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Aromatic heterocycles I

The aromaticity of heterocycles (rings containing one or more non-carbon atoms). Created by Jay.

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  • orange juice squid orange style avatar for user Amanda Dickey
    How do you tell if a lone pair will be localized or delocalized?
    (16 votes)
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    • female robot grace style avatar for user SwizzleStick
      From my Ochem textbook: if the heteroatom is connected to its neighbors by single bonds, it's possible for one lone pair on the heteroatom to delocalize (as seen in thiophenes, furans, and pyrroles). If the heteroatom is doubly bonded to either of its neighbors, the lone pair is in an sp2 orbital and cannot delocalize.
      (10 votes)
  • leaf orange style avatar for user ASHOK SOLANKI
    what is difference in aromatic , non aromatic and anti aromatic ?
    (4 votes)
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    • blobby green style avatar for user Angus Dobson
      Aromatic: Ring of overlapping P-orbitals, planar molecule, 4N+2 pi electrons (completely filling MO bonding orbitals with no unpaired electrons).
      Anti-Aromatic, Ring of overlapping P-orbitals, planar molecule, 4N pi electrons (leaving two unpaired and very reactive MO orbitals).
      Non-Aromatic: If neither of the above are true.
      (9 votes)
  • leaf green style avatar for user beste_sevil
    Is it because oxygens of thymine are negatively charged,it acts as a base?
    (3 votes)
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  • blobby green style avatar for user Matias Lozano
    When analyzing heterocycles in general, as long as a neutral atom with lone electron pairs, like N, has resonance where the electrons move to another atom without becoming a bond within the ring, they will always be delocalized?
    (3 votes)
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    • blobby green style avatar for user Patrick Warner
      Delocalized electrons are any electrons that can participate in resonance. If drawing resonance structures and a lone pair cannot be validly moved, then that lone pair is localized. Certain electron withdrawing substituents work to delocalize electrons that were localized, which is described in the example with thymine.
      (1 vote)
  • leafers ultimate style avatar for user Navid
    Why is it that pyridine has a localised lone pair on N while otherwise on pyrimidine?
    (1 vote)
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  • leaf green style avatar for user khinlay
    How did u get SN=2+1=3 on thymine?
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    • spunky sam blue style avatar for user Ernest Zinck
      The steric number of an atom is the number of atoms bonded to that atom plus the number of lone pairs on that atom. Both N-1 and N-3 are directly attached to three atoms (C, C, and H), and they have no lone pairs.
      ∴ For each N atom, SN = 3 + 0 = 3.
      (3 votes)
  • primosaur ultimate style avatar for user Ian Timothy
    So why is thymine aromatic if the major resonance structure is not? I understand that you can draw an aromatic resonance structure, but why would that make it aromatic?
    (2 votes)
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    • starky seedling style avatar for user deka
      1. in fact, the major resonance structure in thymine is the rightmost one with 3 double bonds at the end of the video. because it has the lowest energy and thus is most stable. since it has the largest number of double bonds, which have lower energy than single bonds

      2. in other words
      a. stability: double bonds > single bonds
      b. # of double bonds: right(3) > middle(2) > left(1)
      c. major to minor resonance structure: right > middle > left (more stable to less stable)

      3. in sum, we get the total resonance structure as weighted sum of each contributor. put the calculation simple, 3/6*right + 2/6*middle + 1/6*left = total resonance structure of thymine



      and now you see why we consider thymine as an aromatic molecule (mathematically, it is more than half-aromatic)
      (1 vote)
  • piceratops ultimate style avatar for user kekie
    Why are they delocalized?

    I think it's because the lone pair is in a p-orbital as it looks that way when you draw out the electron config.
    (1 vote)
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    • female robot amelia style avatar for user ss loves science
      It is because of the electron-withdrawing nature of the oxygen atom. The oxygen atom pulls the electrons of C=O bond towards itself resulting in a positive charge on carbon. The lone pair of Nitrogen try to get delocalized so that this positive charge on carbon gets reduced.
      You are right in saying that lone pair are present in a p-orbital but then they were present in p-orbital in the nitrogen of pyridine also. And in pyridine, they were localised. That's because they were not required to participate in resonance (the pyridine ring has enough pi-electrons for resonance to take place.)
      (3 votes)
  • aqualine seed style avatar for user Ûžâîr Ghâffâr Râmâÿ
    Is pyrimidine an aromatic compound or not?explain
    (1 vote)
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    • blobby green style avatar for user Patrick Warner
      it is aromatic, as it has a continuous system of overlapping p orbitals. The nitrogen atoms of pyrimidine both have lone pairs that cannot be delocalized into the ring. Since there are 3 electron domains the nitrogen is sp2 hybridized and thus there is an extra p orbital. Because of these p orbtials chilling on the nitrogen, the 6 electrons in the pi bond system have the ability to move around, while the lone pairs on t e nitrogen atoms are forced to stay put. Thus it is aromatic.
      (2 votes)
  • leaf green style avatar for user vidyaovya06
    what is homocyclic compound
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Video transcript

