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Lecture 19. Sulfur Chemistry

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whatever discussion section on Friday at 5 o'clock so we can discuss this last problems that's optional you don't have to show
up at will you know stressed the on the chance to get some extra studying for the final exams which is on Monday in this room and I forgot whether it's 10 o'clock at 10 30 or find out until you on Friday Tom so we got 3 lectures left escaped 1 of them then you're not responsible for that material so we're skipping the longline notes lecture 18 nucleophilic signifies we have already talked about the most nucleophilic signal bonds in organic chemistry and that bonds the metal things like carbon lithium bonds carbon sodium bonds carbon magnesium bonds has other tricks you can play to make this bond more nucleophilic on the way but that we're skipping them so as to lectures were going to drop down from the 2nd row we focus so much on carbon which we ought to visit class in organic chemistry and already dropped down now and talk third-row atoms is we go to the 3rd World and I can get all the way down to the to the side uh matches at 10 30 10 30 at 10 30 in this room on Monday ,comma at all remind you again on Friday OK so what happens when we dropped down from 2nd row Adams to Adams things change a lot so we try to enumerate 43 things are important the change when we
dropped from the 2nd notices ropes that are based on periodic trends but the 1st thing is that the award the bigger so we drop down from the
2nd row like oxygen this this particular columns called the chalcogenides when least drop down from oxygen to sulfur now using 3 P orbitals in 3 s orbitals although molecular orbitals will most of them will tend to be bigger orbitals will be bigger lone pair orbital unsold from huge it's easy to overlap with stuff so 2nd thing changes when you drop down to this to the 3rd round you've got longer bonds and the longer bonds have an impact on the ability of P water lost overlap in the pipelines and then the 3rd thing that's important here ,comma is the Electra negativity is less so on right lower Elektra negativity to the point where when you look at the Lecture negativity of sulfur it's 2 . 5 that's the same Elektra negativity is carbon so when you look at a carbon sulfur bond haven't we think about those bonds when sulfur has the same Elektra negativity is covered such good talk about some classes of compounds we where we can ponder on this are on the impact of this someone stirred up by talking about on this what does this mean that if sulfur right next oxygen and I want to try to contrast this with a carbon yield bond a C double Bongo was a pipeline so let me draw so some comparison molecules for you remind you of a simple picture that we gave a acetone before we we drew acetone and considered this residents structure where we gave the electrons in this pipe to the more Elektra negative oxygen atom that should make total sense and that's a reasonable resonant structure because oxygen is
Electra negative and what we said is that this this winter ionic resin this this elude like resonance structure is important to the tune of about
25 per cent so my number here is close to its 77 % but I can't remember that swells a 75 percent there's about 75 per cent of high bond here with the Cardinals it's about 25 per cent like this 25 per cent charge on oxygen and carbon but it's about 75 per cent like this so 75 per cent of so it's contrast this picture that we've already discussed on for carbon deal with the picture of herself oxide side that would be the analogous to sulfur and so the the 1st thing that I'm going to do when I grow up the solve radishes remind you when I draw on a soapbox side its stature he drove it's not flat there's a lone parents openly Donald drawl that lone pair I would like always draw because someday you're going to need that Ferrero pushing and if it's not drawn there you won't remember it and
inside we think about this was dropped the same kind of idea oxygen is more elected negative sulfur over is about the
same Elektra negativity is carving and that is what I would like to do here and start here already started to draw stuff I wanna modified isn't some freakish way that makes it hard to forget their ego maybe that'll make it easier for us just to have a picture and I feel like if I overemphasize it'll be easier to remember on this sort of distinction between sulfur and carbon but that the bonds are longer so what's the impact of this when you look at the double bond character here it was 75 per cent double bond character up for a CEO it's only about 35 30 per cent of the double bond character the 30 percent Pike character Furcal Fox side so it's more like a soul for oxygen single bond and so what is
the best representation for this I think we all agree that the common representation we should draw for carbon Hill was see
