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Lecture 14. Introduction to Amines: Properties and Synthesis.

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I Goodmorning out well I feel we now come to a very nice place in the course of giving working extremely hard we've just gone through what I said I
felt was really the intellectual pinnacle Our southward chemistry we've been through a very rich collection of carbon chemistry you've experienced it would be more late need all chemistry on this question In this week discussion you'll be getting reinforce some of the things we talked about in
class last week with all of these wonderful reactions the Algol reaction that Clayson reaction of Michael's
reaction the Robinson undulation reaction to all this ability to recognize interrelationships of molecule beta hydroxy carbonyl compounds alpha-beta unsaturated carbonyl compounds 1 3 died carbonyl compounds 1 5 died carbonyl compounds and cycle had seen and so at this point Italy's this far in the lecture part of the course that's behind us and now you're going to be working on that and reinforcing these concepts through the discussion section and the homework problems in our last so we come into the last few chapters of the the class and I think this is a fine point the course we've done a lot of hard work were still going to have a lot of nice ideas this week we're going to be talking about the chemistry of amenities and in some ways course like this this is this is neither here nor there chapter of the class because you've got another big richness of the the chemistry of the means already learned about their reactions to mate and you learned about the chemistry is acids and his bases you some generation never means when you studied aromatic chemistry and electrical like aromatic substitution so in a way this week chemistry is a bit of a refrain will see a few new cool reactions some call syntheses sees a few mechanisms said next week we're going to come into the chemistry of carbohydrates and carbohydrates are going to bring in some carbon geochemistry will see chemistry of acid towels and death and the formation and the breakdown will see some chemistry of the mall Quito talked of summarization and some acid catalyzed
reactions will come way back to ideas of Styria chemistry we got a little bit of this as we talked about some of our summer of all chemistry we reviewed some ideas of any Indian merchandise emerged and you'll get more that out try to
bring in some of the molecular modeling that we did if things work out right maybe I'll ask you to bring your computers into class or think about that next week would be prepared to maybe bring your laptop in next week and then the final week of classes looks looks like it's going to be a big thing because we've got a couple of chapters I wanna pick out a few highlights I guess this chapter think by remember the numbers this Chapter 20 and I may have the numbers wrong but there's a chapter on amino acids peptides and proteins and some of this is going to be redundant with your biochemistry chapters I want to focus on 1 aspect of that which is another real intellectual pinnacle of of organic chemistry and that is the solid phase synthesis of peptides and will bring in some nice reactions you'll see hammered bond formation you'll see some concepts of and instability of of an ions and you'll see a really profound idea of being able build up molecules repetitively step after step biologically important molecules molecules that are all sorts of things hormones that lead to uterine contractions in the pregnancy and then birth and so forth and this was 1 of the intellectual triumph and if everything works out in our time in the last and I'll give you a selection from the objective and checked the selection of work done and if everything works out right now very last class 1 of my big laments in organic chemistry is that a lot of the really modern concepts and in some of the chemistry you're going to see goes back more than 100 years we've talked about some of his chemistry off in some of the reactions we it's just like the elderly reactions to the planes should fly if everything goes right in the last lecture will get just a taste of organic metallic chemistry not going I mean we've already done green yard chemistry but chemistry in which medals connect his complaints form carbon-carbon bonds so we'll see how things go so today I want to start by talking about means and talking about their properties in the city season means a
really cool molecules of really important biologically the president so many biologically active natural products many of these are called alkaloids and a produced by plants and I want to drive out 2 of these molecules and I want you to draw along with me they look really hairy from going to draw driveways the first one out Russell
