N‐Methylation of N‐Methylaniline with Carbon Dioxide and Molecular Hydrogen over a Heterogeneous Non‐Noble Metal Cu/TiO2 Catalyst

Liu, Ke; Zhao, Zhuofeng; Lin, Weiwei; Liu, Qiang; Wu, Qifan; Shi, Ruizhi; Zhang, Chao; Cheng, Haiyang; Arai, Masahiko; Zhao, Fengyu

doi:10.1002/cctc.201900582

Cited by 20 publications

(17 citation statements)

References 49 publications

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“…Thus, from 2014 on, several contributions were reported by the groups of Shi, Shimizu & Toyao, Wang & Su, Lin, Yu, Cheng & Zhao and Tamura & Tomishige. In this context, [CuAlO x ] 130 , [Pd/CuZrO x ] 131 , [Pt-MoO x /TiO 2 ] 132 , [Au/Al 2 O 3 -VS] 133 , [PdGa/TiO 2 ] 134 , [Cu/CeO 2 ] 135 , [Re/TiO 2 ] 24 , [Cu/TiO 2 ] 136 , and [Pd-ZnO/TiO 2 ] 137 systems were presented as active heterogeneous materials, at different reaction conditions (temperatures from 140 to 230 °C and hydrogen pressures from 25 to 70 bar), for the direct synthesis of N -methylamines by using CO 2 /H 2 .…”

Section: Related Catalytic Hydrogenative Transformationsmentioning

confidence: 99%

Homogeneous and heterogeneous catalytic reduction of amides and related compounds using molecular hydrogen

et al. 2020

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Catalytic hydrogenation of amides is of great interest for chemists working in organic synthesis, as the resulting amines are widely featured in natural products, drugs, agrochemicals, dyes, etc. Compared to traditional reduction of amides using (over)stoichiometric reductants, the direct hydrogenation of amides using molecular hydrogen represents a greener approach. Furthermore, amide hydrogenation is a highly versatile transformation, since not only higher amines (obtained by CO cleavage), but also lower amines and alcohols, or amino alcohols (obtained by C-N cleavage) can be selectively accessed by fine tuning of reaction conditions. This review describes the most recent advances in the area of amide hydrogenation using H 2 exclusively and molecularly defined homogeneous as well as nanostructured heterogeneous catalysts, with a special focus on catalyst development and synthetic applications. T he development of green and sustainable methods is a central focus of modern organic synthesis and its applications in various areas of the chemical industry. In this respect, many reduction reactions, traditionally employing stoichiometric amounts of metal hydrides with inherent low atom efficiency 1 , can be favorably replaced by catalytic hydrogenations. In fact, the combination of molecular hydrogen and catalysts does not only allow avoiding formation of waste products 2 , it also opens the door to clean transformations based on renewable energies as the conversion of solar or wind energy to "green" hydrogen is likely to be implemented in the coming years. Among the many reduction reactions known, amide hydrogenation can be encountered as one of the most desired considering the importance of the derived amines in several branches of chemical industry. In fact, since the start of the Green Chemistry Institute Pharmaceutical Roundtable in the United States in 2005, several projects aimed to the achievement of a practical amide hydrogenation methodology have been supported 3,4. The long-term interest of the pharmaceutical industry in this specific transformation is explained by the fact that it ideally affords structurally complex amines, present in many of the currently employed drugs. Furthermore, amines are also in bulk and fine chemicals used in the manufacture of plastics, textiles, surfactants, dyes, and many more 5. Amides play a central role in the chemistry of life, as they are the key elements to generate peptides and proteins from amino acid monomers. At the same time, they are present in artificial

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Section: Related Catalytic Hydrogenative Transformationsmentioning

confidence: 99%

Homogeneous and heterogeneous catalytic reduction of amides and related compounds using molecular hydrogen

et al. 2020

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“…56 N-Methylaniline can also react directly with activated H 2 to form aniline by demethanation. 69 3.3.4. Preliminary Reaction Mechanism of CO 2 with Amine/H 2 and the Critical Role of CUS.…”

Section: Preliminary Reaction Mechanism and The Critical Role Of Cusmentioning

confidence: 99%

Critical Role of CUS in the Au/MOF-808(Zr) Catalyst for Reaction of CO₂ with Amine/H₂ via N-Methylation and N-Formylation

Liu

Ran

et al. 2020

Ind. Eng. Chem. Res.

