5456-97-3

Usage

InChI:InChI=1/C12H17NO/c1-3-4-9-13-12(14)11-7-5-10(2)6-8-11/h5-8H,3-4,9H2,1-2H3,(H,13,14)

Upstream product

• 3848-42-8 O-(4-nitrophenyl)-N-(4-tolyl)carbamate 
• 109-73-9 N-butylamine 
• 201230-82-2 carbon monoxide 
• 624-31-7 4-tolyl iodide 
• 106-38-7 para-bromotoluene 
• 104-87-0 4-methyl-benzaldehyde 
• 83039-57-0 2,5-dioxopyrrolidin-1-yl 4-methylbenzoate 
• 13939-06-5 molybdenum hexacarbonyl 
• 122-00-9 para-methylacetophenone 
• 874-60-2 4-methyl-benzoyl chloride 
• 111-92-2 dibutylamine 
• 99-94-5 p-Toluic acid 
• 104-84-7 para-methylbenzylamine 
• 824-79-3 sodium 4-methylbenzenesulfinate 

Downstream Products

• 1303614-32-5 C₁₂H₁₆N₂O₂ 
• 19277-56-6 n-butyl 4-methylbenzoate 

Relevant academic research and scientific papers

Amide Bond Formation via the Rearrangement of Nitrile Imines Derived from N-2-Nitrophenyl Hydrazonyl Bromides

We report how the rearrangement of highly reactive nitrile imines derived from N-2-nitrophenyl hydrazonyl bromides can be harnessed for the facile construction of amide bonds. This amidation reaction was found to be widely applicable to the synthesis of primary, secondary, and tertiary amides and was used as the key step in the synthesis of the lipid-lowering agent bezafibrate. The orthogonality and functional group tolerance of this approach was exemplified by the N-acylation of unprotected amino acids.

A CO2-Catalyzed Transamidation Reaction

Transamidation reactions are often mediated by reactive substrates in the presence of overstoichiometric activating reagents and/or transition metal catalysts. Here we report the use of CO2as a traceless catalyst: in the presence of catalytic amounts of CO2, transamidation reactions were accelerated with primary, secondary, and tertiary amide donors. Various amine nucleophiles including amino acid derivatives were tolerated, showcasing the utility of transamidation in peptide modification and polymer degradation (e.g., Nylon-6,6). In particular,N,O-dimethylhydroxyl amides (Weinreb amides) displayed a distinct reactivity in the CO2-catalyzed transamidation versus a N2atmosphere. Comparative Hammett studies and kinetic analysis were conducted to elucidate the catalytic activation mechanism of molecular CO2, which was supported by DFT calculations. We attributed the positive effect of CO2in the transamidation reaction to the stabilization of tetrahedral intermediates by covalent binding to the electrophilic CO2

NaOTs-promoted transition metal-free C-N bond cleavage to form C-X (X = N, O, S) bonds

Multifunctional transformation of amide C-N bond cleavage is reported. The protocol applies to benzamide, thioamide, alcohols, and mercaptan under similar reaction conditions catalyzed by NaOTs. It is noteworthy that NaOTs can not only be recycled and reused for up to three cycles without significant loss in catalytic activity, but also catalyze gram-grade reactions. This study provides a novel solution with mild conditions and a simple procedure for transformation of multiple amides.

Visible-Light-Mediated Difunctionalization of Alkynes: Synthesis of β-Substituted Vinylsulfones Using O- And S-Centered Nucleophiles

An inimitable illustration of a green-light-induced, regioselective difunctionalization of terminal alkynes has been disclosed using sodium arylsulfinates and carboxylic acids in the presence of eosin Y as the photocatalyst. The present methodology is further demonstrated by employing NH4SCN as an S-centered nucleophile instead of carboxylic acid. The mechanistic investigation reveals a radical-induced iodosulfonylation followed by a base-mediated nucleophilic substitution. The mechanism is supported by various studies, viz., radical-trapping experiment, fluorescence quenching, and CV studies. In this protocol, (Z)-β-substituted vinylsulfones are obtained, exclusively covering a broad range of alkynes and nucleophiles, which are often unaddressed. The present strategy can tolerate structurally discrete substrates with steric bulk and different electronic properties, which provides a straightforward and practical pathway for the synthesis of highly functionalized (Z)-β-substituted vinylsulfones. Herein, C-O and C-S bonds are assembled simultaneously with the concomitant introduction of important functional groups, viz., ester, thiocyanate, and sulfone.

