27668-90-2

Upstream product

• 159387-83-4 ethyl 3-oxo-3-phenyl-2-(p-tolyl)propanoate 
• 108-88-3 toluene 
• 622-47-9 4-tolylacetic acid 
• 14062-19-2 p-tolylacetic acid ethyl ester 
• 5524-56-1 ethyl 2-p-tolyl-2-oxoacetate 
• 623-73-4 diazoacetic acid ethyl ester 
• 624-31-7 4-tolyl iodide 
• 4294-57-9 para-methylphenylmagnesium bromide 

Downstream Products

• 102697-36-9 2,2-Dimethyl-3-methylene-1-p-tolyl-cyclopropanecarboxylic acid ethyl ester 
• 1299470-88-4 ethyl 3,3,3-trifluoro-2-(p-tolyl)propanoate 
• 1451218-33-9 ethyl 2-(4-nitrophenylamino)-2-(4-tolyl)acetate 

Relevant academic research and scientific papers

Electrochemical two-electron oxygen reduction reaction (ORR) induced aerobic oxidation of α-diazoesters

Electrochemical oxygen reduction reaction (ORR) is a powerful tool for introducing oxygen functional groups in synthetic chemistry. However, compared with the well-developed one-electron oxygen reduction process, the applications of two-electron oxygen re

Tropylium-Catalyzed O-H Insertion Reactions of Diazoalkanes with Carboxylic Acids

Herein, we describe the application of a nonbenzenoid aromatic carbocation, namely tropylium, as an organic Lewis acid catalyst in O-H functionalization reactions of diazoalkanes with benzoic acids. The newly developed protocol is applicable to a wide range of diazoalkane and carboxylic acid substrates with excellent efficiency (43 examples, up to 99% yield).

Blue LED-Mediated N-H Insertion of Indoles into Aryldiazoesters at Room Temperature in Batch and Flow: Reaction Kinetics, Density Functional Theory, and Mechanistic Study

Mild blue light-mediated N-H insertion of indole and its derivatives into aryldiazoesters has been reported in a batch and flow strategy to afford the corresponding N-alkylated product in moderate-to-excellent yield. Detailed high-performance liquid chromatography-based reaction kinetics measurements, control experiments, and kinetic isotope effect reveal that 3-substituted indoles with electron-withdrawing groups such as -CN and -CHO facilitated the product formation, whereas the electron-donating group retarded the process. The neutral indole performed in between them. Furthermore, Hammett plot and density functional theory-based transition-state optimization studies showed substantial correlation of the electronic nature of the substituents at the C3 position of indoles with the rate of the N-H insertion reaction. The strategy was utilized to synthesize a key intermediate for the natural product (-)-psychotrimine.

Copper on charcoal: Cu0nanoparticle catalysed aerobic oxidation of α-diazo esters

By using a charcoal supported nano Cu0catalyst (Cu/C), a highly efficient oxidation of α-diazo esters to α-ketoesters with molecular oxygen as the sole oxidant has been developed. In the presence of the Cu/C catalyst, 2-aryl-α-diazo esters with both electron-donating and electron-withdrawing groups can be oxidized to the corresponding α-ketoesters efficiently. Furthermore, this Cu/C catalyst can catalyse the reaction of aryl α-diazo ester with water to form aryl ketoester, 2-aryl-2-hydroxyl acetate ester and 2-aryl acetate ester. In this case, water is split by α-diazo ester, and the diazo group is displaced by the oxygen or hydrogen atom in water. Mechanistic investigation showed that the reaction of α-diazo ester with oxygen proceeds through a radical pathway. In the presence of 2,2,6,6-tetramethyl piperidine nitrogen oxide, the reaction of α-diazo ester with oxygen is dramatically inhibited. Furthermore, the reaction of α-diazo ester with water is investigated by an isotopic tracer method, and GCMS detection showed that a disproportionation reaction occurred between α-diazo ester and water.

Blue LED Induced Manganese (I) Catalysed Direct C2?H Activation of Pyrroles with Aryl Diazoesters

Herein, we have reported a blue LED mediated manganese pentacarbonyl bromide catalysed incorporation of carbene moieties from aryl diazoesters onto 1H-pyrroles via their selective C2?H activation. A manganese metal-carbene has been identified as the active catalyst to facilitate the reaction. Eighteen mono substituted pyrrole derivatives were isolated in good to excellent yields (67→82%) and the disubstituted products were also formed in minor quantities (5 to 8%). HPLC based kinetics study enabled optimization of the reaction. Control experiments, FT-IR, NMR and GC-MS based characterization elucidated the putative reaction mechanism. (Figure presented.).