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MOF-808(Zr) with the coordinated unsaturated (CUS) Zr4+ centers was synthesized by the thermal reflux method, and a series of Au/MOF-808(Zr) catalysts with different Au loading percentages have been prepared by the impregnation–reduction method. The related X-ray diffraction, Fourier transform infrared spectroscopy, high-resolution transmission electron microscopy, X-ray photoelectron spectroscopy, N2 adsorption–desorption, Inductively coupled plasma-mass spectrometry, and NH3 temperature-programmed desorption characterizations have been undertaken to understand the structure of catalysts. The catalytic activity in CO2 with aniline/H2 to N-methylation and N-formylation has been studied in a batch reactor. Results show that the MOF-808(Zr) structures in catalysts are of high quality and damage-free. The Au nanoparticles (NPs) are highly dispersed on the surface of the MOF-808(Zr) cage with a mean size of 2–20 nm. Also, the catalysts could catalyze the conversion of CO2 with aniline/H2 to N-methylation and N-formylation products with a high efficiency. With a 3.0 wt % Au/MOF-808(Zr) catalyst, the conversion of aniline is 18.4%, and the selectivity of N-methylaniline is 80.9% and that of N,N-dimethylaniline is 19.1%. The preliminary reaction mechanism and the critical role of CUS were also studied. It is determined that H2 is adsorbed and activated on Au NPs. CO2 is adsorbed on the CUS Zr4+ acidic sites and O2– basic sites. The primary and secondary amines are adsorbed on the CUS Zr4+ acidic sites, where they react with CO2 and H2 to form N-formamide. Subsequently, N-formamide reacts with activated H2 to yield N-methylamine.

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“…Examples of such catalytic systems involve organometallic complexes of ruthenium 4 , rhodium 5 or iron 6 . Amines were successfully methylated by CO2/H2 over solid catalysts as well, such as CuAlOx 7 , Pt-MoOx/TiO2 8 , PdGa/TiO2 9 or Cu/TiO2 10 . These systems, however, require a high pressure of H2.…”

mentioning

confidence: 99%

Additive-free selective methylation of amines with formic acid over a Pd/In2O3 catalyst

Genre

Benaissa

Godou

et al. 2021

Preprint

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N‐Methylation of N‐Methylaniline with Carbon Dioxide and Molecular Hydrogen over a Heterogeneous Non‐Noble Metal Cu/TiO₂ Catalyst

Cited by 20 publications

References 49 publications

Homogeneous and heterogeneous catalytic reduction of amides and related compounds using molecular hydrogen

Homogeneous and heterogeneous catalytic reduction of amides and related compounds using molecular hydrogen

Critical Role of CUS in the Au/MOF-808(Zr) Catalyst for Reaction of CO₂ with Amine/H₂ via N-Methylation and N-Formylation

Additive-free selective methylation of amines with formic acid over a Pd/In2O3 catalyst

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N‐Methylation of N‐Methylaniline with Carbon Dioxide and Molecular Hydrogen over a Heterogeneous Non‐Noble Metal Cu/TiO2 Catalyst

Cited by 20 publications

References 49 publications

Homogeneous and heterogeneous catalytic reduction of amides and related compounds using molecular hydrogen

Homogeneous and heterogeneous catalytic reduction of amides and related compounds using molecular hydrogen

Critical Role of CUS in the Au/MOF-808(Zr) Catalyst for Reaction of CO2 with Amine/H2 via N-Methylation and N-Formylation

Additive-free selective methylation of amines with formic acid over a Pd/In2O3 catalyst

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N‐Methylation of N‐Methylaniline with Carbon Dioxide and Molecular Hydrogen over a Heterogeneous Non‐Noble Metal Cu/TiO₂ Catalyst

Critical Role of CUS in the Au/MOF-808(Zr) Catalyst for Reaction of CO₂ with Amine/H₂ via N-Methylation and N-Formylation