JOURNAL OF ORGANIC CHEMISTRY
·
2021
·
IF 4.354
Hao Song,Yao Xiao,Zhuohua Zhang,Wanjin Xiong,Ren Wang,Liangcheng Guo,Taigang Zhou
A simple and efficient copper-catalyzed selective transfer hydrogenation of nitriles to primary amine-boranes and secondary amines with an oxazaborolidine–BH3 complex is reported. The selectivity control was achieved under mild conditions by switching the solvent and the copper catalysts. More than 30 primary amine-boranes and 40 secondary amines were synthesized via this strategy in high selectivity and yields of up to 95%. The strategy was applied to the synthesis of 15N labeled in 89% yield.
研究领域:
有机化学
·
催化化学
✓ 已验证
DOI
PubMed
高影响因子
NEW JOURNAL OF CHEMISTRY
·
2019
·Vol. 44
·期 2
·549-555
·
IF 3.069
Jianjian Wang,Qingjie Tang,Shiwei Jin,Yanxin Wang,Ziliang Yuan,Quan Chi,Zehui Zhang
The development of new heterogeneous non-noble catalytic systems for the selective hydrogenation of nitriles into primary amines is a challenging task. In this study, a mesoporous Al2O3 supported Ni catalyst (denoted as Ni/Al2O3-600, where 600 represents the reduction temperature) demonstrated a high catalytic activity for the hydrogenation of nitriles under mild conditions (60–80 °C and 2.5 bar H2) with ammonia as the additive. This catalytic system has a wide substrate range and the Ni/Al2O3 catalyst demonstrated a good tolerance to other functional groups, which was possibly due to its high catalytic activity under mild conditions. A plausible reaction pathway was proposed for the hydrogenation of nitriles into primary amines, and it was found that ammonia played a great role in the enhancement of the selectivity of primary amines by the inhibition of the side reaction to generate secondary amines. In addition, the Ni/Al2O3-600 catalyst could be reused five times without activity loss through convenient magnetic recovery.
研究领域:
催化化学
·
有机合成
✓ 已验证
DOI
高影响因子
SYNTHETIC COMMUNICATIONS
·
2024
·
IF 1.8
Xiaoyun Ma,Xiaoyan Wan,Jun Zhao
A method for the preparation of nitriles from primary amides using trichloroacetonitrile and a catalytic amount of cupric acetate is described. Using this method, amides including aromatic amides, aromatic heterocyclic amides and aliphatic amides were converted into the corresponding nitriles in moderate to good yields. Trichloroacetonitrile reacted with amide in the presence of cupric acetate to form trichloroacetamide, which has been isolated and confirmed.
研究领域:
有机化学
·
合成化学
✓ 已验证
DOI
高影响因子
ACS Catalysis
·
2025
·
IF 13.1
Jia-qi Bai,Mei Ma,Huangfei Liu,Zhangkai Qian,Durui Liu,Yuncai Zhao,Yijing Gao,Jingshuai Chen,Mengdie Cai,Song Sun
The hydrogenation of nitriles is an environmentally friendly and atom-economical route to prepare high-value amines; however, it is still a challenge to control selectivity because of the occurrence of hydrogenation, self-coupling, and hydrogenolysis reactions during the hydrogenation process. It is highly desirable to develop efficient non-noble-metal catalysts for the hydrogenation of nitriles to secondary amines, although several noble metal catalysts have been reported. Herein, we successfully prepared a Cu–Ni/W20O58 catalyst and found that the Cu4.4–Ni0.6/W20O58 catalyst showed a 92.3% yield with initial TOFs of 270.0 h–1 at 373 K and 3 MPa H2 for the hydrogenation of benzonitrile (BN) to dibenzylamine (DBA), which was much superior to that of the monometallic Cu4.4/W20O58 and Ni0.6/W20O58 catalysts. Moreover, the Cu4.4–Ni0.6/W20O58 catalyst could be reused at least 4 times and was effective for the hydrogenation of various nitriles with superior selectivity to secondary amines. Furthermore, the reaction mechanism of BN hydrogenation for the Cu–Ni alloy of Cu4.4–Ni0.6/W20O58 was proposed on the basis of spectroscopic studies such as XRD, TPR, TEM, XAFS, and XPS, kinetic studies such as the effect of BN concentration and H2 pressure, the isotopic effect of hydrogen, and the effect of the reaction temperature and DFT calculations. The rate-determining step was the hydrogenation of benzylidenamine (BI) to the half-hydrogenated intermediate by one H atom over the Cu4.4–Ni0.6/W20O58 catalyst. The Ni–W20O58 interface was responsible for the adsorption and activation of BN, and the electron-rich Cu acted as the site for H2 dissociation; the synergistic effect of Cu and Ni led to the superior catalytic performance of the Cu4.4–Ni0.6/W20O58 catalyst.
