Molecular Catalysis
·
2022
·
IF 5.089
Xiao-Chao Chen,Lin Guo,Guang-Hui Shi,Kai-Chun Zhao,Yong Lu,Ye Liu
Carbon dioxide (CO 2 ) was found to serve as a novel and green catalyst for the first time in N -formylation of amines with N, N -dimethylformamide (DMF), wherein only the aliphatic amines were applicable to afford the formamides in the yield of 71∼95%. The isotope labeling experiment with DMF- d 7 indicated that the N -formyl group in the formylated product was originated from DMF rather than CO 2 . The control experiments and the in situ high-pressure FT-IR spectra demonstrated that the formation of the carbamate salt of cyclohexylammonium cyclohexylcarbamate ( A ) derived from the reaction of CO 2 with cyclohexylamine was the driving force for this reaction. Accordingly, the mechanism of CO 2 -catalyed N -formylation of aliphatic amines with DMF was proposed, involving the formation of carbamate salt intermediate with enhanced nucleophilicity in anion in favor of the attack on carbonyl-group of DMF.
研究领域:
有机化学
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绿色化学
✓ 已验证
DOI
高影响因子
C-Journal of Carbon Research
·
2024
·Vol. 10
·期 3
·62
·
IF 3.9
Xuexin Yuan,Qiqi Zhou,Yu Chen,Hai-Jian Yang,Qingqing Jiang,Juncheng Hu,Cun-Yue Guo
In the present work, inexpensive and commercially available diethyltriamine pentaacetic acid (DTPA) was used as an initiator to catalyze the N-formylation reaction of CO2with amines via the construction of C-N bonds in the presence of xanthone as the photosensitizer and PhSiH3as the reducing agent. After a systematic study of various factors, the optimal conditions for the photocatalytic reaction were obtained: 2.5 mmol of amine, 2.5 mmol of PhSiH3, 10 mol% of DTPA, 20 mol% of xanthone, 1 mL of dimethylsulfoxide (DMSO), atmospheric pressure, and 35 W UV lamp irradiation for 48 h. Under the optimal conditions, the catalyst system afforded high performance for the N-formylation of amines (primary and secondary amines) and CO2, and the yields of the N-formylated products of dialkylamines were above 70%. Further studies exhibit that the catalytic system has a wide scope of substrate applications. For various alicyclic secondary amines, heterocyclic secondary amines, aliphatic primary amines, and aromatic primary amines, the corresponding N-formylation products can be obtained efficiently. In addition, the catalyst can be recycled by simple precipitation and filtration. After five cycles of recycling, there was no significant change in the catalytic and structural properties of DTPA. Finally, a possible reaction mechanism is proposed.
研究领域:
化学
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环境科学
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材料科学
✓ 已验证
产品关联
DOI
高影响因子
CATALYSIS TODAY
·
2024
·
IF 5.2
Peng Bai,Yicheng Zhao,Yongdan Li
Photocatalytic N -formylation of amines with CO 2 is a promising strategy to convert CO 2 into value-added chemicals sustainably. In this work, Pd-Bi bimetallic modified ZnO enriched in oxygen vacancies is constructed for photocatalytic CO 2 formylation of benzylamine at room temperature without any reductants. The Pd and Bi sites reduce the band gap energy of ZnO, promote the separation of the photogenerated charge carriers and enhance the adsorption capacity of CO 2 . The yield of N -benzylformamide reaches 31.7 mmol g −1 with a selectivity of 85.3 % after 3-hour radiation in N , N -dimethylformamide (DMF) solvent. The aldehyde group involved in the formylation of benzylamine is derived from the decomposition of DMF, which is regenerated with the aldehyde group coming from the reduction of CO 2 . The decomposition-regeneration cycle of DMF solvent enlarges the reaction region, which is beneficial to the activity and selectivity of the formylation process. The synergistic photocatalytic system shows a good universality. This study provides a new approach to high-efficiency CO 2 utilization and formamide production.
