Lecture 26: Synthetic Applications of Electrophile Aromatic Substitution

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Lecture 26: Synthetic Applications of Electrophile Aromatic Substitution
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This is the second quarter of the organic chemistry series. Topics covered include: Fundamental concepts relating to carbon compounds with emphasis on structural theory and the nature of chemical bonding, stereochemistry, reaction mechanisms, and spectroscopic, physical, and chemical properties of the principal classes of carbon compounds. Index of Topics: 00:50 - Reactions of Substituents on Benzene 02:17 - Reactions of Alkyl Substituents on Benzne 04:36 - Oxidation of Alkyl Groups Bonded to Aromatic Rings 07:36 - Reduction of Substituents Bonded to Benzene 09:54 - Clemmensen Reduction (HCl, Zn/Hg) 11:23 - Wolff-Kishner Reduction (H2NNH3, KOH) 14:23 - Nucleophilic Aromatic Substitution via Addition/Elimination 14:50 - Synthetic Applications of Electrophilic Aromatic Substitution
Stop codon Biosynthesis Benzoic acid Steel Substitutionsreaktion Complication (medicine) Wursthülle Chlorine Benzene Chemistry Molecule Potassium Sodium hydroxide Halogenation Human body temperature Dominican Republic Cryogenics Redox Active site Storage tank Mineral Periodate Alkane Peroxide Walking Chemical reaction Kupplungsreaktion Hydrogen Acid Computer animation Functional group Aromatic hydrocarbon Carbon dioxide Carboxylierung
Palladium Metal Substituent Biosynthesis Stickstoffatom Reaction mechanism Asset Hydrochloric acid Carbon (fiber) Chemical reaction Tin can Amalgam (chemistry) Benzene Mercury (element) Hydrogen Computer animation Zinc Redox Substrat <Chemie> Base (chemistry) Cobaltoxide Carboxylierung Medical history
Stickstoffatom Gas Chemical plant Action potential Chemical reaction Amalgam (chemistry) Nitroverbindungen Molecule Mercury (element) Gesundheitsstörung Acid Computer animation Zinc Functional group Redox Carboxylierung Screening (medicine)
Kohlenhydratchemie Benzene Chemistry Molecule Thermisches Kracken Ballistic trauma Kohlenstoffgruppe Periodate Substituent Octane rating Tuberculosis Walking Sulfur Chemical reaction Solution Stockfish Systemic therapy Paste (rheology) Zinc Nitrierung Chemical compound Freies Elektron Medical history Stuffing Ionenbindung Biosynthesis Activity (UML) Substitutionsreaktion Amalgam (chemistry) Reactivity (chemistry) Nitroverbindungen Mercury (element) Ageing Sodium hydroxide Human body temperature Tachyphylaxie Redox Faserplatte Ausgangsgestein Process (computing) Alkane Stickstoffatom Reaktionsgleichung Structural steel Singulettzustand Rearrangement reaction Carbon (fiber) Hybridisierung <Chemie> Water Slate Synthetic oil Computer animation Functional group Pharmaceutical drug Medical prescription
you have to remember idiots .period Creole undercover today by the way I made this sapling deadlines Saturday in the reason I did that is because there is an extra practice sampling that's not worth any points from the opening on early Sunday morning that has a synthesis from all of the 7 chapters mixed together so I can have a deadline United Sunday so that's why it's a sad early deadline for settling under any questions before we get started anybody focus on lowering the doings at the site more complicated things than we've seen so far in Chapter 18 10 keeping to learn to know about this is that things that we can do in 1 step on benzene part meaning it is down some sort of Al-Khobar you work was something more complicated armor benzene ring he needed for a simple thing on and then change the simple thing to something more complicated so there is a tendency for students to you if I had this really complicated thing hanging off the benzene ring slap of chlorine on their with a L C L 3 expected to call on the benzene ring in do what you want but that's not the case we know what happens so often Rubino put Nigel group known as the player now and it's over and we know how to put a simple algebra the United rodeos and the only thing is that we have not had put directly on the benzene ring if you wanted something on more complicated you have to put 1 of these simple things on any changes to something else so this is where I all of the chemistry that we've already talked about this year comes in so we just got a user than we already use reactions from Chapter 7 Chapter 8 9 10 11 12 13 of 15 16 to now convert those functional groups and do what we want alright so here's some examples here it's a lot of people ask me is the final Guinevere is the final going to be mostly unused of absolutely not the 1st midterm was on for weeks the 2nd term was on for weeks and not going to have a mid-term is where I know I'm going to have a tests were double on 2 weeks of material you would not want to take that test would have a very lonely OK so you don't want