研究领域:
催化化学
·
材料科学
·
环境化学
✓ 已验证
产品关联
DOI
高影响因子
ChemPlusChem
·
2020
·Vol. 85
·期 8
·1783-1788
·
IF 2.753
Rongxiu Guo,GuangQi He,Lei Liu,Yongjian Ai,Ze-nan Hu,Xinyue Zhang,Haimeng Tian,Hong-bin Sun,Dun Niu,Qionglin Liang
Graphical Four in one : A quaternary-component catalyst containing platinum, copper, and iron, which are supported on Fe 3 O 4 nanospheres can be used in the selective synthesis of symmetrical secondary amines by transfer hydrogenation of nitriles with excellent conversion and selectivity. A variety of nitriles were tested for the synthesis of symmetrical secondary amines, and no hydrogenolysis byproducts were detected. Hydrogenation of nitriles is an efficient and environmentally friendly route to synthesize symmetrical secondary amines, but it usually produces a mixture of amines, imines, and hydrogenolysis by-products. Herein we report a magnetic quaternary-component Pt−CuFe/Fe 3 O 4 nanocatalyst system for the selective synthesis of symmetrical secondary amines with ammonia borane as hydrogen donor. The catalyst with a low Pt loading (0.456 wt%) is the source of the activity, and the d-band electron transfer from Cu to Fe enhances the selectivity. This synergistic effect results in the transformation of benzonitrile to dibenzylamine with excellent conversion (up to 99 %) and nearly quantitative selectivity (up to 96 %) under mild reaction conditions, nevertheless, the reaction TOF is as high as up to 1409.9 h −1 . A variety of nitriles are suitable for the synthesis of symmetrical secondary amines. More importantly, unwanted hydrogenolysis byproducts, especially toluene, is not detected at all. In addition, the catalyst is magnetically recoverable, and it can be reused up to five times.
研究领域:
催化化学
·
绿色化学
·
材料科学
✓ 已验证
产品关联
DOI
PubMed
高影响因子
CHEMICAL RESEARCH IN CHINESE UNIVERSITIES
·
2016
·Vol. 32
·期 4
·586-593
·
IF 1.086
Zhang Guofu,Zhang Guihua,Lei Jie,Li Shasha,Xu Shengjun,Ding Chengrong,Shan Shang
A facile, practical and scalable catalyst system for alcohols ammoxidation into nitriles is developed using amino acid as ligand, oxygen as terminal oxidant and copper iodide(CuI) as catalyst. The catalyst system shows excellent functional groups compatibility for a wide range of testing substrates, even the substrates bearing oxidation-sensitive groups such as MeS—, alkenyl and —NH 2 can also work well. In addition, the protocol is readily scaled up to more than 20 g and the product can be obtained just through filtration or distillation without conventional column chromatography.