In previous videos, we've already seen that benzene is aromatic because it fits the following criteria. Benzene contains a ring of continuously overlapping p orbitals. So each of the six carbons in benzene-- each of those six carbons has a double bond to it. So each of those six carbons is sp2 hybridized, which means that each of those carbons has a free p orbital. And because benzene is a planar molecule, those p orbitals can overlap side by side and allow for delocalization of the pi electrons in benzene. So if we count the number pi electrons in benzene, we can see there are two, four, and six. So six pi electrons fits Huckel's Rule, which is the second criterion, which says that the ring has to have 4n plus 2 pi electrons. In this case, n is equal to 1. So 4 times 1 plus 2 gives us 6. So six pi electrons for benzene. Just to remind you, n can be equal to 0, 1, 2, 3, or any other whole number. And that's called Huckel's Rule. So you need Huckel's Rule pi electrons in the ring for a compound to be aromatic. If we look at the pyridine molecule, pyridine is an analog to benzene. The only difference is that pyridine has a nitrogen in the ring instead of one of these carbons right here. So we say that pyridine is a heterocycle. A heterocycle is a cyclic compound that contains a heteroatom in the ring. A heteroatom is any atom other than carbon-- so something like nitrogen, oxygen, or sulfur. And heterocycles cycles can be aromatic, too. So let's go ahead and analyze pyridine in a little bit more detail here. So here's the dot structure for pyridine. And we'll start by looking at the carbons on pyridine. So pyridine has five carbons. Each of those carbons has a double bond to it. So each of those carbons is sp2 hybridized, meaning there's a free p orbital on each of those five carbons. I'm just going to sketch in those p orbitals on those five carbons like that. Let's analyze the nitrogen, and let's figure out the hybridization of this nitrogen atom. The best way to do it is to figure out the Steric number of this nitrogen atom. And so the Steric number is equal to the number of sigma bonds plus number of lone pairs of electrons. So watch an earlier video if you'd like to see how to do Steric number in more detail. So we could say this is the sigma bond. We could say this is a sigma bond. And then we could say there's one pair of electrons on that nitrogen. So the Steric number is equal to the number of sigma bonds, which is 2, plus number of lone pairs of electrons, which is 1. And so the Steric number is equal to 3. So this nitrogen must have three hybrid orbitals, and therefore it's sp2 hybridized. So it has three sp2 hybridized orbitals, and therefore, one p orbital-- so an unhybridized p orbital. So this nitrogen is also sp2 hybridized, and so we can go ahead and sketch in the p orbital like that. And if we look at the number pi electrons in pyridine, there's two, four, and six pi electrons. So that fulfills Huckel's Rule. So there are six pi electrons. And we can see that the pyridine molecule is a ring of continuously overlapping p orbitals-- these p orbitals can overlap side by side-- and those six pi electrons can be delocalized throughout the ring. And so since this meets both of the criterion, pyridine is an aromatic molecule. So it has some extra stability associated with it. Now, this lone pair of electrons on this nitrogen, that lone pair of electrons occupies an sp2 hybridized orbital. So we said this nitrogen's sp2 hybridized, which means it has three sp2 hybrid orbitals. So one of those sp2 hybridized orbitals formed a bond with this carbon over here. One of them formed a bond with this carbon over here. And the last sp2 hybrid orbital actually contains that lone pair of electrons. So the lone pair of electrons on that nitrogen does not participate in resonance. That lone pair of electrons is localized to that nitrogen. And so any time you see a situation like pyridine where you have a nitrogen with a lone pair of electrons and some electrons already participating in resonance-- so those would be the electrons in magenta here-- the electrons in magenta participate in resonance. So the electrons in blue cannot participate in resonance. They are localized to this nitrogen atom. OK. So we've seen that pyridine is aromatic. Let's go ahead and do an example that's similar to pyridine. This is pyrimidine So let's see if we can analyze the pyrimidine molecule the same way that we analyzed the pyridine. So once again, if I start with my carbons here, each of these carbons is connected to a double bond. So I have four carbons, and therefore each carbon is sp2 hybridized. I can go ahead and sketch in a p orbital on each of my sp2 hybridized carbons like that. When I study the nitrogens in pyrimidine, I can see it's the exact same situation that we had in pyridine. So I can see that there's a sigma bond here, a sigma bond here, and a lone pair of electrons here, like that. And so I can see that this nitrogen is sp2 hybridized. And I can see that these pi electrons here are going to be participating in resonance. So for that nitrogen, it's sp2 hybridized. It has a free p orbital, so I can go ahead and draw in the p orbital there. And I know that the lone pair of electrons in blue-- since this nitrogen is sp2 hybridized-- that lone pair of electrons is going to occupy an sp2 hybridized orbital. It's the exact same situation for this nitrogen. There's a sigma bond. There's a sigma bond. We have a lone pair of electrons on that nitrogen. And then we also have some electrons already participating in resonance. And so this nitrogen is also sp2 hybridized. I can go ahead and draw a p orbital on that nitrogen, which