121-69-7Relevant articles and documents
Fluoro-functionalized polymeric N-heterocyclic carbene-zinc complexes: Efficient catalyst for formylation and methylation of amines with CO2 as a C1-building block
Yang, Zhen-Zhen,Yu, Bo,Zhang, Hongye,Zhao, Yanfei,Ji, Guipeng,Liu, Zhimin
, p. 19613 - 19619 (2015)
A fluoro-functionalized polymeric N-heterocyclic carbene (NHC)-Zn complex (F-PNHC-Zn) was designed and synthesized by taking fluorous imidazolium salts as precursors through a two-step alkylation. The resultant F-PNHC-Zn was applied in catalyzing the formylation and methylation of amines using CO2 as a C1 building block in the presence of organosilane, which showed much higher activity than the corresponding non-fluorous PNHC-Zn under identical conditions. N-Methylanilines with both electron-withdrawing and electron-donating groups all could be converted to the corresponding formamides and methylamines in >90% conversion. Quantitative conversion of N-methylaniline was obtained even under very low CO2 pressure (0.05 MPa diluted by N2). Moreover, F-PNHC-Zn was highly stable and easily recyclable for these reactions. This journal is
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Merz,Weith
, p. 1571,1576 (1886)
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Photoinduced, ionic Meerwein arylation of olefins
Mella,Coppo,Guizzardi,Fagnoni,Freccero,Albini
, p. 6344 - 6352 (2001)
Irradiation of 4-chloroaniline or of its N,N-dimethyl derivative in polar solvents generates the corresponding triplet phenyl cations. These are trapped by alkenes yielding arylated products in medium to good yields. B3LYP calculations show that the triplet cation slides with negligible activation energy to a bonded adduct with ethylene, whereas it forms only a marginally stabilized CT complex with water (chosen as a representative σ nucleophile). The structure of the final products depends on the preferred path from the adduct cation with the alkene. In the case of aryl olefins, this deprotonates to stilbene derivatives, while, from 2,3-dimethyl-2-butene and allytrimethylsilane, allylanilines are obtained by elimination of an electrofugal group in γ. In the case of mono- and disubstituted alkenes the cation adds chloride rather than eliminating and β-chloroalkylanilines are obtained. The regio- and sterochemistry of the addition across the alkene are best understood with a phenonium ion structure for the adduct. The nucleophile entering in fi can be varied under conditions in which the adduct cation is trapped more efficiently than the starting phenyl cation. Thus, β-methoxyalkylanilines are formed when the irradiation is carried out in methanol. β-Iodoalkylanilines are obtained in acetonitrile containing iodide and unsubstituted alkylanilines in the presence of sodium borohydride. A case of intramolecular nucleophilic trapping is found with 4-pentenoic acid. The reaction is a wide-scope ionic analogue of the radicalic Meerwin arylation of olefins.
Interaction of retinoic acid radical cation with lysozyme and antioxidants: Laser flash photolysis study in microemulsion
Li, Kun,Wang, Mei,Wang, Ting,Sun, Dongmei,Zhu, Rongrong,Sun, Xiaoyu,Wu, Xianzheng,Wang, Shi-Long
, p. 1064 - 1070 (2013)
All-trans retinoic acid (ATRA) plays essential roles in the normal biological processes and the treatment of cancer and skin diseases. Considering its photosensitive property, many studies have been focused on the photochemistry of ATRA. In this study, we investigated the transient phenomena in the laser flash photolysis (LFP) of ATRA in microemulsion to further understand the photochemistry of ATRA. Results show that 355 nm LFP of ATRA in both acidic and alkaline conditions leads to the generation of retinoic acid cation radicals (ATRA?+) via biphotonic processes. The employment of microemulsion system allows us to investigate the reaction of hydrophobic ATRA?+ with molecules of different polarity. Therefore, we studied the reaction activity of ATRA?+ to many hydrophobic and hydrophilic molecules. Results show that ATRA?+ can efficiently interact with lysozyme, tyrosine, tryptophan and many antioxidants, such as curcumin (Cur), vitamin C (VC) and gallic acid (GA). The apparent rate constants of these reactions were measured and compared. These findings suggest that ATRA?+ is a reactive transient product which may pose damage to lysozyme, and antioxidants, such as Cur, VC and GA, may inactivate ATRA?+ by efficient quenching reactions. 355 nm laser flash photolysis of all-trans retinoic acid (ATRA) in microemulsion leads to the formation of retinoic acid cation radicals (ATRA?+) via biphotonic processes. Deprotonated form of ATRA is more favorable for the formation of ATRA?+. ATRA?+ is proved to be reactive to lysozyme, tyrosine and tryptophan which is suggestive of its destructive effect on proteins. Meanwhile, some antioxidants, such as curcumin, gallic acid and vitamin C, can efficiently interact with ATRA?+, which indicates that it may competitively protect proteins from the attack of ATRA?+ by inactivating free radical.
