Rearrangement of oximes

One of the more important approaches to 1-azirines involves a similar base-induced cycloelimination reaction of a suitably functionalized ketone derivative (route c. Scheme 1). This reaction is analogous to route (b) (Scheme 1) used for the synthesis of aziridines wherein displacement of the leaving group at nitrogen is initiated by a -carbanionic center. An example of this cycloelimination involves the Neber rearrangement of oxime tosylate esters (357 X = OTs) to 1-azirines and subsequently to a-aminoketones (358) (71AHC-(13)45). The reaction has been demonstrated to be configurationally indiscriminate both syn and anti ketoxime tosylate esters afforded the same product mixture of a-aminoketones... 

BECKMANN Rearrangement or fragmentation Acid catalyzed rearrangement of oximes to amides or cleavage of oximes to nitnies... 

The Beckmann rearrangement of oximes of the thiophene series has been applied (besides the preparation of 2-acetamidothiophene ) to thiophenocycloalkenones (192) which gave the cyclic amide (193) hydrolyzable to the amine (194). The Beckmann rearrangement was... 

Rearrangement of oximes to give TV-substituted carboxylic amides... 

The rearrangement of oximes 1 under the influence of acidic reagents to yield A -substituted carboxylic amides 2, is called the Beckmann rearrangement. The reaction is usually applied to ketoximes aldoximes often are less reactive. 

If the rearrangement of oxime sulfonates is induced by organoaluminum reagents,the intermediate (71) is captured by the nucleophile originally attached to the Al. By this means an oxime can be converted to an imine, an imino thioether (R—N—C—SR), or an imino nitrile (R—N—C—In the last case, the nucleophile comes from added trimethyl si lyl cyanide. The imine-producing reaction can also be accomplished with a Grignard reagent in benzene or toluene. ... 

Beckmann rearrangement of oxime is an acid catalysed reaction. The environmental problems associated with the use of sulphuric acid instigated interest to use number of solid acid catalysts [1], There are only scanty references about Lewis acid ion-exchanged MeAlPOs. Beyer et al. [2], Mihalyi et al. [3] and Mavrodinova et al. [4] already suggested the presence of Lewis acid metal ions as MO+ species in zeolites. The present study focussed the synthesis and characterisation of Fe3+, La3+ and Ce3+ ion-exchanged MAPO-36. The catalytic results of Beckmann rearrangement of cyclohexanone oxime over ion-exchanged catalysts are delineated in this article. 

A simple montmorillonite K 10 clay surface is one among numerous acidic supports that have been explored for the Beckmann rearrangement of oximes (Scheme 6.27) [54]. However, the conditions are not adaptable for the aldoximes that are readily dehydrated to the corresponding nitriles under solventless conditions. Zinc chloride has been used in the above rearrangement for benzaldehyde and 2-hydroxyacetophe-none, the later being adapted for the synthesis of benzoxazoles. 

Where Rj= CH3 or Ph and R2 = Ph or substituted phenyl Scheme 6.27 Beckmann rearrangement of oximes on clay. 

Photochemical Beckman rearrangement of oximes results in the formation of carboxamides as the major product151 (equation 92). 

The Beckmann rearrangement of oximes to produce amides is promoted by perrhenate ions under phase-transfer catalytic conditions, in the presence of trifluoro-methanesulphonic acid in nitromethane [6]. Under these conditions, the rearrangement reaction is frequently accompanied by the solvolysis of the oxime to the ketone. This can be obviated by the addition of hydroxylamine hydrochloride. No reaction occurs in the absence of the ammonium catalyst or with the O-acetyl oximes. 

Perrhenate-catalysed Beckmann rearrangement of oximes (Table 9.8)... 

Beckmann, E. Chem. Ber. 1886, 89, 988. Ernst Otto Beckmann (1853—1923) was bom in Solingen, Germany. He studied chemistry and pharmacy at Leipzig. In addition to the Beckmann rearrangement of oximes to amides, his name is associated with the Beckmann thermometer, used to measure freezing and hoihng point depressions. Mazur, R. H. J. Org. Chem. 1961,26, 1289. 

Oximino cyanoacetate or malonate esters (Me02CC(CN)=N0Ts or (Me02C)2C= NOCOPh) reacted with diazoaUcanes (RCHN2) to give unstable 1,2,3-triazolines . Synthesis of Al-imidoylbenzotriazoles via benzotriazole-mediated Beckmann rearrangement of oximes is also described . ... 

A free radical cyclization of oxime ethers tethered to an aldehyde has been used in the synthesis of azepine derivatives . For example, oxime ether 389 is cyclized to azepine 390 by reaction with Sml2 in HMPA and f-BuOH at —78°C (equation 170) . Similar free radical cyclization of oxime ethers can be carried out also in the presence of Bu3SnH/AIBN in benzene . Oxime 0-methyl ether 391 underwent thermal cyclization in refluxing o-dichlorobenzene (ODCB) leading to the mixture of two products 392 and 393 in ratio 69 31 in overall yield of 91% (equation 171) °. Rearrangement of oxime 0-tosylates in the presence of piperidine also leads to azepine ring formation . ... 

The Beckmann rearrangement of oxime esters is catalysed by Brpnsted or Lewis acids and these conversions are usually non-stereospecific, as demonstrated by the studies of Beckmann rearrangement of 1-indanone oximes derivatives 240a with aluminium chloride as a catalyst " (equation 88). 

In fused ring systems, the Beckmann rearrangement of oximes at the carbon adjacent to a common carbon of the two rings usually proceeds by preferential migration of the ring system (the common carbon atom undergoes migration preferentially). This behaviour can be mainly attributed to the increased stability of the oxime in which the Af-hydroxyl (or derivative) is directed towards the outside of the molecule. 

The Neber rearrangement is usually performed with ketoxime tosylates but ketone trimethylhydrazonium halides (519), iV,iV-dichloro-5ec-alkyl amines (520), N-chloroimines (521) and A-chloroimidates (522) may also be precursors for the reaction. Only the Neber rearrangement of oxime derivatives will be analysed in this chapter. 

Trimethylsilyl polyphosphate (PPSE),1 The reagent is prepared from P205 and [(CHj),Si]20. It is a colorless, volatile liquid, soluble in the usual organic solvents. It is comparable to polyphosphate ester for the Beckmann rearrangement of oximes to amides (3, 230 231). but it is prepared more easily. 

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