepared using different ILs and solid supports.17
The Heck reaction can be performed in organic solvents, ionic liquids, and CO2. However, less attention has been paid on the Heck reaction in a solvent-free condition,18 although it is environmentally benign and economically profitable. Based on the consideration of minimizing the amount of ILs used, avoiding the use of organic solvents, easy recovery of catalyst, in this work, Pd nanoparticles were immobilized on molecular sieves SBA-15 using IL 1,1,3,3-tetramethylguanidinium lactate (TMGL). The Heck reaction was performed in solvent-free conditions with the immobilized Pd catalyst (designated as SBA-TMG-Pd). It is shown that the catalyst has an excellent activity and reusability for the Heck reaction.
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Entry | Bases | Solvents | Temperature/°C | Pd (mol%) | Reaction time | Isolated yields (%) |
a The molar ratio of methyl cinnamate to cinnamic acid is 60 : 40; b The molar ratio of methyl cinnamate to cinnamic acid is 38 : 62. | ||||||
1 | Et3N | — | 140 | 0.01 | 65 min | 91 |
2 | CH3COONa | — | 140 | 0.01 | 65 min | 64 |
3 | Na2CO3 | — | 140 | 0.01 | 65 min | 60 |
4a | NaOH | — | 140 | 0.01 | 65 min | 68 |
5 | Et3N | NMP | 140 | 0.01 | 65 min | 82 |
6b | Et3N | H2O | 140 | 0.01 | 65 min | 92 |
7 | Et3N | — | 140 | 0.001 | 2 h | 93 |
8 | Et3N | — | 120 | 0.01 | 3 h | 92 |
The Heck arylation reaction of a variety of vinylic substrates with different functional groups was also investigated using SBA-TMG-Pd as the catalyst in solvent-free conditions, and the results are illustrated in Table 2. It is known that the catalyst is very effective for the reactions with iodobenzene as the arylating agent. For all the olefins examined, moderate to excellent yields were achieved. When monosubstituted vinylic substrates, such as acrylic acid and different acrylate esters, were employed (Table 2, entries 1, 2, 3 and 4), high yields and only E-isomers were obtained, which was confirmed by 3J (H–H) = 16 Hz. However, when styrene and acrylonitrile were used, except for the main product, a little of 1,1-diphenyl ethylene and Z-isomer were detected, respectively (Table 2, entries 5 and 9). As for the bulky substrates, such as disubstituted olefins (Table 2, entries 6, 7 and 8), the yields were moderate. When 1-iodonaphthalene and 1-fluoro-4-iodobenzene were used as arylating agents (Table 2, entries 10, 11, 12, 13 and 14), the reaction could also proceed smoothly with high yields. For aryl bromides, the catalyst showed lower activity (Table 2, entries 15 and 16).
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Entry | Aryl halides | Alkenes | Products | Reaction time | Isolated yields (%) (a/b) |
a Reaction conditions: ArI (2 mmol), alkene (2.2 mmol), Et3N (2.4 mmol), the amount of Pd is (0.01 mol%); b ArI (2 mmol), acrylic acid (2.2 mmol), Et3N (4.4 mmol); c ArI (2 mmol), methacrylic acid (2.2 mmol), Et3N (4.4 mmol); d The amount of Pd is 0.05 mol%; e The amount of Pd is 0.05 mol%. | |||||
1 |
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65 min | 91 |
2 |
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1.5 h | 92 |
3 |
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2 h | 93 |
4b |
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45 min | 94 |
5 |
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4 h | 90 (95/5) |
6c |
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1.5 h | 67 |
7 |
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3 h | 72 |
8 |
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4.5 h | 60 |
9 |
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1.5 h | 89 (88/12) |
10 |
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3.5 h | 88 |
11 |
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1.5 h | 90 |
12 |
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4.5 h | 85 (80/20) |
13 |
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7 h | 92 |
14 |
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60 min | 92 |
15d |
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15 h | 33 |
16e |
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8 h | 54 |
Experiments were also conducted to examine the recyclability of SBA-TMG-Pd. As can be seen from Fig. 1, after six repeated catalytic coupling reactions of iodobenzene with methyl acrylate, no obvious deactivation of the catalyst was observed, and the catalyst still remained as a grey powder. For comparison, we examined the reusability of the Pd catalyst supported on SBA-15 in the absence of the IL (designated as SBA-Pd). The results in Fig. 1 indicated that the deactivation of SBA-Pd was obvious. The catalyst was observed to become a white powder after 2 recycles. In other words, SBA-TMG-Pd had a much higher stability, although the catalytic activity of the two catalysts was similar in the first run.
