525-06-4Relevant articles and documents
Synthesis of 3-alkylseleno-2-cylcobutenone via [2+2] cycloaddition reaction of alkyneselenolate with diphenylketene
Koketsu, Mamoru,Kanoh, Masanori,Ishihara, Hideharu
, p. 805 - 807 (2002)
3-Alkylseleno-2-cyclobutenones were synthesized by reaction of alkyneselenolate with diphenylketene via [2+2] cycloaddition. The complete structure of the 2-cyclobutenone was determined by X-ray diffraction.
Synthesis and time resolved infrared analysis of photochemical oxiranyl carbene and diphenyl ketene precursors
Tippmann, Eric M.,Curtis, Ryan
, p. 4785 - 4787 (2016)
Synthesis of a nonnitrogenous phenanthrene-based precursor of oxiranyl carbene yielded a photochemical source for diphenyl ketene after an in situ intramolecular rearrangement. The initial carbene precursor targeted rearranged from a putative spiro-oxiranyl intermediate to a cyclobutanone. Photolysis of the phenanthrene–cyclobutanone generated an infrared signal centered at 2100?cm?1consistent with diphenyl ketene formation. Time-resolved infrared spectroscopy followed the reaction progress and measured bimolecular rate constants (kobs?=?9.1?×?106?M?1?s?1; butyl amine) consistent with diphenyl ketene formation. Quenching experiments combined with Stern–Volmer kinetics suggests a radical pathway is likely involved in the formation of diphenyl ketene from the phenanthrene-based precursor. The generality of the rearrangement is also discussed.
Coordination behaviors of diphenylketene adsorbed in the nanocages of zeolite NaY and AgY
Shibata, Shintaro,Masui, Yoichi,Onaka, Makoto
, p. 663 - 670 (2020/12/29)
We investigated in detail how polar cumulene molecules like diphenylketene were accommodated in faujasite zeolite pores based on 13C CP/MAS and DD/MAS NMR analyses as well as quantum chemical calculations after adsorbing the molecule into the zeolite NaY or AgY having “hard” sodium ions or “soft” silver ions. Since the diphenylketene has such a specific structure that a carbonyl group (a hard base) is accumulated by a carbon-carbon double bond (a soft π base), which is conjugated with two benzene rings (soft π bases), it is possible for the diphenylketene to adopt multicoordination modes to different metal ions in the zeolite. Compared with the coordination modes of benzophenone and 1,1-diphenylethene adsorbed in the NaY and AgY, those of diphenylketene were identified, and specific coordination behaviors in the zeolite’s supercages were classified depending on the hard or soft metal characters: The C=O and phenyl coordination modes to Na+ in NaY prevail, while the C=C and phenyl coordination to Ag+ in AgY is favored. We also unveiled the difference in the molecular mobility depending on the types of cations in the zeolite by comparing the 13C CP/MAS and DD/MAS NMR spectra.
Ketenes from N-(2-Pyridyl)amides
Plüg, Carsten,Kanaani, Hussein,Wentrup, Curt
, p. 687 - 692 (2015/04/27)
Methoxycarbonylketene 4a, methoxycarbonyl(methyl)ketene 4b, chloroketene 4c, cyanoketene 4d, diphenylketene 4e, and 2-pyridylketene 4f have been generated by flash vacuum thermolysis of the corresponding 2-pyridylacetamide derivatives 3a-f and isolated in Ar matrices for FT-IR spectroscopic characterisation. The N-(2-pyridyl)-2-pyridylacetamide 3f yielded 2-pyridyl isocyanate in addition to 2-pyridylketene.
