Now, if we agree that Brian anti-apartheid spread or not, you think that might work? >> Good morning. I'm hoping a day to finish up Chapter nine, which is the last chapter you are responsible for, for your exam, which is now one week from today. We don't finish jeopardized today, and it will certainly finish it on Monday. And the plan is to reserve all at Wednesdays plants period for whatever questions you might have pertaining to your exam coming up, right. And some of those questions have already been sent in by email, so we'll get to some of those to refresh your memory a little bit about what we've talked about so far. Which main theme of chapter five, chapter nine, electrophoretic aromatic substitution reactions. Section 9.5 spells out what the possibilities are. And you need to know what's possible on how to do those things. Then at the end, the last class we were looking at Section 9.7. What happens if you already have one substituent on an aromatic ring and you decide you wanted to put a second substituent on the aromatic ring. That's where the concepts. So things like ortho pair of directing groups, better directing groups, activating groups deactivate and groups them into play. Table 9.1 at the bottom of page 289 in your textbook summarizes most of that information. Where this largely comes in handy with problems lie with them. >> The tools that you can do the practice exam. >> And suddenly you will see at the end of chapter nine of your textbook, I need to convert one compound into another. In general, that's referred to as a synthesis problem. Starting from molecule a, how would you make molecule B? But I want to walk you through a couple of examples of problems like that, that use these concepts so that hopefully those concepts will make a bit more sense. So with that in mind for those of you following along in the lecture. Now let's look at page 92. This problem appears that, that page 92 starting from a crazy how would you make this stop them? Now, one thing that I hope is obvious is that you will have to put the nitro group on the aromatic ring and the bromine atom on the aromatic ring. And you have to know how to do those things. Specifically. You have to know if you were working in a laboratory, what bottles you would have to pull off the shelf and mix in with your benzene to make this happen. But another interesting question that comes up here is which one do you want to put on the aromatic ring first and why? So I'll throw that question out from a strategy point of view before we address the specifics of how to do these things. In this example. Which one do you want to put on the ring first? The micro group or the bromine atom? My yes, because okay, and the significance of the fact that bromine has lone pairs, if we go back to the previous page and easy way to tell whether some substituent is ortho para versus meta directing? Is it in general? Orca, apparently written groups have at least one lone pair on the atom directly attached to bromine falls into that category. And what makes that important is the comp out there trying to make is parallel. So the sensible thing to do in that case, put your work, they'll pair directing group on the ring. First, nitro happens to be emitted directly group. So to put that micro group by the Reagan first, well, even if you do successfully put the bromine on the ring second, you probably aren't going to get era if you put a meta directing, group idling first, Whatever's on the ring first sort of plays traffic cop and tells the second thing where to go. And in this case, what you want is a traffic cop. It says go pareto, pareto pair. So you're correct. The strategy is to put bromine on the ring first because that is the ortho Eric reckoning roof. How does one attach a bromine atom to an aromatic ring? >> What reagents Wikipedia's necessary. Turn back to your notes and look it up that an in-depth Yes. >> Yep. >> Elemental bromine, Derek bromide catalyst, should work pretty well. >> Okay. >> So starting from benzene, we can do this to make Romo bed and then only have to do is put the nitro group. But when we do put the nitro group on, we'll probably get a mixture of Ortho and Para products. But yelling this pathway will certainly give us a better yield of the product that we get. The nitrile group on the right, there's what reagent do we need to put the nitro group on the aromatic ring? >> A big part of it gets sulfuric acid, usually the catalyst for that. >> But yes, the micro part does come from the HNO3. Okay, so there's the answer to the sympathy rockets. Step one, bromine, in my step to a mixture of nitric acid and sulfuric is that's that makes sense. >> All right. >> Let's look at another example starting from benzene. >> How would you make this? Count them yet we're still ahead, pretty good. But how do you know accounting? Well, see, this is why I say you gotta know what's in section 9.5. We talked about the mechanisms for generating the electric miles before, right? Ok. The reason for using these particular reaction conditions is that's how we generate NO2 plus. And the reason for using these particular reaction B, this would generate BR plus whatever you're attaching to the aromatic ring must have a positive charge on it. And the reason that the reaction conditions listed in the textbook are what they are, because if this is what people have found over the