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Lecture 14. Alkali Organometallics (Pt. II)

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OK so let's pick up where we left off we've been talking about alkali organic telex wary of organic compounds
bonded so you think you create a lithium potassium even magnesium different column the same idea and so we talked about the various methods for accessing things I calculate the arms or or green yard reagents on the 1st method that we mentioned is just direct reaction with metal like a reductive litigation for again metallic chemistry and really you don't use this in the lab this is not typical This is the way they prepare commercial reagents the cheap ones that you buy on a huge scale you lithium met with him ventilating and stuff like that that's not the kind of thing you would do in the less traditionally organic synthesis if you're making very complex organic ingredients you usually most often using something like this you a lithium halogen exchanging take cheap computer lifting the you and then instantaneously essentially you react with the Aral iodide bromides wide-eyed guides you get exchange to make the vinyl lithium Moreira lithium that you want to start in with lives that's more commonly the way that you only can help with him that another exchange reaction to lithium exchange on where you can take any sort of a standing count for example this when you could have a here because the longer is an oxygen which would push that out but you can make these kinds of state in all of the seasonally there's and do with unit in exchange if you want to make this kind of Alcock see of Allcock C L kill lithium solos the 3 common ways on to get access to Falcone within seconds of the 4th we'll talk about that is that is very common is reductive litigation this is not an simple exchange reaction on and here's the way this is typically 1 of the basic idea is that if you take lithium wire that's the way you by lithium you this political wires are stored in oil was not in contact with their
oxygen and that and then you simply makes that with naphthalene very cheap this is what they make and model balls out of you get something called lithium Nat land
lithium affluent side and so how do you think of what would you get if lithium dumped electrons into this system How do you even depicted we don't have good depiction for that let me give you 1 way of thinking about that at all simply erase this bond here now draw that pipe on 2 electrons and so now if we imagine dumping 1 extra electron we can at least see where we might put that extra electron on and the problem is we have so many residents structures we can draw or it it just becomes that nobody draws so here's here's 1 resident structure but suppose I put that extra electron over here now you just imagine all the other residents structures you can grant that it would be a good exercise and they you can get a sense for what lithium will now but when I looks
like focuses very easy to make ability and naphthalene I'd want to simplify mixing with him wire which snaffling and it is the most beautiful and intense blue you have ever seen in your life and the beauty of this reagent is that it's super easy to make displaced during these 2 things together and then
any place on the planet where you have a file final group I'm here for example you simply drop in this reagent and instantaneously you get conversion from file final to lift him so he would be an example you take this lithium naphthalene agent and for whatever reason I'm going to drop this weird structure this kind of looks uncomfortable on minus 78 is you drop this and and there you go you got calculating ambition could make from Hale lied 52 were easily you can make a Camille either don't have to go through some toxic 10 species very easy to put pressure put 2 of these electrons calls on 1 card and I hope you did a better job it least said it would of be clear for whatever
reason extra electron and you control the residents structure now 1 of the problems with this is that the the reaction to cut just the tone of naphthalene left over there's just a ton of naphthalene and thereafter this
reaction is over so In order to make it easier to remove that a lot of people start with this naphthalene derivative and then they can just wash away with an acid wash at the end on a note slightly changes the reduction potential your ability to put a dampener like training but the main point years is 1 the to an acid washing get rid of all this greasy Nathalie it's just going to junk up your column focused on here's what schools so they want to think about what's going on or give you a little plants snippet like react a piece of reactivity while I'm not going to draw full mechanisms were not really talking a lot about radical mechanisms they know as soon as I start talking about this naturally we have to start out donating an electron somewhere so did you 1 way to think about the initial structure if other file Penelope attached to anything like the usual here's a
way to think about what's going on there's lithium can find floating around they will coordinate and to this sulfur and so that dumps electron it into this