looks really really so we're going to start drawing benzene ring life and we're going to connect that to the besides little hexane range will make it a cyclo Hecht seen rings for those of you who wealth for everyone here you'll know my handwriting is no great shakes and yet a few simple tricks like being able to drive hexagon being able to drive deadline really help for going to connect these 2 brings together by way of and ether linkage from the benzene the sidewall hexane ring and also some mystery at chemistry over will put on a couple of hydroxy groups 1 on the benzene ring and of course there's no scarier chemistry on that hydroxy group and then we'll have another hydroxy group it's going down the other words in history chemistry going down will draw on 1 more hour six-member drilling here so far everything is pretty easy to visualize now we got some overlapping bonds son going to plug a Bond film legend of a line coming out of the black to a nitrogen here and again if you're good at drawing hexagons you can do a lot of things and the rest so will have another bond off of the nitrogen get a show the bonds coming out all over here like so connect that to the bond to the nitrogen so crossing if you wanna get fancy and people are really good can do this beforehand if they just planted drawings are not really good at drawing the put a little break in there to help indicate that we're going evolves so so that doesn't brochure bond it's sort of a way of drawing perspective so you've got that will set out so users stereo chemistry over here hydrogen similar finisher molecule walked by putting the matter to the group on the nitrogen
said he would know what this molecule and Australia it said that the pope more clearly the studio had enough but hardly OK so I didn't see more freedom in the chapter I saw OK so great
and that's the really important molecules of organic chemistry and what I teach my graduate level spectroscopy Forsyth tell the
students that it took 10 minutes 50 years to determine the structure of morphine and now this is something that our graduate students can do
in the force of a new unit didn't seen were being but I stopped at least 1 related compounds in the chapter
1 thing is part of a family of what are called alkaloids alkaloids nitrogen containing compounds produced by plants morphine in particular is an opioid it's produced by the opium poppy incredibly important in pain relief after you know it all decades upon decades of pharmaceutical research when you have a really bad pain terminal cancer pain and all sorts of horrible things more green is still the drug that is given of course an opioid it's an addictive drug by you some point of view of terminal cancer doesn't doesn't matter many of the synthetic drugs that also were contained bind to the same receptor in the brain and it's really hard to seperate pain relief from the ability to get addicted the 1 I saw the chapter I've never taken
more green myself as a driver in any other context the 1 that I've seen is a chapter has amassed group over here if you have instead of a hydroxyl groups you have a matter that the group that's another opioid it's coding great cough
medicine I've taken that 1 it's a potentially usable potentially addictive morphine and opium of course are widely sought after I mean we've got tremendous trouble with drug trade from Afghanistan and so forth were poppies grow but what really makes morphine unfortunately valuable as a street drug and highly sought is its dire satellite shared in
other words if you take morphine and you treat it with acidic and hydride you get the guy ascertain over here and over here as taxis with anyone that heroin and very easy
to make perilous so as I said morphine is at and its specific delay
after Sharia me in the nitrogen with 3 groups on it I wanted dropped 1 other alkaloid textbook really goes to the town talking about everything from
neurotransmitters like opening and Stewart Sira told into nicotine and other addictive highly addictive compound to I'm all sorts of other molecules for
Armenians permit so I'll drop 1 other molecules based on a cyclone heptane hostility still drawn out that skeleton also you little trick of mine as well so we not enjoy a cycle hexane rain but I can assure you that
everything else you've been fate if you can drop 1 so the 1 on the side collect structure that I like to be able to draw on his nor warning of and if I can draw this
it's a cycle saying a boat with afraid if I can drive that I can sort of fake everything else because the structure that I'm drawing now is basically nor borders with 1 extra methylene over here and you can take it and we have in the British position nitrogen Mathilde from methylated tertiary mean group just like we haven't morphine don't think this once a new textbooks of it will have a methyl ester group over its disposition will have the things so we'll group over this position you
know what this molecule of cocaine I have had that
1 medicinally when I was in college I used to get
terrible nosebleeds and so jittery that apparently the treatment involved some silver trade up your nose but before that it was preceded by the simple case of nose that was another 1 I used in my graduate level suspect class 1 of my colleagues is authorized to have a bottle of cocaine for research purposes as very happily walking around with 1 gram bottle of cocaine that was to to become the final exam for graduate students far-right
itself at this so all of
these compounds significance saying how I'm 1 of 1 of the cool things about this is that by this point in the course you should be good enough with functional groups so when I go ahead and from the big hearing molecule like morphine and I say Yeah we treat it with acidic and hide right even maybe your textbook examples might have included treating I isup open all With this edict and hydride forget isopropyl acetate you can understand that these same principles of reactivity apply you've got a basic amino group and there are the amino group is going to behave as a base you can extract alkaloids tech Aquarius acid solution by appropriating them and then you can go ahead and remove various impurities and then go intrigue would face an extract back into organic solvents even recognize the
