58784-42-2

Upstream product

• 35665-96-4 4-nitrophenyl 2-(4'-methoxyphenyl)acetate 
• 206358-99-8 C₉H₁₀O₂ 
• 31706-15-7 3-(4-methoxy-phenyl)-3-oxo-propionaldehyde 
• 100-06-1 1-(4-methoxyphenyl)ethanone 
• 6832-17-3 2-diazo-1-(4-methoxyphenyl)ethanone 

Downstream Products

• 104-01-8 4-Methoxyphenylacetic acid 
• 115348-15-7 N,N-diethyl-2-(4-methoxyphenyl)acetamide 
• 1497283-38-1 C₁₃H₁₉NO₂ 

Relevant academic research and scientific papers

Gold nanoparticles supported on supramolecular ionic liquid grafted graphene: A bifunctional catalyst for the selective aerobic oxidation of alcohols

Gold nanoparticles supported on supramolecular ionic liquid grafted graphene have been synthesized and used as a bifunctional, efficient and recyclable heterogeneous catalyst for the aerobic oxidation of various primary and secondary aliphatic and aromatic alcohols to the corresponding aldehyde and ketone derivatives in water as a green solvent at room temperature. The Royal Society of Chemistry 2013.

Amination of phenylketene revisit. Substituent effect on reactivity

The asymmetric stretching frequencies of the ketene group of the m,p-substituted phenylketenes were found to be correlated with σ The substituent effects for the second-order rate constants of phenylketenes with various amines were not correlated linearly

Aminoxyl radical addition to arylketenes

Kinetic studies of the addition of the aminoxyl radical TEMPO (2,2,6,6-tetramethylpiperidinylaminoxyl, TO) to the 4-substituted phenylketenes 8 (4-RC6H4CH=C=O, R=NO2, CN, Cl, H, CH 3, CH3O) and to 3-p

Ketene-forming eliminations from aryl phenylacetates promoted by R2NH in MeCN. Origin of the curved Hammett plot

Elimination reactions of YC6H4CH2C(O)OC6H3-2-X-4-N O2 promoted by R2NH MeCN have been studied kinetically. The reactions are second-order and exhibit Bronsted β = 0.52-0.87, |βlg| = 0.37-0.65, and ρH = 1.9-4.1. The β and ρH values decrease as the leaving group becomes less basic and the |βlg| values decrease with a stronger base. The results are interpreted in terms of an E1cb-like transition state with extensive Cβ-H bond cleavage, significant negative charge development at the β-carbon, and limited Cα-OAr bond cleavage. For all reactions, the Hammett plots are curvilinear and show downward curvature. The curvature is more pronounced as the leaving group becomes poorer. The results have been attributed to the highly carbanionic transition state, which is moved towards the reactant on the horizontal reaction coordinate by a stronger electron-withdrawing substituent.

Spectroscopy and absolute reactivity of ketenes in acetonitrile studied by laser flash photolysis with time-resolved infrared detection

Laser flash photolysis with time-resolved infrared detection of transients (LFP-TRIR) has been used to study the IR spectroscopy and reactivity of a number of substituted ketenes, prepared by the 308-nm photolysis of α-diazocarbonyl precursors in acetonitrile solution at room temperature. The correlation of the experimental ketene asymmetric stretching frequency to the Swain-Lupton field (F) and resonance (R) effect substituent parameters was unsatisfactory, whereas the correlation to the inductive substituent parameter (σ1) of Charton gave excellent results. This suggests that the asymmetric stretching frequency of substituted ketenes depends mainly on the inductive (i.e., field) effect of the substituents. The mechanism and kinetics of the reactions of these ketenes with various amines in acetonitrile were also studied. An intermediate species identified as either zwitterionic ylide or amide enol formed in the nucleophilic addition of the secondary amine to the C(α) of the ketene is observed by TRIR. The decay of this species is assisted by the amine and is concomitant with the formation of an amide, the final product of the reaction. Our kinetic data on ketene amine reactions show a general trend, indicating a much higher reactivity (ca. 3 orders of magnitude difference in the corresponding rate constants) of secondary amines compared with that of tertiary amines. Secondary diethylamine shows reactivity similar to those observed for primary amines, while secondary piperidine seems to be, in general, somewhat more reactive. The observed trend is rationalized in terms of the steric effects exerted by both amine and ketene substituents. Our data on para-substituted phenyl ketenes provide support for the negative charge development on the ketene moiety in the transition state, with electron-withdrawing substituents accelerating and electron-releasing substituents slowing down the addition reaction.

Reactions of aryl phenylacetates with secondary amines in MeCN. Structure-reactivity relationship in the ketene-forming eliminations and concurrent E2 and E1cb mechanisms

Elimination reactions of aryl esters of arylacetic acids 1 and 2 promoted by R2NH in MeCN have been investigated kinetically. The reactions are second-order and exhibit β = 0.44-0.84, β(lg) = 0.41-0.50, and ρ(H) = 2.0-3.6. Bronsted β and β(lg) decrease with the electron-withdrawing ability of the β-aryl substituent. Hammett ρ(H) values remain nearly the same, but the β(lg) value increases as the base strength becomes weaker. Both ρ(H) and β decrease with the change of the leaving group from 4-nitrophenoxide to 2,4-dinitrophenoxide. The results are consistent with an E2 mechanism and a reaction coordinate with a large horizontal component corresponding to proton transfer. When the base-solvent system is changed from R2NH-MeCN to R2NH/R2NH2+-70 mol% MeCN(aq), the Bronsted β, ρ(H), and β(lg) decrease. Finally, the ketene-forming elimination reactions from p-nitrophenyl p-nitrophenylacetate promoted by R2NH/R2NH2+ buffers in 70 mol% MeCN(aq) have been shown to proceed by concurrent E2 and E1cb mechanisms.