benzene ring so that is a drawl 1 of the double bonds and benzene as just 2 electrons you can imagine that I could run that is a possible and so will happen if I put an extra electrons at the lithium can here at the other X-ray electron over 1 of these places and years world drawing like that and now you can imagine this thing fragmented you can imagine this thing fragmentation in such a way that you would end up initially with a radical here on your carbon atoms and fragmenting psyche 1 electron be here and I'm not going to show you how I get to that residents structure but the residents structure that I get to for this for this style fennel species is lithium ion monoxide so when you fragmentation get carbon radical that desperately
wants another electrons and lithium is happy the lithium naphthalene I is happy to dump an electronic tools to view a radical and I think it is a byproduct that by-products floating around in your reaction mixture not hurting you will be more
reactive than the helplessly in the tumor as a consequence of this because the whole idea behind this is that involves formation of a radical intermediate that then gets converted into an online you have lithium is you see this on this set of relative rates do you get the fastest rates for reductive litigation for tertiary alcohols remember tertiary alkalinity instead much more reactive screaming out reactive than primary Alcan lithium but he still without phenol they form fastest popular themes 1 passes when you've tertiary that's faster than
just primary of 5 panels getting converted into primary applicants and that's faster than In fact very hard To
do this because it's very hard to make just the fennel radical where there a single of electron inaudible sticking out the side of benzene and this would be very very slowly trying to do just style families can let's method number for productive litigation if you wanna make Annapolis filed panel somewhere anywhere taxi were on the Buell group will be able to convert that into another of focus on what come back to this idea of of lithium halogen exchange you can make the same argument over our 4 a of fertility in exchange but let me just remind you of the mechanism for this reaction important .period put behind this reaction I this exchange reaction and what makes it work is the fact that there is an equilibrium that favors side talk about the deliberate it again if you wanna draw the mechanism for this reaction would look like this you'd have this initial 8 formation of an 8 complex to bonds to the halogen the desired date and now this bond both of these bonds become nucleophilic and so you can imagine this attacking lithium and that's how you get the product so that let's forget the the Aral pushing mechanism for now we had like you know how to do that but let's forget their which mechanism and just focus on the thermodynamics here which you expect if we take a series on of alkalinity ends and we laugh allow them to exchange the somebody measured an entire series of compounds to figure out in which direction should this equilibrium the most powerfully most powerfully director so everything years compared the Fanna lithium formation thus could make a table where we looking at the
equilibrium constants for this reaction I'm trying to write a few them winning in equilibrium constants for this process during the start
off the year with formation of vinyl lithium and what we find is that the equilibrium constant this is very poor and finally found a lithium and I'm going to try to be a little bit more space conscious here because of that several compounds you cycle probe lithium finally be utility and not finally that Beutel lithium I never secondary algae lithium but you're never going to make our work with armed with cycle Penta lithium but you might work with SEC utility and that's a secondary applicants it's
very ,comma Clementon take away 1 of these carbons and is having fuel a secondary legal group denounced as a very powerful donor for lithium so if you really wanted to
drive lithium halogen exchange go a secondary al-Khalifa trade if you wanna drive looking knowledge in exchange you would just put in vinyl lithium the equilibrium obviously people infidelity lithium and found like I did have a one-to-one equilibrium constant and if you really want to make a panel at end of the institute's al-Khalifa was Beutel lithium will vary will will will dry this equilibrium report and the information and finally the best would be a tertiary uplifting he really wants on that and I don't have any actual number here all I can say is it's it's greater than 10 million it's greater than a secondary out you really see people want to buy absolutely
drive al-Khalifa information from a deal like this rowing into listed as the region so it's a pretty amazing on pretty amazing reaction and what's amazing is that this team halogen exchange
the attack 1 iodide that I showed you this attack of Anelka Lydia attacking some sort of a halo of Israeli aerial here well let me draw another alkyl group this attack like this on iodine to make this Friday is faster than into that's what what may be strange to you is vastly faster than a century reaction so in other words you don't get to this happening and I don't even want to put a regular opera -dash Dario they're going to give you an idea you don't get s into but in these types of processes to keep the temperatures low will just get straight up exchange of lithium privileges and status which ends here is that likened focus so very powerful and very easy to simply add Bureau lithium tier of alkali