研究领域:
材料科学
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环境科学
·
化学工程
✓ 已验证
产品关联
DOI
高影响因子
NEW JOURNAL OF CHEMISTRY
·
2024
·
IF 2.7
Yufen Wang,Yantao Wang,Yongqing Ma,Asma Mohmmad Elsharif,Chen Zhang,Weiran Yang,Christophe Len
A new transition-metal-free catalytic system which uses sodium iodide as the catalyst with formic acid as the hydrogen donor in a biphasic medium was reported for the reduction of the hydroxyl group and various unsaturated groups such as CC, CC, CN and CO. Using the same catalytic system, reductive N-formylation of nitroarenes with formic acid was explored to produce the corresponding amide in high selectivity. Moreover, the catalyst stability was evaluated and reaction mechanisms were studied and proposed for the three model reactions.
研究领域:
有机化学
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催化化学
✓ 已验证
产品关联
DOI
高影响因子
CATALYSIS COMMUNICATIONS
·
2020
·
IF 3.612
Pengbo Wang,Qian He,Hao Zhang,Qingdi Sun,Yujie Cheng,Tao Gan,Xiaohui He,Hongbing Ji
Several research studies have been conducted on N -formylation of amines using phenylsilane and CO 2 . However, most of these studies involved tedious processes of catalyst preparation or complex procedures. In the present study, we describe the use of a simple and commercially available ZnO catalyst for selective N -formylation of amines under mild condition. High-yielding N -formylation products with good recyclability and wide substrate scope were obtained, which can promote fine chemical synthesis and CO 2 capture.
研究领域:
有机化学
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催化化学
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绿色化学
✓ 已验证
产品关联
DOI
高影响因子
ACS Sustainable Chemistry & Engineering
·
2021
·
IF 8.198
Jian Fang,Zhi-Qiang Wang,Xinjia Wei,Yuan Ma,Honghui Gong,Xue-Qing Gong,Zhenshan Hou
The N-formylation reaction of various amines with CO2 is a promising method to utilize CO2 for the production of high value-added chemicals. Herein, an efficient Ru catalyst system consisting of Ru complex ([PPN][Ru(CO)3Cl3]) and the ionic liquid 1-butyl-3-methylimidazolium hydrogen phosphate ([Bmim]2[HPO4]), has been developed for the N-formylation reaction. Activity evaluation demonstrated that the catalyst system exhibited good to excellent yields of formamides under very mild conditions with the assistance of ionic liquids (ILs). Furthermore, the catalyst system could be reused at least five times with a slight loss of activity in N-formylmorpholine production. Further characterization by 1H nuclear magnetic resonance (NMR), 13C NMR, and density functional theory (DFT) calculations showed that the ILs ([Bmim]2[HPO4]) could facilitate the adsorption of CO2 by a concerted action of both cations and anions of the ILs to form phosphorus carbonate intermediate, thus effectively promoting the reaction. DFT calculations demonstrated that the formation of Ru–H was the first step, and then the CO2 absorbed by [Bmim]2[HPO4] inserted directly into Ru–H by cooperating with the Ru sites to form HCOO– species. After that, formate species dissociated from Ru catalysts and dehydrated to form formamides by the catalytic action of Ru complex and the basic IL.
研究领域:
化学工程
·
催化化学
✓ 已验证
DOI
高影响因子
APPLIED CATALYSIS B-ENVIRONMENTAL
·
2021
·
IF 19.503
Qiang Cao,Long-Long Zhang,Chang Zhou,Jing-Hui He,Antonio Marcomini,Jian-Mei Lu
Transformation of CO 2 into value-added chemicals with efficient and recyclable catalyst is an effective way to reduce carbon emissions. It is valuable to develop an efficient catalyst that can promote the N-formylation reaction under mild conditions with a high activity and excellent recyclability. Single atom catalysts (SACs) possess ultimate atom utilization efficiency and outstanding catalytic performance. Herein, we synthesize Zn SACs (Zn-TpPa) anchored on a COF (TpPa-1) using a facile solution method. Catalyzed by Zn-TpPa, CO 2 and N-methylamine are transformed into N-methylformanilide under mild reaction conditions with a TOF of 17,155 h −1 , which is the highest among all reported recyclable Zn-based catalysts. Zn-TpPa can also catalyze N-formylation of many other amines with excellent yields. The higher reactivity was attributable to the well-dispersed Zn active sites on COF and outstanding adsorption of CO 2 owing to high surface area of COF. Our research provides a facile method for constructing SACs as well as an effective pathway for CO 2 transformation and environmental protection.
