a b s t r a c tPhotoinduced electron transfer (PET) reactions promoted by 2-aryl substituted 1,3-dimethylbenzimidazolines (Ar-DMBIH) were investigated. Excited states of Ar-DMBIH, formed by irradiation using light above 360 nm, initiate PET reductions of various organic substrates, including transformations of epoxy ketones to aldols, free radical rearrangements such as the Dowd-Beckwith ringexpansion and 5-exo hexenyl cyclization, deprotection of N-sulfonyl-indols, and allylation of acyl formates. In these processes, Ar-DMBIH possessing 1-naphthyl, 2-naphthyl, 1-pyrenyl and 9-anthryl substituents formally act as two electron and one proton donors while the hydroxynaphthyl substituted derivative serves as a two electron and two proton donor. On the basis of the results of absorption spectroscopy studies, cyclic voltammetry and DFT calculation, a mechanistic sequence for these reduction reactions is proposed that involves initial photoexcitation of the aryl chromophore of the Ar-DMBIH followed by single electron transfer (SET) to the organic substrate to generate the radical cation of benzimidazoline and the radical anion of the substrate.
The visible light-promoted reduction reactions of some organohalides were investigated using 2-aryl-1,3-dimethylbenzimidazolines (Ar-DMBIH) possessing 2-naphthyl or 2-hydroxynaphthyl substituents. In these reduction reactions, single-electron transfer from photo-excited Ar-DMBIH, attained by Xe lamp irradiation through an appropriate glass-filter (λ > 390 nm), to the halide substrates leads to the carbon–halogen bond cleavage, followed by the rearrangements of the formed carbon radicals such as 5-exo hexenyl cyclization and the Dowd–Beckwith ring expansion. Addition of 1,8-diazabicyclo[5.4.0]undec-7-ene was found to enhance the reducing ability of hydroxynaphthyl-substituted DMBIH. A household white light-emitting diode was also used as a light source for these reactions.
We have previously reported our attempts to control microbubbles (microcapsules) behavior in flow by primary Bjerknes force to increase the local concentration of the bubbles at a diseased part. However, there was a limitation in efficiency to propel bubbles of μm-order size. Thus we consider that forming aggregates of bubbles is effective to be propelled before entering into an ultrasound field by making use of secondary Bjerknes force under continuous ultrasound exposure. In this study, we observed the phenomena of aggregates formation by confirming variation of diameter and density of aggregates under various conditions of ultrasound exposure. Then we elucidated frequency dependence of the size of aggregates of micro-bubbles.
A benzimidazoline ligand in combination with a Ru‐ or Ir‐complex promotes photoinduced electron‐transfer reactions of α‐halomethyl substituted substrates to form primary alkyl radicals via selective C‐halogen bond cleavage.
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