100-61-8Relevant articles and documents
Flash vacuum pyrolysis of 3-oxo-2-arylhydrazonopropanals and related derivatives
Ibrahim, Yehia A,Kaul, Kamini,Al-Awadi, Nouria A
, p. 10171 - 10176 (2001)
Flash vacuum pyrolysis (FVP) of 3-oxo-2-arylhydrazonopropanals at 500°C and 0.02 Torr yielded the corresponding derivatives of anilines, N-formylanilines, N-benzoylanilines and benzoylnitriles. Similar FVP of phenylhydrazonomalononitrile, phenylhydrazonoa
Palladium-catalysed N,N'-disubstituted urea synthesis by oxidative carbonylation of amines under CO and O2 at atmospheric pressure
Giannoccaro, Potenzo
, p. 271 - 278 (1987)
N,N'-disubstituted ureas have been obtained in good yields by reaction of aromatic and aliphatic primary amines in alcohol solution with CO and O2 under mild conditions (70-90 deg C, 1 atm) and in the presence of catalytic amounts of PdCl2 or a palladium(II) complex.Under more drastic temperature and pressure conditions carbamate esters were obtained instead.In the aniline carbonylation, the catalysis involves the following reactions: .Reaction (1) occurs at room temperature but more drastic conditions (70-90 deg C) are necessary for reaction (2).The influence of onium salts, such as PhNH3+X- (X=Cl, I) or CuCl2, on the catalytic activity has also been studied and the best results obtained with CuCl2.A side reaction involving carbon monoxide oxidation was almost suppressed when the reactions were carried out in alcohol, but enhanced when THF or dimethoxypropane was used as solvent.
Oxygen activation by iron(III)-porphyrin/NaBH4/Me4N·OH system as cytochrome P-450 model. Oxygenation of olefin, N-dealkylation of tertiary amine, oxidation of sulfide, and oxidative cleavage of ether bond
Mori,Santa,Higuchi,Mashino,Hirobe
, p. 292 - 295 (1993)
Oxygenation of olefin, N-dealkylation of tertiary amine, oxidation of sulfide, and oxidative cleavage of ether bond were conducted with tetraphenylporphyrinatoiron(III) (Fe3+TPPCl), NaBH4, Me4N·OH, and molecular dioxygen in benzene-methanol solution. Fe3+TPPCl, NaBH4, and molecular dioxygen were essential for these reactions and the yields were decreased when Me4N·OH was absent. Olefins were converted to alcohols, which were not produced from the corresponding epoxides under the same conditions. In styrene oxygenation, an electron-donating substituent on the substrate decreased the reactivity, whereas in N,N-dimethylaniline demethylation, it enhanced the reactivity. Despite the use of the same reagents, the key intermediates of these two reactions are different. Fe2+TPP-σ-alkyl complexes produced from Fe3+TPPCl, olefin, and NaBH4 were identified as intermediates under anaerobic conditions. Fe2+TPP-σ-alkyl complex reacted with molecular dioxygen to give oxygenated products. Examination of the relative reactivities of p-substituted N,N-dimethylanilines in the NaBH4 reaction system revealed first, that the demethylation proceeded via one-electron abstraction, and second, that the reactive species of the demethylation reactions seems to be an iron-oxenoid.
Redox inactive metal ion triggered N-dealkylation by an iron catalyst with dioxygen activation: A lesson from lipoxygenases
Zhang, Jisheng,Wang, Yujuan,Luo, Nengchao,Chen, Zhuqi,Wu, Kangbing,Yin, Guochuan
, p. 9847 - 9859 (2015)
Utilization of dioxygen as the terminal oxidant at ambient temperature is always a challenge in redox chemistry, because it is hard to oxidize a stable redox metal ion like iron(iii) to its high oxidation state to initialize the catalytic cycle. Inspired by the dioxygenation and co-oxidase activity of lipoxygenases, herein, we introduce an alternative protocol to activate the sluggish iron(iii) species with non-redox metal ions, which can promote its oxidizing power to facilitate substrate oxidation with dioxygen, thus initializing the catalytic cycle. In oxidations of N,N-dimethylaniline and its analogues, adding Zn(OTf)2 to the [Fe(TPA)Cl2]Cl catalyst can trigger the amine oxidation with dioxygen, whereas [Fe(TPA)Cl2]Cl alone is very sluggish. In stoichiometric oxidations, it has also been confirmed that the presence of Zn(OTf)2 can apparently improve the electron transfer capability of the [Fe(TPA)Cl2]Cl complex. Experiments using different types of substrates as trapping reagents disclosed that the iron(iv) species does not occur in the catalytic cycle, suggesting that oxidation of amines is initialized by electron transfer rather than hydrogen abstraction. Combined experiments from UV-Vis, high resolution mass spectrometry, electrochemistry, EPR and oxidation kinetics support that the improved electron transfer ability of iron(iii) species originates from its interaction with added Lewis acids like Zn2+ through a plausible chloride or OTf- bridge, which has promoted the redox potential of iron(iii) species. The amine oxidation mechanism was also discussed based on the available data, which resembles the co-oxidase activity of lipoxygenases in oxidative dealkylation of xenobiotic metabolisms where an external electron donor is not essential for dioxygen activation.
