The one where I went to an O-Chem lecture...

Oh baby. That was exhilarating. I went to an ochem lecture. The teacher was going 2000 miles an hour, but that was cool. As sarah reminded me, it's a night class, so if she wasn't energetic, they'd all fall asleep. I took notes on my computer, so that immediately keyed everyone in the room into the fact that I'm not a real ochem student. What madman would in his right mind take notes on ochem, using a keyboard? Oh that's right. I did. And here they are, uncut.

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START NOTES

2.44 Continued - Our Part B

Which Rxn is Faster Why?

An hexagon, with some lines on the inside, and an F on top. Some NO2, on two sides --> Ome, with an MeOH on the bottom….yields another ring, with some OCH3, and still has the two NO2s on it. AND… an F Ion…

The same as above, only without the F, and adding a Cl. Same arrow, same product, with a Cl ion as well.

Obviously, R.dis in NAS Rxn is Nu attacking Genzene to form Non-aromatic but resonance stablizied intermediate.

So then the question becomes which one is faster. And apparantly Allie was WRONG. They're not the same. There is one that is faster. Hahah.

The top one is more e(-).

The top one is indeed the more electrophylic ring.

You can then look at the Reactive intermediate stability, which gives you another ring, with an MeO, and an F coming off the top, of the TV antennas. With the same damn NO2's coming off the side.

The other ring has a CL and an MeO on the top, with the fucking NO2's on the side again.

The top one is better Inductive Withdrawyer??

The top one is more stable intermediate, with lower Ea for formation. Therefore, a faster reaction.

Well no, of course the F is faster. Silly professor.

The Cl- is better LG than F-, but so what? LG doesn't leave in R.dis.

She is really into this.

No questions.

Now, we're moving on to Part C. The obvious next section.

Benzyne Rxn.

Let's review an example

How about a ring with a Cl on top.

It is not electron deficient enough to participate in NAS Rxn.

Let's put a dot on the "carbon" which looks like the intersection between 3 of these lines that make up the hexagon with a single antenna on top. Extremely interesting.

Let's put an arrow with some crap on top: NH2, NaNH2, with an NH3 under pressure.

There's two rings, with an NH2 on top, and a carbon marker on top, as well as a flipped one, with the NH2 coming off at a 45Deg angle, with the carbon still on top. My hypothesis, is that someone got a freaking big ass magnet, and flipped the hexagon.

50/50 … Mad dog?

Mechanisms Required

A ring with 3 antennas - an H, a Cl, and another H. - let's keep marking the carbon on top

- Point at the right H, with an NH2

And of course, the arrow leads to a ring with just a Cl on top, with two dots and a "-" in a circle on the side. By the way, the dots are an Sp2 orbital perpendicular to aromatic PI system. Uh oh - she has the wrong resonance form. Fuck, now I'm completely lost.

She's going to make Benzyne - remember "yne" is associated with a triple bond. I know what a triple bond is. It's 3 of the singular ones.

Benzyne - Highly unstable. Kind of like my mental state if I ever actually had to take this class.

From the benzyne, let's bring a NH2 out, and let it attack one of the benzyne carbons.

Let's redraw something. What? I have no idea.

NH2 (two dots on the top and bottom) pointing to a "3 line" ring, and an arrow popping off the 3 lines, and going onto the right 45 deg angle. With an arrow now, and there's a ring with an NH2 antenna, with two dots, and a death star.

The other 50 percent of the time (oh, that's what 50/50 means), it goes to the 45 deg spot first, then the arrow goes from the 3 lines, to the top position. And you get an arrow, with the NH2 on the 45 deg spot, on the right, with 2 dots, and the deathstar on the very top position. Don't forget that frickin carbon marker.

Now we're going to do it with hydroxyde. Which is harder to swallow because it really burns going down.

Another Example (which obviously needs to be underlined)

Cl on top of a hex ring, now an arrow, with NaOH, H20, delta High P….. GIVES…

OH on top of it all. (ya know the antenna thing again)

And this time, she's going to put the OH on the other side of the blue carbon, on the left side - it doesn't matter. It's just next to it. That's that.

She keeps looking at me wondering wtf I'm doing typing something and not drawing fun pictures.

22.1 Claisen Condensation Rxn.

Holy shit - we killed a ring. It looks like an upside down funnel, with an O sitting on top, smothering an OR. Now, arrow 1) (-)OR, HOR (whore?), 2) H30 + GIVES..

