Halogens hydrogen deficiency

The index of hydrogen deficiency can be calculated for compounds containing carbon, hydrogen, nitrogen, halogen, oxygen, and sulfur from the formula... 

It is important to produce HCl rather than elemental chlorine, CI2, because HCl can be easily scmbbed out of the exhaust stream, whereas CI2 is very difficult to scmb from the reactor off-gas. If the halogenated hydrocarbon is deficient in hydrogen relative to that needed to produce HCl, low levels of water vapor may be needed in the entering stream (45) and an optional water injector may be utilized. For example, trichloroethylene [79-01 -6] C2HCI2, and carbon tetrachloride require some water vapor as a source of hydrogen (45). 

The reactions of halogens and hydrogen halides with alkenes are electrophilic addition reactions. This means that the initial attack on the organic molecule is by an electron-deficient species that accepts a lone pair of electrons to form a covalent bond. This species is called an electrophile. In the case of the reaction with hydrogen bromide, the mechanism for the reaction is as shown. 

The relative stabilities of radicals follow the same trend as for carhoca-tions. Like carbocations, radicals are electron deficient, and are stabilized by hyperconjugation. Therefore, the most substituted radical is most stable. For example, a 3° alkyl radical is more stable than a 2° alkyl radical, which in turn is more stable than a 1° alkyl radical. Allyl and benzyl radicals are more stable than alkyl radicals, because their unpaired electrons are delocalized. Electron delocalization increases the stability of a molecule. The more stable a radical, the faster it can be formed. Therefore, a hydrogen atom, bonded to either an allylic carbon or a benzylic carbon, is substituted more selectively in the halogenation reaction. The percentage substitution at allylic and benzyhc carbons is greater in the case of bromination than in the case of chlorination, because a bromine radical is more selective. 

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