function of the free of investor group over here OK cases that there is a tertiary means but has opposed the group is a tertiary Amin will move in the right to Shearier meaning that just write a generic
structure or really had an activity so so fussy as to go are 1 or 2 or 3 and but of course you can have 3 different groups we used her Sharia means as reagents you've views triathlon mean that as a base the
tertiary mean of course has 3 different carbon atoms attached to the after the nitrogen adamant along Paris well on the nitrogen a secondary Amin but again I'm not going to be so fast has to say all our time or 1 or 2 but you have to our local groups to our groups under nitrogen to Providence containing roofs you already encountered review is certainly again and again in our in our late chemistry we use this meeting we've used apropos of the secondary meaning state primary meaning by the way you'll see people write 1 know what were primarily to for a secondary for not for tertiary that's fine too I don't know for a primary means of course were talking R & H 2 0 here so I'd give us an example of methyl Amin of the series 3 H 2 but but now Of course 1 thing is to keep in mind is there is a fundamental difference
between talking about a means and talking about alcohol so we use the notation primary secondary and tertiary for alcohols of course were talking we always have and always right when you go
ahead and have to are groups on and off the connecting 2 different classes of compounds but with alcohol as you say OK ethanol is a primary alcohols I support the known as a secondary alcohol Putin also tertiary alcohols that's 1 thing that's different alright I wonder
what maybe show us a couple of Al-Amin said these examples here all alkali means that there's some real differences in reactivity and even differences in the structure and bonding of aromatic it means an aliphatic mean so just show you a couple of Arel Carroll means so the Kurds the
chemistry of means is sold so many of these compounds have
common names that are used in preference to arm may be a more systematic name in fact the common names have really gotten wrapped into the systematic name so you wouldn't call that compound no 1 no chemists call that compound panel will mean or no benzene they'd call it at all when they get
somebody could call at a you know the incident certainly if it's the substituent you College college after a that a 2nd but I'll just give you 1 1 other idea for substitution I don't think we're going to be used as systematic maybe in a discussion of nomenclature as we've
been with some of the other compounds in part because it means people differed so much from systematic nomenclature and how they refer to them so if we're going to refer to
substituent Southern nights and people just part of the capital letter and a few typesetting it he said it I I came to this compound has 2 9 2 to methyl group on nitrogen so this would be an end dimensional and for what
maybe I give you 1 1 more examples of you have memory I talked about substituent so I said OK if you have like a carboxyl against City in general things are substituent so so for example if you have a hydroxy group and carboxyl attested in the long chain Alco group you'd call it a hydroxy acid evader hydroxy acid and used 3 hydroxyl traditionally answers similarly in terms of writing and in terms of priority the amino groups
this pretty far down the totem pole so if you have a Keatonâ you have and how the hybrid you have a acid in the molecule overnight you're going to be naming it is an amino substituted molecules so this molecule here 4 of which the but we don't need him as an animal when we call this P amino insulin-like unlike answers for 4 I saw 1 of the
things that's really defining about it means is a matter of practice Friday by the 1st through 2nd word that I would think about when I think about it means it is the basis for the finals also the
think problem is the nucleophilic we've already seen lots of their chemistry as bases and 2 good chance to review and
also to straighten some concepts in their minds so we always think of basis city we think of the PKK of the conjugate acid as a measure of basis so the
PKK of the conjugate asset of an alkali meeting
something like fire Philomena dies of Pope Paul VI for methyl Amin decay
of the conjugated instead of just write it in generic form and so like this to decay is is on the order of 10 to 11 of the few numbers you should keep in your head that's 1 you can keep 10 you can keep the lightening people doesn't much matter no what a lot of students find confusing and I hope I hope I hope for at this point you don't but it's always good to have a reminder to get things in Europe straighten your head is that if you have a longer or you have a primary or secondary Amin all of these compounds are in for a terrorist but it's very important to keep the straight our ahead so when we talk about dying Isa propellor lobbying and we talk about making LDA were thinking about a completely different people every so we know Dyess approach will mean when we think about making out the area we say all the people it is about 400 at a cost of adoring and I hope I hope I hope by this point that you're on top of this is worth thinking about 2 different equilibrium 1 in which the amenities of the news and have said so when you take the ice of problem in and say you lithium we have an equilibrium outlined so far to the right that for all intents and purposes I barely think of it as In equilibrium where we get Dyson probable Menon butane and hear what we're saying is that are certain to according reacts with a very strong base to give a slightly less strong base and conjugate acid called you with in his butane people about about this now ,comma