double so why should you drop a flocks of you'll find as I sometimes look like this and sometimes I don't like them from trying not to have charges flying all over the place although like this but every time I draw there's some thinking why that's not a very good representation and in fact if you want to understand the activity so Fox so fine a this is actually the best residents structure for you to be destroyed along the it's bothering me that any such move 15 OK so when you see as double Bondo think of it like that this led to the very simple lessons so you don't have strong pipe bombs and it should draw a picture over here and I'm going propose board beckons just drop picture to help you think about the effect of what's what's the impact of having orbitals the very beginning very far
away when the draw up a pipeline of the construct pie bond hearing the Tupi were
warbles of I think about this pie bound for Aqaba it's composed of 2 P warbles like this that overlap and I will face those and the carbon and oxygen are close enough to where you get good overlap that's why you get 75 per cent of a public bond here in Aqaba Neil now it's contrast that with this picture for as for Fox side as Sinaloa had these huge orbitals here this story appeal like orbital and now have this sort of diminutive orbital over here on oxygen and yes the orbital on sulfur is this P like water once offers bigger fish is too far away to give effect overlap so again and overemphasizing this picture just to get the idea that yes the bigger which is too far away to effectively so that it's not really getting get 30 per cent but it's not like a colonial power OK so
when you see this don't treat it like a carbon Hill so let's talk about
some ways in which has doubled Bondo is different former colony in surprising ways if we work so start off with a question mark here to talk about this issue of conjugation where I want it is I want to ponder on this equilibrium is taught America equilibrium where if you just imagine talk Tom arising at key tone like this to where you can have either the double bond conjugated to the carbon for the double bond not conjugated the carbon which is the sides do you think is more stable a number of Adams just isomers of each other the tide left or right others give listening this has a vinyl substituent attached to the Cardinals hasn't little substituent attached to the car Kerviel's with eliminating those fragments I hope that you would guess that this is the more stable and it has conjugation between the prices are he'll the pie double 1 can donate into the empty pistes orbital the carbon on but but that's not the only reason it's more stable than it is from my so if you look at the actual equilibrium here is better than 99 to 1 in favor of the conjugating so I hope that's kind of intuitive but if you're impressed by the power of that carbonyl images remind you it's simple out keen to want to be more substituted right if I just take this simple internal often versus an external event the equilibrium ratios and this is this is an entropy value but essentially very good here still 1991 right so now lie with this so stable wasn't so stable because of the you know just a simple CH 2 gives you the same effect messages more substituted less substituted focus now it's going drop a sulfur system worried and then ran out of room here but we'll see what I can do OK vinyl on sulfur and sulfur so it's still 99 to none greater than 99 to 1 is just 90 91 so sulfur not as good as I can tell you that oxygen very much wants to be next to a pipe bomb not and how we've talked about that before finally will not find that 2 more examples to give you let's put this all hear that looks a lot like a carbon you How much like a carbon Hill is it too well it's still favors the vinyl mesh call this Al although the totally not possible
conjugated system here with no problem with with number that possibility for conjugation between a double bond the soul oxide oxygen that's not starting to be
20 that right isn't that a the little of 22 whatever you get the best of water mixture but Universiade still group wanted to be conjugated that's almost as old as the bravado hates being conjugated in somewhere it's an we'll get to my last example they couldn't quite fit get on there and that's a sophomore is called the sole phone functional groups and you look at that it's like Wow that's like twice as good as the Hill it's got to double 1 no it's not the same as a carbon Yellen is not twice as good as a renewal and so now it's 70 30 where is just a simple H 2 heavily wanted to have an internal level by so is the tendency for you this is for you to think infamy to think that this pie bond is somehow donating into the sole founder of the best double Bondo pie group it priced are in the same way that you get with the carbon Hill and that's not all true and this affected the longer bond lengths here that make it very difficult for this pie bond overlap and can give you conjugation into that sulfur and that's all for functional OK so as double Bondo is not the same as Seidel Bondo and sulfurous farther away from carbon than than CC .period about but this would think about from some other types of chemistry society it never lifted everything here the people of different from that of the International Book or so we spent