to do that and I don't even have to try to make a cumulative because of the foot something simple on the benzene ring in the news of the reactions it's going to be cumulative far-right so for example we we can put unwanted benzene ring and use Chapter 15 material turn that into a brawl life with a functional group on the weekend treat that within an outline that we could take out kinds of making convert them into Quito's out hides you know how to do that but we could also do us into reactions here so this would be Chapter 7 In 3 miners cyanide that's also Chapter 7 of and or we could put in OH and we can oxidize so Simpson substitution reactions from Chapter 7 and then this would be Chapter 12 to oxidize that came out of foreign turns it into a carboxyl gas events on the next page so we haven't talked about that reaction you could that's something else that you could do under the words you can't when you're not going to be able to do is with this group on directly by Justice throwing a chlorine on this and then adding the ALC operates about that's that's sort of the take-home message here could have to do these more complicated ways all here's some more examples of things we can do it week in and out of continues NBS peroxide he or alive British bromine on their region eliminated and now we can do all the reactions from Chapter 10 we convert that into it now ,comma I you would should be a will steel in all of these things or we could do any of the Chapter 10 reactions so what you're getting the idea that this emphasis on this on this final is going to be very cumulative without me even trying to make a cumulative so there are Tzotzil knows all reactions that you know except for protesting her maiden wouldn't talk about that right now and there's a couple a new reactions in this chapter there are we used to do to make changes on groups that are bonded to advancing parts of this 1st was oxidation alkyl groups wanted the aromatic rings we use of familiar reagent for you which has remained in a heat sodium hydroxide and the heat is key here we used for testing for making in Chapter XI in Chapter 12 to make a 1 to die all right and I always grow cold because that reaction is done at a low temperature if you keep this up it's a it's a very strong oxidizing agent and it does much more vigorous reaction so that's the difference here too he verses is found the Chapter 12 OK mental for reaction yes it it is a time I so what happens is if you have it doesn't matter what this Alco group that is as long as there is a ban Zoellick hydrogen all of these have been Zoellick hydrogen so must have been so acquired it is not matter how long the changes as long as there's a pencil it can be found but methyl it can have 1 benzoate hydrogen are making have to benzoate hydrogen sorcery does not matter I'm no matter what you what how long that Cheney and you're going to trip over all of these into a carboxyl against so the potassium making a it's going it's basically chew up that ring it's going to turn it into a mostly carbon dioxide and then you're going to get in stops right when you get to the benzene ring again so no matter how long that changes and if you have something here that has no been Zoellick hydrogen and so therefore no reaction have to have a pencil cottages for the store so that's good because now that's the way that we can put it on an acid ,comma so Odessa directly onto a benzene ring had learned how to do that before parts of comparing that with this 1 see the difference years to this is low temperature if you if you and I use high temperature for this reaction from Chapter 12 you with this would you would chew up this molecule also and turned into carbon-dioxide so the temperature is key here are act so that any reaction there's a couple more new reactions and this
is going to the season in the ICC me just expanded the number of things we can put on a benzene ring is also looking into a nitro substituent can be reduced using catalytic hydrogenation or by using metal tin IRAs plus hydrochloric acid the product is 1 but this is the 1 that I use I don't I don't use I don't usually is 10 for that reaction you might see in your book you might see on unsettling and I'm so what you get here for both of these h to employee reduces to and an 2 so now we have a way to make anyone that we could have hoped for I zinc and mercury amalgam and the hydrochloric acid and you're going to make and 1 also but since you were in asset and it will be probed so if you use this method to make and when you have to add an extra base so what we would call it is a basic worker so to new ways to make airline that will be very useful and synthesis another