Capillary-Bound Dense Micelle Brush Supports for Continuous Flow Catalysis
Cai, Jiandong,Cui, Yan,Lin, Geyu,Liu, Qiuwen,Manners, Ian,Qiu, Huibin,Sun, Yan
, p. 24637 - 24643 (2021)
Flow reactors are appealing alternatives to conventional batch reactors for heterogeneous catalysis. However, it remains a key challenge to firmly immobilize the catalysts in a facile and flexible manner and to simultaneously maintain a high catalytic efficiency and throughput. Herein, we introduce a dense cylindrical micelle brush support in glass capillary flow reactors through a living crystallization-driven self-assembly process initiated by pre-immobilized short micelle seeds. The active hairy corona of these micellar brushes allows the flexible decoration of a diverse array of nanocatalysts, either through a direct capture process or an in situ growth method. The resulting flow reactors reveal excellent catalytic efficiency for a broad range of frequently utilized transformations, including organic reductions, Suzuki couplings, photolytic degradations, and multistep cascade reactions, and the system was both recyclable and durable. Significantly, this approach is readily applicable to long capillaries, which enables the construction of flow reactors with remarkably higher throughput.
On the mechanism of the N,N-dimethyl amination of Grignard reagents: A kinetic study
Erdik, Ender,Uelhue, Selma Ates
, p. 671 - 676 (2007)
A direct kinetic study is reported for the electrophilic amination of substituted phenylmagnesium bromides with N,N-dimethyl O-(mesitylenesulfonyl) hydroxylamine in THF. Rate data, Hammett relationship, and activation entropy are consistent with a SN2 displacement involving the attack of carbanions to sp3N in the amination reagent (AR). Copyright
Brown et al.
, p. 1193,1196 (1978)
A novel access to 3-aryl-2-norbornyl cation
Mella, Mariella,Esposti, Silvia,Fagnoni, Maurizio,Albini, Angelo
, p. 738 - 739 (2003)
A novel access to a 2-norbornyl cation under mild, non acidic conditions is found in the addition of photochemically generated 4-dimethylaminophenyl cation to 2-norbornene. Deprotonation to nortricyclene or nucleophile addition ensue depending on the solvent characteristics.
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Biehl et al.
, p. 2454 (1970)
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Efficient degradation of azo dyes using Ag and Au nanoparticles stabilized on graphene oxide functionalized with PAMAM dendrimers
Rajesh, Rajendiran,Kumar, S. Senthil,Venkatesan, Rengarajan
, p. 1551 - 1558 (2014)
Herein, we report the stabilization of silver and gold nanoparticles (Ag/Au NPs) on graphene oxide (GO) functionalized with PAMAM dendrimers. The grafting of the PAMAM dendrimers on GO has been investigated using TGA and Raman spectral studies and the stabilization of the Ag/Au NPs on the dendritic structures has been confirmed using XRD, UV-Vis and FT-IR spectra, SEM and TEM studies. The catalytic activity of the prepared nanocatalysts towards the degradation of organic azo dyes, namely methyl orange and congo red, has been tested. The prepared nanocatalysts were found to exhibit excellent catalytic activity towards the complete degradation of both methyl orange and congo red within only a few seconds.