slain by the time they're going to do indeed we worked up on an LDA reaction be using some reassesses like Gateway SHC now
which our ideas is H Rio plus speakers agency such a strong and said that its associates fully in water you're going ahead and you're trading in Europe the dies improbable Amin candidates Rio plus PKA 17 of negative 1 . 7 and now the approach laziness so now and again you have this equilibrium that lies so far to the right that I'm not even bothering to write it as an equilibrium we're now we're talking about say God give you an exact number it's a lot happens be 11 in this case the begins his parents so that equilibrium lies way way
way to the right now once saying it's important to keep in mind In avoiding confusion is there's a huge difference between means and the men in a means you have a
nitrogen that's pyramidal of the services and amenities and it has a long hair an Alcoa means it has a long hair that CNN sp 3 word at all but but but but but but but but but confirmed how Colombian it's not participating the
electrons are not participating in any significant residents and so that won't care is available at the now to where a lot of
students get confused the 1st time around is leading in comparison to enemy since alternates a generic and but of course costs could be in this case Steinhafel was set by now the huge differences yes you'll have a lone pair at the time and nitrogen but that nitrogen is tied
up by residents so it's not available the lone pair is not available if I have to characterize Hamid's
I'd say sampling not basic not exactly true their basic but very weakly basic PKA a sort of into the negative range negative 1 for the conjugate says but they're not basic on nitrogen the lone pairs on oxygen that actually approach made that long Perez tied up by knighted by by residents and in fact because you have a good degree of double bond character for all intents and purposes yearlong pair really is more life as featuring hybridizing United is almost pulsate mold till the approximately planar just think of it as player and think of it as approximately P 2
so I want to make a comparison between the meanest like dice of probable Amin and Triathlon meaning methyl ammonia costs on meeting but basically the parents of the the same family much as water is the same here is the parent to alcohol and means that have aromatic groups in them so when I draw
111 we also have the situation that in some ways it is like our Amit you've got a
nitrogen with long here but that long tail is participating in residents the lone parents donating into the aromatic ring you learned about Electric fell like aromatic substitution you'll learn that amino groups were worth power directors said they were pushed electron density to be worth knowing Parra positions of an aromatic ring and in turn the table to stabilize a positive charge that from 1 during the electrical account had a substitution
reaction so long hair is tied up by residents but but but but but but but but but but experience it's sort of halfway between the degree to which it's tied
up by residents of committee and the degree Part 2 which is available in a simple aliphatic amino simple Alcoa mean that PKK of the conjugated has said so that we can say that this is a
parallel perilous just fancy word for aromatic and the decay of if you wanna ride it has the aura In a 3 plus the conjugated instead of a generic Darryl means could be analyzed variable that by substituent there were talking about 5 books not the size and so in other words not
not as basic as animated but not nearly as basic as an there are other nitrogen containing organic compounds there are all sorts of nitrogen containing Hatteras cycles and some of them you should already know from discussion of aromatase today in structure and bonding so for example
Fiorentina the is the nitrogen analog all drug alone terror here just to be very explicit this is a period in the region using it as a reagent and some installations reactions parodying is the nitrogen analog advancing the
nitrogen is participating in the aromatic ring system and instead of having a ch group that has a long hair of electrons the but the lone pair of electrons is
SPQ hybridized but at the end of the remember when you use more s character you hold your electrons closer
to the nucleus that makes them more stable less willing the share so when you use more as character parent less available to bond to a proton that lone pair is less basic unless nucleophilic than a regular meetings so that
PKI period Danny on the conjugate answered of period Dean .period innumerable ions it is also about PTA of followers I want to give you
1 other nitrogen containing Harris cycle 1 that you've
probably seen before in your discussion of an In this nitrogen containing Hatteras cyclist parole now ,comma also another 1 I think that