reaction is the claimants and or the will Kisha reduction and dumb I'm not going to ask you mechanisms for either of these but with these 2 reactions and so this is art we have that in previous 1 we have this 1 so this is unclear for new reactions in this chapter besides electrical charismatic substitution tenderness reactions Cummins an oral history you replace a carbon to hydrogen we know that that's not the same thing that hydrogen and palladium does hydrogen palladium will reduce that amount an alcohol but if you want to take in replace those that oxygen with 2 hydrogen is this is a reduction reaction on the need to use common center will Fisher I'm so the if you do this with the substrate here it's going to reduce the key talent or link and I don't know why I'm drawing out when I just saying it's going to be reduced ch stage 2 CH the carboxyl gas it's not attached so let's write down what we just added We did this a hydrogen here hydrogen here ,comma a gas is not reduced so these regions reduce considerable Commissioner Erkki tone aldehydes only I want us to do
thus registered Hiroki tones and elder hides a link so Clemens and location a reduces T. Johnson otherwise only that's why when nothing happens to the carboxyl gasses so zinc mercury amalgam does that and Waukesha does the same thing nn also only works for Quito's the heights not provide similar gasses not Esther not in it's not possible Our so just keep in
mind that lets go back here I got was both on the screen this is the same thing so that means that if you have a let's say you have a molecule that has a nature group panicky telling you only minor reduced the Quito you will use Clemmensen reductions if you want to reduce the nitro group Anarchy telling you'll use Clemens introduction if you just wanna reduced if you just wanna reduced the key town on you want to reduce nitrogen you use will so the so that the bottom here we talk about why 2 ways to do the same reaction because sometimes we have other functional groups and the molecule that will be affected by those regions without be careful about that so if you'll notice some middle Commissioner is acidic conditions and this is basic conditions so if you have more if you have functional groups in your molecule better incident acid you would want a usable Fisher if you don't if you have molecules that is if you have other functions into the sensitive debates you would use plants and so that's why we have 2 different things are so that's the top of the next stage saying conditions and location space so more and more we're getting into molecules that have more than 1 functional group and when you have more than 1 you've got to consider all of functional groups and the potential
reactivity questions anybody so that's
corner reactions plus elective Ilic aromatic substitution in Chapter 18 the Act so Aghazadeh now the hybrid which 1 if there was an old ideas that both get reduced yet are we going to skip nucleophilic aromatic substitution effect will come back to this in my class will do it in Chapter 25 students skipped this it's a sad day chemical reaction I think he'd like people in Munich time so I'm sorry again at the way until next quarter OK so that takes us directly to use synthetic applications of electric arc aromatic substitution which I believe now is the right 1 .period made the decisions made administration changes .period early in the early part of 1 of the 1st things you need to keep environment you're doing what Obilic aromatic substitution you're putting on more than 1 group on the benzene ring the order is critical if you did the right steps but they're in the wrong order you'll get the wrong company you don't get partial credit OK so you have to think about the water when you putting things on a benzene rings so that for example this compound right 1 of these groups were starting from benzene so if we put the nitro group on the 1st what would happen we won that we want to put this group bonding with the problems that led to problems I chose many directing is not alone in that opposition number 2 carrier mitigated on because past doesn't work with Nitro substituted benzene ring so free of cracks doesn't work with deactivated manner records repressed as it works camp the nite approved by the 1st half to put this group on so we can use here's the good sentences In sadly that the wrong order is going to give you know points because you not making the call we talked about some other ways to put it to interpret whereupon the scanner use of real crafts with a L C offering of what we wanted you to ensure that this reaction goes pretty clearly what we wanted to hear yet Largs excesses benzene OK so then we're going to get interviewed agree upon this is an arena nitrate are we taking any worthwhile yeah I wouldn't even consider it so I mean a similar meaning at all bulky so mainly parent family members right the bad sentences and really it's aromatic chemistry is not as difficult as the synthesis synthesis that you've already done earlier in this court these are not as hard students tend to