Hydrocarbons, hydrocarbon ketones methylene groups

Ketones oxidize about as readily as the parent hydrocarbons or even a bit faster (32). Although the reactivities of hydrogens on carbons adjacent to carbonyl groups are perhaps doubled, the effect is small because one methylene group is missing in comparison to the parent hydrocarbon. Ketones oxidize less readily than similar primary or secondary alcohols (35). 

The multiple cleavage modes in ketones sometimes make difficult the determination of the carbon chain configuration. Reduction of the carbonyl group to a methylene group yields the corresponding hydrocarbon whose fragmentation pattern leads to the carbon skeleton. 

Oxidations with chromic oxide encompass hydroxylation of methylene [544] and methine [544, 545, 546] groups conversion of methyl groups into formyl groups [539, 547, 548, 549] or carboxylic groups [550, 55i] and of methylene groups into carbonyls [275, 552, 553, 554, 555] oxidation of aromatic hydrocarbons [556, 557, 555] and phenols [559] to quinones, of primary halides to aldehydes [540], and of secondary halides to ketones [560, 561] epoxidation of alkenes [562, 563,564, and oxidation of alkenes to ketones [565, 566] and to carboxylic acids [567, 565, 569]. 

Phenols are oxidized by NaBiO3 to polyphenylene oxides, quinones, or cyclohexa-2,4-dienone derivatives, depending on the substituents and the reaction conditions [263]. For example, 2,6-xylenol is oxidized in AcOH to afford a mixture of cyclohexa-dienone and diphenoquinone derivatives (Scheme 14.123) [264] and is oxidatively polymerized in benzene under reflux to give poly(2,6-dimethyl-l,4-phenylene) ether (Scheme 14.124) [265]. Substituted anilines and a poly(phenylene oxide) are oxidatively depolymerized by NaBiO, to afford the corresponding anils [266]. Nal iO, oxidizes olefins to vicinal hydroxy acetates or diacetates in low to moderate yield [267]. Polycyclic aromatic hydrocarbons bearing a benzylic methylene group are converted to aromatic ketones in AcOH under reflux (Scheme 14.125) [268]. 

Potassium hydroxide or alkoxide is not always necessary the hydrazones of Michler s ketone, fluorenone, and benzophenone yield the corresponding hydrocarbons in the presence of hydrazine hydrate alone,508 and so do the hydrazones of some ketones that contain a sulfo group, e.g., 4-(methylsulfonyl)-acetophenone hydrazone.509 Apparently these decompositions occur when the methylene group of the hydrazone contains mobile hydrogen atom. 

Thioacetals are valuable intermediates for organic synthesis in their own right. For example, thioacetals are desulfurized by Raney nickel to give the corresponding hydrocarbon. This provides another path from an aldehyde or ketone to a methylene group that does not require either strong acid or strong base. Therefore, this method complements the Wolff—Kishner and Clemmensen reductions. 

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