Extractions&Ire - 2018-02-16
Tertiary-butanol is eliminated with an acidic catalyst to yield isobutene with a boiling point of -8C, all performed on a stinking hot day. What could go wrong??
Of course the Australian guy has a wild spider for a roommate
4:45 the carbocation seems to be more stable than your grip on the chalk :D
i think when we did this reaction in orgo, we needed to add the t-butanol like 1/2 a ml at a time over an hour. doesn't it ruin the reaction if you do the addition too quickly?
Walter White would never except that spider into his lab!
Well Explosions and Fire isn't going for anything like a 99.1% Yield or making products intended for direct human consumption.
steingat accept*
Except means leaving out or not getting
@Dom Vasta 99.1? Maybe closer to 49%.
The product walt was making was racmic. Only one enantiomer was active, so his yield was 99.1 /2.
Glad it worked for you! Exited to see part two.
Australia. My god you people are nuts.
"Oh yeah mate that's just a HUNTS-MAN spider that lives above my head. He comes out every night and kills and eats bees larger than infants. Yeah don't worry bout it mate."
One more thing:
LA-CRI-MATE-OR not LA-CHROM-IT-OR
Onyx V.O. That's actually not a Huntsman spider. They're a lot bigger, and they're around too but they're not web builders and generally a lot more chill, so everyone puts up with them. I've never seen one of those black spiders get so big, it lives an easy life it's practically obese haha.
And thanks, I'll do my best in future :P
@Extractions&Ire I have henry the huntsman he is really chilled just scares people and i don't know why .Apparently they drink the drool from your mouth
This is so fuckin cool!! I've never seen sub-zero distillation before, but it makes perfect sense. Of course this is a thing, why wouldn't it be?! I had just never thought of it. So freakin cool, ty for this vid!!
Well done! Hopefully the next steps work out for you. It would be awesome to see the end product and it’s use.
AllChemystery thanks! It is frustrating not being able to store the end product well, it means the next step has to be 'all or nothing' and doesn't let me trial it slowly, but with a bit of perseverance, we should get there!
HAHAHAHA That outro got me :')
Really good video ! I really hope the next reaction works, it's amazing !
Don't underestimate your knowledge, just dive in some simple papers on reactions and you'll be able to do anything. I'm in 3rd year of O-chem at the university and we're just approaching this level of complex synthesis, you're not doing basic chemistry ! Really Nice.
I wish I could feel sweaty outside right now. -20C where I am rn.
6:34 isn‘t even the reverse reaction the dominant industrial process to making ethanol? Ethanol from Ethylene/Ethene
Sees title: "Yeah, yeah, I understand completely."
I have done the reaction between t-Butanol and hydrochloric acid to make t-butyl chloride last week and I'm currently editing the video :D Nice video!
Random Experiments Int. - Experiments and syntheses Thanks! And yes, a very similar reaction, just a change in how good the nucleophile is. Did you think you saw any isobutene bubble away? I suppose the chloride just reacts too quick with it.
It's hard to say. I tried the simple method, where the acid and t-butanol are simply shaken in a separatory funnel, dried and distilled afterwards. In the beginning there was quite a lot of pressure, but this could also have been due to the conc. hydrochloric acid.
i think when we did this rxn, we had to add it dropwise slowly over an hour? maybe i'm thinking of a different rxn, but i'm pretty sure it was this one. they said if we added it too fast, it would stall the rxn?
I kinda wanna try synthesizing this following your process, then putting an apple in a jar with some 1-MCP and seeing how long it lasts.
Hey mate, huge fan of your channel. Its so nice to see chemistry becoming more open, promoted and excepted in the community, and great to see loads of people getting excited about it.
I wish that it was taught differently at school. I didn't realise to after I left school, how awesome and cool it actually is. Had it have been presented to me back then in less of a shit/sanitised way, I so could see myself as having made a career out of it.
Thanks for taking one for the team, doing all the hard work for us so that we can live it thru your eyes, and our screens and um thru our eyes.
Yea anyway thanks mate.
Sick vidoes. Both channel. 10/10.
I love your channel man, I enjoy your structure, your clear, your E funny and its good stuff. Keep it up
But while this is amazingly cool, I would love to see a way to mass produce butanol efficiently! ~( 'w')/
Dude this taught me so much about elections and reactions, so much better then my teachers holy shit
Well explained.
