Home > Community > Why would a polar protic solvent favor the addition of HBr to an alkene?
Upvote

27

Downvote
+ Solvents
+ Biochemistry
Posted by
Nikola Milovic

Why would a polar protic solvent favor the addition of HBr to an alkene?

David A. Smith  Follow

A polar protic solvent will help stabilize the carbocation that is formed in the process of electrophilic addition. When the nucleophilic $\pi$ bond grabs the hydrogen from the $\ce{HBr}$, one of the carbons that was part of the $\pi$ bond is left deficient of an octet.

More

Upvote

VOTE

Downvote
Dario Cansino  Follow

why a protic solvent?

Protic solvents tend to have higher dielectric constants than typical, unreactive, non-protic solvents. Look at the following table.

\begin{array}{|c|c|c|}\hline\text{Solvent} & \text{Dielectric constant} \\ \hline\text{methanol} & 32.6 \\ \hline\text{ethanol} & 24.6 \\ \hline\text{methylene chloride} & 9.08 \\ \hline\text{chlorobenzene} & 5.69\\ \hline\text{chloroform} & 4.81 \\ \hline\text{diethyl ether} & 4.27 \\ \hline\end{array}

The higher dielectric constant stabilizes ions which means that 1) $\ce{HBr}$ will tend to be more dissociated and 2) (as Dissenter noted) the resultant carbocation intermediate will be more stabilized thereby lowering the energy of the transition state leading to it.

More

Upvote

VOTE

Downvote
Gambo Nurudeen  Follow
Propylene carbonate: 64; Acetonitrile: 39; dimethylformamide: 38; HMPT: 30More
Upvote

VOTE

Downvote
Jaap Folmer  Follow
unreactiveMore
Upvote

VOTE

Downvote
Jakob Kr?mer  Follow
. I dont know the reaction conditions were discussing, but acid-catalyzed hydration of a nitrile would be a distinct possibility.More
Upvote

VOTE

Downvote
Jack Ellison  Follow
@AbelFriedman Yes, propylene carbonate, DMF and HMPT are also subject to acid hydrolysis and could generate by-products that would contaminate the reaction.More
Upvote

VOTE

Downvote
James  Follow
@AbelFriedman Thats why I highlighted More
Upvote

VOTE

Downvote
more replies
Asghar Hosseini  Follow

High-dielectric solvent assist dissociation because they shield charge. Since the proton's electric field is so high, it always finds a base to bind to, which will in your case be $\ce{Br-}$. So you also have to consider the solvent's basicity. Read this article.

The assertion that you need a protic solvent is wrong, you need a sufficiently basic solvent.

More

Upvote

VOTE

Downvote