研究领域:
化学
·
催化反应
✓ 已验证
产品关联
DOI
高影响因子
Nano Research
·
2020
·Vol. 13
·期 8
·2079-2084
·
IF 8.183
Wang Hong-Hui,Lv Li-Bing,Zhang Shi-Nan,Su Hui,Zhai Guang-Yao,Lei Wei-Wei,Li Xin-Hao,Chen Jie-Sheng
The rational design of highly active and stable atomically dispersed M-X 4 (M = Fe, Co, Ni, etc., X = C, N) -based catalysts holds promises for wide application in almost all realms of catalysis. Despite great effort in the construction of specific M-X 4 centers, the possible effect of non-coordinated heteroatoms on the catalytic activity of metal centers has been rarely explored. Herein, we develop a new type of M-X 4 catalyst composed of Fe-N 4 centers and non-coordinated B heteroatoms (FeNC+B) and find the key role of non-coordinated B adjacent to Fe-N 4 centers in tailoring their electron density and final catalytic selectivity. The experimental and theoretical results demonstrated that non-coordinated boron atoms could decrease the electron density of Fe-N 4 centers to a suitable level and thus boost the selective production of nitriles from amine oxidation by depressing the formation of imines due to the flattened energy barrier of the reversible conversion of imines back to amines. As a reusable heterocatalyst, the state-of-the-art FeNC+B catalyst provides a turn-over frequency (TOF) value of 21.6 mol benzonitrile ·mol Fe −1 ·h −1 (100 °C), outpacing that of bench-marked nonnoble-metal-based homogeneous catalyst by a factor of 3.4.
研究领域:
催化化学
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材料科学
·
理论化学
✓ 已验证
DOI
高影响因子
APPLIED CATALYSIS A-GENERAL
·
2023
·
IF 5.5
Huanyu Zhao,Yurong He,Xiaochen Wang,Jie He,Anqiu Liu,Zehui Zhang
Selective hydrogenation of nitriles is a feasible route to synthesize primary amines. While highly desirable, conducting the synthesis under mild conditions is challenging. We report non-precious zinc and aluminum oxides supported Ni catalysts (Ni/ZnAlO x ) facilely prepared by calcination and reduction of NiZnAl layered double hydroxide (LDH) precursors. The optimized Ni/ZnAlO x -600 catalyst demonstrates great activity towards the selective hydrogenation of nitriles to primary amines. Proper-size metallic nickel provides the hydrogenation centers, and the presence of Ni-Zn alloys indicates strong metal-support interactions, which can produce electron-deficient nickel species and enhances the chemisorption of the C N bonds on the catalyst surface. The introduction of Zinc provides strong Lewis acid sites which also contribute to the catalytic activity. Based on the catalyst characterizations and control experiments, a plausible mechanism is proposed. This catalyst shows good stability and is conducive to the transformation of a variety of aromatic and aliphatic substrates, demonstrating potential application prospects.
研究领域:
化学
·
催化科学
✓ 已验证
产品关联
DOI
高影响因子
Reaction Chemistry & Engineering
·
2025
·
IF 3.1
Weidong Liu,Jianguo Liu
Reusable catalysts based on non-noble metals with broad applicability for nitrile catalytic hydrogenation are key to achieving more sustainable primary amine production. Herein, a simple and efficient carbon-coated non-noble nickel-based catalyst (Ni/NiO@C-600-200-1-H₂O) was developed for the hydrogenation of aromatic substituted nitriles to aromatic substituted amines under relatively mild conditions (120 °C, 10 bar H₂, 4 h). The carbon-coated structure endows the catalyst with excellent anti-agglomeration properties, significantly enhancing its cyclic stability. The catalyst exhibits high tolerance toward various functional groups, including halogen, methyl, and methoxy, achieving remarkable conversion rates (over 99%) and product selectivity (up to 98.25%). Additionally, the catalyst's magnetic properties facilitate easy recovery and reuse. When applied to a continuous flow reactor for benzonitrile hydrogenation under optimized conditions, the catalyst demonstrated a conversion rate and selectivity exceeding 99%, with continuous operation lasting up to 31 h.
