Elimination of tert-Butanol with Sulfuric Acid: 1-MCP ep01
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- Опубліковано 14 лют 2018
- 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??
- Наука та технологія
Of course the Australian guy has a wild spider for a roommate
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 :)
Dude I know you probably won't read this. However I personally would like more videos like this. Especially since all of the updates to the lab and to your video production. Keep on keeping on.
As a physicist with sort of a tangential understanding of advanced chemistry, I enjoy your explanations of the theory behind making reactions happen.
I love the theoretical explanation. I am not a chemist but love to learn the details
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!
My dad is a good leaving group.
😂😂😂
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!!
"If this fails, the whole synthesis is cactus"
At times I'm on the verge of needing an English-English translator
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 love your channel man, I enjoy your structure, your clear, your E funny and its good stuff. Keep it up
Well explained.
Thank you kind man, for sharing you experience like this!
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
Exactly - which is why he was tormented by a fly.
4:45 the carbocation seems to be more stable than your grip on the chalk :D
Wow! I felt like I was in uni again sitting in front of my organic chem teacher hahaah This would make an excellent example for alcohol elimination/carbocation stability lesson. Very well explained btw
I worked as a mechanic for 30 years towards the end I devoloped contact dermatitis with anything petrol related so gloves became a necessity. I have nerve damage and sweat when I get cold. So when winter would come my gloves constantly dripped sweat. My body hates me because I and several others did so many bad things for it growing up. Your vids are cool they make me not feel so stupid seeing that others fail with their projects. Not saying your in any way a nincompoop just that it's nice to see smart people fail occasionally. You make me laugh hard in some of your vids. Thanks for all your efforts mate cheers
Very entertaining, enjoyed much!
This is a good refresher of my orgo 1 and orgo 2 material from pre-covid.
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.
Dude this taught me so much about elections and reactions, so much better then my teachers holy shit
In case you didn't know, tert-butanol is a prescription sedative, although it hasn't been prescribed for 50+ years. I have tried it, helped me sleep a treat. Tastes gross, but mix it with dextrose and put it in a gelatin capsule and it's no problem. And yes, don't worry, I purified it highly before ingestion.
EDIT: I do not recommend to the average reader to try synthesizing tert-butanol and/or ingesting it, you can form toxins if you do it wrong and it's extremely potent (1mL made me very tired and relaxed) so don't bother unless you're a professional or a fellow hobbyist. The reason it is no longer prescribed is apparently concerns over abuse & overdose. I can't really imagine anyone would really try to abuse this(although the mild effect was quite pleasant and long lasting), so I think it is no longer prescribed as a precautionary measure in case someone were to attempt suicide (as a functioning analogue of ethanol, it produces similar respiratory depression), and a lot of unstable people end up just taking a bottle of whatever is near by as a suicide attempt. The medical industry has tried to help over the years, by weeding out drugs that are dangerous in overdose when safer ones are available. Like t-Butanol and barbiturates. Since the dawn of benzodiazepines, there is no longer a need for a patient's sedative to be dangerous if overdosed on.
@QueHubo Parcero no shit Sherlock, I’m talking about ACUTELY dangerous drugs (you cannot overdose on benzodiazepines alone, there is a “ceiling” effect they have on respiratory depression, so unless Pt is on some other depressant, they CANNOT overdose on a benzodiazepine even if the dose was accidentally super high, they will just be comatose for a few days - This is untrue for alcohol or barbiturates, because benzodiazepines bind at a different, allosteric receptor) - if you wanna be a dick about it basically every medicine in existence is EXTREMELY dangerous if taken in high doses every day and suddenly stopped - think about it - and even then, benzodiazepine withdrawal is still less dangerous than ALCOHOL withdrawal…that is impressive, given Alcohol (ethanol) is one of the simplest organic molecules possible, but is one of the most dangerous molecules too. Benzodiazepines are structurally orders of magnitude more complex and literally exist in an extra dimension (ethanol is 2D) yet manage to mimic the THERAPEUTIC effects of ethanol so accurately while avoiding SO many other pitfalls that ethanol regularly visits…
As the wise Paracelsus once stated, “The only thing that separates medicine and poison is dosage”
Nice! Good luck with the chlorination!
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?
Great explanation :)
After Watching This the number of 1-MCP and keeping fruit fresh videos that I get recommended after watching the first video re this on this channel
this is the lowest production quality channel i've seen in a while. love it.
God damn it, the funny Australian man tricked me into actually learning chemistry.
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.
Borus the spider. Much respect for letting it stay there and do its job .
Drops chalk. Enters unfazed mode
Nice work! Laa-cruh-may-ter
Beautiful. Your first reaction probably didn't work because of the diluted acid. Dehydration is removing water, so besides acid and high temperature, a dehydrating agent could help
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
*Sees title:* "Yeah, yeah, I understand completely."
You're forming tButylBisulfate and water. Congratulations. I distilled from Sodium Bisulfate and Aluminum Phosphate. The presence of tButyl cation and Isobutene gives polymers.
drops his chalk and doesnt flinch: good chemist behaviour
What kind of cody's lab is this? I like it
I no say words good.
