<b>Formation of Imines by Electrophilic Substitution at Saturated Carbon in the Beckmann and Schmidt Reactions</b>

Lansbury, Peter T.; Colson, James G.

doi:10.1021/ja00880a050

Cited by 10 publications

(2 citation statements)

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“…The isomerization of oximes by polyphosphoric acid observed in some Beckmann rearrangements, however, may best be explained by the suggestion that they occur through + an electron-deficient nitrogen >C=N (91). Similarly, the formation of imines by electrophilic substitution or insertion at a saturated carbon atom in some Beckmann rearrangements may involve a discrete imidonium ion intermediate (CXXI), though a concerted process (201) is a distinct possibility (182) [see also (23) ].…”

Section: G Imidonium Ion Intermediates Rnr'mentioning

confidence: 99%

Preparation and Properties of Imido Intermediates (Imidogens)

Abramovitch¹,

Davis²

1964

Chem. Rev.

200

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Section: G Imidonium Ion Intermediates Rnr'mentioning

confidence: 99%

Preparation and Properties of Imido Intermediates (Imidogens)

Abramovitch¹,

Davis²

1964

Chem. Rev.

200

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“…Thus, the reaction in which H20 is lost from an ortho-substituted diaryl sulfone ion seems to give rise to a car bene group, which is then inserted into an ortho carbon-hydrogen or carbon-carbon bond in the second aryl group. [Lansbury and Colson report such an intramolecular carbene insertion in a liquidphase reaction (16).] Isomer Distribution from Toluene Sulfonation.…”

Section: Any Proposed Reactionmentioning

confidence: 99%

Mass Spectra of Diaryl Sulfones.

Meyerson¹,

Drews²,

Fields³

1964

Anal. Chem.

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TheBeckmann Reactions: Rearrangements, Elimination–Additions, Fragmentations, and Rearrangement–Cyclizations

Gawley

1988

Organic Reactions

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The Beckmann rearrangement, the acid‐mediated isomerization of oximes to amides, was discovered by Beckmann in 1886. As one of the oldest and most familiar transformations in organic chemistry, it has been reviewed several times. What has become known as the Beckmann fragmentation was in fact first observed by Wallach in 1889 but was not developed extensively until the 1960s. It has been referred to by several names over the years and has also been reviewed. The rearrangement cyclization is the intramolecular cyclization of a nitrilium ion generated by Beckmann rearrangement from an oxime. Within the context of an aromatic terminator, the process was first reported by Goldschmidt in 1895. Wallach reported the first case of an aliphatic terminator in 1901, although the reported structure was incorrect, and Perkin was apparently the first to observe a heteroatom terminator, but he also reported an incorrect structure. The process has been exploited only quite recently. This chapter is an update of these reactions, last reviewed in this series in 1960. Not covered are transformations that have been labeled Beckmann‐type reactions but are mechanistically unrelated. The most prominent of these is the so‐called photochemical Beckmann rearrangement, first observed by De Mayo in 1963 and discussed in a review several years ago. Worthy of mention, however, is the fact that many oximes that suffer fragmentation under acidic conditions undergo rearrangement when photolyzed. Throughout this chapter, the ( E ) and ( Z ) nomenclature is used to describe oxime geometry.

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Formation of Imines by Electrophilic Substitution at Saturated Carbon in the Beckmann and Schmidt Reactions

Cited by 10 publications

References 1 publication

Preparation and Properties of Imido Intermediates (Imidogens)

Preparation and Properties of Imido Intermediates (Imidogens)

Mass Spectra of Diaryl Sulfones.

TheBeckmann Reactions: Rearrangements, Elimination–Additions, Fragmentations, and Rearrangement–Cyclizations

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