Upside down funnel x2, only the one on the right smothering an OR + (whore)

The double funnel is called Beta keto ester

Remember ** Alkoxide -or must match ester or….

• Beta-Keto-Ester must have at least ONE hydrogen alpha to BOTH Carbonyls (um, upside down funnel much?)

Oh crap: In the above yield, the funnels grew legs, with H shoes.

She wants to let us know what's going on in the reaction vessel. If it's english, probably a lot of.. Um, consensual "bonding time" (get it? Vessel? Ship?)

Rxn Vessel Activities:

Funnel with O smothering an OR (-) OR now arrow: "invisible" transesterification Rxn. -- Only invisible when (-) OR matches ester OR

Transesterification? Oh my God.

The other thing that can happen is the funnel grows one leg wearing on H shoe, with Pka +25. You can get a small arrow going down, and a larger arrow going up - the smaller one is defying gr4vity. Below the arrows, is a funnel with an O on top, smothering an OR, with cookie monster on the bottom left foot. This is called ester enolate. H-OR Pka + 16, arrow, with a funnel smothering an OR, captained by an O. Claisen Condensation.

Now we'll talk about the mechanism. Ya know, the important shit. This is why I'm here.

Mechanism Required:

Captain O, on OR smothering funnel, with one H shoe on the left foot:

An O(6 dots)R, which is negative (duh), gets added to the H shoe.

Now, two uneven arrows top is shorter, and rightly pointing, and left is longer, and leftly pointing.

Yields Funnel, captin O, smothering OR, cookie monster underfoot, plus an H-O(4dots)R

The cookiemonster goes to another captin O ship, and gets placed right underneath the hold.

Arrow underneath that….

Captain O got a new ship, with two bonds on the left side, got 6 dots, but kept the OR - he was reliable.

Now we're playing hangman. WE've got:

O head, 6 dots, his deathstar, two arms, one right "OR" (hand), a lower torso, a left leg, two bond toes, with an O, and a giant ass RO, singlular bond Bunion on top.

Big Left arrow in between, and a small right arrow. Double funnel, smothering OR on right side. And a 6dot OR, with a deathstar.

Growing two H legs again undereath the double funnel. Don't forget the Pka of +10 - quite acidic.

Now from the Right mutant H foot, goes an arrow to that OR with the 6 dots and a deathstar from before…. WHICH ALL YIELDS…

Double funnel (quite stable apparantly, under these conditions), Captain O with arrowdynamic ship on the left, (he's got 6 dots), captain O on right, old school ship, but he's got an OR under the right foot. They both share a mutant H leg on the bottom. The Pika is +16

Now I'm going to stop for a second. There's acidic water? It apparantly protonates all deathstar OR's. So we won't go back to separate ester molecules.

Did she say that the deprotonation was the driving force for that reaction? Did she? I'm not sure I caught that.

Transesteification Issue Again

Captain O with an O underfoot, with an upside down V (spread eagle) on the right.

Arrow: 1) DS OCH3, CH3OH. 2) H30+……… ?

Same left, but now there's a DS OCH3 -> <- Captain O with an OCH3 underfoot, with DS hovering over an earthworm. (spread eagle with O on left) Two esters now in Rxn Vessel

Captain O with spreadeagle man again, with DS yields a SELF reaction:

Two captain O's with a spreadeagle O on the right

Captain O with OCH3 underfoot yields (self): Double captain O, with a OCH3 underfoot

Now: She may have done something wrong. She's thinking… pointing… talking outloud… (things are fine….) things are attacking other things…. How is that possible…. Scratch chin… let's see what happens with the other one…

Two things:

1. Captain O, with DS off left side, with O spreadeagle on right, PLUS Captain O with OCH3 underfoot Yields: Double captain O, with O spreadeagle undefoot.

2. Captain O, with DS off left side, with O underfoot, stabbing a CH3 and a captain O, with DS off left side, with O spreadeagle on right, yields Double captain O with an OCH3 underfoot

A good question has arisen. I have not a clue what she's saying.

Do you have to worry about the acid catalytes? Not that she knows of. Stupid question.

Hydrogen alpha to both Carbonyls very important:

Captain O with a OCH3 under right foot, with a tv antenna off left foot (new rudder), gives arrow:

1. DS OCH3, CH3OH, and 2) H30 + (as always)

Captain O with OCH3 underfoot, and the TV antenna off left foot, with a DS inbetween the two antennas. Ohhh, sexy.