dives and convert those Anelka listings of emission what I feel is the most obvious way To make something reminiscent of
of and iron and that's the probe nations we just take out canes organic compound and probing them and what are the limitations mechanistic lead it seems like the simplest mechanism to this simply deep ruminating see ages and the term were use for that his methylation but with the with the the insulin according comeback and remind you would but if you wanted to just simply deep probe now you you want obey thermodynamic said he simply wanted to make and al-Khalifa like this by deep-rooted meaning anything you have to remember you need something more basic than anything if you really wanted someone dynamically to to have a lot of plausible process will do and it's hard to think of there much more basic and I think but it's not hard to think of things that are more basic than on the way the taken out lithium then it ought to be able just the utility of ought to be able to thermodynamic Leedy probe protons these S P 2 hybridized these protons NSP to hybridize carving and out of the way more it are to be given more facile to deep prone at the end of and of an al-Qaida just using something that's more basic than outcome and so what kinds of things can we use of typically don't have room here at admits misallocated MySpace here but long and you can use of the 1992 permits only remind you of the PPE case for this so that and really this is a PKK prime he gave Prime means what if I had a proton instead of lithium but I can't ask about the PKK this this isn't an answer but I stuck the H-back their new considered possible now I can talk about the peak year in public that he came across to the PKK for a simple outlines love 15 which we talked about this case to case for his P-2 hybridized vinyl rope is about ,comma 41 of 42 so far and that for a simple terminal alkaline it's about 24 and and then I want you to remember this later the PKK forever and we talked about this for just a simple and need to be put made enemies might I suppose baloney make LDA that is isn't thinking of about 36 OK solicitor thermodynamics let's talk about a reaction that is just completely impractical basically what I'm telling you is this summer dynamically you can do this now about the age there but I just told you is that it's the manically favorable to deep probe made benzene rings With the lithium find orders of magnitude the equilibrium constant favors formation of the final but you have never seen anybody deeper benzene would you you never seen the problem is not the the Madonna makes the problem is Connecticut is just too slow there's no problem of course you could draw all euro pushing mechanism where you take the super nucleophilic electrons in his bond here and attacked the Proton which is just 1 the book itself Cal acidic 2 things have to be before you can do just simple methylation simple nation reactions on top
of about painted compounds and I'll show you an example where it can be acidic enough to penetrate here
probably the 2 of us off more organic chemistry course in the United States 1 of the 1st How killing 9 reactions you learn about is the probe needing a settled In this direct approach nations and don't have to be very basic to have good enough rates for the probe nation you can take people at the energy from alkaline you could taking a green yard which is traditionally very nucleophilic the memory of a 2nd even this occurs at a fast enough rate that's what's astounding Granada not super basic they're very nucleophilic but it's surprising that even agree not created is basic and arms 2 to pull off that Proton that convenient rates and I don't want to draw that as a lone pair enjoyed all this and byproduct of this would be
a thing of focus all of course the equilibrium is favorable and can the PKK is over there and see that this equilibrium favors this side by 15 minutes 24 by
26 watertight detracts from the meetings at the rate of go so it's very easy to the probe made all kinds but the 4 4 4 4 4 4 was surprisingly easy that's the basis of a summit this year coupling so Minnesota Shearer coupling you take kinds and palladium and try after and copper and under those mildly basic condition during the probe meaning that outcome facility surprising number surprising sort of backed away from the city takes sodium at dockside in him
on ethanol as the source for this and you do this substitution for reaction it was so what's the
