Alkyl hydrogen carbonates, protonated

Di-isopropyl and diethyl carbonate cleave at a higher temperature, also via alkyl-oxygen cleavage, with initial formation of protonated alkyl hydrogen carbonates. The alkyl hydrogen carbonates can also be formed by protonation of their sodium... 

The mechanism of alkyl hydrogen exchange was not clarified, but a possible mechanism was postulated. Partial hydride abstraction by a Lewis acid site may have occured forming a carbocation-like species followed by exchange of a proton at a R-carbon. Such a mechanism predicts exchange to occur preferentially at methyl groups adjacent to the most stable carbocations (benzylic > 3° > 2° > 1°). This is consistent with the observed relative rates of epimerization of steranes during thermal maturation of sediments (83). 

Related to these reactions is the oxidation of alkyl halides or tosylates to carbonyl compounds with dimethyl sulfoxide (or trimethylammonium A/-oxide). The reaction is effected simply by warming the halide (normally the iodide) or sulfonate in DMSO (or MeaNO), generally in the presence of a proton acceptor such as sodium hydrogen carbonate or a tertiary amine. Oxidation never proceeds beyond the carbonyl stage and other functional groups are unaffected. The reaction has been applied to benzyl halides, phenacyl halides, primary sulfonates and iodides and a limited number of secondary sulfonates. With substrates containing a secondary rather than primary halide or sulfonate elimination becomes an important side reaction and the oxidation is less useful with such compounds. 

Liquid electrolyte lithium-ion technology uses mixtures of aprotic organic solvents (which are not likely to donate a proton) because the graphite-lithium electrode is very unstable in the presence of compounds with labile hydrogen.22 The solvents used are alkyl earbonates (carbonates of ethylene, propylene, dimethyl, etc.) ethers, in which a lithium salt that... 

We have seen that in an E2 reaction of an alkyl chloride, alkyl bromide, or alkyl iodide, the proton is removed from the /8-carbon bonded to the fewest hydrogens (Zaitsev s rule, Section 10.2). Now, however, we see that in an E2 reaction of a quaternary ammonium ion, the proton is removed from the /8-carbon bonded to the most hydrogens (anti-Zaitsev elimination). 

A proton and a halogen add to the double bond of an alkene to yield an alkyl halide Addition proceeds in ac cordance with Markovnikov s rule hy drogen adds to the carbon that has the greater number of hydrogens halide to the carbon that has the fewer hydro gens... 

Intermediate formation of formyl chloride is not necessary since the actual alkylating agent, HCO", can be produced by protonation of carbon monoxide or its complexes. However, it is difficult to obtain an equimolar mixture of anhydrous hydrogen chloride and carbon monoxide. Suitable laboratory preparations involve the reaction of chlorosulfonic acid with formic acid or the reaction of ben2oyl chloride with formic acid ... 

The efficiency of reduction of benzophenone derivatives is greatly diminished when an ortho alkyl substituent is present because a new photoreaction, intramolecular hydrogen-atom abstraction, then becomes the dominant process. The abstraction takes place from the benzylic position on the adjacent alkyl chain, giving an unstable enol that can revert to the original benzophenone without photoreduction. This process is known as photoenolization Photoenolization can be detected, even though no net transformation of the reactant occurs, by photolysis in deuterated hydroxylic solvents. The proton of the enolic hydroxyl is rapidly exchanged with solvent, so deuterium is introduced at the benzylic position. Deuterium is also introduced if the enol is protonated at the benzylic carbon by solvent ... 

In organic compounds having C—H bonds, the carbon atom being more electronegative will pull the bonding electron towards itself and so hydrogen can go out as a proton. Therefore, in presence of a base this H will be attracted by the base and a carbanion will be obtained. This acidic hydrogen will be abstracted by bases like NaOH, t-BuOe or alkyl lithium where the alkyl radical will behave like a base. 

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