The four-centre reactions of alkanol–alkoxide negative ions with alkyl ethers and orthoacetates. An ion cyclotron resonance study

Abstract
Alkoxide–alkanol negative ions [R1O HOR2] react with carbon ethers (e.g., Me3COR3) by the four-centre reactions [R1O HOR2]+ Me3COR3→[R2O HOR3]+ Me3COR1, and [R1O HOR2]+ Me3COR3→[R1O HOR3]+ Me3COR2. The former reaction predominates when R1 < R2. 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, [R1O HOR2]+ Me2C(OR3)2→ Me2CO + R1OR3+[R2R HOR3]. Evidence is presented which shows that the six-centre reaction does not occur.

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