Visible-Light-Induced C(sp2)-C(sp3) Cross-Dehydrogenative-Coupling Reaction of N-Heterocycles with N-Alkyl- N-methylanilines under Mild Conditions
Zhang, Hong-Yu,Chen, Jianjun,Lu, Cong-Cong,Han, Ya-Ping,Zhang, Yuecheng,Zhao, Jiquan
, p. 11723 - 11735 (2021)
Disclosed herein is a cross-dehydrogenative-coupling reaction of N-heterocycles including 1,2,4-triazine-3,5(2H, 4H)-diones and quinoxaline-2(1H)-ones with N-methylanilines to form C(sp2)-C(sp3) under visible-light illumination and ambient air at room temperature. In this process, easily available Ru(bpy)3Cl2·6H2O serves as the catalyst, and air acts as the green oxidant. This method features high atom economy, environmental friendliness, and convenient operation and provides an efficient and practical access to aminomethyl-substituted N-heterocycles with extensive functional group compatibility in 40-86% yields.
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Dunlop,Jones
, p. 416 (1909)
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Tarbell,Vaughan
, p. 231 (1943)
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REVERSIBLE PROTON TRANSFER IN THE 2,3,5,6-TETRACHLOROPHENOL-N,N-DIMETHYLANILINE HYDROGEN-BONDED COMPLEX STUDIED BY LOW-TEMPERATURE 1H NMR SPECTROSCOPY
Ilczyszyn, Marek,Ratajczak, Henryk,Ladd, John A.
, p. 499 - 504 (1989)
Low temperature 1H NMR studies of the bridging OHN signal in the hydrogen-bonded complex formed between 2,3,5,6-tetrachlorophenol and N,N-dimethylaniline in C2H5Cl solution have shown that separate signals for the molecular and ion-pair forms of the complex can be observed below -135 deg C (138 K).Analyses of the observed lineshapes have yielded values for the thermodynamic quantities ΔH0, ΔS0 as well as for the activation quantities ΔH, ΔS.
Zn(ii)@TFP-DAQ COF: An efficient mesoporous catalyst for the synthesis of: N -methylated amine and carbamate through chemical fixation of CO2
Sarkar, Priyanka,Chowdhury, Arpita Hazra,Riyajuddin, Sk.,Biswas, Surajit,Ghosh, Kaushik,Islam, Sk. Manirul
, p. 744 - 752 (2020)
Selective N-methylation and carbamate formation reactions were demonstrated via the chemical incorporation of CO2 using a Zn-loaded TFP-DAQ COF (covalent organic framework) as an active catalyst under mild reaction conditions. The selective N-methylation and N-formylation reactions were performed by simply varying the type of solvent. The Zn(ii)@TFP-DAQ COF catalyst was characterized via different characterization techniques such as PXRD, FTIR, UV-vis, N2 adsorption-desorption studies, FESEM and TEM. The catalyst material showed pores in the mesoporous region with a high surface area of 1117.375 m2 g-1. The as-synthesized material was applied as a cheap catalyst for the N-methylation of secondary amines and in carbamate formation reactions with high yields of the desired products up to 98.5% and 97%, respectively, with >99% selectivity. The catalyst was found to be completely heterogeneous and reusable for multiple reaction cycles.
The reaction between sodium hydrogen telluride and phase transfer catalysts
Li,Zhou
, p. 3635 - 3639 (1995)
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Yamdagni,R.,Kebarle,P.
