Cycloalkanone oxime

Cycloalkanone oximes 157 reacted with nitrile imines forming spirotriazolines 158 in 48-61% yields (equation 69) . 

Recently [89IZV(ip)] the effect of the cycloalkanone oxime ring size on their pyrrolization rate under the action of acetylene in the KOH/DMSO system at 86°C and atmospheric pressure has been examined (Scheme 19). 

The rate constant for various stages of cycloalkanone oxime pyrrolization were calculated according to Scheme 20, taking into account a constant concentration of acetylene. 

Rate Constants" of Pyrrolization of Cycloalkanone Oximes (k,) and Vinylation6 of the Pyrroles Formed ( 2) ... 

The reaction between sulfonyl chlorides and cycloalkanone oximes in the presence of pyridine is followed by Beckmann rearrangement to the imidochlorides, which give the corresponding lactim ethers with alcohol.58... 

Addition-elimination sequence. Addition of a photochemically generated free radical to an electron-deficient double bond engenders different consequence depending on the structural features of the substrates. Routes to functionalized nitroalkanes" and cycloalkanone oxime ethers demonstrate the versatile method. 

ITQ-2 zeolite prepared by delamination of MCM-22 precursor, is formed by disordered individual sheets of crystalline zeolitic layers in where the Bronsted acid sites are of zeolitic nature and the vast majority of them aecessible to large molecules. The delaminated zeolite combines the acid characteristic of microporous zeolites with accessibility of the sites of mesoporous Al/MCM-41 and amorphous silica-alumina. The superior catalytic performance of delaminated zeolites compared to conventional zeolites and Al/MCM- 1 is examplified for reactions involving large reactant molecules, namely the preparation of dimethyl acetals, the Beckmann rearrangement of bulky cycloalkanone oximes and hydroxylation of aromatics. 

The reaction of isatoic anhydrides with the anions derived from active-methylene compounds has led to the isolation of a considerable number and variety of quinolones.There have been two reports of the preparation of cycloalkano-pyridines, e.g. (137), by thermolysis of cycloalkanone oxime O-allyl ethers, e.g. (135) an intermediate nitrone (136) is formed (Scheme 56). 

A new route to lactams (e.g. e-caprolactam, 96%) by the reaction of 1-nitroso-and 1-nitro-l-halogeno-cycloalkanes, e.g. (12), with triphenylphosphine, or via the one-step reaction of the cycloalkanone oxime with halogen and triphenylphosphine, goes via successive Perkov and Beckmann reactions, " as shown in Scheme 1. 

Snegirev, V.F. Antipin, M.Y. Khrustalev, V.N. Struchkov, YT. Reaction of perfluoro-2-methyl-2-pentene with cycloalkanone oximes. New examples of the Beckmann-Chap-man rearrangement. Izv. Akad. Nauk SSSR, Ser. Khim. 1994, (6), 1073-1077. Rauscher, W.H. Tucker, H. The synthesis of ethyl adipamate and 2-oxo-6,6-dihydroper-fluorohexamethylenimine. 7. Am. Chem. Soc. 1954, 76, 3599-3601. 

Synthesis from Aldehydes and Ketones. Treatment of aldehydes and ketones with potassium cyanide and ammonium carbonate gives hydantoias ia a oae-pot procedure (Bucherer-Bergs reactioa) that proceeds through a complex mechanism (69). Some derivatives, like oximes, semicarbazones, thiosemicarbazones, and others, are also suitable startiag materials. The Bucherer-Bergs and Read hydantoia syntheses give epimeric products when appHed to cycloalkanones, which is of importance ia the stereoselective syathesis of amino acids (69,70). 

An oxidative cleavage of cycloalkanones to unsaturated aldehyde-esters has been developed. Thus, for example, cyclononanone was converted into 2,2-dithio-trimethylenecyclononanone, which was cleaved using lead(iv) acetate (66 %), and the product so obtained treated with methanol and sodium periodate to give (208 in = 5). Cyclododecanone was similarly converted into (208 n = 8). 1,2-Bis(trimethyl-silyloxy)cycloalkenes, prepared by acyloin condensations, have been converted into 2-alkyl-2-hydroxycycloalkanones by treatment with methyl-lithium and an alkyl halide, and the oximes of these a-hydroxyketones cleaved to give open-chain co-cyanoketones using mesyl chloride-pyridine. ... 

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