beginning students often find confusing because you look at that he said others alone pair of electrons on the nitrogen it looked like it was To be based and that all terrible like and ends up being
part of the aromatic spices than that of the prison result if you probably made it you're going to give
up a ton of residents energy that long hair just like the lone pair an animated is for all intents and
purposes not basic tore all can
program a thought would approach makes it actually ends up probe mating on carbon not on nitrogen so thoughts questions at this point yes White if there so OK when we're talking about basis and this is the 3rd in the world is talking about with the concept of a of Stamford when you're thinking about how basic something is you have to throw a switch in your mind and say that means I need to think about the conjugate answered when you're talking about how acidic something is so we're not discussing the acidity of parole then you're thinking about OK What is the What are we doing to give up a proton and the kinds of things so remember in your mind's eye when we're thinking about the success of the of football
on languages you're thinking about this species here with 2 protons and you're saying all where goodness I've had to give up all of that residents energy all of that Arum excessively that terrible that doesn't form parole
doesn't have quite as much resonance energy has been seen so you don't have it's not quite as approach made on the ring and it's very reactive in elective Billick aromatic substitution now OK so so as I said to me the basis of really characterizes the meaning and the other thing if I had to think about a means and sort of say what do I think about it means I'd say tell that to some extent I think
of them like alcohol but unless so in everything except the basis of the animals show you what I mean in a series of discussions of properties in spectroscopy so it means they're kind of like alcohols but less so they're less polar then alcohols the vendor Wal there the dipole dipole interactions are weaker the hydrogen bonding is weaker results they last longer than a local malls in less hydrogen bonding 10 alcohols the few compounds it's tender worth having been your head as a reference point methanol or ethanol a sort of big ones you probably work with them in laboratory you should know that methanol as a liquid would you don't know the exact boiling point you at least would know it's of volatile liquid boils lower than water it happened several boiling point of of 64 highly toxic in the lower boiling point and ethanol but not that much lower and unlike ethanol it causes blindness president and has not been flying drunk so if I compare saying methyl means which it said OK it's about the same way it should have no doubt the same it's about the same size she should have about the same vendor walls interactions and so then differences are going to be in hydrogen bonding and dipole dipole interactions so methyl Amin by contrast is against another words the molecules don't have enough interaction with each other to cohere into a liquid at room temperature it's a gas until you call it a negative 6 at atmospheric pressure of course if you have a higher profits liquid now by contrast again the simple compounds if you look at something about the same size of things you look at Athens again it's just too big a you know to heavy atoms to 2nd row Adams has about the same size in the same way but you don't have a dipole interactions you'll have been the walls interactions you don't have to be binding affidavit of course is aghast at boiling point is negative 88 degrees so by the time you down to a molecule of that size you really have to go cold elected this in it's a welcome is like halfway between methanol and are staying in terms of its interactions it doesn't hydrogen bond
as much it doesn't participate as thin as many dipole dipole interactions with strong guys hold dipole interactions and not surprising ways that tracks with Electra negativity because all the negativity
is basically a statement of the property of elements and some nitrogen is less electoral negative that oxygen nitrogen the electorate negativity is during the period .period called and oxygen in the Electra negativity is 3 points for of the another words the nitrogen polls the electrons away from the hydrogen last Sunday a hydrogen bomb blast you've got smaller died polls and the molecule and so for both reasons that shows and you can see this in itself you want now separated out the hydrogen cyanide compounds from the dipole dipole component or give another comparison so delicate time FOR mean CH 3 3 nitrogen so that's gas it's swelling .period always just above freezing of water it's boiling point 3 degrees and if we compare it to something comparable in size the butane now we have a lot of Wyoming .period although not that much longer to CH 3 CCH incisive butane virtually the same size and shape as Streisand as trying that and the boiling point it's also was the asked the boiling point is now negative 12 degrees so you can look at that and say OK we've got we've got dipole dipole interactions in try Madeleine and those raised the boiling point a little bit over price of butane and just as in the walls in July but it's not in use different items
