First direct detection of 2,3-dimethyl-2,3-diphenylcyclopropanone.
3,5-dihydro-3,5-dialkyl-3,5-diaryl-4H-pyrazol-4-ones stimulate interest as potential precursors for 2,3-diarylcyclopropanones. Photoreactions of trans-3,5-dihydro-3,5-dimethyl-3,5-diphenyl-4H-pyrazol-4-one were studied by continuous-wave (CW) and pulsed laser UV photolysis revealing an intermediate that undergoes rearrangement to form cis- and trans-1,3-dimethyl-1-phenyl-2-indanones with the yield of ca. 60%. Steady-state photolysis (254 and 350 nm excitation) in different solvents produced an intermediate cyclohexadiene as evidenced by UV/vis, IR, and 1H NMR spectra. In contrast, the nanosecond laser pulsed photolysis at 355 nm produced 2,3-dimethyl-2,3-diphenylcyclopropanone along with two products of retro-1,3-dipolar addition phenylmethylketene and 1-phenyldiazoethane. These can be observed by time-resolved IR (TRIR) spectroscopy as characteristic absorption bands at 1814, 2101, and 2038 cm-1, respectively. Similar retro-1,3-dipolar addition showed 1-phenyldiazoethane formed following flash photolysis of 1-pyrazoline (trans-4,5-dihydro-3,5-dimethyl-3,5-diphenyl-3H-pyrazol-4-ol). The formation of the corresponding cyclopropanone as well the products of retro-1,3-dipolar addition during photoreaction of starting pyrazol-4-one is directly confirmed by the nanosecond TRIR spectroscopy for the first time. On the basis of the CW and pulsed laser UV photolysis, a dynamic equilibrium between cyclopropanone and intermediate 2,4-diphenyl-3-pentanone-2,4-diyl (dimethyldiphenyloxyallyl) was proposed.
Moiseev
Andrey G
AG
Center for Photochemical Sciences, Bowling Green State University, Bowling Green, Ohio 43403, USA.
Abe
Manabu
M
Danilov
Evgeny O
EO
Neckers
Douglas C
DC