be better on the test with this kind of stuff so that it is for you and then if you try to do this 2nd no reaction sir reaction fails why I know grass no freedom grass on deactivated madam directing rings now some students take this to mean that there's no there's no any reactions on deactivated rings that's not true there's no free of cracks on deactivated by the directive as they do all the other reactions just 1 questions on that synthesis anybody yes I think it's a good idea you might get a pornography .period OK so that just so that it shows that you recognize that its union over alkylation OK so that last example we just put the group's directly on honoring and there were what they wanted we may have to do a functional group manipulation if we have things that are more complicated so love for example let's say we want to make this compound so we're thinking were you know we want and we certainly can't of upon 1st will never get this they in which I use real crowds To put this group bonds are we going to get that is a major part now it's going to rearranged so here's the trick waited this 1 here's the good synthesis rather than 3 crafts alkylation Oregon do freight across salacious and that's going to do great things for us because we gotta Alltel group on there we're going to be able to convert this into his work with Gary suburban near the consistent into an out and alkyl groups by doing which reactions the ones we just talk about Collins a reduction will reduction we can turn that into the group we want we will get any rearrangement free across a Salesian doesn't give reiterated rearrangements bureaucrats alkylation does the timing here is important so this is a good 1st step do we want wanting him in this common elderly wanted to at 1st wanted the Niger group on 1st nature group on 1st because if we get rid of this 1st banality North appeared director and then Idaho it's not going to go on where where where where this final I don't really like you guys you guys like this better because you do really well on OK Serena make less scored on the matter position now already get rid of that currently Norwegian to we want pick for that don't do Clinton said you see how consumers missing out on this question here just principle on stuff you don't want to use the Clemenceau the Clemens and will reduce the Nitro the Carbondale we don't want the nite the carbon unit reduced if we did we news conference and we have to usable Fisher so what's what Commissioner it's to an age and sodium hydroxide not zinc mercury amalgam HCL this will also reduce nature groups the other thing that's nice about these things we're doing with the leptophilic aromatic substitution is we don't really have to worry so much about staring chemistry with a lot of these sentences far-right so that's good since this is the bad I can't put nitro on 1st because of from Friedel crafts forward can't put proper along directly why will rearrange number to and it will it's it's directors say activating group so it was in off appearance so really a lot of things missile systems got it you gotta know what you're doing here got me thinking about what you're doing so isolated steps will get you anything if you're not your steps are not leading to the 1st part Paris questions on that 1 and they Wearing software group be used as a blocking a directing group which can be easily removed once it has served its purpose alright so we care about them we don't want this group on benzene we don't want what the writer who versus like the other 2 begin with this group on and that's already rearranged so that I can go directly or but it's an on appeared director board ways your minor products because it's kind of all the rights and if we so if we want this to be a major products of Mazomanie we get 20 per cent Nitro here maybe and in 80 per cent in the Arab position so are major products going to come from the pair because this is faulty so when entering and we can do instead is blocked compare opposition With this self-renewal group and so this is what it looks like well 1st of all say we you don't want and will do that if we take this In a L C L 3 that we use access benzene To avoid over alkylation we can make this but we probably in the next step Agent 3 H 2 SO 4 are going to get here as a major and that's because sister hysterical far-right so if we want if want to increase our heels we're going to soften it this would be a major product that doesn't mean we won't get any in auto opposition but will get a mail online around the author opposition by virtue reasons the size of pro-poor group is hindered and the sulfur no group is also known as sole 1st pretty large so we're going to get this as a major the we that as a major products we have to seperate if we get any author which we probably will be have 2 seperate that 1st but this is our major product is this guy right here