mechanism for this substitution to replace this chloride within epoxy but completely amazing is that if you measure the rates the rate is 1st order there's a first-order dependence on the concentration of sodium oxide why is it that was why is it that if you had 10 times more with the rate gets 10 times faster what they tell you for certain it is not a simple lesson 1 reaction right for S N 1 reaction is the rate that has nothing to do with the nuclear volatile fast inform the public so it can be innocent 1 reaction but it's also the unlikely that this is a lesson to to attack the Treasury Center it turns out that what's happening here is that the mechanism involves deep probe nation initially To make this terminal alkaline who would have thought that nobody would have thought that that you wouldn't have thought that I would that and now the loss of chloride is very fast it's slow here to make a cobbled can iron but now where over there that out there said satellite Anaheim makes it now fast true the court and I'm going to go straight to a weird-looking resonant structure In other words Let me now use this with that negative charge sooner now this pipe bomb becomes very nucleophilic and helps to push out that leading Group and what you get is a copying that's not part of this is Peter there's 2 4 6 electrons on this system it's like a cargo can iron and a iron on 1 part of it and that reacts very quickly with nucleophile solution so you can draw on as this only my thoughts I that's attacking more I'm not going to show all the steps but or
ethanol attacking but that is not very quickly attacked not understand the attack back over here with the leading to less so than you can
redraw this inorganic conditional the steps going back to the final product certainly knows this card use their full what they did is there in this reaction in the presence of compounds that have double bonds and what they showed as they were able to get cycle propane since their head right you can't explain this kind of reaction formation of these products without invoking according to national local carbon you're not going to get to this so that's all some other major piece of evidence that there's a carbon OK so very difficult to pull protons it's and there's not a problem from a dynamically with pulling protons this to on centers the problem is 1 of kinetics of summer dynamically lithium-ion be able to make things like this simply by by different names
without kind it is fast enough to get a huge thermodynamic favorability for pulling protons of about kinds and its kinetically fast so
initially trick a simple trick for deep relating directly programming has been to hybridize protons honestly to hybridize cards and it's all about entropy while maintaining the novel Sanchez it's partly about some of them and basic ideas this 1 and what about but it
has to do with prior coordination and we're going to see this idea over and over and over again in Paolo reactions in Ninole boarding chemistry so
that we can start off by simply laying out lot of problems a synthetic problem and they're used to not be a good solution to this problem we will so the wanted to do electrified look aromatic substitution of ethanol for example with a simple electrify like methyl iodide I would you do this so 1st of all it's not easy to make methyl cat alliance you can under some conditions to Friedel crafts with Mathilde the alliance but it's not easy to do this and if you did some real crafts How did start from getting the pair substituted products from the leptophilic aromatic substitution get mixtures or so and and so here's how you
get around this the way you do this if you use deep nation and you use this oxygen atoms in an indirect way to help you with the probe made that ch such abuse you 1st convert your all into some sort of and
not an extra Esther like derivatives something that stable so in this case the maker ,comma Banny Kirby and meat because the longer the nitrogen and donating government makes it hard for things to attack the Kerviel never nitrogen store for the company this is 1 of the better derivatives for helping basis coming this is 1 of the better functional groups for helping common and 20 proving that so you treat this would be the lithium which is a good nucleophile and a good basis the fastest thing that happens is not for the carbon lithium-ion to attack the carbon that's not the fastest the fastest thing that happens is that this lone pair comes in
attacks the lithium atoms and always easing step to associate with each other "quotation mark
but and watch what happens when we do that so there might be lithium it's now coordinated oxygen and I have to put the charges right here if I want this to a structure to be correct but put a 3rd bond oxygen that's no knock psyllium species with a positive charge there but 1 accordingly the Lydia is now a little sooner draw that negative charge I realized why In contrast the ability might start with now every single bonds to this lithium is now more basic and more nucleophilic at that negative charge tells me it's now more reactive when it's coordinated than just floating around another words when it's close to these Oracle positions that carbon looking bond is now more basic
and so when it's coordinated yeah faster rates and approve nation then you do interviews with
just floating around and colliding with so this is the intermediate that you get and so on that ultimately you can draw long pairing of the fennel and haven't really pick up a lithium-ion concerned getting this sort of way In the lithium it's dangling over here now we coordinates on sleeping mats that you can fill in that that extra step on your and so now you get this intermediate that looks like this and then there's a lifting so in other words in the final product is oxygen is still coordinated to that lithium and Sinaloa on your electrify like methyl iodide is a very reactive with Electra files that carbon with