Thank you kind man, for sharing you experience like this!
5:30 Not exactly, the nearby carbons won't succesfully stabilize the cation uf they're tertiary carbons, they need to have at least 2 hydrogens to hyperconjugate.
Love the explanation of how the tertiary carbo-cation shares the positive charge, making it more energetically favorable, and how acidic conditions make an alcohol a better leaving group. Brings me back to my days in orgo class. Really well explained, and funny, and educational. I love this channel :)
Wew lad. 38 dungrees is way to high for my taste. I like being able to reX my compounds by just putting them outside into the snow.
And name the spider spidey mcspiderface
dungrees? hello fellow AvE viewer.
lucky you :)
I was freezing my ass today at -2°C in the workshop WITHOUT heating
The Chemical Workshop aw man, that's pretty cold, the dry ice would last a lot longer where you are than at mine!
Structure in the opening bit of the video is drawn with the bond going between the O and the H [TRIGGERED]
Oh and also your primary carbocation that you drew is actually a methyl carbocation
So like the reaction is happening at 50C, which is only 10C over ambient. Here in Glasgow folk take their t-shirt off at 15C and catch fire at 20c, lol, seriously, I remember last summer one day the sun came out and it got to 28C when I was driving home from work and I have never felt so fucking hot in my life.
Great explanation :)
Silly question... If distillation under vacuum helps lower the boiling point, could you potentially use positive pressure to help raise it to a reasonable temp?
Nice! Good luck with the chlorination!
OH2 lmao
ahhh I miss science class
Good luck with the forthcoming chlorination - sunlight should help!
AguaFluorida Thanks mate!
When carbocations leave, do carbodogions enter?
oh-haitch group
My dad is a good leaving group.
😂😂😂
Borus the spider. Much respect for letting it stay there and do its job .
Nice work! Laa-cruh-may-ter
Why haven't you made EGDN yet?
I was in the middle of studying for my ACS exams when I got distracted and stumbled across your videos. Now that I'm watching this series of videos, I can make the argument that I am, in fact, studying for the organic portion of the ACS exam.
0:36 "I soy butene" eh?
Soy Nick. ¿Donde esta la biblioteca?
Lachrymator = La cri mator (Le cry maker)
I no say words good.
Alright so I think I have this figured out:
Ditbutyl ether is likely the product you were seeing in the first attempt but a simple SN2 would not explain this as it is a tertiary alcohol. (https://chem.libretexts.org/Core/Organic_Chemistry/Ethers/Synthesis_of_Ethers/Dehydration_of_Alcohols_to_Make_Ethers)
Instead I think something much more interesting is happening:
The first attempt was heated to 55 C assuming the E1 product (the intended alkene) was formed and is soluble is the reaction mixture at this temp this could rapidly do an SN1 with the remaining t-buOH to form the tbutyl ether product.
The driving force for this reaction can be explained by Le Chatelier’s principle: As the tbutyl ether phase separates from the reaction solution equilibrium in the SN1 step is pushed toward product. As a result of this the E1 equilibrium will also be pushed to the E1 product. This is all assuming that the E1 is rate limiting otherwise you would have some E1 alkene distilling over.
Now in the second reaction you heated it hotter. This lowers the solubility of the E1 alkene thus making it distill over instead of going through the alternative pathway state above.
What do you guys think?
https://pubs.acs.org/doi/abs/10.1021/ja01851a512?journalCode=jacsat
After some digging this is a pathway to di tert butyl ether. But as you can see it quite dissimilar to the process followed by Tom. Not to say this is the only pathway. Lol. I like your idea. Maybe some some kind of workup on the black tar sludge from the first attempt?? Lol. As if you didnt have enough to do with this synthesis :)
Daniel Coleman this paper is great, thanks for this. I assume the silver carbonate is doing a metathesis like reaction precipitating silver chloride, bubbling CO2, then forming the carbocation and tBuOH which under go SN1? I stoichematrically it kinda makes sense:
2 tBuCl + Ag2CO3 +H2O -> [tBu(+) + 2 AgCl + tBuOH + CO2 + OH(-)] -> tBuOtBu + H2O + CO2 +AgCl
Driving force of CO2 release and silver salt formation.