is awful parent directing this is not a directing right and the good news is they both agree on where the next substituent should go so then we nitrate at this point the age of 3 thanks to so forth here's our self-renewal group In and will this'll be right here all results to the author director of apparent director and now added to the momentum director so both agree aware that should go an hour were done here or anywhere used to limit H 2 SO 4 and he's that will take that off everything else will stay on in Nassau major product now pretty handy thing to be able the do the only yesterday as if this was a and if we were going to be doing a Friedel craps instead of a nitrogen would that work yes for a across for freedom across and few of us this is a strong deactivating it this was a strong activating you could do for your perhaps if you have a strong activating and strong dear deactivating you can do for your across this is meek activating strong deactivating so you wouldn't be able to free crops in the 2nd step this is just 1 of the largest 1 to point that out corroborates To add multiple groups Sierra use more than 900 gas 2 hours aboard increased temperature wise Xtra Heat meeting the nitro group added deactivates care for on if you want to have more than 1 you have to you have to use increased temperature so when we do raisins were very careful we do it in my lab using on it and we we call everything down and a staff before we do the nitrogen to make sure that that solution doesn't get so hot that more than 1 nite sugar will go on why wouldn't we want more than 1 nitro group on well only just to be an example here a few heeded the stock rather than did this and I stress if you let the temperature get away from you here this is what you would remain what is that compound TNT right try Naito tolerance so now you know how to make the into thinking you can tell from Pressel friends are policy that we had time for nucleophilic aromatic substitution OK to wait no going back the walls said about that but can you got enough on your plate Wallace reactions can be used to your advantage gained considerable doubt rights were more complicated sentences are desired far-right some let's make a little planned for this molecule we're starting from benzene we certainly need and this is an outfield group we certainly do not want to put this on 1st heard that on 1st remember that Alco group on correct so does everybody agree we need put this group on 1st so and having to do that so we don't get rearrangement forget it now know that we we worry arrangement we have to easily and then use walkers requirements said this will realize rearranged like a shot they abandoned the group said he put balance 1st this isn't or the position this is the only me I'm here opposition this is Oracle Parra director so that's a good rate plan for us so that's the plan here and I will talk about the rest 1st put on this group here it is an auto period director so now you can put on the other groups in the correct position and we really do have to do that 2 steps for going easily and then we're going to get rid of that a subgroup of the carbon group 1st I rates sooner once that's support what goes on next the script is on only a 1 2 3 4 Bunal benzene 1 will goes on next madam has to go on that absolutely has to go on next because if you put the Niger on 1st this is this is going to go along with perhaps it won't work this would have to be a strong activating with an eye to approved to work with processes weak activating so we absolutely have to put that on group on 2nd quarter matters here Serena put on a subgroup next can put on the Niger River because there's no freedom crafts was drew pondering I unless there was an activist strongly activating the cancel out and will not give free of grass are and so then the 3rd step of course is going to have to put the knife to respond barracks got the plan what's right outta synthesis In the 4 directions Starting with spending work in a slate this is so we don't get rearrangement counter carbons Units 1 2 3 4 2 4 Kardashian everyone put on in the 2nd step I religious use of Clemson reduction OK so far so good 1 to 381 worker could then a slave every 1 of these steps has to be carefully timed really that bad we will get worse nothing you can do about it they usually go together unless you have a really starkly hinted so you will get some water there's nothing you can do about that just goes along with their medical history and men a gentle terrain H 2 answer for so the good news here is that we have made sustained or so Parra director and this is a matter director so the nice thing is they both agree on where that nitro group so are pretty good I'm pretty complicated synthesis that we can do with all that everything we've learned in the chapter but that's the last page right there and I were done mostly in the you