title: Formation of dimethylketene and methacrolein by reaction of the CH radical with acetone.
abstract: The reaction of the methylidyne radical (CH) with acetone ((CH(3))(2)C[double bond, length as m-dash]O) is studied at room temperature and at a pressure of 4 Torr (533.3 Pa) using a multiplexed photoionization mass spectrometer coupled to the tunable vacuum ultraviolet synchrotron radiation of the Advanced Light Source at Lawrence Berkeley National Laboratory. The CH radicals are generated by 248 nm multiphoton photolysis of bromoform and react with acetone in an excess of helium and nitrogen gas flow. The main observed reaction exit channel is elimination of a hydrogen atom to form C(4)H(6)O isomers. Analysis of photoionization spectra identifies dimethylketene and methacrolein as the only H-elimination products. The best fit to the data gives branching ratios of 0.68 ± 0.14 for methacrolein and 0.32 ± 0.07 for dimethylketene. A methylketene spectrum measured here is used to reanalyze the photoionization spectrum obtained at m/z = 56 for the CH + acetaldehyde reaction, (Goulay et al., J. Phys. Chem. A, 2012, 116, 6091) yielding new H-loss branching ratios of 0.61 ± 0.12 for acrolein and 0.39 ± 0.08 for methylketene. The contribution from methyleneoxirane to the reaction product distribution is revised to be negligible. Coupled with additional product detection for the CD + acetone reaction, these observations pave the way for development of general set of reaction mechanisms for the addition of CH to compounds containing an acetyl subgroup.
authors: Department of Chemistry, West Virginia University, Morgantown, West Virginia 26506, USA. Fabien.goulay@mail.wvu.edu
authors: Fabien
authors: F
authors: Goulay
authors: Adeeb
authors: A
authors: Derakhshan
authors: Eamonn
authors: E
authors: Maher
authors: Adam J
authors: AJ
authors: Trevitt
authors: John D
authors: JD
authors: Savee
authors: Adam M
authors: AM
authors: Scheer
authors: David L
authors: DL
authors: Osborn
authors: Craig A
authors: CA
authors: Taatjes
mesh_terms: D000096:Acetone / Q000737:chemistry*; D000171:Acrolein / Q000031:analogs & derivatives* / Q000737:chemistry; D005030:Ethylenes / Q000138:chemical synthesis / Q000737:chemistry*; D005609:Free Radicals / Q000737:chemistry*; D007659:Ketones / Q000138:chemical synthesis / Q000737:chemistry*; D007700:Kinetics; D010782:Photolysis; D013696:Temperature; D022882:Trihalomethanes / Q000737:chemistry
chemical_list: D005030:Ethylenes; D005609:Free Radicals; D007659:Ketones; D022882:Trihalomethanes; D000096:Acetone; D000171:Acrolein; C039175:methacrylaldehyde; C008223:ketene; C015044:bromoform