7495-84-3Relevant articles and documents
Iridium-Catalyzed Amidation of in Situ Prepared Silyl Ketene Acetals to Access α-Amino Esters
Chang, Sukbok,Gwon, Yunyeong,Kim, Dongwook,Lee, Minhan
supporting information, p. 1088 - 1093 (2022/02/10)
Disclosed herein is a convenient Ir-catalyzed amidation of esters to access α-amido esters. Initially prepared silyl ketene acetals are directly employed, without separate purification, for subsequent amidation with an oxycarbonylnitrenoid precursor using the Cp*(LX)Ir(III) catalyst. The α-amidation was facile for both α-aryl and α-alkyl esters. Density functional theory studies revealed that the generation of a putative Ir-nitrenoid is facilitated by the chelation of the countercation additive during the N-O bond cleavage of the nitrene precursor.
How much does the hybridization of a carbon atom affect the transmission of the substituent effect on the chemical shift?
Jeong, Eun Jeong,Lee, In-Sook Han
, p. 295 - 299 (2015/03/03)
1H and 13C NMR spectra of aryl esters of propionic acid, acrylic acid, and propiolic acid were systematically examined to find out the substituent effect on the chemical shift. The values of the chemical shift of the carbonyl carbon showed an inverse correlation with the Hammett ?3 values, and the magnitude of the slope was the largest with the propiolates. The ?± carbons of acrylates and propiolates also showed an inverse correlation with much smaller values of the slopes than those of the carbonyl carbons; but those of the propionates showed absolutely no correlation. However, the ?2 carbons of acrylates and propiolates showed normal correlation with larger values of the slopes. The signs and the magnitudes of the slopes may be understood by the transmission of the substituent electronic effect through bonds as well as through space. The propiolyloxy group also showed a significantly large effect on the 13C chemical shift values of the benzene ring.
Microwave-induced deactivation-free catalytic activity of BEA zeolite in acylation reactions
Chandra Shekara,Jai Prakash,Bhat
scheme or table, p. 101 - 107 (2012/07/14)
Solventless liquid-phase acylation of p-cresol with different aliphatic carboxylic acids like acetic, propionic, butyric, hexanoic, octanoic, and decanoic acids was investigated over BEA zeolite under conventional as well as microwave heating. An unanticipated huge difference in activity was observed between two modes of heating. Under conventional heating, conversion of all the acids was less than 20%, while under microwave heating, the conversion was in the range of 50-80%. Ester formed through O-acylation and ortho-hydroxyketone formed through Fries rearrangement of the ester were the only products. Conversion of carboxylic acid increased with chain length up to hexanoic acid and then it showed a decrease in the trend. With all the acids, O-acylation occurred rapidly followed by slow conversion to ortho-hydroxyketone. The ketone/ester ratio increased with catalyst amount, temperature, and reaction time. Used catalyst samples were characterized by TGA, XRD, and IR studies to understand lower activity and deactivation behavior under conventional heating. The results showed absence of coke precursor/coke on the catalyst used in microwave-irradiated reactions in contrast to catalyst used in conventionally heated ones. Higher yield in the case of microwave-assisted reactions is attributed to the prevention of coke precursor/coke on the active sites by microwaves.