environment you can be doesn't have to
be methyl iodide that you could use that as your electrified Oliphant wanted and use this to attack whatever electrified was going to be tours that nucleophilic on lithium bond and and now at your leisure you can hide realize that carbonate down back down to a now calls itself this is 1 common way to make methylation work takes slow reactions and the simple trick of having a coordinating group that souped-up the reactivity now speeds up reactions nearby so that we call directed and there's all kinds of groups you can have here they generally involve you know five-member 4 of 5 members 6 members having transition states to bring this basic bond to the the CHT you want to 1 of the proposed projects that extend this idea half of the importance of this type of tree coordination among others you know it
all we believe that the transition from 1 of the things that we it was support With the hybridization of these carbon atoms in methane the sp phrase that just ibid diarization the carbon atoms in speak to was libraries Asian discovered at a hearing alkaline space of a more as character 50 % as caregivers is 25 or more as character of the easier it is to the programming Morris character the easier it is for the last peak character the easier it is to be proven Colombia's remind you of hybridization the cycle propane when you look at the hybridization order page down to make the 60 degree angles you end up with on these carbon-carbon bonds here being on about an S P 5 scenes where it's about 80 per cent of the characters the main originalfunder-the Maffett but this is more character than normal in this by his boss what's important is that you're using extra pay character to make these carbon-carbon bond you have less the character to make these bonds outside the hybridization these these bonds outside is is approximately but as P-2 . 2 it's close the S P 2 hybridized
those bonds on the outside of a cycle program more like this it should be easier to the probe make cycle propane than it is to probably just a symbol of King the
looks IRS P-3 but a lot as P 3 focus and keep that in mind OK so I went about 2 reactions on Pollock's arranger approximates Thomas would start off with this a very traditional reaction you taken side and you treat this with Alidia Mamet based the question is what happens to it happens with an epoxy thinks so the amendment well it's me like it's basic but you don't use with humanity nucleophile I can't think of any case he would purposely ever do that when use the Mamet's you're using them as bases and here's the base promoted reaction that you see in this case we it said the 2 elimination I think there's a problem here is the
leading group that have action leading group I'm leading groups and there's a proton gets pulled that's need to elimination of the
managers of very powerful states there is what's going on in this reaction and in other words the it's not that this lithium-ion comes along but what's the most basic part of this it's the lone parents not the nitrogen lifting and on its long-term it's the most reactive but that's not the 1st thing that happens the 1st thing that happens is that the lone pairs on this OCS arraigned come along and it ends coordinate with that lithium and when he does that relate to keep track of our charges a Idaho positive charge on oxygen what does that do the positive charge knocks it makes these carbon-oxygen bonds easier to operate it makes the oxygen of better Leading Group at the same time that
you're making an oxygen bottle of better Leading Group me finish the other part of this you now make this nitrogen more basis every part of the
nitrogen atom attached to that looking now becomes more a so this bond is easier to cleave this nitrogen atom is no more basic than I have this accelerated the proclamation the important part here about this is you end up with us up on this requirement for a certain elimination and they've shown despite putting deuterium on 1 side and Proton the other they show that in every case is the proton on the same basis as the approximate gets Pollock it's not intimidation like to so it's not really a need to be to the immunity on this is a sin elimination of Alcocer 1 reaction Parkside with bases again looks kind of like a need to so that doesn't really that's not a minor Bender I've added to the job of running through the
years when you read your story from here on I forgot to bring the radio OK so apart sides you can do eliminations with you really
restrained at school schools so again if you were able to resist the temptation to innocent tuition the Parkside than than that kind and makes sense the let's talk about another reaction we cannot start up by showing you the observation that led people to realize something cool is going on something else call goes on with apart sides and bases but we think there another apart said it's not a five-member grain seeing you treat this with lithium die Ethel hammered you get the expected soon elimination product in this
kind of thing that looks like any 2 elimination seen yields only 16 per cent for this it's not very efficient it turned out that the major product in this reaction it is up by
