Dipropyl ketone, reaction

The interactions of tellurium tetrachloride and aliphatic ketones in refluxing chloroform were investigatedReaction mixtures containing two mol of ketone per mol of tellurium tetrachloride yielded bis[2-oxo-l-alkyl] tellurium dichlorides (Vol. IX, p. 1060) from all alkyl methyl ketones investigated except ethyl methyl ketone. No tellurium dichlorides were isolated from analogous reactions with alkyl ethyl ketones or dipropyl ketones. ... 

When the vinyllithium intermediate (190) is treated with water, the procedure provides a useful synthetic method for the conversion of ketones to alkenes (Scheme 79). The method is illustrated by the conversions of the tosylhydrazones of phenyl isopropyl ketone (194) and dipropyl ketone (195) to the alkenes (196) and (197), respectively (Scheme 79). In this method, experiments have demonstrated that the hydrogen is derived from the water, as indicated in Scheme 79, and thatTMEDA is an excellent solvent. The vinyllithium intermediate (190) may be trapped by other electrophiles thus, with carbon dioxide and DMF, the reaction affords ,[i-unsaturated carboxylic acids and aldehydes like (198) and (199) (Scheme 80). 

DIPROPYL KETONE (123-19-3) CtH O Combustible liquid. Forms explosive mixture with air (flash point 118°F/48°C cc Fire Rating 2). Violent reaction with strong oxidizers, aldehydes, nitric acid, perchloric acid. Incompatible with strong bases, amines, amides, inorganic hydroxides hydrogen peroxide. A variety of unstable peroxides may be formed fi"om the reaction with hydrogen peroxide. On small fires, use dry chemical powder (such as Purple-K-Powder), foam, or CO2 extinguishers. 

Reduction of Ketones to Secondary Alcohols. A variety of ketones are reduced by TUD, in an aqueous ethanolic solution in the presence of NaOH, to the corresponding secondary alcohol in good yield. Generally, reduction of ketones requires 1-3 equiv of TUD and 2-6 equiv of NaOH for example, dipropyl ketone gives heptan-4-ol (74%), benzophenone gives benzhydrol (100%), and 3-pyridyl phenyl ketone gives 3-pyridylphenylmethanol (100%). From the reaction mixture, almost theoretical amounts of the byproducts, sodium bisulfite and urea, are obtained. 

In the course of this study, the authors determined /Lvalues for dibenzyl, methyl phenyl, methyl p-nitrophenyl, di-p-tolyl, di-isopropyl and tetramethylene sulphoxides and for diethyl, dipropyl and dibutyl sulphites. The /Lscales are applied to the various reactions or the spectral measurements. The /Lscales have been divided into either family-dependent (FD) types, which means two or more compounds can share the same /Lscale, family-independent (FI) types. Consequently, a variety of /Lscales are now available for various families of the bases, including 29 aldehydes and ketones, 17 carboxylic amides and ureas, 14 carboxylic acids esters, 4 acyl halides, 5 nitriles, 10 ethers, 16 phosphine oxides, 12 sulphinyl compounds, 15 pyridines and pyrimidines, 16 sp3 hybridized amines and 10 alcohols. The enthalpies of formation of the hydrogen bond of 4-fluorophenol with both sulphoxides and phosphine oxides and related derivatives fit the empirical equation 18, where the standard deviation is y = 0.983. Several averaged scales are shown in Table 1588. 

As mentioned so many times throughout this entire course, there are almost always multiple correct solutions to a synthesis problem. For example, in this case, the desired transformation can be achieved using several reactions from previous chapters. The starting ketone can be converted into an ester via a Baeyer-Villiger oxidation, followed by hydrolysis to give propanoic acid. This acid can then be converted to an acid chloride upon treatment with thionyl chloride, followed by conversion to the product upon treatment with lithium dipropyl cuprate ... 

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