Pyrolysis of Oxime Carbonates: Novel Conversion of Aldehydes into Nitriles under Mild Conditions

Prokipcak, J. M.; Forte, P. A.

doi:10.1139/v71-218

Cited by 17 publications

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“…The general synthesis procedure used for the preparation of these compounds can be found in previous work (1). The complete list of E-benzaldoxime carbonates prepared and used in this study along with physical constants and elemental analyses is given in Table 1.…”

Section: Synthesis Of Benzaldoxime Carbonatesmentioning

confidence: 99%

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The Mechanism for the Thermal Decomposition of E-Aldoxime Carbonates

Prokipcak¹,

Forte²

1975

Can. J. Chem.

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J. M. PROKIPCAK and P. A. FORTE. Can. J. Chem. 53,3481 (1975). Pyrolysis of aldoxime carbonates at relatively low temperatures (100-120°C) produced nitriles in excellent yields. These decompositions followed first-order kinetics and the decomposition rates showed little dependence on inductive effects or solvent polarity. Low entropy values along with the fact that the E and Z-isomers behaved quite differently led to the proposal of a cyclic transition state for the decompositions.J. M. PROKIPCAK et P. A. FORTE. Can. J. Chem. 53,3481 (1975). La pyrolyse des carbonates d'aldoxime a des tempkratures relativement basses (100-120 "C) conduit aux nitriles avec d'excellents rendements. Ces dkcompositions se produisent suivant une cinktique du premier ordre et les vitesses de dkcomposition ne sont que peu affectees par les effets inductifs ou la polaritk du solvant. En se basant sur le fait que les entropies sont basses et que les isomeres E et Z se comportent tres diffkremment, on suggkre un etat de transition cyclique pour ces dtcompositions.[Traduit par le journal]

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Section: Synthesis Of Benzaldoxime Carbonatesmentioning

confidence: 99%

“…It was shown in an earlier publication (1) that the thermal decomposition of E-benzaldoxime carbonates was a useful synthetic route in the preparation of nitriles. This route was particularly valuable since the conversion of the E-aldoxime carbonates to the corresponding nitriles required no acidic or basic reagents.…”

Section: Introductionmentioning

confidence: 99%

The Mechanism for the Thermal Decomposition of E-Aldoxime Carbonates

Prokipcak¹,

Forte²

1975

Can. J. Chem.

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“…1c-f One of the classical methods for the conversion of aldehydes to nitriles involves dehydration of the corresponding aldoximes and several efficient dehydrating agents have been developed for this transformation. 3 Among the phosgene derived reagents, chlorosulfonyl isocyanate, 3q N,N¢-carbonyldiimidazole, 3s and phenyl chloroformate 4 have been shown to be mild and effective dehydrating agents for this transformation. During the course of our studies directed towards development of efficient sulfur containing building blocks 5 and reagents, 6 we became interested in exploring synthetic transformations of (S,S)-dimethyl dithiocarbonate (DMDTC, 1), 7 which could be easily prepared in high yield through AlCl 3 induced rearrangement of dimethyl xanthate.…”

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S,S-Dimethyl Dithiocarbonate: A Useful Reagent for Efficient Conversion of Aldoximes to Nitriles

Khan¹,

Peruncheralathan²,

Ila³

et al. 2004

Synlett

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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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Pyrolysis of Oxime Carbonates: Novel Conversion of Aldehydes into Nitriles under Mild Conditions

Abstract: A new synthesis of nitriles is reported based on the pyrolysis of oxime carbonates. !On rapporte une nouvelle synthese des nitriles qui fait appel A la pyrolyse de carbonates d'oximes.

Cited by 17 publications

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The Mechanism for the Thermal Decomposition of E-Aldoxime Carbonates

The Mechanism for the Thermal Decomposition of E-Aldoxime Carbonates

S,S-Dimethyl Dithiocarbonate: A Useful Reagent for Efficient Conversion of Aldoximes to Nitriles

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

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