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Unraveling the Mechanisms and Outcomes of Hydrohalogenation Reactions: From Alkenes to Alkynes

Alkyne and alkene hydrohalogenation are chemical reactions that involve the addition of a hydrogen halide such as hydrogen chloride or hydrogen bromide to an unsaturated hydrocarbon. These reactions are important in organic chemistry and have numerous applications in industry.

In this article, we will discuss the mechanism, regiochemistry, and stereochemistry of alkyne and alkene hydrohalogenation.

Alkyne Hydrohalogenation

The mechanism of alkyne hydrohalogenation involves the addition of a hydrogen halide to an alkyne resulting in the formation of a vinyl cation or carbocation. The process is initiated with the strong acid protonating the alkyne triple bond creating a stable carbocation.

The polar hydrogen halide then react with carbocation to form a geminal dihalide.

The regiochemistry of alkyne hydrohalogenation obeys Markovnikov’s rule; the hydrogen atom of the hydrogen halide bonds to the carbon atom that has more hydrogen atoms attached to it.

This is because the carbon cation that is generated from the reaction of the alkyne with the hydrogen halide is more stable if it is attached to the maximum number of hydrogen atoms. The carbocation formed via this addition has a secondary character and highly resistant to rearrangements.

The stereochemistry of alkyne hydrohalogenation depends on the type of reaction conditions applied. When using a strong acid, such as sulfuric acid, the reaction proceeds via an anti-Markovnikov addition mechanism, producing an intermediate vinyl cation that can have E and Z isomers.

When using a protic acid (one that contains hydrogen), the reaction follows a free-radical mechanism which results in a racemic mixture of E and Z isomers.

Alkene Hydrohalogenation

The mechanism of alkene hydrohalogenation is an electrophilic addition reaction. The polar hydrogen halide adds to the alkene to generate a carbocation, which, in turn, is attacked by the halide ion.

This reaction is a Markovnikov addition, which states the hydrogen halide proton will add to the carbon atom having more alkyl or hydrogen groups.

The regiochemistry of alkene hydrohalogenation follows Markovnikov’s rule.

The more substituted carbocation is more stable and has more electron density on it, so the hydrogen atom of the hydrogen halide will add to the more substituted carbon atom to produce a geminal dihalide. This mechanism occurs fastest with secondary and tertiary alkenes.

When one molecule of a hydrogen halide is used to react with an unsymmetrical alkene, stereoisomers of the product are produced. The product is a mixture of two enantiomers that are mirror images of each other, called racemates.

In the presence of a chiral reagent, such as optically active tartaric acid, chiral geminal dihalides may be obtained selectively.

The stereochemistry of alkene hydrohalogenation depends on getting a product from a chiral alkene.

Enantiomers of geminal dihalides may be obtained selectively when the reaction is accomplished in the presence of chiral reagents. With the presence of a chiral reagent, optically active geminal dihalides may be achieved cleanly and selectively.


The addition of a hydrogen halide to an alkene or alkyne is a fundamental addition reaction found in many organic chemical processes. Alkene hydrohalogenation follows a Markovnikovs rule, but can generate stereoisomers of geminal dihalides, which can be used for more complex syntheses.

Alkyne hydrohalogenation follows the Markovnikov rule as well but has additional mechanisms where a secondary carbocation can form along a different regiochemistry than the Markovnikov rule.

Overall, these reactions have significant implications on the design and synthesis of new compounds in industry and academia.

The mechanism, regiochemistry, and stereochemistry of the process thus provide the necessary information to predict the outcome of the reaction accurately and produce the desired compound.

3) Geminal and Vicinal Dihalides in Alkenes

Alkenes are organic compounds that have a carbon-carbon double bond, and their reactions are highly useful in the synthesis of various chemicals and materials. Geminal dihalides refer to a type of compound where the two halogen atoms are bonded to the same carbon atom in an alkene.

The word ‘geminal’ is derived from the Latin word geminus, which means ‘twin’.

The formation of geminal dihalides occurs by the addition of two halogen atoms to one carbon atom of an alkene molecule during a chemical reaction.

The stability of geminal dihalides arises from the stabilization of the negative charge on the carbon-based anion ion, which is due to the second halogen atom favoring nucleophilic attack. This ion is negatively charged as a result of one of the halogens being replaced with hydroxide.

