8013-52-3Relevant articles and documents
Flowing afterglow study of the gas phase nucleophilic reactions of some formyl, acetyl and cyclic esters
Frink, Brian T.,Hadad, Christopher M.
, p. 2397 - 2407 (2007/10/03)
A variety of nucleophiles have been investigated for their reactions with formyl and acetyl esters in the gas phase in our flowing afterglow. The reactions that are permitted in the gas phase are more varied than those seen in the condensed phase. The rates of reactions of methyl and ethyl esters as well as various lactones have been undertaken with various nucleophiles: H2N-, HO-, CH3O, NCCH2-, F-, CH3C(=O)CH2-, CH3S- and O2NCH2-. For example, the reaction rate of NCCH2- + HCO2CH2CH3 has been found to be (1.3 ± 0.2) x 10-10 cm3 molecule-1 s-1 and the only product is HC(O-)=CHCN which results from nucleophilic acyl substitution (BAC2) followed by a proton transfer within the ion-molecule complex. Other reaction mechanisms that have been observed include β-elimination (E2), bimolecular nucleophilic substitution at the alkyl group (BAL2), and the Riveros reaction (elimination of CO). A mechanism for the F- + HCO2CH3 reaction has been determined at the B3LYP/6-31 + G(d) level. Most notably, channels were determined computationally (6AL2 and Riveros), and these channels are also observed experimentally. Furthermore, the BAC2 pathway which proceeds via nucleophilic attack on the carbonyl group also leads to the Riveros products, F-(CH3OH) and CO.
The Four-centre Reactions of Alkanol-Alkoxide Negative Ions with Alkyl Ethers and Orthoacetates. An Ion Cyclotron Resonance Study
Hayes, Roger N.,Paltridge, R. Lee,Bowie, John H.
, p. 567 - 572 (2007/10/02)
Alkoxide-alkanol negative ions 1O-...HOR2> react with carbon ethers (e.g., Me3COR3) by the four-centre reactions 1O-...HOR2> + Me3COR3 -> 2O-...HOR3> + Me3COR1, and 1O-...HOR2> + Me3COR3 -> 1O-...HOR3> + Me3COR2.The former reaction predominates when R1 2.In the case of di- and tri-ethers, the four-centre reaction can, in principle, compete with the alternative six-centre reaction.For example, for Me2C(OR3)2, 1O-...HOR2> + Me2C(OR3)2 -> Me2C=O + R1OR3 + 2O-...HOR3>.Evidence is presented which shows that the six-centre reaction does not occur.