years, worked pretty well. So I, you know, do a couple of homework problems. So let's take a look at this one. Starting from benzene. How would you make this? First of all strategy, given that you're trying to make, Has the mega orientation. Which of those two things do you want to put on the ring first? Yes. >> Cardio. >> Ok. This base rate we showed earlier that bromine is an ortho para, directing group, will be roaming around the ring first. Then we're probably going to get ortho and para products here. We don't want that, but what the better product. And it turns out that this guy is a meta directing group. Again, going back to the previous painful directing substituents have either a full positive charge or a partial positive charge. The atom is directly attached to the arithmetic, right? So in this case, the carbonyl group of the ketone is polarized. Oxygen's more electronegative than carbon is that imparts a partial positive charge. Left bar button item, which makes this guy a minute directing route. You can confirm all of that by looking up the information and at one table, table 9.1 in your textbook. But the easiest way, I think to do that is look for things like load. There's partial positive charge it up like that. Ok, so we want to do this first. How do we do that? What conditions, what reagents do we need? >> Put the ketone feast on the aromatic ring, but aluminum chloride and what else? >> And you need something that looks like this but with a chlorine attached where the carbonates, yep, and things like that are called acyl chlorides. We'll see more about them in subsequent chapters. But yeah, that's basically called a fetal grafts installation reaction. Aluminum chloride is the catalyst that removes the chloride ion from this and leaves behind that with a positive charge that's the electrify all that attaches itself to the aromatic ring maintenance. And then the last step should be obvious. You have that information on the screen. What reagent do we need to put the Bromine out, save it before probing very robot. Are there any questions about either of these two examples? We had a request over problem four on the practice exam from number four says propose a reasonable synthesis of each product on the right below, beginning with the indicated starting material on the left. In each case, we're going to use any other organic or inorganic reagents that you wish. You do not need to show intermediate structures, but doing so may help the greater to assign partial credit. More than one step will be required in each case. So be sure to list the steps in the correct order. That sort of thing is pretty much what we were just doing. Two-step process that we have to make sure you get the steps in the right order, otherwise it doesn't work. So with that in mind, let me for the moment cover up problem a. We'll get back to that in a moment and ask you to work that problem BY starting from Benghazi. How would we make this? >> Count them? >> Now again, strategy point. What do you want to put on the ring? First, the isopropyl group for the night. For group I've got my curly, they met interacting. Ruth, if you put the nitrile group on the ring first, you're going to get metal products. If you get anything or the point alkyl groups like this, methyl ethyl, isopropyl or you don't think like that all tend to be ortho paired. Or I can go to the correct strategy is to put that on the ring first. >> And how do you go about doing that yet again? >> Aluminum chloride. And what else? Yes. Well, fluorine attached to this piece, right? In other words, this piece has to come from somewhere. Okay? Yes, that's correct. That is a if we don't crash alkylation reaction. So to put an isopropyl bees on the aromatic ring, we'd use isopropyl chloride, aluminum chloride. Capitalists, those are typical fetal crafts reaction conditions. And that will give you the ISO probe on the benzene ring. And then Hadoop with an iPhone Groupon. >> You'd be back again. >> Hno3. And what else? Sulfuric acid. >> Yeah. >> Make sure you write that boat neat. Both real situation, that's the answer. Because the logic makes sense to the reaction conditions make sense. Okay? These will become more second nature with practice, which is why your mission this weekend is two. We also had a request to go over part a of the same problem. This has nothing to do with electric feel like aromatic substitution, but it does have to do with other reactions that we've seen that let me just say this about synthesis problems. There are two fundamental approaches that can be taken to a synthesis problem. Which one you can use is simply a question of what the problem is and what you're more comfortable with. The two basic approaches are to start with the starting material and try to work your way over to the product or start with a product and mentally work your way backwards towards the starting material. In this case, you really could use either technique. But what's crucial is identifying functional groups here. What functional group is this? The answers aren't springing it. >> You do need to know that aldehyde functional group is this. >> Yes, that's an ether. Okay, so you can approach this problem from one or two points of view. Either what kinds of reactions do we know that ethers do? Or what kinds of reactions do we know that make aldehydes? Your thoughts on either of those questions? Yes. Ethers