a lot of time talking about elites in this class we have carbon heels next to a CAT makes it very easy to deeper made that relative to a simple out came so simple Qaim has a PKK propane whatever on the order about 50 of Macedonia's a pick around 20 and so what about this this is dire medical solve oxide that's a sole Fox I found true that Steinhafel Fox been nowhere near as acidic as a as the protons Alpha to and again if you put a curb on I'm here your tendency will be to want to draw this conjugation arms and money just trying super-duper exaggerate this but tendency wanted me to donate their long hair and makeup C est double bonds but it there is some stabilization but it's nothing like having her
arms having a short bond very close to a carbon yourself against 15 orders of magnitude less acidic for dinner so if
you want to be probe that you need a very strong base like Anelka lithium to effectively coordinate and Guinasso worse sodium hydride which is irreversible OK so that's compares some Thompson carbon lines next to sulfur as we change the substitution pattern when it it's just bothering me not to see lone parents sulfur and the hidden OK so was good and compare the online stabilizing ability arm of several different sulfur compounds or start off the final week there but this and I'm going to give you a number for the PKK pine and other words stuck a proton back on there what would be the PKK if I put the proton back on there would be the PKK that Proton I'm so the case disassemble fire weaker you get some stabilization by
45 a simple a simple out he would be 50 but that's all for digital of 5 orders of magnitude
stabilization of that carbon when note the proposal Fox I there discovered that was again this is picture he drove that's about 35 per cent out of 15 orders of magnitude over just a simple came and we put to double by nose like this you get even more stabilization but none none of these like the key town on Esther the losers good is the key to the so let me just remind you this is called was sold oxide functional group we have just 1 s double bond along sulfur and this other 1 over here we call us it's not a very good oxygen this is called a cellphone functional group so I I use this term so far oxide just 1 oxygen 1
October communities soulfulness to Oxo groups the OK so
character the the analogy to sum the analogy to Carpentier was and is only a slight analogies between festival Mondo NC double bottom of and ions next the sulfur can be very useful for synthesis but not 1 is just 1 sulfur atoms apartments was talk about a very common functional synthesis and that's called a dive buying these are analogs of acid tells he tells so this is called a diet by and this now was to solve problems on that 1 ,comma and is now much easier to be pregnant than just having 1 forever that's not to say that you can use we bases on you still need a strong base like Buda lithium to the probe make that but now this is a very common functional were transformation and that's to metal late next
to these 2 sulfur atoms and this is particular to the six-member brings the five-member rings you can get stable in
finds at that so the PKK this ch depends on the AA group here so but all this while in my hand and it's this group right here so we are is equal to age if have to wages on their the PKK this 31 Guevara's equal to Alco group like methyl Salem methyl NH there it's not as acidic on the PGA is 38 and would draw UK 38 but you can still be probe made this with Anelka lithium affairs and help you prepare so what that does is it gives you the ability to use this a nucleophile CC bond forming reactions so for example if you wanted to do on all the specific here if you wanted to do an innocent to reaction news these present to reaction it's
not very interesting with Mathilde if you much larger substrate
and then hide realize this is usually requires special conditions there's an analogy here too at the tower you can hide realize this really at mercury up strip away this the sulfur ,comma some metal you cannot hide rises back to at key times you can make bonds where this component here axes the carbonized community have anything like that in organic chemistry we have a ceiling and iron so some people call this this species in a steel and iron equivalent is almost like a carbon your carbon is acting as an anime ECO and iron equivalent located to sulfur atoms and provide enough 89 stabilization where you can make an alliance that at these kinds of positions and come back to this so far oxide sold phone the kind of business and
government look at the people from the Of course
we will but the lone pairs on fire there's on sulfur a nucleophilic it makes it very easy to oxidize just about anything any kind of an oxidizing agent and virtually all oxidizing agents Elektra just about any oxidizing agent will react with these lone pairs on the fly with the so anything can do that hydrogen peroxide instantaneous so if you had
1 the equivalent of a proxy acid this could use to make a