研究领域:
化学
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环境科学
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催化材料
✓ 已验证
产品关联
DOI
高影响因子
GREEN CHEMISTRY
·
2018
·Vol. 21
·期 3
·567-577
·
IF 8.586
Wenfeng Zhao,Xiaoping Chi,Hu Li,Jian He,Jingxuan Long,Yufei Xu,Song Yang
Catalytic fixation of CO2 to produce valuable fine chemicals is of great significance to develop a green and sustainable circulation of excessive carbon in the environment. Herein, a series of non-toxic, biodegradable and recyclable acetylcholine-carboxylate bio-ionic liquids with different cations and anions were simply synthesized for producing formamides and methylamines using atmospheric CO2 as a carbon source, and phenylsilane as a hydrogen donor. The selectivity toward products was tuned by altering the reaction temperature under solvent or solvent-free conditions. N-Methylamines (ca. 96% yield) were obtained in acetonitrile at 50 °C, while N-formamides (ca. 99% yield) were attained without a solvent at 30 °C. The established bio-ionic liquid catalytic system found a wide range of applicability in substrates and possessed a high potentiality in scale-up to gram-grade production. The developed catalytic system was fairly stable, which could be easily reused without an apparent loss of reactivity, possibly due to the strong electrostatic interactions between the cation and anion. The combination of experimental and computational results explicitly elucidated the reaction mechanism: PhSiH3 activated by a bio-IL was favorable for the formation of silyl formate from hydrosilylation of CO2, followed by a reaction with an amine to give an N-formamide, while an N-methylamine was formed by further hydrosilylation of the N-formamide.
研究领域:
绿色化学
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环境科学
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有机化学
✓ 已验证
产品关联
DOI
高影响因子
CHINESE JOURNAL OF CHEMICAL ENGINEERING
·
2021
·
IF 3.171
Yipeng Zheng,Zhennan Cao,Zheng Zhou,Gaodong Yang,Zhibing Zhang
A series of SO 3 -functional Brønsted acidic ionic liquids (SBAILs) were prepared to catalyze the N -formylation of aniline with DMF . The reaction conditions such as ionic liquid type, reaction temperature, catalyst loading and molar ratio of reactants were investigated. To the best of our knowledge, kinetic model for the N -formylation of aniline with DMF using SBAIL was firstly built and simulated. The studies on the reaction order of the reaction were evaluated by initial concentration method, and the kinetic parameters such as reaction rate constant and activation energy were proposed and used to explain the catalytic activities of the SBAILs catalysts. Accordingly, the recycling experiments showed that the SBAIL [Bsmim][HSO 4 ] can be easily recovered and reused with stable activity. Further, the temperature-controlled study emphasized that the ionic liquid was easy to be separated and environmentally friendly.
研究领域:
化学工程
·
催化化学
✓ 已验证
产品关联
DOI
高影响因子
Journal of CO2 Utilization
·
2023
·
IF 7.7
Qin Wen,Xuexin Yuan,Qiqi Zhou,Hai-Jian Yang,Qingqing Jiang,Juncheng Hu,Cun-Yue Guo
The catalytic fixation of greenhouse gas CO 2 has been a hot topic of research, in which the reduction and functionalization of CO 2 is important for application. In present work, cheap and readily available alkanolamines were used as efficient catalysts with phenylsilanes as reducing agents to achieve the N-formylation reaction by constructing C-N bonds via the reaction between CO 2 and amines (aliphatic or aromatic amines) under mild conditions (40℃and 0.1 MPa). Further studies showed that present catalytic system has wide substrates application. Mono-N-formylated compounds were obtained as main products with good to high yields for all amines. It is worthy noted that for p-aminobenzylamine containing two amino groups as substrate, both amino groups are formylated and N-formylation reaction occurs mainly in aliphatic amine with high electron cloud density. Scale-up research has been performed effectively with high conversion of amine (80%) to obtain the mono-formylated product selectively. Finally, the mechanism of the reaction between amine and CO 2 is proposed via control experiments and spectra verification. Systematic mechanism studies have revealed that after polarization by polar solvent DMSO, N-methyldiethanolamine activates CO 2 by forming internal salts, which are subsequently reduced by phenylsilanes to formoxysilane intermediates and finally to form N-formylated products.
