5131-95-3Relevant articles and documents
EPR studies of the formation and transformation of isomeric radicals [C3H5O].. Rearrangement of the allyloxyl radical in non-aqueous solution involving a formal 1,2-hydrogen-atom shift promoted by alcohols
Elford, Patrick E.,Roberts, Brian P.
, p. 2247 - 2256 (1996)
At 220 K in cyclopropane solvent, hydrogen-atom abstraction from allyl alcohol by Bu'O., EtO., PhMe2CO., (Me3Si)2N. or triplet-state acetone gives the 1-hydroxyallyl radical 3 as a ca. 3:1 mixture of the syn- and anti-isomers. In contrast, the allyloxyl radical does not react with allyl alcohol to bring about abstraction of hydrogen, but instead undergoes a more rapid alcohol-promoted rearrangement to give 3 as a ca. 1:1 mixture of the syn- and anti-forms. 2-Methylallyl alcohol, ethanol and propan-2-ol also induce this formal 1,2-H-atom shift in the allyloxyl radical. In the presence of ethan[2H]ol, both 3 and (3-OD) are formed and as [EtOD] is increased from 0.3 to 3.6 mol dm-3 [3-OD]/[3] first passes through a maximum value of ca. l and then decreases to 0.38. It is proposed that there is more than one mechanism for the alcohol-induced rearrangement of the allyloxyl radical, one that involves assisted migration of hydrogen from the α-carbon atom to the oxygen atom and another that results in incorporation of deuterium from the EtOD. The importance of the latter mechanism decreases at high alcohol concentrations and this behaviour is thought to be related to the extent of association of the alcohol by hydrogen-bonding. The allyloxyl radical was generated by UV photolysis of allyl tert-butyl peroxide and by ring opening of the oxiranylmethyl radical, derived from epibromohydrin or epichlorohydrin by halogen-atom abstraction. Ab initio molecular orbital calculations predict that an unassisted 1,2-H-atom shift in the allyloxyl radical will involve a very large activation energy. The alcohol is believed to serve a dual function in promoting the rearrangement: first, to increase the acidity of the α-CH2 group by hydrogen-bonding to the oxygen atom of the allyloxyl radical and, secondly, to provide a basic oxygen atom to facilitate the transfer/removal of a protic α-hydrogen atom.
The reactivity of ketyl and alkyl radicals in reactions with carbonyl compounds
Denisov
, p. 2110 - 2116 (2007/10/03)
A parabolic model of bimolecular radical reactions was used for analysis of the hydrogen transfer reactions of ketyl radicals: >C+OH + R1COR2 → >C=O + R1R2C+OH. The parameters describing the reactivity of the reagents were calculated from the experimental data. The parameters that characterize the reactions of ketyl and alkyl radicals as hydrogen donors with olefins and with carbonyl compounds were obtained: >C+OH + R1CH=CH2 → >C=O + R1C+ HCH3; >R1CH=CH2 + R2C+HCH2R3 → R2C+HCH3 + R2CH=CHR3. These parameters were used to calculate the activation energies of these transformations. The kinetic parameters of reactions of hydrogen abstraction by free radicals and molecules (aldehydes, ketones, and quinones) from the C-H and O-H bonds were compared.
Kinetics of the gas-phase reactions of NO3 radicals with a series of alcohols, glycol ethers, ethers and chloroalkenes
Chew, Andrew A.,Atkinson, Roger,Aschmann, Sara M.
, p. 1083 - 1089 (2007/10/03)
Using a relative rate method, rate constants have been measured for the gas-phase reactions of the NO3 radical with methacrolein, a series of ethers, glycol ethers, alcohols and chloroalkenes at 298 ± 2 K and atmospheric pressure of air. The rate constants determined (in units of 10-16 cm3 molecule-1 s-1) were: methacrolein, 33 ± 10; diethyl ether, 31 ± 10; di-n-propyl ether, 49 ± 16; diisopropyl ether, 40 ± 13; ethyl tert-butyl ether, 45 ± 14; 1-methoxypropan-2-ol, ≤15 ± 5; 2-butoxyethanol, ≤31 ± 11; propan-1-ol, ≤21 ± 8; propan-2-ol, ≤17 ± 6; butan-1-ol, ≤27 ± 10; butan-2-ol, ≤25 ± 8; heptan-4-ol, ≤60 ± 20; cis-1,2-dichloroethene, 1.3 ± 1.3; 1,1-dichloroethene, 18-6+9; trichloroethene, 3.6-1.5+2.0; tetrachloroethene, -2.0+3.0. Carbonyl products of the alcohol reactions arising after H-atom abstraction at the carbon atom to which the -OH group is attached were observed, and rate constants for this reaction pathway obtained. Significant discrepancies with the literature concern propan-2-ol, ethyl tert-butyl ether and 3-chloropropene, with our relative rate constants for these compounds being factors of ca. 2, ca. 2, and ca. 8 lower, respectively, than previously reported absolute rate constant determinations.