pact signed some drop proxy acid there with you can immediately see the week oxygen oxygen bond he lumbers attack instead of making up oxides This is how you make on very efficiently in a controlled manner ourself oxide from from group 1 of the ways he could use hydrogen peroxide so maybe odyssey just a proxy acid with a weak oxygen oxygen but what's important is you can stop here there's still a nucleophilic alone here on the the sole Fox and you can oxidize this again you can stop here and isolate that all Fox that if you want or you can add a 2nd equivalent of your proxy access then that allows you to generate the cellphone if you like another oxidizing agents later that's the important point is on when you got no
oxygen and sulfur more nucleophilic it's faster to put on the 1st oxygen but then
when you put that oxygen on now it's not as reactive as it originally was that's why doesn't immediately oxidize you can stop at that stage and then isolate that orders that a 2nd equivalent and so the 2nd oxidation is slower so does doesn't although not all reactions work like that a lot of times you can't stop in the middle and things continued oxidize on but this this lone pairs less reactive that's kind of what has long pair with the optimum there's less reactive to lawmakers here OK so on and please contrast something and this is not so obvious I think so when we compare these 2 functional groups or maybe I should say contrasted to functional groups if you look at these that these 2 functional groups the soul of oxide versus the sole phone and you think about nations and what I
don't have years they don't have
to complicate prime these and I'm sorry about that so I'll just give you the people generalization and that is if you think about protonation or activation of these functional groups in if I drop some sort of a resident structure like this but this is polarize resonance structure books write draw this out is as is all mine isn't as plus you can understand why it's relatively easy to probe made hisself oxide social plots and oxygen generator the basic and what happens when we put a 2nd oxygen on them it really depends on how comfortable you are so he's a resident structures are not drawing the products of these protonation processes and maybe depends on how comfortable you are with this so what happens if I put this is the alternate resonance
structure where polarized that bond about this other double bond here so if I choose to draw that also is an
ominous now I it's maybe not so comfortable that you the correct Lewis structure for this would have a plus to charge and sulfur the my way of thinking about this is that she may be there's not as much negative charge what you find in practice is it's harder to probe so oxygen and easier to prove made so far outside oxygen it's more an ionic on the so Fox oxygen is that it is a missile from soulful montages if you want to somehow activate a cellphone type oxygen that's very difficult it's extremely difficult to activate cellphone type oxygen on but not impossible With protons so typically the way you would do that another word if you've got some sort of a reaction that involves a softening leading group there is no point in time where you need to probably
those oxygen is to make this a better leaving this is already a fantastic leaving I don't care how acidic the conditions are you
don't need to prove that if you wanted some reaction that would coordinate those oxygen and make them better this is the way people doing the use aluminum which is which forms super powerful aluminum oxygen bonds this is what it takes it takes this kind of Oxo Felicity to get anything to coordinate to these of Axel bonds on a cellphone so if you somehow feel like you want to activate a softening leaving them to make it better be a need to do that and aluminum are taking him in there don't even think about coordinating things approximating those oxygen on a cell phone or a softening of the group OK so on Dahabshiil you just over a single
example I don't know why I should covered this year when I talk about approximation just to remind you of the note of the
nuclear Felicity army of sulfur and how easy it is oxidized sulfur oftentimes EDF by you leave them sitting don't do this but leave them sitting out on the bench opening colossal side's buildup just to oxidation with air so if you treat this with 2 equivalents of MCP so proxy acid 1 are the functional groups that can react to conform Parkside here here dying a very nucleophilic things conjugation triple bond over here and in the sulfur the 1st Bequelin MCP PBA of course goes after the sulfur To make us ourself oxide but even that 2nd long parents over still reacts faster than any normal carbon governed by bond is is still faster that the oxidation of sulfide sites to cellphones is still faster than than the
formation of a pox I'm so so alone here's a reactor the more reactive than CC pipe bombs to a typical oxidizing agents but they're