Geminal dihalides possess high resonance stabilization as the negative charge of the halides delocalizes along the alkene molecule via resonance, creating a stable compound. Some examples of geminal dihalides are dichloromethane, dibromomethane, and difluoromethane.

Vicinal dihalides, on the other hand, are organic compounds containing two halogen atoms attached to adjacent carbon atoms in an alkene. The formation of vicinal dihalides occurs through an electrophilic addition reaction where the halogen elements attach to the alkene.

In this reaction, the -electrons of the alkene molecule act as nucleophiles, opening the halogen, making it more electrophilic. The reaction proceeds in such a way that the halogen is attached to the first carbon atom of the alkene, followed by attachment to the carbon atom adjacent to it.

This attachment occurs simultaneously as the electron pair in the alkene is transferred to the carbocation intermediates produced in the reaction, leading to stereocontrolled reactions. Some examples of vicinal dihalides are 1,2-dibromoethane, 1,2-dichloroethane and 1,2-difluoroethane.

4) Difference between Alkyne and

Alkene Hydrohalogenation

Alkynes and alkenes, both unsaturated hydrocarbons, have a double and triple bond respectively, and they undergo hydrohalogenation reactions. Although these two reactions are similar, there are differences between the two, such as their mechanism and the products formed.

In alkyne hydrohalogenation, the triple carbon bond is protonated by the hydrogen halide compound, generating a secondary carbocation, followed by a nucleophilic attack by halide ions. As the alkynes have a greater degree of polarization than alkenes, the addition of HX to alkynes results in the formation of geminal dihalides as products.

These dihalides are produced in a Markovnikov’s addition pattern, with the halide group attaching to the carbon atom that will form more stable carbocations. In contrast, alkene hydrohalogenation involves the electrophilic addition of halogens to the carbon-carbon double bond, generating a carbocation that undergoes nucleophilic attack by a halogen anion and forming a halogenated alkane product.

The product formed follows Markovnikov’s rule, with the halogen attaching to the more substituted carbon atom of the alkene, which forms a more stable intermediate.

In general, the reaction between alkenes and hydrogen halides is significantly faster than that of alkynes, making alkene hydrohalogenation a more commonly encountered process.

Both processes have important industrial applications, such as the production of chlorofluorocarbons and plastics.

In conclusion, the differences between alkyne and alkene hydrohalogenation come in their mechanisms and the products formed.

Alkyne hydrohalogenation produces a geminal dihalide, following Markovnikovs rule, and alkene hydrohalogenation produces a halogenated alkane, also following Markovnikovs rule. Both reactions have fundamental principles that are important to understand in organic chemistry and the production of various substances, from pharmaceuticals and textiles to plastics and metals.


Anti-Markovnikov Addition in Alkynes

Alkynes, or triple-bonded hydrocarbons, can undergo anti-Markovnikov addition reactions when reacted with certain reagents. Anti-Markovnikov addition is a type of addition reaction where an electrophile bonds to the less substituted carbon atom of the double bond or triple bond, an opposite pattern to the classical Markovnikov addition.

In this article, we will discuss the anti-Markovnikov addition in alkynes and how it occurs.

Anti-Markovnikov Addition

The addition of hydrogen bromide (HBr) to a double bond or a triple bond in an alkene has a classical Markovnikov pattern. This pattern states that the hydrogen atom attaches to the carbon that has the most hydrogen atoms bonded to it, while the bromine atom attaches to the carbon that has the least hydrogen atoms bonded to it.

However, alkynes have been found to undergo anti-Markovnikov addition when reacted with hydrogen halides in the presence of peroxides. Peroxides act as initiators for a free radical mechanism that leads to anti-Markovnikov addition.

This mechanism involves the hydrogen bromide breaking up into hydrogen and bromine radicals in the presence of a peroxide. The Br radical will then react with any hydrogen bromide remaining, generating a second radical.

These radicals can initiate a radical chain reaction that leads to the formation of a vinylic or allylic radical intermediate. The electron density in the alkyne is lower, making the carbon atom carrying the triple bond less nucleophilic than the other carbon atoms.

As a result, the site where the radical attacks is predictable-always at the least-substituted end of the triple bond, in contrast with classical Markovnikov addition. This results in the bromine atom attaching at the least substituted carbon atom of the alkene or alkyne molecule.