cyclo acting system with 2 five-member during the court To have you explain that I do something none of this is going to help you can immediately see it you're not going to explain that unless you can figure out how to make the CHT CH 2 groups on the other side reacted or or something so reactive maybe not making these reactive but you're making something so reactive that he can react with those CH 2 groups that the only way you're going to make a 5 that kind of evidence is unwilling to redraw this apart side in a different confirmation
on to remind you that when you have a 10 9 Member brings there's significant trains angular interactions it doesn't look
like a stop sign it looks more like this and there is a very bad but if you have to cycle eyes and a psychic of making a member during this is going to screw you it's going to kill those kinds of bumping into but also really enhances the possibility that things here will react on the other side so you can imagine if you have some sort of Parkside here and you have an alkyl lithium there's another competing reactions it who work with Bay things the based in my bases in this case potentially out lithium's not only to the oxygen coordinate irreversibly but you can also get this deep-rooted nations remember the C H bonds on the outside of Street the renderings are more acidic than normal From a dynamically more acidic and kinetically more acidic than normal and so you end up getting
deeper alternation of the city is not a factor people who with his no the
Senate getting metal aviation on the apart several competing with them so that we know but this is a competitive process that competes with the window open and here's what I don't think you could guess is that this part so that I would guess that would never guess that but this pops open and that pops opening gives you what's called a car being waiting interviewed it's not a car being because there's a lithium attached to where you would have had a carbon coordinates with another lithium for Limoges that is no minus-4 otherwise it'll be confusing to end up with this species it's like all to
cobble Kanye that sucks well but at least there's some somewhere I hear there's a nucleophilic pair of electrons so
you really bring strain that is very electron rich program that really is range-trading this ,comma be annoyed it's sort of like this it's not a car being with or without NDP orbital a car being what evidence DP orbital and the cargo and a carbon iron sticking out of it as no carbon either the car with him that's called cardinal to do it took away the lithium ion that would be a copies sold justly will occur to you as you can tell at electron deficient that carbon only 6 electrons so the C bonds on the other side of the ring a poised to form a bond across that ran so you here and at the same time you're donating into that NTP work sorry I'm wrong structure but here reader
area so represent orbital very unhappy very unhappy I take these electrons chains annually interact and maybe I should
readjust the shape of my range with closer I could reshape this is that the bond this was hot and I don't even think I'm using the right carbon atoms I'm not going to take the time to redraw this but you could read it agreed to has the shape .period could see that this is directly across from that and then this nucleophilic bond at the same time can come and adds to that and pull proton offer you basically do ch insertion across the board with this cardinal who would have guessed that you could never have guessed that in a million years that's something or somebody has to show you that illegal holy cow please do that yet OK so and begin that wasn't predicted somebody stumbled on the reaction but won't stop and I credit the bunker fiction nearby Clinton disturbing way by showing you some pictures and hope I can do about the projector here to talk about the structures of these things that I've been drawn from you and how it's all lie and how we're going to deal with that both called
OK so what when I show you these al-Khalifa the arms
and on things of that nature how should we think about those so I'm pretty sure if you've
taken an undergraduate organic emissions fascinated states
you were introduced will Allcock side intermediates in Wales like this this is an excellent way for you to help you understand the basis city in reactivity of the outcome because you were trained to think when I see minus charter know that this is based and so what's the matter depiction of the case and I would argue be that this is better or forget to occasionally
wasn't he might look like pattern we depict these mediation crystal structures of these compounds we can get a better idea of how to think about these are not just in the silence even solution is the structure of potassium TV dockside
over here if you've been using this depiction how many Bonda the are the 2 potassium here 0 over here the CIA there's 1 coming over here in the real structure 3 have to me 1 1 bomb looks closer to reality than 0 bonds right there is no such thing as free TV and talk side floating around there is no such thing not
even close this come down here and look at it and he's not later mingling with a couple of more about that later How many Bonsall eliminated
