4237-46-1Relevant articles and documents
Time-resolved ESR studies on ketyl type radical - Amine complexes
Kawai, Akio,Aoki, Atsushi,Kobori, Yasuhiro,Obi, Kinichi
, p. 10021 - 10026 (1996)
Time-resolved (TR) ESR spectra were measured for α-hydroxybenzyl-amine (α-HB) and α-hydroxydiphenylmethyl - amine complexes. Hyperfine coupling constants (hfcc) of the complexes were determined, and considerable increase in hfcc was recognized on the hydr
Specific solvent effects on the structure and reaction dynamics of benzophenone ketyl radical
Kawai, Akio,Hirakawa, Makoto,Abe, Toyohiko,Obi, Kinichi,Shibuya, Kazuhiko
, p. 9628 - 9636 (2001)
Complex formation reaction between benzophenone ketyl (BPK) radical and triethylamine was investigated by means of transient absorption and time-resolved ESR methods. The formation constants (Kf's) in benzene, toluene, o-xylene, and anisole were measured by a transient absorption method. The enthalpy and entropy changes upon the complex formation were determined by van't Hoff plots of Kf values around 300 K. The ΔG values in the complex formation reaction at 298 K were calculated from these thermodynamic parameters, which show notable difference from those in aliphatic solvents and chlorotoluenes previously reported. The BPK conformation in these solvents was investigated by analyzing the time-resolved ESR spectra of BPK and by the DFT calculation. The hyperfine coupling constant of hydroxy-proton (aOH) was found to depend on solvent as well and there exists a clear correlation between the aOH and Kf (or ΔG) values. It was concluded that the conformation of BPK, especially the conformation between OH and two phenyl groups, depends on the solvation and is an important factor to control the complex formation reaction.
A novel lanthanum metal-assisted reaction of diaryl ketones and electrophiles
Umeda, Rui,Ninomiya, Masashi,Nishino, Toshiaki,Kishida, Makoto,Toiya, Shunsuke,Saito, Tomoki,Nishiyama, Yutaka,Sonoda, Noboru
, p. 1287 - 1291 (2015/03/05)
A novel and efficient lanthanum metal-assisted carbon-carbon bond formation of diaryl ketones and various electrophiles, such as carbonyl compounds, esters, nitriles, and epoxides, has been developed. When diaryl ketones were allowed to react with dialkyl ketones in the presence of lanthanum metal and a catalytic amount of iodine, the cross pinacol coupling reaction proceeded to give the corresponding unsymmetrical 1,2-diols in moderate to good yields. α-Hydroxy ketones were prepared by the lanthanum metal-assisted reaction of diaryl ketones with esters or nitriles, followed by hydrolysis with aq HCl. It is interesting to note that for the epoxides, the coupling reaction proceeded via the Meinwald rearrangement of epoxides to give the corresponding 1,2-diols.
Reactions of organolithiums with dialkyl oxalates. A flow microreactor approach to synthesis of functionalized α-keto esters
Nagaki, Aiichiro,Ichinari, Daisuke,Yoshida, Jun-Ichi
supporting information, p. 3242 - 3244 (2013/05/08)
Reactions of functionalized aryllithiums with dialkyl oxalates were achieved using a flow microreactor to obtain α-keto esters with high selectivity by virtue of fast 1:1 micromixing.