E and Z Alkenes

E and Z alkenes are isomers that are formed when there are substituents on the carbon atoms of a double bond leading to different geometries. Concerted stereochemistry can be achieved in anti-Markovnikov alkene additions when a reaction such as hydrogen bromide is used in the presence of peroxy acids.

Z-isomers react similarly to classical Markovnikov addition, generating an intermediate allyl cation that is stabilized by resonance. The reaction leads to the addition of the hydrogen atom to the carbon atom which carries the most hydrogen atoms.

The reaction proceeds with the commonly seen Markovnikovs pattern. E-isomers follow the pattern of anti-Markovnikov addition, with the hydrogen atom attaching to the least substituted carbon atom.

In anti-Markovnikov addition, the bromine atoms bond to the less-substituted carbon atom due to the radical ion intermediate stability and the more efficient hydrogen abstraction on the more substituted carbon atom.

Terminal Alkynes

Terminal alkynes are compounds where the triple bond is found at the end of the molecule. The anti-Markovnikov addition of hydrogen bromide can be used to convert terminal alkynes to alkenes, forming a more substituted product.

The addition of HBr to a terminal alkyne initially produces vinylbromide as the intermediate product. The reaction proceeds through the same free-radical mechanism mentioned earlier.

Being an intermediate product, vinylbromide can be further reacted with HBr, creating 1,1-dibromoalkene. This product has the addition of two bromine atoms across the triple bond.

The 1,1-dibromoalkene reacts with a base such as potassium hydroxide (KOH) to produce the final product, a substituted alkene. This reaction gives the original alkyne a more substituted double bond, following an anti-Markovnikov addition pattern.


The anti-Markovnikov addition in alkyne chemistry provides a reliable means of generating anti-Markovnikov adducts and rearranging triple bonds. Peroxides are essential initiators in anti-Markovnikov addition reactions, beginning a sequence of free-radical reactions that ultimately give way to less substituted carbon atom products.

This mechanism has various industrial uses, including the production of highly substituted alkenes. The chemistry of terminal alkynes is also highly relevant in organic synthesis, where their conversion to alkenes using hydrogen bromide and peroxides can be an important step in more complex syntheses.

In conclusion, the article has discussed the mechanisms, regiochemistry, and stereochemistry of alkyne and alkene hydrohalogenation reactions. Alkyne hydrohalogenation follows Markovnikov’s rule but can also undergo anti-Markovnikov addition in the presence of peroxides.

The geminal and vicinal dihalides formed in these reactions have unique properties and applications. Alkene hydrohalogenation strictly follows Markovnikov’s rule, and the addition of hydrogen halides produces halogenated alkanes.

Understanding the differences between these reactions is crucial for predicting reaction outcomes and designing synthetic routes in organic chemistry. The concept of anti-Markovnikov addition in alkynes and the conversion of terminal alkynes to alkenes provide valuable tools for creating highly substituted compounds.

Overall, the mechanisms and outcomes of hydrohalogenation reactions have broad implications in various industries and play a key role in the synthesis of essential chemical compounds.



What is the difference between Markovnikov and anti-Markovnikov addition? – Markovnikov addition follows the rule that the electrophile adds to the carbon atom with more hydrogen atoms, whereas anti-Markovnikov addition occurs when the electrophile adds to the carbon atom with fewer hydrogen atoms.

2. How does alkene hydrohalogenation follow Markovnikov’s rule?

– In alkene hydrohalogenation, the electrophile (hydrogen halide) attaches to the carbon atom with more alkyl or hydrogen groups, producing a more stable carbocation intermediate. 3.

When does alkyne hydrohalogenation undergo anti-Markovnikov addition? – Alkyne hydrohalogenation undergoes anti-Markovnikov addition in the presence of peroxides, which initiate a free-radical mechanism leading to the attachment of the halogen to the less substituted carbon atom of the alkyne.

4. What are geminal and vicinal dihalides?

– Geminal dihalides refer to compounds where the two halogen atoms are attached to the same carbon atom, while vicinal dihalides have halogen atoms attached to adjacent carbon atoms in an alkene. 5.

What are the applications of hydrohalogenation reactions? – Hydrohalogenation reactions are essential in organic synthesis and industrial processes, playing a role in the production of pharmaceuticals, plastics, chlorofluorocarbons, and other valuable compounds.

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