Base-promoted elimination reactions of (E)- and (Z)-arylaldehyde O-benzoyloximes. Effects of stereochemistry, β-aryl group and base-solvent on the nitrile-forming transition states

Elimination reactions of (E)-2,4,6-(NO 2 ) 3 C 6 H 2 CH NOC(O)C 6 H 4 X (3) promoted by R 2 NH/R 2 NH 2 + in 70 mol% MeCN (aq) have been studied. The reactions produced elimination products and exhibited second-order kinetics. The β and |β lg | values remained nearly the same for all leaving groups and bases. The results can be described by the negligible p xy interaction coefficient, p xy = ∂β/∂pK lg = ∂β lg /∂pK BH ≈ 0, which provides a strong support for the (E1cb) irr mechanism. For eliminations from (E)-ArCH NOC (O)C 6 H 4 X (1, 3) and (E)-2,4,6-(NO 2 ) 3 C 6 H 2 CH NOAr 0 (2, 3), the change of the β-aryl group (Ar) from 2,4-dinitrophenyl (1) to 2,4,6-trinitrophenyl (3) increased the rate by 270-fold without appreciable change in the transition state structure. On the other hand, the leaving group (OAr 0 ) variation from benzoate (3) to 4-nitrophenoxy (2) induced a change in reaction mechanism from (E1cb) irr to E2. These results have been attributed to the cyclic transition state for the nitrile-forming eliminations involving the benzoate leaving group.

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Base-promoted elimination reactions of (E)- and (Z)-arylaldehyde O-benzoyloximes. Effects of stereochemistry, β-aryl group and base-solvent on the nitrile-forming transition states

Cited by 2 publications

References 28 publications

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Stereoselective Bromocyclization of Allylated Aldoxime Ethers

Elimination Reactions of (E)‐2,4,6‐Trinitrobenzaldehyde O‐Benzoyloximes Promoted by R₂NH/R₂NH₂⁺ in 70 mol% MeCN (aq). Effects of the β‐Aryl Group and Leaving Group on Nitrile‐Forming Transition States

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Base-promoted elimination reactions of (E)- and (Z)-arylaldehyde O-benzoyloximes. Effects of stereochemistry, β-aryl group and base-solvent on the nitrile-forming transition states

Cited by 2 publications

References 28 publications

Stereoselective Bromocyclization of Allylated Aldoxime Ethers

Stereoselective Bromocyclization of Allylated Aldoxime Ethers

Elimination Reactions of (E)‐2,4,6‐Trinitrobenzaldehyde O‐Benzoyloximes Promoted by R2NH/R2NH2+ in 70 mol% MeCN (aq). Effects of the β‐Aryl Group and Leaving Group on Nitrile‐Forming Transition States

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Elimination Reactions of (E)‐2,4,6‐Trinitrobenzaldehyde O‐Benzoyloximes Promoted by R₂NH/R₂NH₂⁺ in 70 mol% MeCN (aq). Effects of the β‐Aryl Group and Leaving Group on Nitrile‐Forming Transition States