do either. Cleavage. What can you do? What what reagent do you use to deal with either cleavage? >> I don't need this term strong acid. >> Considering the particular compound you're trying to make here, what would be a good choice for your strong acid, hydroiodic acid pH. I, you see that iodine atom right there? It has to come from somewhere. Okay, HI, either Cleveland's sounds reasonable. Protonate the oxygen iodine attacks one of those two carbons next to the oxygen and opens the ring up in the process. And when that happens, you get a primary alcohol that looks like this. Now, I just gave away the rest of the answer here, but the alternative approach you could have taken to solving this problem is to say, what reactions do I know that make aldehydes? At the moment, we've talked about exactly one oxidizing a primary alcohol using PCC as you're oxidizing it. So either way you approach the problem, you should come up with the same answer. Step one, break open the ether using HI step to oxidize the resulting primary alcohol. Music BCC, to make the album it sound reasonable. So the point is, there are plenty of problems like this in your textbook for additional practice. And in general, I recommend doing synthesis problems not only for their own merit, but it's a very good way to learn the reactions that you're supposed to know anyway, rather than just trying to memorize everything. So take a shot at similar synthesis problems in your textbook. And certainly by the end of today, you should hopefully be able to handle chapter nine synthesis problems as well. And of course, if you have any questions about any of those, feel free to email those questions in or bring them up during class time. Let me back up for just a moment because we skipped over one section earlier in Chapter nine that becomes relevant. Now, section 9.4, vital question is, what is a benzoic position? It has it contribute to benzene reactivity. Ok? >> Just to put this into perspective for a moment, here's a reaction that I hope looks familiar from your first exam. >> Let's product. Remember what cold aqueous Potassium permanganate guys without peat? Yep. Let's do all ages across the double bond. So the eventual product looks something like this. >> Okay. >> Let me do the exact same thing using Tiwi and is the same thing going to happen now? Why not? Yeah, it'll stay aromatic. Benzene and related compounds like to do reactions that allow them to retain the extra stability they get competing airmen. >> Our reaction does take place here. It's just a different kind of reaction. >> A phenomenon known as Ben Zelig oxidation, involves oxidation of the benzoic carbon atom. And the benzoic carbon atom is the carbon atom right next door to the benzene ring. It turns out toluene will in fact react with KML for not by doing anything with the double bonds in a benzene ring, they remain intact, which keeps the benzene part aromatic. But we can oxidize the side chain. And typically when we do, we get the corresponding carboxylic acid. That reaction is discussed in section 9.4 your textbook, and they provide other examples on page 277, for example, of the same sort of thing. It turns out that it doesn't matter how long the carbon chain is here. It could be one carbon long, it can be three carbons long, it can be ten carbons long. When you oxidize who came and O4, and he's still chop it down to the carboxylic acid functional group. This is an exception that statement we made before about you don't break carbon-carbon bonds during an observation like oxidation routine. One thing that is crucial now, the benzoic carbon atom must have at least one hydrogen attached to it for this to work. In this case, we took this compound. You can oxidize the methyl group, the carboxylic acid. But notice that the tert-butyl group remains intact because the benzoate carbon atom with the tert-butyl group has no hydrogens attached. I say all of this as a preface to the next synthesis problem. I want to show it. Starting from benzene. How would you make para nitro benzoic acid polymer? That problem for a minute or two. From a strategy point of view, what makes this one a little bit more challenging than the other two probably looked at earlier. >> So let's go ahead at this point of view, which of those two things do you want to put on the ring? >> Yes. That's what makes this a little bit more challenging, no matter which one of these to you. But in the ring first, you're in trouble because they're both meta directing groups. So now what do we do that I thought I saw a light bulb go on. >> Everything from nature, actually okay. >> Or on the right threat. The point is we don't wanna put the knife or group on the ring first, because that's where this is going to come from, is putting some alkyl group on the ring first and then oxidizing it. Okay? So pick an alkyl group. You can keep it simple ahead. Ch3. Okay, now what route we put a methyl group on the ring? First? Is that methyl group ortho parallel or meta directing or go Cara. But yet the point is we can impact but some alkyl group other rate first, that almost doesn't matter what. Then we can go ahead and put that I programmed by using a mixture of nitric and sulfuric acids. And by doing so, we're taking advantage of the fact that the methyl group is import the up-arrow directing group, we should get a significant yield of Medicare. And