Questions; Solutions; Contributors and Attributions; Objectives. The halogenation of alkenes is carried out in a neutral organic solvent such as carbon tetrachloride (CCl 4 or dichloromethane, DCM (CH 2 Cl 2) that cannot act as a nucleophile when the halonium ion is formed. In the presence of peroxides, H adds to the C atom with a less count of H atoms. The resultant product is 2-bromopropane pictured below. If the two carbon atoms at the double bond are linked to a different number of hydrogen atoms, the halogen is found preferentially at the carbon with fewer hydrogen substituents, an observation known as Markovnikov's rule. Although Markovnikov’s rule was initially described by observations from the addition of hydrogen halides to alkenes, it is also used to explain the regioselectivity of other reactions such as the acid-catalyzed hydration of alkenes. 8.3: Halogenation of Alkenes - Addition of X₂ Last updated; Save as PDF Page ID 31466; Introduction; Electrophilic addition mechanism consists of two steps. A hydrohalogenation reaction is the electrophilic addition of hydrohalic acids like hydrogen chloride or hydrogen bromide to alkenes to yield the corresponding haloalkanes.. In a Markovnikov addition of HBr (Hydrogen Bromide) to propene, the H (Hydrogen) adds to the C atom with more H atoms. Interestingly, it was observed over time that this selectivity only works when pure reagents are used. Summary; References; Problems ; Exercises. After completing this section, you should be able to. The product is a haloalkane also called an alkyl halide. The halide will add to the more substituted carbon following Markovnikov’s rule. Halogenation of alkenes is an example of an anti-addition (stereospecific). hv (electromagnetic energy; UV light) is not essential, but it is preferred. This means that both halogen atoms will be adding to the carbons of the double bond in a trans fashion. Halogenation of an alkane requires the presence of heat or light. An Anti-Markovnikov halogenation is a free radical reaction of the hydrogen bromide to an alkene. Generally, you’re not going to have much stereoselectivity in this reaction, you’ll form a 50/50 mixture of two enantiomers. Chlorination of Methane by Substitution. UV Light energy is used to excite and ultimately break the O-O bond in the peroxide initiator, in order to produce the alkyloxy free radical(s). Image will be uploaded soon. In halogenation of an alkane, the alkane is said to undergo fluorination, chlorination, bromination or iodination depending on the identity of the halogen reactant. Reaction Overview: The hydrohalogenation of alkenes involves breaking a carbon to carbon double bond, followed by the electrophilic addition of a hydrogen atom and halogen.