not know even here when I draw this that's that's we'd better than this but in reality you don't have 1 bond the lithium you go through the middle here In the substances and here the oxygen oxygen is connected to harmony with the owners of 3 Lydia Street lithium was connected with to this and reality are the kinds of structures you haven't solutions to rethink every single thing time you run reactions and things don't make sense ,comma back and remember
these these pictures here OK
give you my makes my Of course there long peers over these oxygen that's why it's coordinating so heavily that's why you go all aggregation about potassium but a that lone pairs everywhere the only way to make them happy is to have lone pairs according to something that's gonna look and alkalinity and there's no longer carbon when I look when a drawn-out looking like this I don't have any lone pairs to talk about and the how we think about the structure of al-Khalifa human solution In solution not a crystal structure where you can be biased by some packing forces lack of solving it he put this in ths this is the structure of the lithium In teacher there are many studies have shown that the system and it's actually an equilibrium so what is cool and how we didn't but we try to unwrap this structure for you so each year's each be long chain right here and each Beutel lithium carbonate lithium-ion is part of this sort of cubic lattice with 4 cardinal for lithium but it's nothing like this a free carbon iron a free lithium on the
bonds to lithium in the real structure here therefore is not 0 there's 4 now in ths half of course we
have lots of th at present there's an equilibrium you'll see this other just diners with Lithia again with the this time has for so over here you can see each lithium is bonded industry carbons over here it's the responded only to it's an extra teacher of molecules that is helping
the lithium to satisfy the act the committee wants to satisfy the what's the charge that the only if you if you do the formal
charges here you have ministry charge under the Soviet dative bonds and drawing and charge balance these are not true Lewis structures and Lewis structure adaptive at minus-3 and with focus on earlier I limit helped you deconstruct dispute with him think it's disturbing to see this kind of
stuff and I don't know if this is going to make it more disturbing alert for less distressing was trying to understand the reactivity of you lifting we look at you looking
merely ordinary thinking All my God that bond nucleophilic that's what you want the thinking at the same time your rethinking 1 of those
little money has to electrons anyone date that the unwanted knocked out of electrons just like every other 2nd out and saw you want to make that happen we're
going to do it this super-duper Dupre nucleophilic carbon lithium bond and you want to use it to donate into the anti-war rules on lithium right now it's at least a little better get a little better now with the releases for electrons but it still wants a and this is what's going to drive other Bolivians to attack this notice that other structure should binders filled in the carbon hydrogen bonds now that I do that How many bonded occurred in here right if you have
some sort of bias against carbon with firebombs forget that bias but there's nothing wrong with that and we talked about this before there's nothing wrong with firebombs card just don't violate the active we have not violated the active will this
carbon steel has 8 electrons electrons as carbon atoms have I take these elections I share them between these 2 lithium I'm not adding extra electrons and the sharing those electrons will know this may be disturbing to you but we have to get over that
I'll 1 last picture before we go back to the track would take lectures but on just to move down a little lower in the periodic table to Cooper so
Drossin cooperates in just a moment but I will not mind you it's like this alkalinity and things they be drawn and out then all cooperate break the ephemeral copper species we don't draw like this when we draw things of of the era when mechanisms but this is the structure of the will copper compounds but out of that is benzene ring and that to bonds to copper breach of these carbons we have on and here's the coop rate so over here with could break where there's too alkaline copper now look at this it's like each copper each carbon on the benzene from the copper is also bound to lithium have a the structures that
we draw we need all of you lithium-ion right and that the correct structures my mom and I want you to keep that in mind and I'll tell you how we should deal with that on this as we go along here it was good would
you want to know what the hell look at what we going to show you how I would like you to deal with this so if you go look up the structure of sodium TV Utah oxide sodium about that it's aggregates it doesn't look like this and yet when we do Errol pushing I want you to draw it is not going to be drawn Tass TV talk is a monomer on which you draw sodium Alcock side as the monomer but I never want you to forget these are aggregated solution theory dealing with reduced sentences will come the other oxygen the label groups all over the place don't forget that sodium is not happy with
