Ch. 10 - Addition ReactionsWorksheetSee all chapters
All Chapters
Ch. 1 - A Review of General Chemistry
Ch. 2 - Molecular Representations
Ch. 3 - Acids and Bases
Ch. 4 - Alkanes and Cycloalkanes
Ch. 5 - Chirality
Ch. 6 - Thermodynamics and Kinetics
Ch. 7 - Substitution Reactions
Ch. 8 - Elimination Reactions
Ch. 9 - Alkenes and Alkynes
Ch. 10 - Addition Reactions
Ch. 11 - Radical Reactions
Ch. 12 - Alcohols, Ethers, Epoxides and Thiols
Ch. 13 - Alcohols and Carbonyl Compounds
Ch. 14 - Synthetic Techniques
Ch. 15 - Analytical Techniques: IR, NMR, Mass Spect
Ch. 16 - Conjugated Systems
Ch. 17 - Aromaticity
Ch. 18 - Reactions of Aromatics: EAS and Beyond
Ch. 19 - Aldehydes and Ketones: Nucleophilic Addition
Ch. 20 - Carboxylic Acid Derivatives: NAS
Ch. 21 - Enolate Chemistry: Reactions at the Alpha-Carbon
Ch. 22 - Condensation Chemistry
Ch. 23 - Amines
Ch. 24 - Carbohydrates
Ch. 25 - Phenols
Ch. 26 - Amino Acids, Peptides, and Proteins

Halogenation is one of the most popular addition reactions and is the primary method for making vicinal dihalides

Concept #1: General properties of halogenation. 


Now we're going to talk about one of the most common addition reactions in this entire section and that's called halogenation. So let's just get right into it. Halogenation is the process of taking a double bond and adding a diatomic halogen and at the end what we're going to get is anti-dihalides, anti vicinal dihalides. So let's go ahead and just talk about the general features of this reaction.
First of all, the mechanism is going to have an intermediate and that intermediate is going to be similar to other ones we've learned. It's going to be a bridged ion. So maybe you can already start to visualize what you think that might be. Sorry about that.
The stereochemistry is going to be anti. As I just showed you guys, you're going to get anti-dihalides, so it would be anti. And then my product is going to be, like I said, vicinal dihalides. Now just to remind you guys, the word vicinal is a word to mean that there's two things next to each other, so this relationship here would be vicinal because they are right next to each other. Vicinal is also the same as saying one, two. Basically, you have something on the one position and something at the two position and that would be vicinal.
So will there be rearrangements in this mechanism? No. There won't be because there's no carbocation. And then finally, since I'm adding two of the same thing, I'm not going to worry about Markovnikov because I'm adding two of the same thing, so it doesn't matter. So let's just scratch that out.
As you guys can see, the reaction looks pretty simple. We've got a double bond, so we know this is addition. We've got an electrophile that we're adding. Now notice that I have CCl4 down here. If you guys remember, this is actually going to be an apolar solvent. Apolar solvents are inert. That's not going to do anything, so don't even worry about it. That's just something that it happens to help the reaction, but it's not going to do anything.
Another common solvent that you might see is CH2Cl2. That just means – it's the same thing. It just means instead of having four chlorines, you have two chlorines and two H's. Regardless, these are just solvents that don't do anything.
At the end what we get is those vicinal dihalides. Let's go ahead and look at the reaction. 

Opening of 3-membered intermediates/molecules always results in anti-addition.

General Reaction:

Concept #2: A worked-example of the halogenation mechanism.     


So the mechanism works like this, basically you've got a double bond and this double bond is nucleophilic it's looking for something to give its electrons to and I know that halogens seem to have a lot of electrons but they're also very what's called polarizable so what means is that electrons wind up moving a lot and wind up causing imbalances in the electron cloud so at some point there's going to be a part of the X or a part of the halogen that's not to have too many electrons and the double bond is going to pounce on that, so what's going to happen is that the double bond is going to grab one of the X, now the X doesn't like to have that many bonds so it's going to go ahead and break a bond if you make a bond you have to break a bond but similar to other bridged ions that we've looked at before if we make that bond then we have to make another bond back to the double bond what's going to show is it's going to make a bridge instead of just a single bond to one side, OK? So those are our three arrows, we're going to wind up getting is A bridged ion in this case this is called the halonium ion because instead of you know and I basically have instead of my carbocation I have a 3-membered ring and one of those atoms is a halogen, OK? For example if this was a bromine I would call it a Bromonium Ion, alright? Now this positive charge is going to be distributed throughout all three of those atoms so I'm going to have a partial positive here and I'm going to have a partial positive here, partial positive there, OK? But one of these atoms is going to have the most positive density can you guys guess which one? It's going to be the atom that is the best at stabilizing positive charges and that one's going to be the most substituted side so if they both had the same substitution then this X negative could really attack anywhere but since in this case one of them is tertiary and one of them is secondary what that means is that I'm going to go for the more substituted one so my X negative is going to basically do what we call a backside attack an SN2 reaction if you haven't learned that yet that's OK but just you know the backside attack and then if we make that bond we're going to break a bond so then we break the bond to the X, just like any reaction that involves a three membered ring any time that we break it open from the base we're going to have to make anti-products because there's a lot of potential energy in that three membered ring and once you break it going to snap open and they're going to face opposite directions so what that means is that if my X negative attack from the top my X on the ring is going to go towards the bottom so it's going to cause ante products so over here what I would get for my final product is I would get Let's say the X had attacked from the top then that means that this methyl group would face towards the bottom and that means that this methyl I mean that means that this X would face towards the bottom so what I'm going to get is an anti-product, OK? Now I noticed that do have any chiral centers here, I actually do I have 2 chiral centers so what that means is that I'm also going to get the enantiomer and the enantiomer would just be if it had attacked from the bottom then I would get this X at the bottom of this methyl group at the top and then this X at the top...Oppps oh my God this program can be a little dumb sometimes sorry about that guys really, I'm struggling here there we go, cool? So those are two enantiomers these would be produced in even amounts so that would be racemic, makes sense? Cool so this mechanism really wasn't bad as the ones that we've learned for other addition reactions it's pretty simple, OK? I hope that makes sense let's go ahead move on to the next topic.

1. Electrophilic Addition

2. Nucleophilic Substitution (SN2)