sold so many ways ,comma means of are lesser versions of alcohol use it's currently in terms of what you see in the media in the spent part of the cost you you get priority you're not going to see it but we actually look at Real IRA suspects the CIA itself any of our
spectrum you have been in age stretched the stretch is essentially at the same place as alcohols Internet region about 3 thousand that region kind of around 30 302 30 500 sold the animated stretch but also it's like always stretch In other words don't typically say further text that you can use 33 in my graduate course I give more beautiful but you can use 33 135 100 numbers but would you look at actual spectrum what you see is
the bands a lot weaker now you're not going to see the excessive but maybe you will of the citizens spectrum the rumor but what I mean is an alcohol really stands out really yells at you and I mean kind of whispers you can look with a smaller mean and you go ahead and you say Oh yeah I can see it but by the time we get to a big compound with an amino groups it's a very very angry if you have a 2nd if you have a primary amino actually banned
the correspond to an asymmetric and symmetric stretch the other thing in your text doesn't mention his right I always
when I read and I are a spectrum I generally look at the region from about 1600 on up right at the very bottom of that region there's an NHK and so it's right about 60 Nunavut but the
gates just below it the thing that I'll mention to you since you may see in your lab costs amid see
1 of your homework courses about homework problems it's just below where the carbon Eurogroup group occurs so the carbon group we said normally about 1700 but then we said parameters that can be about 16 50 years 660 yourself and this is just on the lower edge of that some reading this spectrum you want to make sure you don't think about alright Panama's Spector again this idea kind of like an alcohol but less self comes up with list of how I organize it my own thinking so you want and need To me what I'm thinking about
and alcohol the normally thinking about the hydrogen is on the carbon next to the oxygen and so on taking all that sort of thing we therefore ppm the kind of a range of you wanna keep 1 number in your mind that give you more detailed number but when I'm thinking about enemy and again I'll just sort of writer generic structure and nitrogen is less Elektra negative it's polling electron density away from that
hydrogen less and as a result it's not shifting it as far downfield so generally the hydrogen Alford to an oxygen and alcohol are going to be kind of these 3 ppm Range in mean it's going to be in the 3rd through 3 Ranger textbook gives 2 . 3 Authority which I think is a
good sort of general general assessment but remember those those are always lose another words after loneliness to fly out to 3 ppm by the time you go to a more seriously congested grouper more substitute lifestyles of health kingdom was 1 to with 3 2 here on the eve of an so it will we talked about alcohol when you talk about alcohol's inspectors said they were all over the map due to hydrogen bonding in kind of the same thing about the nature of its new text but didn't .period the feisty the out and that's a good general store unless you're
narrow-money like an animal in which case it's going to be a little bit for a little further down but the NIH is often very broad and hard to see and so for those of you will go beyond the text of a lot of course
also often broaden hard to see invite and taken on a more spectrum and you may be looking for the NIH
and say all this can be and I mean I don't see an NIH and in fact it's just that the NIH so far brought down in the
sea 13 animal on the carbon 13 animal respected again were sort of like an alcohol but less so in other words for an alcohol I think for the oxygen down to carbon all about that in the 70 pct of of it's pretty characteristic because by that point you're down far enough and the carbon you're away from everything else for the media really not that well separated the carbon that down to a nitrogen is in about 30 to 50 ppm Range which isn't that far from other sorts of problems that
may not have elected negative substituent on them all right so that it gives the quickly view of the spectroscopy about means preventive properties in as I said a lot of what we're going to to see particularly today it is the refrain of some of the chemistry you've seen of means before like in the aromatic chapter so In the synthesis of a means by way of a quick
review you wore that nite tration that Elektra fell like aromatic nite tration was a
very common reaction in a way to substituted aromatic group and the nice thing if it's really really easy to
reduce the nitro groups but in the text of
its 3 different ways but I can give you a hundred different ways to reduce the nitrogen and I
flew down to an amino group saying attacks were taught you that catalytic hydrogenation with hydrogen and palladium on carbon can reduce the nitrogen or you can use a metal medals or reducing agents in general
metals want to go to a metal had ion the 160 electrons so
tired and hydrochloric acid and hydrochloric acid visa 3 conditions from the text for of federal good ways to reduce the nite group on the Internet for them too the Nunavut aliphatic
nite throws a little harder to reduce that they can be reduced by catalytic hydrogenation is well under under slightly
different conditions of you've learned that lithium aluminum hydride reduces everything and anything we saw
