10.13: Halogenation—Addition of Halogen
- Page ID
- 30455
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\(\newcommand{\avec}{\mathbf a}\) \(\newcommand{\bvec}{\mathbf b}\) \(\newcommand{\cvec}{\mathbf c}\) \(\newcommand{\dvec}{\mathbf d}\) \(\newcommand{\dtil}{\widetilde{\mathbf d}}\) \(\newcommand{\evec}{\mathbf e}\) \(\newcommand{\fvec}{\mathbf f}\) \(\newcommand{\nvec}{\mathbf n}\) \(\newcommand{\pvec}{\mathbf p}\) \(\newcommand{\qvec}{\mathbf q}\) \(\newcommand{\svec}{\mathbf s}\) \(\newcommand{\tvec}{\mathbf t}\) \(\newcommand{\uvec}{\mathbf u}\) \(\newcommand{\vvec}{\mathbf v}\) \(\newcommand{\wvec}{\mathbf w}\) \(\newcommand{\xvec}{\mathbf x}\) \(\newcommand{\yvec}{\mathbf y}\) \(\newcommand{\zvec}{\mathbf z}\) \(\newcommand{\rvec}{\mathbf r}\) \(\newcommand{\mvec}{\mathbf m}\) \(\newcommand{\zerovec}{\mathbf 0}\) \(\newcommand{\onevec}{\mathbf 1}\) \(\newcommand{\real}{\mathbb R}\) \(\newcommand{\twovec}[2]{\left[\begin{array}{r}#1 \\ #2 \end{array}\right]}\) \(\newcommand{\ctwovec}[2]{\left[\begin{array}{c}#1 \\ #2 \end{array}\right]}\) \(\newcommand{\threevec}[3]{\left[\begin{array}{r}#1 \\ #2 \\ #3 \end{array}\right]}\) \(\newcommand{\cthreevec}[3]{\left[\begin{array}{c}#1 \\ #2 \\ #3 \end{array}\right]}\) \(\newcommand{\fourvec}[4]{\left[\begin{array}{r}#1 \\ #2 \\ #3 \\ #4 \end{array}\right]}\) \(\newcommand{\cfourvec}[4]{\left[\begin{array}{c}#1 \\ #2 \\ #3 \\ #4 \end{array}\right]}\) \(\newcommand{\fivevec}[5]{\left[\begin{array}{r}#1 \\ #2 \\ #3 \\ #4 \\ #5 \\ \end{array}\right]}\) \(\newcommand{\cfivevec}[5]{\left[\begin{array}{c}#1 \\ #2 \\ #3 \\ #4 \\ #5 \\ \end{array}\right]}\) \(\newcommand{\mattwo}[4]{\left[\begin{array}{rr}#1 \amp #2 \\ #3 \amp #4 \\ \end{array}\right]}\) \(\newcommand{\laspan}[1]{\text{Span}\{#1\}}\) \(\newcommand{\bcal}{\cal B}\) \(\newcommand{\ccal}{\cal C}\) \(\newcommand{\scal}{\cal S}\) \(\newcommand{\wcal}{\cal W}\) \(\newcommand{\ecal}{\cal E}\) \(\newcommand{\coords}[2]{\left\{#1\right\}_{#2}}\) \(\newcommand{\gray}[1]{\color{gray}{#1}}\) \(\newcommand{\lgray}[1]{\color{lightgray}{#1}}\) \(\newcommand{\rank}{\operatorname{rank}}\) \(\newcommand{\row}{\text{Row}}\) \(\newcommand{\col}{\text{Col}}\) \(\renewcommand{\row}{\text{Row}}\) \(\newcommand{\nul}{\text{Nul}}\) \(\newcommand{\var}{\text{Var}}\) \(\newcommand{\corr}{\text{corr}}\) \(\newcommand{\len}[1]{\left|#1\right|}\) \(\newcommand{\bbar}{\overline{\bvec}}\) \(\newcommand{\bhat}{\widehat{\bvec}}\) \(\newcommand{\bperp}{\bvec^\perp}\) \(\newcommand{\xhat}{\widehat{\xvec}}\) \(\newcommand{\vhat}{\widehat{\vvec}}\) \(\newcommand{\uhat}{\widehat{\uvec}}\) \(\newcommand{\what}{\widehat{\wvec}}\) \(\newcommand{\Sighat}{\widehat{\Sigma}}\) \(\newcommand{\lt}{<}\) \(\newcommand{\gt}{>}\) \(\newcommand{\amp}{&}\) \(\definecolor{fillinmathshade}{gray}{0.9}\)Halogens can act as electrophiles to attack a double bond in alkene. Double bond represents a region of electron density and therefore functions as a nucleophile. How is it possible for a halogen to obtain positive charge to be an electrophile?
Introduction
As halogen molecule, for example Br2, approaches a double bond of the alkene, electrons in the double bond repel electrons in bromine molecule causing polarization of the halogen bond. This creates a dipolar moment in the halogen molecule bond. Heterolytic bond cleavage occurs and one of the halogens obtains positive charge and reacts as an electrophile. The reaction of the addition is not regioselective but stereoselective.Stereochemistry of this addition can be explained by the mechanism of the reaction.In the first step electrophilic halogen with a positive charge approaches the double carbon bond and 2 p orbitals of the halogen, bond with two carbon atoms and create a cyclic ion with a halogen as the intermediate step. In the second step, halogen with the negative charge attacks any of the two carbons in the cyclic ion from the back side of the cycle as in the SN2 reaction. Therefore stereochemistry of the product is vicinial dihalides through anti addition.
\[\ce{R_2C=CR_2 + X_2 \rightarrow R_2CX-CR_2X}\]
Halogens that are commonly used in this type of the reaction are: \(Br\) and \(Cl\). In thermodynamical terms \(I\) is too slow for this reaction because of the size of its atom, and \(F\) is too vigorous and explosive.
Solvents that are used for this type of electrophilic halogenation are inert (e.g., CCl4) can be used in this reaction.
Because halogen with negative charge can attack any carbon from the opposite side of the cycle it creates a mixture of steric products.Optically inactive starting material produce optically inactive achiral products (meso) or a racemic mixture.
Electrophilic addition mechanism consists of two steps.
Before constructing the mechanism let us summarize conditions for this reaction. We will use Br2 in our example for halogenation of ethylene.
| Nucleophile | Double bond in alkene |
| Electrophile | Br2, Cl2 |
| Regiochemistry | not relevant |
| Stereochemistry | ANTI |
Step 1: In the first step of the addition the Br-Br bond polarizes, heterolytic cleavage occurs and Br with the positive charge forms a intermediate cycle with the double bond.
Step 2: In the second step, bromide anion attacks any carbon of the bridged bromonium ion from the back side of the cycle. Cycle opens up and two halogens are in the position anti.
Summary
Hallogens can act as electrophiles due to polarizability of their covalent bond.Addition of halogens is stereospecific and produces vicinial dihalides with anti addition.Cis starting material will give mixture of enantiomers and trans produces a meso compound.
References
- Vollhard,K.Peter C., and Neil E.Schore.Organic Chemistry:Structure and Function.New Yourk: W.H.Freeman and Company 2007
- Chemestry-A Europian Journal 9 (2003) :1036-1044
Problems
1.What is the mechanism of adding Cl2 to the cyclohexene?
2.A reaction of Br2 molecule in an inert solvent with alkene follows?
a) syn addition
b) anti addition
c) Morkovnikov rule
3)
4)
Key:
1.
2. b
3.
enantiomer
4.