研究领域:
化学工程
·
催化材料
✓ 已验证
产品关联
DOI
高影响因子
JOURNAL OF ANALYTICAL AND APPLIED PYROLYSIS
·
2021
·
IF 5.541
Tingting Jia,Feng Zhou,Huixia Ma,Ying Zhang
The selectivity and stability of catalysts have always been a challenge in the field of catalytic fast pyrolysis (CFP). Herein, a series of waste animal bones collected from local market were employed as catalyst to convert biomass, with only acetonitrile and propionitrile in bio-oil, via catalytic fast pyrolysis and ammonization (CFP-A) process. Combined with characterization and control experiments of calcium-based components in bone, it was found that hydroxyapatite (HAP) was the catalytic active phase, while NaCl and KCl inorganic salts in bone inhibited the production of nitriles. Under the optimized conditions, the selectivity of acetonitrile and propionitrile from cellulose were 74.9 % and 25.1 % in bio-oil, respectively. Importantly, for the raw biomass, it still maintained high nitriles selectivity. The carbon yield of nitriles did not decrease after 10 cycles with HAP. Such a stable catalyst is first reported in the field of CFP, which is important for CFP to be economically sustainable.
研究领域:
能源化学
·
催化材料科学
✓ 已验证
产品关联
DOI
高影响因子
MICROPOROUS AND MESOPOROUS MATERIALS
·
2022
·
IF 5.876
Qiqi Lu,Xiu-Zhi Wei,Jianguo Liu,Longlong Ma
Zeolite-tailored encapsulation of metal nanoparticles exhibits prominent catalytic performance in many fields especially for selective hydrogenation reaction due to the modulation effect of the zeolite microenvironment. Here, Pd nanoparticles encapsulated in MFI zeolite by an in-situ encapsulation method were first used in the selective hydrogenation of nitrile into a primary amine. After introducing KOH for mediating the acid-base property of zeolite microenvironment, the as-synthesized [email protected] manifested an improved selectivity in the synthesis of primary amine from nitrile, while outperformed both commercial catalysts and conventional Pd supported on zeolite catalyst. The remarkable performance of [email protected] could be attributed to both the basic property of the S-1-K zeolite for inhibiting the side reactions and the highly dispersed and ultrasmall Pd clusters for superior catalytic activity. Besides, the best yield of 81% was achieved at 80 °C, 5 bar H 2 , 2 h in ammonia solution via optimization experiments, and the moderate applicability of [email protected] catalyst was obtained by substrate scope test.
研究领域:
催化化学
·
材料科学
·
有机合成
✓ 已验证
产品关联
DOI
高影响因子
iScience
·
2021
·
IF 5.458
Jiarui Zhang,Ruxu Yao,Jinzhu Chen,Tao Li,Yisheng Xu
Nitrile (C≡N bond) activation for direct organic synthesis has been less explored so far due to a high redox potential of nitrile and its low dissociation energy of C−CN bond. Herein, we demonstrate a direct reductive coupling of nitriles and 1,2-phenylenediamines to yield various benzimidazoles in excellent yields (95%–99%) by using rhodium phosphide (Rh 2 P) catalyst supported on lignin-derived carbon (LC) using H 2 (or hydrazine hydrate) as a hydrogen source. The high catalytic performance of Rh 2 P/LC is attributed to enhanced charge transfer to Rh and strong P−Rh interactions. Our isotope trace experiment confirms the presence of H/D exchange between H 2 and the inert –CD 3 group of CD 3 CN via an intramolecular D-shift. Reusability of Rh 2 P/LC is further demonstrated by a seven-time recycling without evident loss of activity. This research thus highlights a great potential in organic transformation with nitrile as a synthetic building block.
研究领域:
有机化学
·
催化化学
✓ 已验证
DOI
PubMed
高影响因子
危险品化学品经营许可证（带存储）