Not entirely dissimilar if my idea is correct still a two step process with SN1 with tBuOH in the latter step.
I think that forming the tBuCl definitely could have happened if the dirty sulfuric acid was contaminated with HCl.
You should take a wooden stick to point on the drawing board!
Alexandre St-Laurent {ASTL32} oh no I'd feel like an old professor
Extractions&Ire Agreed! xD
I had been reading that as "car-bo-cayshun" like some kind of vacation w a serious exhaust problem. Thanks, I'd forgotten it was cat-ion as in negative or cathode related
David Rissanen I'm glad I helped someone out with pronouncing a word, that doesn't often happen to me :P
Now I get your Claisen comment. I pronounce it the same but I have no idea if that is correct.
This is all good stuff and I appreciate the foray into the theoretical. What you covered is a thin spot for me -- I have no formal education in OC at all.
j_sum1 Glad you appreciate the theoretical. Also I noticed Aussie Chemist uploaded a trailer using a Claisen adapter on the same day we both did, that could be the most videos in one featuring a Claisen adapter uploaded to the internet across human history.
We gotta form like a Claisen Club or something
Hope ur spidery boi doesn't die because of your experiments. Good bug snatcher.
I dare you to take a drink every time he says "Haych."
DannyBoyDDD I keep forgetting to edit them out oh noo
Don't you dare edit. I love your videos.
DannyBoyDDD haha thanks mate
make methyl isocyanate next ...just don't inhale and have one hell of a fume hood
you could just do this in canada
nickt someone should just do this reaction except when it's below -8C, it would be so much easier wow
Awesome video. Not sure what the phase separation is. Sometimes salts can effect miscibility, I know in basic solutions THF can phase separate from water but never heard of this with acidic solutions.
mrmax35 The current theory from the comments is that I made an di-tert-butyl-ether, which makes sense because of the high boiling point and phase separation
Extractions&Ire mhmm, so you formed the phase separation before you turned up the heat right? Maybe you were forming the intended E1product but this was soluble in the t-BuOH then further reacted with the the t-BuOH and sulfuric via and SN1. Then the SN1 product phase separation drove the equilibrium forward so you could solubilize more E1 product thus selectively making the symmetric ether.
The second attempt you heated the reaction hotter right? Which means the intended E1 product was less soluble in tBuOH and could distill before SN1 could take place.
Just guessing here still interesting chemistry problem!
Kevin Kenny - 2018-02-16
Another bet on di-t-butyl ether. Dehydration of alcohols with strong acid is a usual way of making symmetric ethers. https://www.masterorganicchemistry.com/2014/11/14/ether-synthesis-via-alcohols-and-acid/
mrmax35 - 2018-02-16
Daniel Coleman https://chem.libretexts.org/Core/Organic_Chemistry/Ethers/Synthesis_of_Ethers/Dehydration_of_Alcohols_to_Make_Ethers
This will shed some light on what I was saying before.
Kevin Kenny - 2018-02-16
Yeah, it was late at night, and my mind didn't make the connection that the acid-catalyzed dehydration is SN2. Still, that organic layer had the wrong boiling point for isobutene.
Durned if I know.
Kevin Kenny - 2018-02-16
Looked it up, and di-tert-butyl ether is hard to make - the usual route is via t-butyl chloride over silver carbonate in an ether solvent. The yields are low - most of the reaction goes to isobutylene and t-butanol. even in good conditions. So color me even more puzzled what the high-boiling organic layer might have been.
kirea - 2018-02-16
I don't think di-tert-butyl ether is a very likely product, at least not in more than trace amounts. I think what is happening when you use dilute sulfuric acid is basically nothing, carbocation forms and then reacts with water, which is present in a large excess, to reform tert-butanol. You need concentrated sulfuric acid for elimination to be favourable. The reaction is not really an equilibrium, because when isobutene does form, it will distill off, but the rate of elimination is going to be roughly proportional to the the carbocation concentration, which is going to be very low when there is a lot of water around to react with. Keep in mind that the reaction is already pretty slow with concentrated sulfuric acid, and the water present in the dilute sulfuric acid will make it even slower.
kirea - 2018-02-16
Regarding the phase separation, it could be possible that sulfuric acid in the water makes tert-butanol separate out.