, p. 3504 - 3510 (1973)
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Unexpected Macrocyclic Multinuclear Zinc and Nickel Complexes that Function as Multitasking Catalysts for CO2 Fixations
Takaishi, Kazuto,Nath, Bikash Dev,Yamada, Yuya,Kosugi, Hiroyasu,Ema, Tadashi
, p. 9984 - 9988 (2019)
Unique self-assembled macrocyclic multinuclear ZnII and NiII complexes with binaphthyl-bipyridyl ligands (L) were synthesized. X-ray analysis revealed that these complexes consisted of an outer ring (Zn3L3 or Ni3L3) and an inner core (Zn2 or Ni). In the ZnII complex, the inner Zn2 part rotated rapidly inside the outer ring in solution on an NMR timescale. These complexes exhibited dual catalytic activities for CO2 fixations: synthesis of cyclic carbonates from epoxides and CO2 and temperature-switched N-formylation/N-methylation of amines with CO2 and hydrosilane.
N-Mannich Bases of Aromatic Heterocyclic Amides: Synthesis via Copper-Catalyzed Aerobic Cross-Dehydrogenative Coupling under Ambient Conditions
Singh, Shailendra K.,Chandna, Nisha,Jain, Nidhi
, p. 1322 - 1325 (2017)
An efficient and facile method to synthesize N-Mannich bases has been developed using an inexpensive copper(I) bromide/air catalyst system at ambient temperature. A cross-dehydrogenative coupling of N,N-dimethylarylamines occurs efficiently with aromatic heterocyclic amides (oxindoles, isatins), cyclic amides (lactams), simple amides (benzamide), as well as imides (succinimide, phthalimide) to furnish the corresponding amidated/imidated derivatives in good to excellent yields. Preliminary mechanistic and isotope-labeling studies suggest the reaction follows a radical pathway and involves an iminium ion intermediate.
Kinetics of One-Electron Transfer Reactions Involving ClO2 and NO2
Huie, Robert E.,Neta, P.
, p. 1193 - 1198 (1986)
Rate constants for the one-electron oxidation of ClO2(1-) and NO2(1-) by several organic and inorganic free radicals have been measured along with rate constants for several reactions of ClO2, NO2 and BrO2.The kinetics of the reactions of ClO2 and NO2 are consistent with simple electron-transfer theory, except for the reaction of NO2 with SO3(2-), which appears to be oxygen atom transfer.Equilibrium constants have been determined for the reactions of ClO2 with aniline at pH 6.9 and N,N-dimethylaniline at pH 9.6.This leads to one-electron redox potentials of 1.03 and 0.87 V for these aromatic amines, respectively, at the corresponding pH.
N, N -Dimethylation of nitrobenzenes with CO2 and water by electrocatalysis
Sun, Xiaofu,Zhu, Qinggong,Hu, Jiayin,Kang, Xinchen,Ma, Jun,Liu, Huizhen,Han, Buxing
, p. 5669 - 5674 (2017)
We have proposed a strategy for the synthesis of N,N-dimethylanilines from nitrobenzene and its derivatives, CO2, and water via an electrochemical reaction under ambient conditions. H+ generated from H2O was used as the hydrogen source. Pd/Co-N/carbon, in which the Pd nanoparticles were supported on Co-N/carbon, was designed and used as the electrocatalyst. It was found that the electrocatalyst was very efficient for the reaction in MeCN solution with 1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ([Bmim]Tf2N) as the supporting electrolyte and 1-amino-methylphosphonic acid (AMPA) as the thermal co-catalyst. A series of control experiments showed that Pd/Co-N/carbon and AMPA cooperated very well in accelerating the reaction. This synthetic route has some obvious advantages, such as using CO2 and water as the reactants, ambient reaction conditions, and high yields of the desired products. This opens up a way to synthesize chemicals by the combination of an electrocatalyst and a thermal catalyst with organic compounds, CO2, and water as the reactants.