First gold(I) complex-catalyzed oxidative carbonylation of amines for the syntheses of carbamates
Shi,Deng
, p. 443 - 444 (2001)
At 200 °C and 5 MPa of initial total pressure, the oxidative carbonylation of amines for the synthesis of the corresponding carbamates by Au(I) complexes as catalysts was conducted with excellent conversion and selectivity.
Carbamate synthesis from amines and dialkyl carbonate over inexpensive and clean acidic catalyst-Sulfamic acid
Wang, Bo,He, Jing,Sun, Run Cang
, p. 794 - 797 (2010)
Sulfamic acid has been proved to be the most efficient and recyclable catalyst in carbamate synthesis from alkylamine and dialkyl carbonate. High selectivity, cost-efficiency and simple product separation were the advantageous features obtained in this process. Sulfamic acid could be reused several times and keep its initial activity in the recycle runs. In addition, sulfamic acid has also exhibited the potential catalytic ability for alkylation of aromatic amines.
Heterocyclization of iminium salts from some β-amino-β-lactams and their gem-difunctional derivatives
Nisole,Uriac,Huet,Toupet
, p. 1081 - 1098 (1992)
β-Amino-β-lactams and their gem-difunctional derivatives of two series (1-benzoazepine and linear analog) lead stereospecifically to two types of heterocycles in strong acidic medium. Iminium ions and benzylic carbocations are proposed as reactive intermediates.
Selective electrocatalytic oxidation of N-alkyl-N-methylanilines to N-alkylformanilides using nitroxyl radical
Kashiwagi,Anzai
, p. 324 - 326 (2001)
Electrocatalytic oxidation of N-alkyl-N-methylanilines was studied using 4-benzoyloxy-2,2,6,6-tetramethylpiperidinyl-N-oxyl as a nitroxyl radical. The reaction with N-alkyl-N-methylanilines led to direct formation of N-alkylformanilides in the presence of H2O in reaction media in adequate conversion (>75.8%), high current efficiency (>89.2%) and high selectivity (>93.8%).
The design, synthesis and evaluation of selenium-containing 4-anilinoquinazoline hybrids as anticancer agents and a study of their mechanism
An, Baijiao,Zhang, Shun,Hu, Jinhui,Pan, Tingting,Huang, Ling,Tang, Johnny Cheuk-On,Li, Xingshu,Chan, Albert S. C.
, p. 4701 - 4714 (2018)
Inhibition of tubulin polymerization is one of the significant strategies in the treatment of cancer. Inspired by the excellent antitumor activity of EP128495 and the beneficial biological activities of selenium compounds, a series of new selenium-containing 4-anilinoquinazoline hybrids were synthesized and evaluated as tubulin polymerization inhibitors. An anti-proliferative activity assay showed that most of the compounds inhibited human sensitive cancer cells at low nanomolar concentrations. A mechanism study revealed that the optimal compound 5a disrupted microtubule dynamics, decreased the mitochondrial membrane potential and arrested HeLa cells in the G2/M phase, finally resulting in cellular apoptosis.
Selective mono-N-methylation of nitroarenes with methanol catalyzed by atomically dispersed NHC-Ir solid assemblies
Chen, Jiangbo,Chen, Zhe-Ning,Tu, Tao,Wang, Jiaquan,Wen, Daheng,Wu, Jiajie,Xu, Xin,Zheng, Qingshu
, p. 337 - 344 (2020)
A series of N-heterocyclic carbene-iridium (NHC-Ir) coordination assemblies based on bis-pyrenoimidazolium salts are prepared, and shown to function as efficient solid molecular catalysts in selective mono-N-methylation of nitroarenes with methanol under mild conditions. The atomically dispersed active Ir(I) centers and the large π-conjugation rings endow the solid catalysts with an exceptionally high activity and selectivity for a broad substrate scope. Such solid NHC-Ir coordination assemblies are robust, which can be easily recovered and reused more than 10 runs without significant loss of their catalytic activity and selectivity. When combined with a subsequent formylation using the same solid catalysts under ambient conditions, this novel protocol can afford diverse formamides in excellent yields, further highlighting the applicability of the present solid catalysts for an efficient diversification of nitroarenes to a broad number of functional amines.