that all the carbon groups got reduced down esters Skoda alcohols carboxyl against its total alcohol the tones and held alcohol and the all evolved in the chemistry of lithium aluminum hydride
was that because it's hard to kick out the nitrogen in the reduction process you reduce U.S. hydride Genentech traditionally intermediate you end up forming a bond to a aluminum your nitrogen kicks out the actions you add another equivalent of hydride until lithium aluminum hydride the airline a each quarter followed by a year's worker reduces most standards down to a meeting with
lithium aluminum hydride refuses just about everything except carbon-carbon bonds in general
and so nite Real's also get blasted down to a means of life takes a stand so nite tree all and I subjected to the same condition the soldiers raided Euromark here you get the level means some mediately it can start
to think about ways of making a means for you could start with a carboxyl against making review the admit to any to enemy in the 1st start with far lies you would have to displacement of sodium potassium cyanide together tonight trio and reduce the means to prevent primary reduce the nite flew to primarily alright itself 1 of the other analogies I like to make his nitrogen oxygen are very similar In a lot of the structure and bonded nitrogen of course forms Greenvale has 3 valence these oxygen has to balance and sees other differences nitrogen is less a lecturer negative enough oxygen sole compounds with bonds to nitrogen end up being less selective like with double bonds to nitrogen and yet in many ways you can see similar
reactivity so in the broadest sense about abstraction if we have some car video compound the town around the time if it could be shipped put in the in the broadest sense of abstraction if we envision setting a hydride nucleophile authority go and get
hydride anymore than you can go ahead and get the car back and I but if we take some hydride source alright this
as hydride stores just say have a two-year note of course you reduce after some sort of a Prius work
up you reduce it again were talking very broad abstractions here you reduce your feet 2 or you're out the hide to announce before now by a similar change and if we
have a carbon nitrogen double bond followed in medium and the mean of acute out the hide and again we have some type of hydride source each minus clothes during games European means to an end the like self very much by analogy now this chemistry
often get put together where 1 can carry out the formation of a new meaning and the reduction in that process is called
reductive elimination of euthanized making means them so again in sort of a very broad view from 30 thousand feet at distraction and if we have some sort of carbonyl compounds and some some foreign age 2 mean and we envision going ahead again reading with the right people I'd ride under the right conditions you can bowl former and reduce the Amin often by way of union on all in the same part of it
Our the reagent that often used to achieve this transformation is sodium Sianna bore a hydride NAB H 3 CTN but now we've
already seen various hydride reducing agents
using lithium aluminum hydride you've seen sodium were a hydride you've I believe seen lithium try as tried to hurt you tops borrower hydride and they all have a slightly different properties lithium aluminum hydride has that aluminum hydrogen bond that's very polarized you wind up with a very potent hydride source for all I is less electoral positive it's more elected negative than aluminum was selected positive bond in this polarized a milder hydride source so and Sianna bore hydride hears same
hydride and used in many ways like sodium or hydride but less of the same group is electron withdrawing its
polling electron density away so sodium Sianna borrower hydride is even less willing to donate a hydride and that's good because it's not good enough reducing agent to reduce 6 seats alone but under the reductive amination conditions you form as the intermediate to form an Panamanian lying of the many of
Miami during the year is more elective like and so sodium or hydride can had hired ride to the media Miami in the course of the
reaction and so often in 1 pot you can mix a key tone and an anti-American tone and ammonia and sodium scion of our hydride sometimes with a little bit of a mild acid like acidic gasses in order to go ahead and form an so
if you take things out of the hide him we treated with ammonia and sodium cyanide more hydride and Navy the recently ended you know that there is eliminating formally in a rather forms transient lady and undesirable hydride and right to that and reduces it to be you can do the same thing with the toner and Ronaldo heights I'll just give you 1 more example if you take cycle Hecht's alone and you take I don't know let's take me opened the loneliness and example to fuel 1 means not Pennsylvania Turkey as an example and subjected to the same conditions stalled astride over here now can form a secondary Levine I think so
economists viz I've emphasized all along I like to be able to build molecules it's useful to be able to take simple stuff and make it into more complex molecules guests including cocaine which 1 can synthesize chemically and work with the nitrogen atom is a beautiful lynch pin form since this is because the nitrogen atom is nucleophilic and so it can and as a nucleophile Union arson to displacement reactions so it seems like it would make sense that a useful way to go ahead and build up complexity in a controlled fashion with the alkaloid that nitrogen but it's not so simple usually the product of the reaction which is also in really an ammonium