just those 2 electrons there so when you draw mechanisms just to deal with how should we draw mechanism for things like this I don't want you to draw Alcock side minus all like this I don't want you to draw this agreement draw regular earlier
America hurts me to think about this you're not going to simply have this dissociate into 2 components if you calculated using cool lower cost you pull a sodium leak from knock oxide that's so energetically expensive it's not realistic there is nothing you can do with the lone pairs that you cannot also long pairs so when I give you a sodium Alcock side professing to be toxic lead in on him and do this right we don't have to dissociate the sodium where the potassium lithium 1st it'll will come off eventually and when I ask you to do this stuff I'm fighting all of your previous training probably on for drawing mechanisms but it's too bad so you get not Sony an intermediate now you can dissociate the sodium now you not pulling minus away from a plus and depending on the concentration actually the bromide might come back in 1st poke some electrons in sodium and & associate that we can simply drop like this at least now about China separated plus from A-minus right that's what makes this so painful that was the most painful to me OK so this is closer to the to the way you would be dealing with these with these types of reactions this is the way I would like to push heroes don't pop off the metal from the Alcock side just don't do that OK so here's what is also OK what I would like you to be able to do for euro pushing frequently will come across things it doesn't have to be utility McCamey and green yard reagent right and
I don't want you to draw this dissociating entered into some sort of ridiculous thing like this this is this is nothing like what's going on in solution don't understand the
different colors say don't do that hold make it associated give an alkylation time that's not what Riyadh look like that's not al-Khalifa look like if you want to do some sort of nucleophilic attack there's nothing you can do with this lone-parent online is that you can do at this very don't make this use the personal bond to attack that I hear there's a lone pair that's the more nucleophilic component but there is no longer on carbon in Beutel magazine reminded of that nature His but and now you can pick up the magnesium said this is the way I would like you to push these types of electrons but we don't have time to quite finish up I'm going I'm going to talk a little bit more about
you relates that I'm not the 1 in this class were not going to draw all these complex aggregates was just going to draw monomeric species in
all or make you feel little bit more comfortable with drawing monomeric species would involve so we come back Monday will finish up on this and hopefully move on to helping US
Chemische Forschung
Metallatom
Vinylverbindungen
Besprechung/Interview
Chemische Forschung
Peroxyacetylnitrat
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Systemische Therapie <Pharmakologie>
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Taxis
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Chemische Verbindungen
Spezies <Chemie>
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Funktionelle Gruppe
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Metallatom
Elektron <Legierung>
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Einsames Elektronenpaar
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Setzen <Verfahrenstechnik>
Konzentrat
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Elektron <Legierung>
Einsames Elektronenpaar
Chemische Bindung
Farbenindustrie
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Setzen <Verfahrenstechnik>
Vorlesung/Konferenz
Magnesium
Alkylierung
Lösung
Spezies <Chemie>
Besprechung/Interview
Zigarre
Vorlesung/Konferenz

Metadaten

Formale Metadaten

Titel Lecture 14. Alkali Organometallics (Pt. II)
Serientitel Chem 201: Organic Reaction Mechanisms I
Teil 20
Anzahl der Teile 26
Autor Vranken, David Van
Lizenz CC-Namensnennung - Weitergabe unter gleichen Bedingungen 3.0 Unported:
Sie dürfen das Werk bzw. den Inhalt zu jedem legalen und nicht-kommerziellen Zweck nutzen, verändern und in unveränderter oder veränderter Form vervielfältigen, verbreiten und öffentlich zugänglich machen, sofern Sie den Namen des Autors/Rechteinhabers in der von ihm festgelegten Weise nennen und das Werk bzw. diesen Inhalt auch in veränderter Form nur unter den Bedingungen dieser Lizenz weitergeben.
DOI 10.5446/19236
Herausgeber University of California Irvine (UCI)
Erscheinungsjahr 2012
Sprache Englisch

Technische Metadaten

Dauer 50:15

Inhaltliche Metadaten

Fachgebiet Chemie
Abstract UCI Chem 201 Organic Reaction Mechanisms I (Fall 2012) Lec 14. Organic Reaction Mechanism -- Alkali Organometallics -- Part 2 Instructor: David Van Vranken, Ph.D. Description: Advanced treatment of basic mechanistic principles of modern organic chemistry. Topics include molecular orbital theory, orbital symmetry control of organic reactions, aromaticity, carbonium ion chemistry, free radical chemistry, the chemistry of carbenes and carbanions, photochemistry, electrophilic substitutions, aromatic chemistry.

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