研究领域:
化学
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环境科学
✓ 已验证
DOI
高影响因子
Journal of Materials Chemistry A
·
2018
·Vol. 6
·期 19
·9172-9182
·
IF 9.931
Yaju Chen,Rongchang Luo,Junhui Bao,Qihang Xu,Jun Jiang,Xiantai Zhou,Hongbing Ji
On the basis of the development of function-oriented synthesis (FOS), we presented for the first time an efficient and one-pot construction of functional ionic polymers (FIPs) through the phenol–formaldehyde condensation process (pre-synthetic approach); FIPs had high density of Brönsted acidic and ionic sites. Considering the electrophilic–nucleophilic dual activation of phenolic hydroxyl groups and bromide anions, the imidazolium-based FIP-Im exhibited high activity for metal-, solvent- and additive-free synthesis of cyclic carbonates from CO2 and epoxides under mild conditions. Then, to obtain higher ionic density and a more flexible skeleton, FIP-Im@QA was also prepared by implanting quaternary ammonium (QA) in the framework of FIP-IMvia the Williamson ether synthesis (post-synthetic modification), which demonstrated high efficiency in the N-formylation reaction of multitudinous secondary amines with CO2 and PhSiH3 at ambient temperature. More interestingly, these function-oriented catalysts were compatible with the target transformation under low CO2 concentration (15% in 85% N2, v/v) and were also reused for more than six times without a significant loss of activity and selectivity. Therefore, this study could not only facilitate the design and construction of FIPs, but also provide sustainable protocols for efficient production of value-added chemicals from CO2 under mild conditions.
研究领域:
化学工程
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材料科学
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环境科学
✓ 已验证
产品关联
DOI
高影响因子
SEPARATION AND PURIFICATION TECHNOLOGY
·
2024
·
IF 8.1
Xinpeng Guo,Jian Yin,Haishuai Cui,Jiating Gong,Siqi Cheng,Yunlong Li,Xinglu Deng,Feiying Tang,Shaofeng Xiong,Pingle Liu
The N-formylation reaction of amines by CO 2 hydrogenation is a promising method for converting CO 2 into chemical products with industrial application value. However, most of the currently developed catalysts are metal-homogeneous catalysts, which contain metal pollution and are not easy to recycle. Thus, we modified carbon nanotubes with N-containing amino compounds and prepared a polyethylenimine (PEI) grafted carbon nanotubes metal-free catalyst, which was applied to the N-formylation reaction of CO 2 and aniline. By adjusting the grafting concentration and the type of amino compound, the acid-base properties and surface defects of the catalyst were regulated. The CNT-0.5PEI catalyst had the optimal catalytic activity after 12 h of reaction at 80 °C, with a conversion rate of 95.41 % for aniline and a selectivity of 94.04 % for the target product N-formylaniline. It reveals that its catalytic performance can be comparable to the reported homogeneous catalysts. Our research found that increasing the surface defects and basic sites of carbon nanotubes was conducive to the enrichment and activation of CO 2 , thereby enhancing the catalytic activity. The experimental and calculation results indicate that the reaction has relatively low activation energy under the catalysis of CNT-0.5PEI, and the catalyst has the strongest adsorption capacity for CO 2 and aniline reactants. In addition, the CNT-0.5PEI displays a wide range of substrate applicability and excellent cyclic stability. Therefore, cheap and environmentally friendly metal-free modified carbon nanotube catalyst is an ideal substitute for scarce and polluting metal homogeneous materials. It has important reference significance for the efficient conversion and utilization of CO 2 catalyzed by metal-free catalyst.
研究领域:
化学工程
·
材料科学
·
环境科学
✓ 已验证
产品关联
DOI
高影响因子
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