then we can convert this into the corresponding carboxylic acid oxidizing it came on board. This is a three step process that involves a little bit of imagination to be able to see that. But that's the sort of thing that typically comes up. Problems like this. So this benzoic oxidation thing, there's just one more weapon that you have in your arsenal to be able to try to convert compound, a compound thing. And there may be some problems that you see at the end of Chapter nine that turns out to be a useful thing. Any questions about any of this? >> All right. >> Now in your textbook on pages two, 92-93, B, B will try to explain why ortho pair directing groups are ortho matter. I think groups why collecting roofs are met a directive groups and they draw a whole boatload a picture pages do 9293. To explain what's going on. Let me just briefly walk you through the details of that. But using the handout I gave out before, which looks like this. So if you picked up this handout earlier, we get it out and look at the front side of it, which has the letters a, B, C, D, E, F, G. And I want to just walk you through the reasoning that's in your textbook and why they're drawing all those pictures would look the way they get what they're trying to do. In the course of this discussion. Let's take you through a what if kind of pathway. In other words, here's this compound, which we saw before, this compound called Anna sold. And we know what happens when we borrow money. Ana soul, we mostly get the mixture of products. The question is, okay, what these pictures are trying to do is to say, all right, we generate BR pluses are electrified. What would happen if that BR plus where to attach itself meta to where the CH3 is. What I've done here is to draw out the different resonance structures that would result from attaching bromine to that particular part. We saw before that whenever you attach any elect profile to an aromatic ring, resonance structures have the positive charges ortho para ortho again to wherever the electrify with. So here's what you would get if the Brahmi detaches itself, meant it to be a CH3. These structures are what you would get if the bromine attaches itself to the CH3. And it turns out, for starters, if you get one more resonant structure in this pathway than you do in this pathway. Because this pathway has the usual three resonance structures. This pathway has those, but also one more resonance structure that comes from moving in this lone pair to make a double bond right here, put the positive charge on the oxygen. So right away, the pathway that goes through d, e, f g is a slightly better pathway, the pathway that goes through ABC, because anytime you can spread out a positive or negative charge, you make the eye and more stable. Anytime you can spread out the positive charge or negative charge over more atoms, you make it that much more state here. We can wrap a positive charge over four different atoms. Here, only three. So right away, this is a somewhat better bandwidth on that. >> Let me just return your attention to a moment to see where I put it up. >> Probably buried underneath. Yep. There it is. And looking for the big handout from day one and specifically Page one of the big hand out day one, which tells you how to draw resonance structures. So I'll take ten seconds for you to stare at that screen and refresh your memory out what's important about drawing resonance structures guidelines 123. And then when I put this thing back up here again, I'm going to ask you to take a look at those seven different resonance structures and tell me which one is the best resonance structure out of a whole bunch of oDesk resonant structure there. I will give you a hint as to do with guideline number one of the best resonance structure there. According to guideline number one Guideline number one says structures with a maximum of octets are preferred. In other words, whenever possible, obey the octet rule. Which of those resonance structures is the only one that obeys the octet. Yes, F is the right answer. What structures a, B, C, G, E, and D have in common? They all have a positive charge on the carbon. Out. Anytime you have a positive charge on the carbon atom, that carbon atom can only have six electrons around it. Structure F has a positive charge on the oxygen atom. But it turns out that all of the big atoms in this molecule, not the hydrogens, of course, but all of the big atoms in this structure, including the positive oxygen, obey the octet rule. So the advantage to going this pathway is not only do you get for resonance structures instead of three, but among those four is the best resonance structure in a whole bunch because it obeys the octet rule. So based on that reasoning, it should not come as a surprise to find that the reaction tends to favor the para pathway over the meta pathway. And I would encourage you for practice to draw the corresponding resonance structures that would result if the for all mean attaches itself. Ortho studio CH3, if you do, you should fight for structures similar to these, one of which will have the positive charge on the question. In other words, is guideline one more important than guideline to? Yes. Any other questions about this? >> Okay. Now flip it over. >> Same thing with nitrobenzene. We know which way the reaction actually goes. If you borrow money, nitrobenzene, you mostly