means that lone pair of electrons is not gonna participate in resonance. That lone pair of electrons is going to occupy an sp2 hybridized orbital. It's going to be out to the side like that. And so for pyrimidine, once again, I have a total of six pi electrons. And those six pi electrons are going to be delocalized as the p orbitals overlap side by side in your ring. And so pyrimidine is also aromatic. It meets the criteria for it. And the lone pair of electrons on those nitrogens, those lone pairs are localized to those nitrogens. All right. The pyrimidine general structure is actually very important in biochemistry. So when you study biochemistry, you'll see how important it is. And here's an example. This is the thymine molecule, which is, of course, found in DNA. And you'll always see in textbooks that thymine has a pyrimidine ring. But at first, it's not so obvious that a pyrimidine ring is present in thymine. Because if I look at the nitrogens in thymine-- we'll start this nitrogen up top here-- I can see that this nitrogen has three sigma bonds to it and one lone pair of electrons. So three sigma bonds-- so the Steric number would be equal to 3 sigma bonds plus 1 lone pair of electrons. The Steric number should be equal to 4, which implies four hybrid orbitals, which would mean that that nitrogen is sp3 hybridized. And if it's sp3 hybridized, you wouldn't have any p orbitals to participate for aromaticity. And so this must not be the case. There must be a way to see a pyrimidine ring here. And the answer is because this nitrogen is actually not sp3 hybridized. It actually has a lone pair of electrons that are delocalized, and not localized to this nitrogen, meaning we can draw a resonant structure for the thymine molecule. So this lone pair of electrons right here in this nitrogen are not localized to that nitrogen as we saw in the previous dot structures. Those electrons can move in here to form a pi bond between the nitrogen and that carbon. That would, of course, push these electrons in here off onto this oxygen. So we can go ahead and draw a resonance structure. So let's go ahead and put the nitrogen in our ring. And let's go ahead and draw in the rest of our ring like that. And so that lone pair of electrons moved in to form a double bond between that nitrogen and that carbon. So that's our situation now. And for the top oxygen here, it had two lone pairs of electrons but it picked up one more lone pair of electrons, giving it negative 1 formal charge. This nitrogen is still bonded to another hydrogen, and we can go ahead and draw in the rest of the molecule as well. So there is our resonance structure for thymine. Now let's go ahead and analyze the nitrogen after we drew the resonance structure here. So if I want to figure out the Steric number for this nitrogen now, I can see that there's a sigma bond here, there's a sigma bond here, and there's a sigma bond here. And now no lone pairs of electrons around this nitrogen. So now the Steric number would be equal to 3 plus 0, which is, of course, equal to 3. So the Steric number of three-- we can say this nitrogen is sp2 hybridized. And so it has a p orbital now. And the lone pair of electrons that was in the nitrogen over here-- I'm going to go ahead and put those in magenta-- they're not localized to that nitrogen. They're actually delocalized. And that lone pair of electrons can now participate in resonance. But we still don't have the exact pyrimidine structure here. And so we can draw yet another resonance structure. So we can do the exact same thing with this lone pair of electrons down here on this nitrogen. So we can look at the other nitrogen now, and we can do the exact same thing. So at first thought, it might look like that lone pair of electrons is localized to that nitrogen, but it's not. It's actually delocalized because of the resonance structure that we can draw. So pretty much the exact same thing we did before. So let's go ahead and draw in our ring here. So we have our two nitrogens in our ring. This nitrogen is bonded to a hydrogen right here. The lone pair of electrons now moves in to here to form a double bond, a pi bond. And this oxygen had two lone pairs of electrons-- it picked up an extra lone pair, giving it negative 1 formal charge, like that. And also, we can draw in the rest of the molecule here. So double bond methyl group. We have here our negatively charged oxygen up here-- so negative 1 formal charge. And over here on our nitrogen, we have our hydrogen, and we have this in here. And I forgot to give a plus 1 formal charge on this nitrogen on this resonant structure right here. So there's a plus 1 formal charge on this nitrogen. Obviously, it still has a plus 1 formal charge over here, and we have a plus 1 form or charge over here for this nitrogen. But if we focus in on both nitrogens, this nitrogen is now in the exact same situation as this top nitrogen. They're both actually sp2 hybridized with a Steric number of two. So they have a p orbital. Each one of them has a p orbital. And we now can see a little bit better that there actually are six pi electrons that can be delocalized throughout this ring. Now maybe it's a little bit more obvious that the thymine molecule contains the pyrimidine ring, and therefore it is aromatic and has some extra stability associated with it. So sometimes drawing resonance structures will allow you to see the possible aromaticity or extra stability in a molecule. So this is an example of a biological aromatic heterocycle-- so a molecule found in biochemistry, which is obviously extremely important, that we can analyze using these simple concepts of aromaticity in organic chemistry.