Miscellaneous Ketones

Benzophenone (benzoyl benzene, diphenyl ketone, diphenyl methanone, a-oxodiphenyl methanone) [119-61-9] 

Benzyl acetone (4-phenyl-2-butanone, methyl phenethyl ketone, /J-phenyl-ethyl methyl ketone) 

Cyclopentanone (adipic ketone, ketocyclopentane, ketopentamethy-lene) [120-92-3] 

Mild irritant low toxicity LD50 intraperitoneal (mice) 727 mg/kg LD50 oral (mice) 2,900 mg/kg (NIOSH 1986) Skin irritant, 

Eye irritant teratogen (paternal effect) low toxicity — LD50 oral (rats) 2,700 mg/kg Irritant mild on skin, could be severe to eyes (rabbits 100 mg) mild to moderate toxicity LD50 intraperitoneal (mice)  

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Miscellaneous Ketone Reductions. The reductive allylation of aromatic ketones occurs with the reagent combination of Me2ClSiH/allyltrimethylsilane/ InCl3 (Eq. 253).427... 

The two major methods of preparation are the cycloaddition of nitrile oxides to alkenes and the reaction of a,/3-unsaturated ketones with hydroxylamines. Additional methods include reaction of /3-haloketones and hydroxylamine, the reaction of ylides with nitrile oxides by activation of alkyl nitro compounds from isoxazoline AT-oxides (methoxides, etc.) and miscellaneous syntheses (62HC(i7)i). 

A number of miscellaneous reactions involving diazonium ions and possible vinyl cations have been reported. Treatment of amine 138 with sodium nitrite in 20% aqueous acetic acid is reported to give methyl cyclopropyl ketone as one of four products (116). The reaction has been postulated to involve a vinyl cation, presumably by the following sequence of reactions (116) ... 

Several other miscellaneous heterogeneously catalyzed reactions have been performed in the liquid phase. Hexane was successfully oxyfunctionalized with aqueous hydrogen peroxide by use of the zeolite TS-1 catalyst [50] and microwave-promoted acetalization of a number of aldehydes and ketones with ethylene glycol proceeded readily (2 min) in the presence both of heterogeneous (acidic alumina) and homogeneous (PTSA, Lewis acids) catalysts [51], Scheme 10.7. 

Hydrogenation of aldehydes and ketones Hydrogenation of miscellaneous organic substrates... 

Abstract This is one of the most important classes of oxidation effected by Ru complexes, particnlarly by RnO, [RuO ] , [RnO ] and RuCljCPPhj), though in fact most Ru oxidants effect these transformations. The chapter covers oxidation of primary alcohols to aldehydes (section 2.1), and to carboxylic acids (2.2), and of secondary alcohols to ketones (2.3). Oxidation of primary and secondary alcohol functionalities in carbohydrates (sugars) is dealt with in section 2.4, then oxidation of diols and polyols to lactones and acids (2.5). Finally there is a short section on miscellaneous alcohol oxidations in section 2.6. 

Abstract This chapter covers one of the most important areas of Ru-catalysed oxidative chemistry. First, alkene oxidations are covered in which the double bond is not cleaved (3.1) epoxidation, cis-dihydroxylation, ketohydroxylation and miscellaneous non-cleavage reactions follow. The second section (3.2) concerns reactions in which C=C bond cleavage does occur (oxidation of alkenes to aldehydes, ketones or carboxylic acids), followed by a short survey of other alkene cleavage oxidations. Section 3.3 covers arene oxidations, and finally, in section 3.4, the corresponding topics for aUcyne oxidations are considered, most being cleavage reactions. 

SCHEME 9. Miscellaneous chiral ketones as catalysts for asymmetric alkene epoxidation O O... 

The solubility of DDT in twenty materials—ketones, petroleum fractions, and several miscellaneous solvents—over the temperature range —30° to 76° F. was determined by the rapid density method developed by Mauke and Sheard. DDT was found to be most soluble in cyclohexanone and less soluble in aromatic petroleum fractions, but the solvent cost per unit of DDT dissolved with them was only one half that for cyclohexanone. Cyclic ketones were better solvents than acyclic ketones with the same number of carbon atoms and the solubility in ketones was found to decrease with increasing molecular weight. 

The twenty solvents investigated were of commercial or technical grade. They can be divided into three groups ketones, petroleum fractions, and miscellaneous. Typical inspection data for the petroleum solvents, consisting of ten aromatic fractions and a paraffinic fraction, are shown in Table I. The ketones and miscellaneous solvents investigated are listed in Table II. 

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