salt in equilibrium with usually the product of the reaction is even more nucleophilic itself I take bends over me and I treated it with methyl iodide CH 3 online even if I use 1 equivalent you'd say Well that should be easy reaction I should just get the model methylated product and the problem areas as the model methylated forms product forms by innocent you displace reaction of protons come on Proton fell off as the reactions proceeding you have be president and so now you have not fallen so you will also end up getting so so you will also end up getting the dining out collated and try out related products as a mixture the tryout related the events will try methyl ammonium ion which is actually used as a journalist writing things like eye-care products so the overall result is you get a mixture of products and so if you
say All I Wanna Be smart I know how to make methyl benzoate mean all ideal would be to treat methyl benzoate my Denzel Amin with methyl iodide and then do a basic work out the problem
is you generally in this isn't always true but you generally cannot get online about the latest product unit controlled so the biggest
problem the big problem is that once they are sent to alkylation has occurred the amino group wants protonated that protons come on and off under the reaction conditions the amino group is still nucleophilic and still available to undergo alkylation in fact it's even a little more and more nucleophilic so
imagine for a moment that I wanted to go ahead and do an essential reaction unimagined comments that I had hacksaw bromides and I wanted to read it with ammonia and I've already said on a previous flak word and get a mixture of products the solution that chemists have developed is to take away
the nuclear felicity of you mean after it's done the alkylation to make it so that it's no longer nucleophilic and the solution to this is called the Gavriel
since this is the primary means of minutes to use pneumonia
surrogate the ammonia surrogate is Salomon creates
th tail light and on the scenes in the inmate is like an animated with 2 carbon
meals under nitrogen is the nitrogen analog of Anaheim the proton having to carbon meals
next away these extra sitting in based like sodium hydroxide and poet architects publicity fears about him and other sources listed about insult you treat this with the basics like potassium hydroxide in ethanol all and then and now you pull off the pro-Chinese generate the angle and the Anaheim is nucleophilic but it's nucleophilic in a controlled fashion so
now if you add your alkyl halide they can participate in arson into reaction if you add your hacksaw bromide Now you go
ahead of the alkaline and then when you didn't know what you can do it now plays in another step trade with strong based on strong acid so I will go and treat them as with sodium hydroxide you can also use hydrazine that we can sodium red-rock side water and and that goes ahead and it makes your enemy and it also makes is the byproduct of hydro lives in the unit and there are other sorts of syntheses using
surrogates using protected groups in order to allow the synthesis of secondary means there will be means synthesis which I will show you alright I think this is
a good stopping point we will pick up with more chemistry of amenities next time
Chemische Bindung
Hybridisierung <Chemie>
Elektron <Legierung>
Bukett <Wein>
Klinische Prüfung
Elektrolytische Dissoziation
Weibliche Tote
Setzen <Verfahrenstechnik>
Gangart <Erzlagerstätte>
Computational chemistry
Internationaler Freiname
Spezies <Chemie>
Amine <primär->
Krebs <Medizin>
Amine <primär->
Organischer Halbleiter
Alkohole <tertiär->
Transformation <Genetik>
Dipol <1,3->
Chemische Struktur
Sammler <Technik>
Systemische Therapie <Pharmakologie>
Aktivität <Konzentration>
Eliminierungsreaktion <alpha->
Chemische Eigenschaft
Chemisches Element
Gekochter Schinken
Optische Analyse
Funktionelle Gruppe
Chemische Nomenklatur
Aktivierung <Physiologie>
Valenz <Chemie>
Hexagonaler Kristall
Organische Verbindungen
Radioaktiver Stoff
Chemische Forschung
Chemische Forschung
Chemische Verbindungen
Pharmazeutische Technologie
Proteinkinase A
Einsames Elektronenpaar
Potenz <Homöopathie>
Substrat <Boden>
Chemischer Prozess


Formale Metadaten

Titel Lecture 14. Introduction to Amines: Properties and Synthesis.
Serientitel Chemistry 51C: Organic Chemistry (Spring 2012)
Teil 14
Anzahl der Teile 19
Autor Nowick, James
Lizenz CC-Namensnennung 3.0 Unported:
Sie dürfen das Werk bzw. den Inhalt zu jedem legalen 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.
DOI 10.5446/19418
Herausgeber University of California Irvine (UCI)
Erscheinungsjahr 2012
Sprache Englisch

Inhaltliche Metadaten

Fachgebiet Chemie
Abstract This is the third quarter course in 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: 5:49-Morphine and Cocaine 15:32-Amines 22:06-Basicity 29:02-pKa and Hybridization 36:14-Physical Properties 42:12-IR Spectrum 44:28-NMR 48:18-Amine Synthesis 52:11-Carbonyl vs Imine 53:52-Reductive Amination 55:06-Sodium Cyanoborohydride 59:46-Alkylating Nitrogen 1:02:19-Gabriel Synthesis of Primary Amines

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