Ch. 18 - Reactions of Aromatics: EAS and BeyondWorksheetSee 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
Sections
Electrophilic Aromatic Substitution
Benzene Reactions
EAS: Halogenation Mechanism
EAS: Nitration Mechanism
EAS: Friedel-Crafts Alkylation Mechanism
EAS: Friedel-Crafts Acylation Mechanism
EAS: Any Carbocation Mechanism
Electron Withdrawing Groups
EAS: Ortho vs. Para Positions
Acylation of Aniline
Limitations of Friedel-Crafts Alkyation
Advantages of Friedel-Crafts Acylation
Blocking Groups - Sulfonic Acid
EAS: Synergistic and Competitive Groups
Side-Chain Halogenation
Side-Chain Oxidation
Birch Reduction
EAS: Sequence Groups
EAS: Retrosynthesis
Diazo Replacement Reactions
Diazo Sequence Groups
Diazo Retrosynthesis
Nucleophilic Aromatic Substitution
Benzyne
Additional Practice
EAS: Sulfonation Mechanism
EAS: Gatterman–Koch Reaction
EAS: Total Benzene Isomers
EAS: Polycyclic Aromatic Hydrocarbons
EAS: Directing Effects
Resonance Theory of EAS Directing Effects
EAS: Badass Activity Chart
Activated Benzene and Polysubstitutions
Clemmensen Reduction
EAS: Dueling Benzenes
Hydrogenation of Benzene
EAS: Missing Reagent
EAS: Synthesis
Diazonization of Aniline
Diazo Coupling Reactions
SNAr vs. Benzyne
Aromatic Missing Reagent
Aromatic Synthesis
Aromatic Retrosynthesis
EAS on 5-membered Heterocycles

Friedel-Crafts Acylation requires an acyl halide to complex with a Lewis Acid Catalyst before the reaction can begin. Here, the active electrophile instead of being a carbocation is an acylium ion.

Concept #1: Friedel-Crafts Acylation

Transcript

Let's take a look at the exact mechanism of Friedel-Crafts Acylation. So Friedel-Crafts Acylation is going to involve an acyl halide typically acid chloride complexing with a Lewis acid catalyst to produce an electrophile but in this case my active electrophile is not going to be a carbocation like alkylation, it's going to be an acylium ion. Now what does an acylium ion look like? It looks like this, you've got a carbon with a double bond to O and an R group with a positive charge. So that is an acylium ion. Can you think of why that would be a good electrophile? Full positive charge. Now it is resonant stabilised so there's two different ways that it can be drawn. That's one way, another way would be to take these electrons and move them into that carbon to become a triple bond and the other way to represent it would be to now move the positive up to the O. So just so you guys know these are both acylium ions obviously the hybrid is going to be a blend of both of these it's going to look like you know some mixture of those contributing structures but the one that's easiest for us to use that helps us to visualise the mechanism the best is this first one because the first one shows the positive on the carbon that's we're going to be attacking. So when I draw the acylium ion I'm going to draw the first resonant structure. Awesome, so notice that what are we trying to get at the end? We're trying to make ketones.

So we're, our end product will be a ketone on the benzene ring. Let's go ahead and take a look at this mechanism. Okay guys, so really there's nothing tricky about this mechanism. What we're going to do is we are going to donate our chlorine to the Lewis acid catalyst and what that's going to give me is an acylium ion. I'm going to get carbon, double bond O, single bond R positive plus my ALCL4 negative. So as you can imagine this is a wonderful electrophile for a benzene to react with and it's going to grab the carbon. Now something to keep in mind guys is that this is not a carbocation intermediate reaction so that means we don't have to worry about shifts so there's no rearrangements. You might say well why, that's not how I spell it let's try it again, arrangement. Guys, the reason that it's not going to rearrange is because this is a resonant stabilised electrophile so it doesn't want to break resonance by moving to the R group it just wants to stay where it is because where it is it can resonate so you don't have to worry about that so you don't worry about any of the complications of rearrangement which is great and we're going to discuss more later why that's so important. So let's go ahead and draw this full mechanism, that's it I'm just going to make a bond. Do I have to break a bond? No I have a full cation there, empty orbital, so I don't have to break a bond I can accept those electrons.

Now I'm going to draw my sigma complex which would look like this, now with C, double bond O, R positive and you guys know what to do. Move it over, draw your double bond, draw my cation here, move it over again and I get my cation up here. Now actually I mean this is right but always remember you need to draw that hydrogen. The hydrogen is important because it's part of the elimination step so let's just draw the hydrogen facing up. What do you think we're going to use, by the way I didn't draw the hydrogens in the other ones it's not necessary you can just draw the hydrogen in the last one if you want because hydrogens can always be implied in a bond-like structure. So what's going to happen in this last step? Yeah guys, you just use your conjugate base, your ALCL4, A L C L oops that's not what I meant let's erase, CLALCL3 negative and as always I'm just going to grab the electrons from that bond and do my beta elimination. What that's going to give me is now a ketone plus I'm going to get my Lewis acid catalyst that's regenerated plus I'm going to get my acid as a byproduct. Once again guys no rearrangements are possible here so there's less to think about, you're always just going to get your ketone on the benzene ring and that's it. Alright, so that's it for this mechanism. Let's move on to the next one.

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