very easy to Hoxha as far as functional groups so let's think about the big size of alone of orbitals on sulfur like lone pair type with it non-binding the canonical non-binding lone pairs so this is not like oxygen oxygen can lone pairs connectors nuclear files but with nowhere near the level of nuclear Felicity was sold for lone pair viewers take a simple he lied those can do very fast as into reactions with filing that so not surprisingly very quickly generate a soulful neon ions In this kind of an alkylation reaction fall right out here so phony on who what is so funny like got Sony and 3 bonds to sulfur you call cellphone industry bounced oxygen you coulda knocks species so the symmetry ,comma you can isolate soulfully insults not super-duper reacted in the same way as an ox only a mile and reactive and very easy to generate like this initialing is 1 example just introduce some caution here but if you do this exact calculation it turns out that sulfur can also be a good Leading Group and so it'll end up finding is that under typical conditions like mixing these together in acetone you'll get exchange so for example this bromide can come back and do it as to reaction and pop back out the whole group so in other words this is reversible the Rome I can come back in part about was trying to draw -dash like so we can come back in pop back up the aisle Reuben take you back the problem as it can also popped out the metal the Denzel you get immediate exchange among all the species and so this fear had depicted where you can attack the at at the Ben Stiller position in part of Denzel bromide and then that releases this product and the original Benthall group is now missing and of course this can now go back and react with another Halil and have a completely get this horrible mixture of things so those kinds of exchanges sulfur cannot book can also act as meeting proves himself only minds so for a long prison nucleophilic and you can also clear so funny lines through this into actions if you're clever you would put a family group on here which you can pop off awareness into action against so what another common example of sulfur long periods as a nucleophile probably the most common example atrocities during the workout there's a speedy
called a species called by sulfite that looks like this and its related draw both by fighting and I
cancel flights this is the sole fighting and iron so this is called sulfite it's kind of basic Mumbai sulfide is more of a much milder in terms of basic city and important word here the end I that I say was not sulfate it's sulfite and sulfites tells you there's a longer and sulfur and that lone pairs nucleophilic and so if you ever find yourself doing the work up that involves by sulfite sulfite you're doing that because you want to work up your reaction in use this lone pair you know by sulfites assaulted by sodium Beisel fight on any edge as S 0 3 and when you don't in the work of the reaction you're trying to clean some weed bond like an oxygen atom and it's very common to use by sulfites
on to work up reactions that involve peroxides such as reminders of what happens when you treat a Beisel fight with
the peroxide it's the same thing is with a fiery fearing a peroxide Sony tried throughout this Feisal fighting in iron and the strong some sort of a peroxide here but suppose I did nose analysis and I peroxide and I want to decompose and blocked the latter or I didn't MC PBA oxidation and I used 3 equivalent of MCP because I want my reaction to be done 3 times faster so I can go out to lunch and enjoying my lunch well you go destroy the excess peroxide somehow and doing a sulfide work up is a way to do that the people of the book and there's a resonant structures so as soon as they this there's a resident structural as the will look more
sensible to do this now looks like a sulfate sulfate tens of for oxygen and
native thinking alike is resonant structure than you can redraw this like this and analysis looks like Feisal think right that this like sulfuric acid comments sulfate salt OK so so sulfur lone pairs a nucleophilic nucleophilic entirely there's the nucleophilic on foreign soil pH oxides somewhat the nucleophilic unsold fight and you'll use it very often in the lab OK so so prolonged connectors nuclear but you can also attacked its soldiers species let's look at some of the alike and counterintuitive reactivity was with different types of sulfur chloride bonds the people of the
world so I want to contrast the reaction of 3 different types of compounds that have sold for Allied bonds will start off with this species which you've probably never seen before but also to get but there is a quiet evening group we call this a sole field some venal chloride specifically this would be found also funeral chloride and you can imagine that a nucleophile could add to sulfur and displays the chloride and I would be very good thinking so it's contrasted now with the sole final chloride notice how the ending tells us
I'm really really attentive to the endings on I'm not going quite there and really really attentive to the endings on these words so female tells me that there's only talk to Bonds to solve so final
