Benzophenone oxime reactions

It is prepared by treating p-chloromethylaniline with benzoyl chloride and hydroxylamine to produce the benzophenone oxime. Reaction of the oxime with chloroacetyl chloride in the presence of sodium hydroxide, and subsequent reduction, yields diazepam. 

Benzophenone, conversion to ethyl /S-hydroxy-0,0-diphenylpro-pionate, 44, 57 Benzophenone oxime, 44, 52 Benzopyrazole, 42, 69 3-Benzoylpropionic add, condensation with benzaldehyde to give a-benzylidene-y-phenyl-A y -bu-tenolide, 43, 3 N-Benzylacetamide, 42,18 n-Benzyiacrylamide, 42,16 Benzyl alcohol, reaction with acrylonitrile, 42,16... 

A mixture of benzophenone oxime (0.16 g, 0.803 mmol), l-benzyl-4-aza-l-azo-niabicyclo[2.2.2]octane dichromate (0.50 g, 0.803 mmol), and aluminum chloride (11 mg, 0.08 mmol) was crushed with a mortar and pestle for 35 s until TLC showed complete disappearance of starting oximes. CC14 (10 mL) was added to the reaction mixture and, after vigorous stirring, the mixture was filtered off. The solvent was evaporated by rotary evaporator to give pure benzophenone (0.129 g, 88%). 

Three O-substituted benzophenone oximes (29 X = OMe, F, Cl) have been subjected to aminolysis by pyrrolidine and piperidine, in benzene solution.483 Kinetics were third order in amine, and involved two routes one accelerates with a rise in temperature, the other decelerates. Of the many mechanisms proposed for this reaction in non-polar media, the results support Hirst s mechanism of electrophilic catalysis48b in this instance. 

The kinetics of reaction of O-(A-ary I carbamoyl) be n zop h cn o n c oximes in NaOMe-MeOH to give benzophenone oxime sodium salt and the corresponding methyl N-arylcarbamates have been studied.6 The Hamnett constants pobs = 0.68 and pkl = —1.32 have been estimated for the E cBR process for which 2 governs conversion of the intermediate ArNrC02N=CPh2 to ArN=C=0 and Ph2C=NO. ... 

Finally, as examples of similar types of reactions, photolytic treatment of O-acyl ester (D) of benzophenone oxime, A-acyloxy-phthalimide (E), and O-acyl ester (F) of A-hydroxy-2-pyridone with a mercury lamp generates the corresponding alkyl radicals via decarboxylation. However, these reactions can be used only for the alkylation of aromatics (solvents such as benzene) and reduction [86-89], so their synthetic utility is extremely limited. 

When treated with benzoic acid in the presence of triphenylphosphine and diethyl azodicarboxylate, benzophenone oxime gave a high yield of f -benzoylbenzanilide (14), formed via rearrangement of the intermediate 0>benzoyloxime (15). Reaction of p>medioxyaGetophenone oxime with l,rsubstituted derivative (l ), whereas in the presence of allyl bromide... 

The reaction is reversible, but the state of equilibrium highly favors the desired products. Preparations of large quantities for synthetic work are illustrated for methyl ethyl ketoxime, cyclohexanone oxime, hept-aldoxime, and benzophenone oxime, the procedures varying somewhat with the nature of the carbonyl compound. In some instances, a readily available and cheap reagent like sodium hydroxylamine disulfonate, HON(SO,Na)j, is first prepared from sodium nitrite and sodium bisulfite and, without isolation, treated with the carbonyl compound, Hydioxylamine-O sulfonic add, Ii,NOSO,H, is still another reagent and, like sodium hydroxylamine disulfonate, is used in the absence of a base. The preparation of hydroxylamine hydrochloride is described. ... 

Example 4.32. Beckmann rearrangement of benzophenone oxime. The overall reaction is as follows ... 

If the reaction path shown is as general as the available evidence suggests, attempts to reduce protonated oximes electrolytically to hydroxylamines are not likely to succeed. Some unprotonated oximes, such as benzaldoxime and benzophenone oxime, are reducible in not too strongly alkaline solution the oxime anion is not reducible. An investigation of the reduction of benzaldoxime in alkaline solution [79] showed that some benzylhy-droxylamine is formed under these conditions. 

The CR NR group can be introduced into ammonia, amines, hydroxy compounds, carboxamides, and sulfonamides to form amidines, imido-esters, etc., via imidosulfonates, obtained by the Beckmann rearrangement of oxime sulfonates.—B Benzophenone oxime benzene sulfonate and aniline warmed in benzene, and, after the exothermic reaction has ceased, further refluxed for 15-30 min. —>- N,N -diphenylbenzamidine. Y 92.5%. (F. e. s. P. Oxley and W. F. Short, Soc. 1948,1514.)... 

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