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Fig. 1 Recycling of SBA-TMG-Pd and SBA-Pd for the Heck reaction of iodobenzene with methyl acrylate at 140 °C with a reaction time of 50 min each time (the amount of Pd is 0.05 mol%). |
The catalysts were characterized by X-ray photoelectron spectroscopy (XPS). Fig. 2 shows the Pd 3d spectrum of the catalyst. It can be seen that the deconvoluted spectrum showed a doublet for two chemically different Pd entities, with peak binding energies of 335.0 eV (Pd 3d5/2) and 340.25 eV (Pd 3d3/2), which confirmed the presence of Pd0 in the catalyst. Moreover, the peak at 336.1 eV suggests the presence of a Pd–O component, which probably resulted from the oxidation of the Pd nanoparticles upon exposure to air.
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Fig. 2 XPS spectrum of the Pd 3d edge of the SBA-TMG-Pd sample. The vertical lines indicate the peak positions of the binding energies of Pd–O, and Pd. |
Fig. 3 shows the transmission electron microscope (TEM) images of the two catalysts. For SBA-TMG-Pd (Fig. 3a), most of Pd nanoparticles existed in the channels of SBA-15, and the diameters of Pd nanoparticles were in the range of 3–6 nm before use. However, for the catalyst SBA-Pd (Fig. 3b), the diameters of most Pd nanoparticles were in the range of 9–12 nm, which is bigger than the pore diameter of SBA-15, resulting in their existence on the outside surface of SBA-15. After six recycles, most Pd nanoparticles on SBA-TMG-Pd still existed in the channel of SBA-15, although some bigger Pd particles were formed (Fig. 3c). For SBA-Pd, after 2 recycles, most of Pd disappeared and few Pd nanoparticles existed on the surface of the support, as can be seen from the micrograph (Fig. 3d). The change of color of the two catalysts further confirmed this. The catalyst SBA-TMG-Pd still remained as a grey powder after six recycles. However, SBA-Pd became white powder after 2 recycles.
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Fig. 3 TEM images of the catalysts (a) SBA-TMG-Pd; (b) SBA-Pd; (c) SBA-TMG-Pd after 6 recycles; (d) SBA-Pd after 2 recycles. |
The difference of the two catalysts was that ionic liquid TMGL was utilized when preparing SBA-TMG-Pd. The presence of the cation of the ionic liquid in the catalyst SBA-TMG-Pd is supported by the fact that the catalyst contained 10 wt% organic compound, as determined by TGA. The existence of the TMG cations was also supported by the FT-IR spectrum (Fig. 4). The characteristic peaks of CH3group at 1412 cm–1, 1455 cm–1, and 2944 cm–1, and the peak of the CN bond at 1612 cm–1 can be observed in the spectrum of SBA-TMG-Pd. TMG group played an important role in stabilizing the catalyst SBA-TMG-Pd. It is known that guanidine has considerable coordination ability.19 The reason for the better reusability of SBA-TMG-Pd than SBA-Pd was that TMG-modified SBA-15 was a better scavenger for Pd than the pristine SBA-15. After the aryl halides were completely consumed, palladium redeposited on the support with the help of TMG. But for SBA-Pd, most Pd was lost in the reaction solution.
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Fig. 4 The FT-IR of SBA-15, 1,1,3,3-tetramethylguanidine (TMG) and the as prepared catalysts. |
Recently, the mechanism of the catalytic processes of the Heck reaction employing a supported palladium source as the catalyst has been intensely disputed in literature. Some researchers deduced that the catalyst was working in a heterogeneous manner,11b,11c,11d,20 while others reported that the support acted merely as a reservoir for a more active soluble form of Pd.9,21 In order to study the behavior of the Pd in our catalytic system, a filtration test was carried out using Pd-TMG-SBA as the catalyst in this work. After 25 min (the reaction was completed in 65 min), the reaction mixture was taken out from the autoclave. To ensure that all solid catalyst was separated, the reaction mixture was centrifuged at 16000 rpm for 30 min. Then, the solid-free filtrate was allowed to continue to react under the same conditions for another 1 h. The results indicated that the reaction continued and iodobenzene was completely consumed. This suggests that the leaching of active palladium species from the solid support occurred during the reaction. However, Pd redeposited back onto the support after the completion of the reaction.9,20 This argument was supported by the AAS analysis of the reaction samples. After reaction, SBA-TMG-Pd was separated from the ethanol solution of the reaction mixture, and the solution was collected and analysed by AAS method for Pd metal. Only less than 0.3% Pd of the initially added catalyst was detected. From the whole catalytic process, the catalyst apparently behaved just like a heterogeneous catalyst, which could be recovered and reused facilely.
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Scheme 1 The synthesis of TMGL. |
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This journal is © The Royal Society of Chemistry 2008 |