told me that there is a double bond 0 so fine and then finally sold O'Neal chloride tells me there's 2 of those Oxo groups on sulfur and which of these is more reactive towards nuclear files in substitution reactions what followed anything about something like this and don't worry about the whether stepwise amount center and the reactivity of the water goes like this it's faster to attack it sold a little a lot is way pasta to attack at Seoul feel type species so funeral chloride Sophie Nate esters than to attack its sole final
ourself and he'll miss the oxygen is a destabilizing this transition state good draw this
out as a as a concerted type process that's ponder on this transition states further displacement so if if I were to displace this Court and go through a tree or by pyramidal transition state with the chloride is leaving that Bonds getting longer than my nuclear coming in Seoul and is my long hair sticking out over here the lecturer negative substituent like oxygen will destabilize this transition state that's the same effect in any to reaction non-carbon so I put these Oxo groups on here and it doesn't matter where you draw this as sulfur plus 2 and 2 0 minus is the bottom line is having elected negative act oxygen atoms on the year they destabilize the string or by Crandall transition state it's all but trading all by pyramidal
transition stayed the same at the U.S. into on carbon having oxygen substituent on carbon slows down as into
reactions so this is why you see this relative reactivity I'm without oxygen is on there that all fuel system is very very fast to substitute the bottom line is it's slow to add to soften over Adams it's not impossible but it's slow so slowly add the sulfur
groups let me give you an example that you already know what you already know that slow to attack its earlier the
1st several months ignoring himself organic chemistry you learn that it's slow to attack itself anew when you make possibly leading groups and you put them in with nuclear files the nucleophile attacks carbon it does not attack sulfur that's why you make sultanate's so doesn't like this it goes like this and that you never have to worry about attacking sulfur and displacement oxide so you already know that it's hard to attack the typical sulfonylureas it's reagent you've probably never seen before maybe you have this is called sold fewer real chloride it looks an awful lot like a region called solve Hong thank you go I think it looks an awful lot like tiny applied wishes has won over there you sign Florida's SO seal to no 2nd oxygen to make
acid chlorides to convert alcohols and applied with this is nothing like
vinyl chloride when you take this you add this to nuclear files the nucleophile reacts faster with the chloride then it does it's almost it it's it's essentially a reagent to use in place of course the end result here is that you attack a chlorine not that sulfur and so you get sulphur-dioxide as a byproduct in chloride minus a leading group that's the same thing you get if you added chlorine gas so as to that region if you want to not to use chlorine gas but it would end up with the same effect and this has to be totally contrasted with find you chloride in which alcohols and carboxyl gasses react at sulfur and that's not a one-step destined to mechanism to two-step mechanism on focus so not easy to attack at that so world but it's not impossible if you don't have a choice will attack at Salford let's take an example
of a classical reagent 3 don't have other choice for an easy choice except to add to the
soul annual sulfur but maybe it's not fair for me to say that so far no group to Italy and reactive that's not right so is an example I was often a group it's very reactive tussle chloride nothing so often here if you had alcohol calls will attack the government of it was so here how called will attack runs on self-renewal chlorides and the the reactions don't require heating is a facile reactions but there is no
alternative choice here to do it into action on carbon softening leaving so tussle chloride will react
relatively quickly I'm not going to draw the determination that oxygen you don't need to see that here I think you get that it's easy to pull that Proton so you already know that it's easy to to convert alcohols and to toss a lady should know that from your undergraduate and chemistry class on during 1 of our problems that we talked about this this is slightly different and I don't want to go through the differences between this combination of reagents triathlon mean and measles quite goes through a slightly different mechanisms we mention so thing in discussion section don't worry about that at the exceptions generally was self-renewal here like to attack directly it's often include Wells where this basic is is a more basic Basin purity pulls a proton of of carbon 1st so don't treat that as the as the general treat the toxic or like this as the general for
making sold ministers pockets of sulfur diving with sofas very easy to
