Radicals are unstable intermediates. So we’re going to have to discuss some ways to stabilize them.
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concept
The radical stability trend.
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radicals air, very high energy and very short lived. So anything that we can do to stabilize them whatsoever, we'll have a really big effect in their likelihood to be formed. So what that means is that we have to figure out what is the trend of stability for radicals. Okay. And I just want to show you guys right now, basically, this is the trend, and what you're gonna notice is that I'm gonna compare this trend to the trend for carbo cat ions. Now, if you don't know the trend for carbo cat ions yet, that's okay. I'm just gonna point out the major differences here. Okay, so first of all, um, radicals are electrons efficient. Now, what I mean by that is that there's a orbital right, And usually each orbital has space for how many electrons to Okay, that's the Pauli exclusion principle. But in this case, we have a radical with just one electron. So that would be what we call an un or partially filled orbital. That's not very stable. Okay, so anyway, that we can push electrons into that orbital that will make it more stable. And there is an effect that does that and that effect is called hyper conjugation. Okay, What hyper conjugation says is that the more our groups you have around an empty orbital or or partially filled orbital, the more stable it will be. Okay, so in this case, what I want to do is I want to basically say OK, the more our groups around my radical, the more stable it's gonna be easy and notice that that trend does hold true. This actually holds true for both carbo cat ions, which are empty. Orbital's completely. There's nothing in there. Okay? And radicals, they're really the same thing. So noticed that for my increasing stability, I have here that I have a tertiary here, a tertiary Carvel, Kati, and is very stable. And I also have a tertiary radical kind of at the top here. Okay, but notice is a slight difference here. It turns out that tertiary is the best type of cargo carrying that I conform. Okay, but it's not the best type of radical, actually have a different type of radical here that's more stable. And that's because it turns out that, unlike carpal cat ions ah, Lilic and Ben's Ilic radicals are actually going to be the most stable now. Ah, Lilic and Ben's Ilic are just words to mean that your next to a dull bond or you're next to a benzene ring. So what that's saying is that if you can resonate, that's going to make the radical more stable than anything. And here I have drawn the A Lilic and the Benz Ilic. This would be a Lilic. This would be Ben Zelic. Okay, notice that both of these are directly next to a double bond. So a double bond and the radical could switch places through resonant structure. And what that would do is that would de localize that electron deficiency over several atoms stabilizing it. Okay, so what I want you guys to be mindful of is that this is actually really important for reactions. These sites here are very, very crucial for reactions later that we're gonna learn later because they're very stable. Okay, So what I want us to do here is determined which of the following radicals would be the most stable By looking at this trend just basically looking. Forget the carbon cat. Anyone, because we're not talking about those were just talking about radicals figure out which of these would be the most stable and why. Okay, don't forget to look at resident structures to make sure that you're looking at both of the ways that the radical could be represented. Because remember that in a resonant structure, they're constantly in hybrid of each other. Okay, so you can't Just like you can't determine stability just based on one of the resident structures, okay?
Unlike carbocations, allylic and benzylic radicals are ALWAYS most stable.
Determine which of the following radicals is the most stable.
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example
Determine which of the following radicals is the most stable.
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all right. So according to my trend, the first thing that you really want to identify is which of these can resonate? Or which of them is a Lilic? Because if it's not a Lilic, that's not gonna be very stable. So we notice is that the Olympic position is just any position next to a double bond. So this would be a Lilic. This would be a Lilic. This would be a Lilic. Okay, All those three would be a Lilic. How about D? Is that a Lilic? No, because there's no double bond directly next to it. A dull one would have to be there or here in order for that to be a Lilic. So I automatically know that d is not gonna be my most stable because it can't resonate. OK, now, what I'm looking at is thes radicals that can resonate. And I'm saying, well, which those would be the most stable. What I notice is that this one is primary. This one is secondary and this one is secondary, so they look pretty the same. In fact, maybe there's one that kind of seems like a loser, and that would be a because they can resonate, but it's only primary the other two. It's like, how would I tell the difference between those? They're both secondary. Well, remember that I said, in order to really determine stability for radicals, you have to resonate. Um, so you want to do is you want to draw the resonance structures for all three of these and see what they look like afterwards. So I'm just gonna show you what one of the resin structures would look like. I'll just do it for a You would use the fishhook arrows to move one electron at a time. So I would say this radical moves into this bond to try to make a double bond. But it can't make a double bond by itself. It needs one more electron. Well, where can it pull in extra electron from the pie bond? So it's gonna take an electron from that pie bond, and now we're gonna make a new, dull bond there. The problem is that that pie bond was made out of two electrons. Now I just removed one of them. So I just have this one random electron hanging out that electron is going to jump onto the carbon next to it and thats gonna become a radical. So that means that the resident structure for this guy would look like this. Okay, now, if I go ahead and count up what type of radical that is? Not only is it a Lilic, but it is secondary. Oh, so see how that changed before it was primary and not secondary? Now we have to do is draw the same thing for the others on what we would find out is that the resident structure for B is now gonna have a radical there. The resident structure for C is gonna wind up having a radical here. Okay, Now, if we analyze the basically how substituted each radical is this one is now tertiary, and this one is secondary. So do we have a winner? The winner has to be be okay because not only is it a Lilic, but it can also resonate toe a tertiary location. Remember that. I said the more are groups that you have around the radical, the more stable it is. So notice that my trend says that primary is less stable in tertiary, which is less stable than e mean. Primary is less stable in secondary, which is less stable in tertiary. So if I have the ability to make it a Lilic and tertiary, that's the best thing on. That's exactly what this one is down here. So this is gonna win and the corresponding structure will win. So it's B All right?