CuO-decorated magnetite-reduced graphene oxide: a robust and promising heterogeneous catalyst for the oxidative amidation of methylarenes in waterviabenzylic sp3C-H activation

A magnetite-reduced graphene oxide-supported CuO nanocomposite (rGO/Fe3O4-CuO) was preparedviaa facile chemical method and characterized by Fourier-transform infrared spectroscopy (FTIR), X-ray diffraction (XRD), UV-vis spectroscopy, scanning electron microscopy (SEM), transmission electron microscopy (TEM), energy dispersive spectroscopy (EDS), Brunauer-Emmett-Teller (BET) analysis, vibrating-sample magnetometry (VSM), and thermogravimetric (TG) analysis. The catalytic activity of the rGO/Fe3O4-CuO nanocomposite was probed in the direct oxidative amidation reaction of methylarenes with free amines. Various aromatic and aliphatic amides were prepared efficiently at room temperature from cheap raw chemicals usingtert-butyl hydroperoxide (TBHP) as a “green” oxidant and low-toxicity TBAI in water. This method combines the oxidation of methylarenes and amide bond formation into a single operation. Moreover, the synthesized nanocomposites can be separated from the reaction mixtures using an external magnet and reused in six consecutive runs without a noticeable decrease in the catalytic activity.

Method for synthesizing amide by using methyl arene and amine in water phase

The invention provides a high-efficient method of synthesizing amide with methyl aromatics and amine. In the method, with the methyl aromatics and the amine as the raw materials in the water phase and TBHP and TBAI respectively as an oxidizing agent and a catalyst, a sp3 C-H bond and a sp3 N-H bond are broken and a C-N bond is formed. Compared with a conventional method of synthesizing the amide from oxidized amide, in which an activated acyl group or amine is required, the method is carried out with water as the solvent so that the method is not only economical but also environmental-protective. The method has a very good application prospect in the field of synthesizing polypeptide, protein and drugs in future.

Rapid Organocatalytic Formation of Carbon Monoxide: Application towards Carbonylative Cross Couplings

Herein, the first organocatalytic method for the transformation of non-derivatized formic acid into carbon monoxide (CO) is introduced. Formylpyrrolidine (FPyr) and trichlorotriazine (TCT), which is a cost-efficient commodity chemical, enable this decarbonylation. Utilization of dimethylformamide (DMF) as solvent and catalyst even allows for a rapid CO generation at room temperature. Application towards four different carbonylative cross coupling protocols demonstrates the high synthetic utility and versatility of the new approach. Remarkably, this also comprehends a carbonylative Sonogashira reaction at room temperature employing intrinsically difficult electron-deficient aryl iodides. Commercial 13C-enriched formic acid facilitates the production of radiolabeled compounds as exemplified by the pharmaceutical Moclobemide. Finally, comparative experiments verified that the present method is highly superior to other protocols for the activation of carboxylic acids.

Oxidative Amidation of Amines in Tandem with Transamidation: A Route to Amides Using Visible-Light Energy

A methodology is reported for preparing amides using amines as an acyl source. The protocol involves the visible-light-promoted oxidative amidation of amines with pyrazole to synthesize N-acyl pyrazoles followed by transamidation. By combining photoredox catalysis with oxoammonium cations in the presence of sodium persulfate as a terminal oxidant, the N-acyl pyrazoles could be prepared efficiently and effectively using blue LEDs. The transamidation step was performed without the need to purify the N-acyl pyrazole intermediate, and a range of amides were generated in good to excellent yields.

Preparation method of amide compounds

The invention discloses a novel preparation method of amide compounds. According to the preparation method, perfluoroalkyl amide is taken as the raw material, a transition metal catalyst is adopted, perfluoroalkyl amide carries out reactions for a while in an organic aprotic solvent at a certain temperature, amide compounds can be obtained high selectively, and the yield is high. The preparation method has the advantages of low cost, high yield, and simple and convenient operation, and can be possibly applied to industrial production.

Broadly Applicable Ytterbium-Catalyzed Esterification, Hydrolysis, and Amidation of Imides

An efficient, broadly applicable, operationally simple, and divergent process for the transformation of imides into a range of carboxylic acid derivatives under mild conditions is reported. By simply using catalytic amounts of ytterbium(III) triflate as a Lewis acid promoter in the presence of alcohols, water, amines, or N,O-dimethylhydroxylamine, a broad range of imides is smoothly and readily converted to the corresponding esters, carboxylic acids, amides, and Weinreb amides in good yields. This method notably enables an easy cleavage of oxazolidinone-based auxiliaries.