get the meetup ROD. The question is why? Ok, here's the what if game structures u, v, and w are what results if you attach the elect profile meta nitro group. But Cheers, X, Y, and Z. Well, what results if you attach the bromine para to make for a good thing to look at those six resonance structures. Tell me which one is the worst resonance structure up there ladder, why, why community? But as we said before that things like micro that have even a partial positive charge, much less a full positive charge like micro does on the atom attached to the benzene ring tend to be met, interacting. The reason why is if you attach the electric filed para to the nitrile group, you wind up with a resonance structure that looks like this with two adjacent positive charges. Not good. You don't want similar charges next to each other. You want similar charges as far apart from each other as they can be got. Similar charges. Repel Going the meta pathway avoids that process. So it's not that the meta pathways so great, but in this case, the parent pathway is worse because it gives rise to this. And again, for practice, try drawing the corresponding resonance structures for workload. And you should see a structure similar to this where the process make sense. By the way, I was noticing just now in the previous case, I penciled in the arrows to show how the electrons move. In this case, I did not. Okay. >> That could be your dad, by the way. >> I don't know. Maybe he's notice there in the big handout from day one, I include occasional dumb songs and poems. This one written by me about two years ago, because four years ago, what was the big movie in every seven-year-old on the planet couldn't get enough of frozen. >> Or the big song from that movie, let it go as I am, who I am. >> I thought, oh, let them flow. Then being electrons and the rest you can sing to yourself in the shower. The last section in chapter nine, section 9.8, is simply titled What are phenols? Well, at this point we know what phenyl are. Phenol itself is just hydroxy benzene in general are compounds that have an O-H benzene. My son, a better question for section 9.8, y or phenol, sufficiently important that we're calling specific attention to the match found several reasons. One is they do tend to be a bit more acidic than alcohols. For example, comparing the acidity of being all with ethanol here, penalize the PKA of about ten that's supposed to ethanol. It has a pK of about 16. There's a reason for that. If you look at page 94 in the lecture notes, that Lynn phenol loses its proton by being treated with some base like hydroxide, let's say. All right, we have a conjugate base. >> I end that looks like this. >> But it turns out that the reason it's easier for phenol to lose its proton than it is for say, ethanol to lose its proton. Is it? This conjugate base is stabilized by resonance. There are other resonance structures that you can draw here. And notice that the negative charge winds up ortho, para ortho again to where the oxygen is. So it's the same kind of theme that we saw before, only this time with a negative charge. More to the point, since you can spread out the negative charge over several atoms, that tends to stabilize the conjugate base, makes it more likely that the conjugate base will be formed in the first place. And that's just another way of saying it makes it easier for the acid to give up its proton. So that's one thing they talk about in your textbook and they show you those pictures. By the way, this is worth pointing out. We touched on this briefly before taking a look at these three compounds. Phenol, territorial phenol, Aaron micro feed off itself, Pk about ten power. Chloroethane, all pk about nine. Eric, high-protein, all PKA about seven. We said before there is something called the inductive effect that says that if you attach electronegative or electron withdrawing root fear acid, that tends to make the acid the stronger by stabilizing the conjugate base. Okay? Especially if we attach the electronegative or electron withdrawing groups, ortho or para, to where the acidic functional group is here, we can stabilize that negative charge and the conjugate base, because those electron withdrawing groups pull that negative charge towards themselves and sometimes creating other resonance structures which stabilize the negative charge that much more. So the more you can stabilize that negative charge, the conjugate base, the stronger the acid tends to be. We'll say more about concepts like that in the next few chapters. Then here's one that is like the last part of the last section in this chapter, but it doesn't go nutrition maters. This might be the whole reason you might care about something like this. Phenols as antioxidants. Why are antioxidants important? Yet they helped destroy free radicals. Let's talk about how that happens. Let go get these two, got back to back and zoom in on these pads and elevate initials BHP and DHEA, which is a dreadful way of naming these things. Be systematic name for this compound is 2-6 di tert-butyl for methyl phenyl. And this is two tert-butyl form epoxy phenol, but somebody decided to call it mutilated hydroxy tall, you eat a metal benzene as you would like to see where it comes. Bus mutilated, hydroxy, Anna soul, and it's always methoxy benzene. Ok, spot point. And that's where the initials PhD MBA Jacob Brown. But