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Giumanini,Lercker
, p. 3756,3757 (1970)
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Billman,Radike,Mundy
, p. 2978 (1942)
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Highly efficient and simultaneous catalytic reduction of multiple dyes using recyclable RGO/Co dendritic nanocomposites as catalyst for wastewater treatment
Sahoo, Prasanta Kumar,Thakur, Dinbandhu,Bahadur,Panigrahy, Bharati
, p. 106723 - 106731 (2016)
Development of a low cost, highly efficient and easily retrievable catalyst with improved reusability is a major challenge in the area of advanced catalysts. In this study, we report a simple one-step approach for the fabrication of a reduced graphene oxide (RGO)/Co dendritic nanocomposite. The structure and morphology of the as synthesized material are thoroughly examined by XRD, Raman, FTIR, TEM, and SEM. The magnetic properties of the RGO/Co dendritic nanocomposite reveal that it exhibits ferromagnetic behavior at room temperature with high saturation magnetization. The catalytic activity of the RGO/Co dendritic nanocomposite was investigated for the reduction of different dyes namely, 4-nitrophenol, methylene blue, methyl orange and rhodamine B individually, and their mixture in the presence of a sufficient amount of NaBH4. RGO/Co dendritic nanocomposite exhibits excellent catalytic activity as compared to the bare Co dendritic structure. The catalyst could be easily separated by an external magnet and recycled magnetically with no major loss of catalytic activity upto five cycles. The high catalytic efficiency, low cost and easy recycle technique make RGO/Co dendritic nanocomposite a proficient catalyst for degradation of organic dyes.
Green and chemo selective amine methylation using methanol by an organometallic ruthenium complex
Abbasi, Alireza,Dindar, Sara,Nemati Kharat, Ali
, (2021/11/16)
Herein a green and convenient catalytic N-methylation of aniline and n-hexylamine using methanol as a dual methylation agent and solvent has been investigated. A new ruthenium carbonyl complex was synthesized and applied as a homogeneous catalyst in methylation reaction. The solid-state structure of the complex was determined by X-ray crystallographic analysis which indicate xantphos ligand bonded to ruthenium (II) as a tridentate pincer ligand by two P donor and one O atom. The catalytic system showed excellent conversion and selectivity toward N-methylaniline, and N,N-hexyldimethylamine at 140°C.
Efficient base-free hydrodehalogenation of organic halides catalyzed by a well-defined diphosphine-ruthenium(II) complex
Gao, Pengxiang,Liu, Qingbin,Liu, Yahuan,Ma, Ning,Wang, Zheng,Zhao, Ziwei
, (2021/10/29)
A base-free, robust catalytic system based on the diphosphine-ruthenium(II) complex cation has been developed for the hydrodehalogenation of a wide range of aryl- and alkyl-chlorides/bromides (27 examples) with molecule hydrogen. Notably, the reaction proceeds at 120 °C with low catalyst loading (0.1 mol%) and exhibits a good tolerance toward functional groups, such as amido, carboxyl, sulfonyl, methoxyl, ester groups. All dehalogenation products are confirmed by GC, GC–MS and NMR spectroscopy. Moreover, a mechanism for the diphosphine-ruthenium(II) complex cation catalyzed dehalogenation process has been proposed. This hydrodehalogenation methodology shows a potential application for the organic transformation and degradation of organic halides.
Method for realizing N-alkylation by using alcohols as carbon source under photocatalysis
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Paragraph 0048-0099, (2021/03/13)
The invention discloses a method for realizing N-alkylation by using alcohols as a carbon source under photocatalysis, and belongs to the technical field of catalytic synthesis. Alcohol, a substrate raw material and a catalyst are placed in a reaction device, ultraviolet and/or visible light irradiation is carried out in an inert atmosphere, after the irradiation is finished, solid-liquid separation is carried out to remove the catalyst, and an N-alkylation product can be obtained through extraction, distillation and purification, wherein the substrate raw material comprises any one of an amine compound, an aromatic nitro compound or an aromatic nitrile compound, the alcohol comprises any one or more of soluble primary alcohols, and the catalyst is metal oxide/titanium dioxide or metal sulfide/titanium dioxide. The method is simple and easy to operate, can be used for efficient photocatalysis one-pot multi-step hydrogenation N-alkylation reaction, and is mild in reaction condition, high in chemical selectivity of N-alkylamine, good in catalyst stability and easy to recycle.