attack harder to attack itself and the only group's easier to attack its sole funeral and ideal and sulfur Sophie Mae to take species for the fall of the Soviet had to bonds to sulfur in the leading group on their attack can be and will be very fast and sketch out of this is not intended to be my picture of a protein with the dice sulfide bond in their hands and we put proteins that I sulfide bonds inside of cells where there is a high concentration of file and I'm not going to draw this the structure of the file glorify on his job like this there's
assisting group in the tripartite missiles every cell in your body has
about 5 million Moeller glued asylum in their hundreds of substantial amount because the PGA this is closer than 9 in 10 depending on the structure of this about 1 per cent of that somebody . 1 1 per cent of the styles existence violating an inside of your sales In other words you got a lot of of violating 9 inside of the cells in your body and when you put proteins in there there's a tendency to do this and that was sent to reaction is 1 of the few good as into reactions in organic chemistry way better than us into reactions cards it's a phenomenally fast into reaction at room temperature I'm tired of harping on how badly I feel as into reactions overemphasized because is a good
break 1 facet room-temperature occurring in cells constantly this is all in equilibrium so in other words the sulfur atom can come back and
really close and popped it back out the lake back that's not interesting what is interesting is observed that this stuff sort of overlapping here what is interesting is if you have another file inside the cell but it is good to find to come back and do it as into reactions and when I will admit set up what did I mean to say what I meant to say is yeah that's right so what is interesting is that you have another file all agree finally comes in and cleans here and then now we break that bond and our original protein that headed I sold by crosslinking there now has a cleaved files and that good biomolecules that's floating around in yourselves ending up as performing an
oxidized died of course this is probe made along the way I wanted well on managers wanted what effect is no longer so for sulfur bonds typically when you expressed proteins In bacteria human proteins
that are normally not expose an oxidizing America it's more reducing in bacteria and so you're die sulfide bonds at a stable in a normal extracellular proteins on unstable inside a bacteria that makes it very hard to produce folded many folded human proteins inside a bacteria with these concentrations the stylus Ohio OK so into reactions it's sulfur for a diving on solve our fast most into actions Carboneau really slow in coming and they give you another appreciation for how reactive dye violence over before that ,comma finding gasses so you can use soap on a
gas a disaster catalyst the like sulfuric acid toluene so funny gazetted a solid very convenient to
measure up to to milligrams of toluene Silvana gas on the balance not convenient tool to weigh up to milligrams of sulfuric acid this is called a sole Fennec acid I don't know what you can buy toluene soulfully gas from all richer any chemical supply company and as you might guess that sulfur lone pairs nucleophilic he typically don't buy this use this as an acid that's not as acidic as toluene symphonic as he typically this because you want to use that sold for long periods a nucleophile finally get down to the last sort of representative here nearly a substance you've never seen I don't think you've ever seen before maybe this is called a sole female gasses the notice how the ending here in it so phonics often excel
feelings so fitted with sulfuric acid are not stable you can't isolate a sulfuric acid is
solved fast to as into substitutions at this diary on sulfur whenever you have sole Fina gas solution they react with each other this overlong bears on mourners as they collide with each other as you wrote about being things down these collide and you simply end up doing a displacement and so what you actually what you end up isolating in the end is not your sulfuric acid but because other styles all fine the product because of this reaction being so facile so as into action deplorable accepted sulfur and in this case extremely fast to the point where you can't isolate certain assets of so feel lines are extremely reactive even with simple CCW bonds so if I take a simple carbon-carbon double bonds and I have diarrhea so With the leading group on there but it's so fast U.S. into actions that even a CC double wilderness into reaction this starts to look a lot like of rumination reaction so as I take my double bond I started to innocent Judas Priest that chloride is sold speed is getting closer and closer and as I start build Koble kind character is long as all the the Carbol can I and I don't want that to happen and it comes back and attacks so this is like when you treat would be are to work or or chlorine you get up ammonium ion Recycling Co Aronian in the same way you get a cycle extreme member during ion here it's not the Parkside it's a so far only a mine with 3 months sulfur but it's important that it's a three-member
terrain so people right at the here's to emphasizes the relationship to the Parkside at the soulfully a Miami and you can probably guess that this