these guys are phenols. Alright, how do phenols help fight free radicals? Well, kind of like what we were just talking about. >> Let me draw you a picture. >> Alright. At this point we know what a free radical it, right? Nasty little thing with unpaired electron like that. Very reactive. But these things somehow get turned loose in your body. They can do all kinds of them, which is why you should arm yourself with phenols. And your mind not phenol itself, but variations on that. The because here's what happens. >> Okay, let's do this. Right? >> There we go. Okay, once the free radical pulls off the H from the phenyl, what's left is a phenolic radical that looks something like this. Now, free radicals in general tend to be pretty reactive, but it's, free radical is a bit less reactive than others. Part of the reason why it has other resonance structures along the lines of what we showed you a few moments ago, we can spread out that dot over the ortho, para, ortho carbon atoms on the aromatic ring. And then on top of that, when you consider a compound like bh TPP, which looks like this, what's another reason you can think of why the free radical that might be generated by removing that hydrogen might not be quite as reactive as many other free radicals. But yeah, we've got a couple of big, bulky tertiary people groups here, right near where that free-radical oxygen is. We've talked about steric hindrance before. If there's too much nearby, whatever it wants to react with, it's going to have a hard time getting in there. So things like this are used in foodstuffs as preservatives. Why? Because when oxygen, which by the lake itself is a free radical, right? The oxygen in the air we breathe looks like that. That's one of the few naturally occurring and abundant substances that is nonetheless a free radical. Well, what makes food spoil it? Leave it out out of the refrigerator and on the countertop. Pretty long oxidants start chewing on it, makes other compounds. But if you have preservatives in air like this stuff, then the oxygen and she was on the preservatives instead, and the rest of the food stays fresher. And the argument has been made that part of the reason we should have antioxidants in our diet is so that the oxygen in the air doesn't, she want us too badly. Because let's face it, votes we are what we eat last week's mashed potatoes. Okay? So the point is you've got preservatives in U. Ok? We all need oxygen to survive, but some of that oxygen goes chewing on your tissues solution Zhuan, the antioxidants instead. Vitamin E structure is shown on page 302 of your textbook. Vitamin E is a phenol. Some people saying, I want to live to be a 100 years old, they get some Vitamin E. It's a longitudinal study, but I'm three-fifths of the way there. I'll let you know that it works. And there was something I was noticing earlier this semester. There's this little illustration at the bottom of page 72 in your textbook goes all the good stuff that you can see at a food label like this. Let me just zoom in and I get that this abbreviation was another one of these things where people just see all this stuff in it. A, wow, I can't believe I'm eating all this. >> What he thought is TB pixelated, it's too much to drink. >> Their TV HP2 stands for, but it's an antioxidant. Dbh Q stands for tertiary B at all. Hydro quit. I'll zoom back now. >> That will save a structure with Islam, it's not bad, it's hydrocodone, but a tert-butyl group on it. >> And you have something that behaves sort of like these dot balanced it. So it's also an antioxidant, serve the same purpose. Now here's the part that really cracks me up and Jaap and why? Because right at the end of chapter nine is a sort of like this at the throwaway paragraph of the entire chapter. But for a lot of people, this might be the whole reason to read this chapter. Similar compounds are added, other materials, blah, blah, blah. The protective properties, the females may explain why the health benefits of food such as green tea, wine and blueberries, each of which contains large amounts of feed. All the compounds have been awarded by nutritionists and others in the medical community. Okay, so what are phenols? That's easy. Why are they important? >> Read the last paragraph of chapter nine, makes sense. >> Yeah, that is the last paragraph of chapter at the end of what you are responsible for your second exam, which is one week on monday. We all get started on Chapter ten, which is fair game for it came numbers on Wednesday. The floor will be open for whatever questions you might have. >> For exam number two, your BATNA? Yep. >> Okay. >> Here's here's the deal with the possibility that maybe aren't our garage Africa is one of those or something else like me. >> And those are the four possibilities that pop out mostly with me. >> Okay. >> And if it's Hofmann Hamilton ether camera that RAF's Thank you. >> Don't count the same thing twice because in that case, your three possibilities are SAS, the matzo could be either S or hats are depending on how you look at. So the general statement that can be made is if it's possible to have a meso compound or several matzo compounds. There will be less than what the two to the n rule predicts. But how much less?
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From Dana Chatellier March 03, 2020
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