Ketones oxygenation

When another group having higher priority for citation as principal group is also present, the ketonic oxygen may be expressed by the prefix 0x0-, or one can use the name of the carbonyl-containing radical, as, for example, acyl radicals and oxo-substituted radicals. Examples are... 

Addition compounds form with those organics that contain a donor atom, eg, ketonic oxygen, nitrogen, and sulfur. Thus, adducts form with amides, amines, and A/-heterocycles, as well as acid chlorides and ethers. Addition compounds also form with a number of inorganic compounds, eg, POCl (6,120). In many cases, the addition compounds are dimeric, eg, with ethyl acetate, in titanium tetrachloride-rich systems. By using ammonia, a series of amidodichlorides, Ti(NH2) Cl4, is formed (133). 

Photochemical substitution reactions of this type which involve selective hydrogen abstractions from intramolecular sites by the m.tt ketone oxygen, are reviewed in chapter 12. ... 

The reaction proceeds via a cyclic TS involving coordination of both the alcohol and ketone oxygens to the aluminum. Computational (DFT) and isotope effect studies are consistent with the cyclic mechanism.190 Hydride donation usually takes place from... 

In all these reactions, crystallographic studies demonstrated the crystal control responsible for formation of the observed products. Thus, the prereaction ketone oxygen-steroidal hydrogen distance is in all cases 3.4 0.5 A, the ketonic carbon-steroidal (to-be-attacked) carbon distance is of the order of 4 A, and the... 

Trichloroacetylbenzoic acid reacts with thionyl chloride to produce a mixture of both chloride isomers. However, the open-chain isomer readily transforms into the cyclic form, which was the only isomer isolated from the mixture in the solid state. The presence of the open-chain isomer in the reaction product mixture, which is generally uncharacteristic for 2-acylbenzoyl chlorides, may be caused by the strong -I effect of the trichlo-romethyl group which decreases the nucleophilicity of the ketone oxygen atom (88MI4). 

They hypothesized that incorporation of the binding features of this structural water molecule into an inhibitor would be beneficial because of the entropic gain due to its displacement and because the conversion of a flexible linear inhibitor into a rigid, cyclic structure with restricted conformation should provide an additional, positive entropic effect. In the initial design, a cyclohexanone with the ketone oxygen as the structural... 

The ketone oxygen is bolded to demonstrate labeling studies.)... 

Although the xanthones contain a ketone oxygen atom, they, like the pyrones (see p. 385), do not react with hydroxylamine, or phenyl hydrazine. 

Thus the reaction of acetone with BF3 is a Lewis acid-base reaction in which a lone pair of the ketone oxygen atom is donated to an unfilled valence orbital of BF3. Bond formation is accompanied by the development of formal charges on both oxygen and boron. 

The phosphate triester reacts with a range of sulfur nucleophiles that add to the carbon a to the ketone and open the six-membered phosphate ring. Thiourea adds not only to the a-carbon, but also to the ketone carbon, resulting in elimination of the ketone oxygen as water, a reaction sequence that mimics the conversion of the Moco precursor to a 1,2-enedithiolate (Eq. 7). 

Protonation of the ketone oxygen atom activates the ketone to nucleophilic attack by the amine. Loss of a proton from 1.13 produces neutral intermediate 1.14. A second protonation, once again on the oxygen atom affords 1.15, which on loss of a water molecule and a proton gives the... 

The formation of an a-siloxy Rh(III) intermediate resulting from initial transfer of the silyl moiety to the ketone oxygen (as opposed to a Rh(III) alkoxide) has been postulated based on spin-trapping experiments and EPR studies. Ojima,... 

Answer The carbon which contain the ketone oxygen must contain the alcohol oxygen in the starting alcohol. Thus A s the required alcohol-... 

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