Arrow right, Arrow right - what the hell is the point of that?

Hangman again. O head, DS off right ear, left arm with Tv antenna hands, Right arm with OCH3 hands, lower torso, two 'intermediate' legs, lower lower torso, double bond right foot, with O foot, CH30 left leg. YIELDS:

Double captain O with OCH3 underfoot, two legs underneath, and a rudder, gives the first damn thing we had. Retro clasen impossible to avoid.

Double Captain O, OCH3 underfoot, two weird legs underneath, and a rudder on left. Arrow: DS OCH3 Ch3OH….. 2 Captain O, OCH3 UF, with Rudder

Same Captain O as before, with the left captain with 4 dots, and an arrow coming from his body, and an OCH3 (6 dots, with DS) going up his ass.

Arrow

Hangman with left hand holding rudder, righth hand holding a captain O with OCH3 underfoot, and the rudder being strapped to his wrist. Arrow, Cap O, OCH3 UF, with rudder. Add a DS in the rudder, and a ROH, you can get Captain O, OCH3 underfoot, with a rudder, but instead of having a DS, it's a H controller.

Intramolecular Claisen Condensation (Dieckmann Condensation)

Good for forming 5, and 6 member rings. All the same restrictions apply. You need an Al cock's eye? Sick shit.

New structure. What shall I name it?

Some weird as scar, with 3 pikes in between the two double bond O wheels. On the side, we have two rightside up V's coming off the O sides. I really have no idea how to explain this.

She keeps looking at me. She knows I don't belong. She knows I'm fucking around. She's smart. She's right.

So basically, we're taking the long ass thing, and folding it up into a ring? I saw something like that on an infomertial one time. It was a big blue plastic storage thingy. You unroll it like a sleeping bag, and then you put your crap in the little cubby holes (like lego's, or whatever, and then when you roll it up, it's a nice, 6 sided cylinder, that holds your crap. That's what this is. What we get after all that crap on the board is…:

A ring, with no crap on the inside, with a captain O, with O underfoot, holding a double antenna, with an H coming off the underbelly of that vessel. Then, the ring's got an exhaust pipe coming off the right side.

Presence of Hydrogen alpha to both carbonyls makes this possible product.

You need to practice forming rings, just count the .. Um, crap. And you've got it.

Ketone + Ester

Captain O, standard model (pka +25) with H (and connector) off left foot, plus Captain O with OCH3 underfoot as well as H connector under left foot… Arrow…1) DS OCH3 CH3OH 2) H30 +

?

Arrow down off first guy with DS OR Captain O with DS off left side. It attacks up the ass of the second captain O.

Hangman: DS off head, pointing to neck. Empty left hand, OCH3 right hand, torso, left foot, two toes, with an O on the end, as well as a single bond instep.

Yields: Double Captain O with Two weird H feet + DS OCH3

Why no net rxn where ketone enolate attack more reactive ketone? Me matt. You prof. This hard.

Captain O with DS off left side, Captain O, standard ---> Hangman O with DS off head, two arms, a body, a torso, a leg, some toes, an O and an instep. Now, it forever loses C=O in ketone that was attacked.

We still have one little bitty section to do. Awwww fun.

23.2A

Alkylation of Beta dicarbonyls

1. Double captain o with OR underfoot. It's also got Two H feet Pka + 10 Arrow: 1) Base 2) CH3I

2. Double captain O with OR underfoot. Cookie monster under the hull, points to a CH3-I --> Double captain O with OR underfoot, and a CH3 single antenna off the very bottom.

Double cap o with OR uf Arrow: 1) LDA 2) excess CH3I Double cap O with OR uf, with tv antenna off bottom

Alkylhalide is subject to SNC restriction

No questions on the above. Noted.

SMILEY FACE!!!!!

Question and answer hour: (Recitation…. Whatever)

Ring with an F on top, an NO2 off the 45deg side, some some arrow going from the left upper side to the left 45 deg side. Um yeah. Also, an NO2 antenna off the bottom. ARROW: O6dotsCH3 with DS Gives….. Ring with OCH3 up top and NO2 off 45 deg, and NO2 off bottom + F ion

Oooh! Ohh! I've heard of P orbitals! YAY!

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END NOTES

Wow, That was amazing. Now, after typing all that, I cannot use my fingers anymore. If you read all of it, You're weird, by the way.

~mendick