reacts like a broom only a minor according you attack occurred nuclear files will attack a car that was happy so phony minds so if chloride was Group still come back in an attack and these will be to each other and in the product and of course the irreversible you can isolate these but have a tendency to want open back up and go backwards from the dainty edition is peaceful falling minds you have to use other leading groups that are not nucleophilic on so it doesn't always have to be a softening so again diving on sulfur very fast as into reactions together 1 last reaction to cover here
I Miss call upon the oxidation of sulfur oxides like I can't talk about sulfur without talking about the reaction the primary
action simply reminds us of the fact that sort bauxite oxygen so basic a nucleophilic Sears a classical ,comma reaction the way you would use it it's very easy divided by a week there it would be very easy to convert that into a ourself oxide the end result from a upon reaction this year trying to convert that group into an outside group and so what you end up making in the end is this species this is a mass fire Lassiter was very easy to hide eyes that we so I have I'm not going to draw the conditions with acid or basically this 1 alibi I just wanna try that direct number of cartons let's talk about how you do this transformation from a C H 2 group here to justice ch like acid here that's the key that's the key thing to recognize is that I started off with a CAT to and in the end of oxidized that's what you do is you treat this with the CD can hydride purity money draw obviously cannot drive that's a very powerful electrified the princes of purity begin generate a slow period in you my hands were treated more powerful electrified aisles ultimately result bauxite pairs are going to attack something in the absence are in low concentrations of purity and you simply get this and you end up getting circulation Of the so-far Fox oxide oxygen hands and wishing that I had drawn their solely to scratch out this bond year cannot draw in the other residents forms so hard
electrified I'll like in a steel group a recital group I would expect to attack oxygen faster than the sulfur and that's true it's about
soft electrify like methyl iodide without a lot of charge on the carbon atoms and I'd expect that to react at the Seoul for long periods but with a steel groups in Silicon Guinness Flight direct faster on oxygen not going to show the detector he drew intermediate here and so when you do that you now have a leading group on sulfur and that can react with basis so in the presence of other base like period Dean of this rate be hearing to be symbolic and all drawn as innocent reaction and I don't even know whether this is a concerted elimination on the 1 CD were initially made the sole finally a nine-year that the Caribbean island and then eliminate most people draw this as as a concerted to elimination of another area to indicate that I don't know
whether that's concerted so ultimately would you not ultimately Penn ultimately you get this all phonemes species looks kind of like a car so probably it's not so
surprising that you can attack there's not a lot of my character bond with tenacity In order to generate this now oxidize carbon atoms such called upon reaction Tuesday oxidized sulfur species to the equivalent of Allah and shows you the nuclear felicity of oxygen towards on carbon atoms that have a lot of partial positive to focus would like to stop right there on and on a comeback on Friday we can sort of shift a little bit over the granite table of phosphorus concerned about some cool reactions of phosphorus continued
Chemische Bindung
Elektron <Legierung>
Fülle <Speise>
Bukett <Wein>
Multiple chemical sensitivity
Nachwachsender Rohstoff
Chemische Industrie
Funktionelle Gruppe
Weibliche Tote
Aktives Zentrum
Aktivierung <Physiologie>
Setzen <Verfahrenstechnik>
Oxoglutarsäure <2->
Spezies <Chemie>
Schlag <Landwirtschaft>
Substrat <Chemie>
Organische Verbindungen
Schwefelorganische Verbindungen
Monomolekulare Reaktion
Chemische Forschung
Transformation <Genetik>
Chemische Forschung
Konkrement <Innere Medizin>
Chemische Verbindungen
Chemische Struktur
Weiche Materie
Systemische Therapie <Pharmakologie>
Schweflige Säure
Aktivität <Konzentration>
Einsames Elektronenpaar
Potenz <Homöopathie>
Chemischer Reaktor
Eliminierungsreaktion <alpha->
Chemischer Prozess


Formale Metadaten

Titel Lecture 19. Sulfur Chemistry
Serientitel Chem 201: Organic Reaction Mechanisms I
Teil 25
Anzahl der Teile 26
Autor Vranken, David Van
Lizenz CC-Namensnennung - Weitergabe unter gleichen Bedingungen 3.0 Unported:
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DOI 10.5446/19234
Herausgeber University of California Irvine (UCI)
Erscheinungsjahr 2012
Sprache Englisch

Inhaltliche Metadaten

Fachgebiet Chemie
Abstract UCI Chem 201 Organic Reaction Mechanisms I (Fall 2012) Lec 19. Organic Reaction Mechanism -- Sulfur Chemistry 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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