Thermal Stability and Explosive Hazard Assessment of Diazo Compounds and Diazo Transfer Reagents

Despite their wide use in academia as metal-carbene precursors, diazo compounds are often avoided in industry owing to concerns over their instability, exothermic decomposition, and potential explosive behavior. The stability of sulfonyl azides and other diazo transfer reagents is relatively well understood, but there is little reliable data available for diazo compounds. This work first collates available sensitivity and thermal analysis data for diazo transfer reagents and diazo compounds to act as an accessible reference resource. Thermogravimetric analysis (TGA), differential scanning calorimetry (DSC), and accelerating rate calorimetry (ARC) data for the model donor/acceptor diazo compound ethyl (phenyl)diazoacetate are presented. We also present a rigorous DSC dataset with 43 other diazo compounds, enabling direct comparison to other energetic materials to provide a clear reference work to the academic and industrial chemistry communities. Interestingly, there is a wide range of onset temperatures (Tonset) for this series of compounds, which varied between 75 and 160 °C. The thermal stability variation depends on the electronic effect of substituents and the amount of charge delocalization. A statistical model is demonstrated to predict the thermal stability of differently substituted phenyl diazoacetates. A maximum recommended process temperature (TD24) to avoid decomposition is estimated for selected diazo compounds. The average enthalpy of decomposition (?"HD) for diazo compounds without other energetic functional groups is-102 kJ mol-1. Several diazo transfer reagents are analyzed using the same DSC protocol and found to have higher thermal stability, which is in general agreement with the reported values. For sulfonyl azide reagents, an average ?"HD of-201 kJ mol-1 is observed. High-quality thermal data from ARC experiments shows the initiation of decomposition for ethyl (phenyl)diazoacetate to be 60 °C, compared to that of 100 °C for the common diazo transfer reagent p-acetamidobenzenesulfonyl azide (p-ABSA). The Yoshida correlation is applied to DSC data for each diazo compound to provide an indication of both their impact sensitivity (IS) and explosivity. As a neat substance, none of the diazo compounds tested are predicted to be explosive, but many (particularly donor/acceptor diazo compounds) are predicted to be impact-sensitive. It is therefore recommended that manipulation, agitation, and other processing of neat diazo compounds are conducted with due care to avoid impacts, particularly in large quantities. The full dataset is presented to inform chemists of the nature and magnitude of hazards when using diazo compounds and diazo transfer reagents. Given the demonstrated potential for rapid heat generation and gas evolution, adequate temperature control and cautious addition of reagents that begin a reaction are strongly recommended when conducting reactions with diazo compounds.

Visible-Light-Mediated S?H Bond Insertion Reactions of Diazoalkanes with Cysteine Residues in Batch and Flow

We describe the application of S?H bond insertion reactions of aryl diazoacetates with cysteine residues that enabled metal-free, S?H functionalization under visible-light conditions. Moreover, this process could be intensified by a continuous-flow photomicroreactor on the acceleration of the reaction (6.5 min residence time). The batch and flow protocols described were applied to obtain a wide range of functionalized cysteine derivatives and cysteine-containing dipeptides, thus providing a straightforward and general platform for their functionalizations in mild conditions. (Figure presented.).

Catalytic O-H bond insertion reactions using surface modified sewage sludge as a catalyst

Developing a greener, sustainable catalyst is a very important but challenging task in organic synthesis. Herein, for the first time, we choose more economical and greener surface modified sewage sludge-derived carbonaceous materials (SW) treated by perch

Catalytic C-C coupling of diazo compounds with arylboronic acids: Using surface modified sewage sludge as catalyst

A green, mild and efficient synthesis of diarylmethines using sewage sludge-derived carbonaceous materials (SW) by perchloric acid catalyzed coupling reactions between diazo compounds and arylboronic acids was developed. The reaction shows a high level of functional tolerance and a broad substrate scope. Furthermore, the highly selective 1,2-alkyl shift products were furnished through the sterically demanding R4, R5 migration of diazo compounds (3-diazochromanone). The structures of 1,2-shift products have been further confirmed by single-crystal X-ray analysis. Significantly, the synthesis of the core structures of darifenacin (a clinical drug for overactive bladder syndrome, OAB) and diclofensine (a stimulant drug showing antidepressant and monoamine reuptake inhibitor activity) further demonstrated the efficacy and synthetic potential of this method. This journal is

Copper-catalyzed carbene insertion and ester migration for the synthesis of polysubstituted pyrroles

Copper-catalyzed carbene insertion/ester migration/cyclization of enaminones and α-diazo compounds occurred efficiently to afford 2-ester polysubstituted pyrroles under mild conditions in moderate-to-good yields. Substituent functionality was well tolerated and13C-labelled experiments demonstrated 1,2-ester migration during the reaction.