4:15 You forgot to mention that the hydrogen is lost. It’s a basic enough thing I suppose but I did get hung up for a moment. Good shit dude
I wish I could feel sweaty outside right now. -20C where I am rn.
This video just made me miss summer time
I think this would work if you had some way of pulling water away to drive it forward; maybe a drying agent?
Hope ur spidery boi doesn't die because of your experiments. Good bug snatcher.
You see... If every organic reactions would be explained this way, everyone would understand it. "The OH group would just fuck off by itself"😂😂
Good luck with the forthcoming chlorination - sunlight should help!
AguaFluorida Thanks mate!
Wouldn't car anti-freeze, or straight ethylene or propylene glyocol, be easier on a pump than a highly corrosive salt solution?
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.
I feel cold during 28 lol
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
6:34 isn‘t even the reverse reaction the dominant industrial process to making ethanol? Ethanol from Ethylene/Ethene
How does the spinny thing in the middle work?
Idk wtf is going on but it sure looks cool
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!
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.
I like that he gave his vacuum pump to a pal brewing alcohol. Yah "bathtub gin" tastes like crap which is why they add stinky gin juniper berries. Perhaps filtering it through activated charcoal? BTW does Australia still hold the record for drinking 52 gallons a year per person?
Sometimes it is so hard to figure out what you have created when exploring new ground. I like how you tried several different cuts at this until you got results. Good deal. Enjoyed watching.
terawattyear I'll admit that usually after the first attempt didn't work, I would've given up for at least the day, but the dry ice forced me to try again and I'm glad I did. Thanks for watching!
Wouldn't liquid nitrogen be an even more favourable cooling method than dry ice+CaCl2?
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.
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?
Depends on how concentrated your acid is
@@p1nkfreud
i guess, but the overall time would still need to be x amount of H+ ions per y amount of time. concentration doesn't really change that. and if the acid is too strong, it'll increase the chances of getting unwanted sideproducts
@@p1nkfreud
this comment was 11 months ago, so i don't remember the specific context, but i think my post was probably relatively on topic. i hope.
"Water loves leaving"... now I feel sad.
This video is giving me ochem flashbacks
17:38 CC, "PUT 20 Mils of Torbjorn on here"
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
I think you could have gotten better a yield, if you did this reaction using Posphorous oxychloride and pyridine because these conditions already require really cold temperatures.
Are yellow buckets oK?
So one thing i don't get is shy the only thing right way up is the bannana box and everything else is up side down
I'm glad to know i wasn't the only Australian who says isopropyl wrong
thats called insertion
Make the tossylate to transform OH to a leaving group.
Methanol is not a primary alcohol, ethanol is. Metnanol would be a "nullary" alcohol.
Also, for cooling you're supposed to use calcium chloride hexahydrate, not anhydrous.
(100g ice + 140g CaCl2x6H2O for best effect.)
The term “nullary” is not commonplace in industry or academia when referring to carbons or alcohols, and both methane and methanol are generally recognized as a primary carbon and alcohol, respectively, out of convenience and clarity.
I don't understand how you can work with a Huntsman spider dangling above your head!
lacrimator (lack-ri-mate-or is how i say it) great vid shows how even things that should be gas at RT are possible for the home gamer, guys like you/cody/doug/chemplayer/rednile/nurdrage have inspired me to get my own glass. But it helps to be doing a degree in the subject too.
Hopefully I'll have a channel too at some point if England's nanny state chemistry laws don't get me arrested. >3% nitric acid is illegal as an explosive precursor, what a joke... and sulphuric acid drain cleaner isn't sold anymore to the public its all been replaced with hyperchlorite/hydroxide mix, you know a even easier "legal" explosive precursor... but my focus isn't going to be explosives. :)
Any tips for when I get started?
baLsmaS you can still get sulphuric acid drain cleaner no problem. A corner shop by me sells it (1l £5.99), right next to the sodium hydroxide. The shop called clas ohlson also sells the same for about 13.99. Or just buy it off apc pure or any chem company
I come for the chemistry. I stay for the mispronunciation.
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. (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?
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.
ahhh I miss science class
Fuck me, almost 2 AM... I WANT TO SLEEP! Well I think I have to watch the vid first :D
Drakkar Calethiel 2am... 2:30am... It's all the same :P
The chemical species that you referred to as transition states... shouldn't they be intermediate not a transition state? Transition state is the chemical species that is at the systems activation energy
Transition states are at the activation energy of a reaction. Intermediates are points in multi-step reactions where the product can be isolated. Transition states can't. If you look at a reaction coordinate diagram, a transition state is at the peak of one reaction (as you correctly pointed out) and an intermediate is at a 'valley' of a multi-step reaction.
EDIT: Carbocations begin to form at the peak of a rxn coordinate diagram but are termed intermediates; as such they are rarely isolated. Transition states involve the bonds actually breaking/forming. Here's a good explanation:
chemistry.stackexchange.com/questions/28221/difference-between-intermediates-and-transition-states
Erwin Rommel I suppose you're right, the correct term is intermediate not transition state. Error on my part, I didn't actually know any better thanks for the link, I'm still learning even when my degree is over!
Why no tert-Propanol? ;)
smells garlic-y. OH NO. oh, you have no sulfur in there. carry on.
38! Thirty fucking eight! Uk is lucky to pass 26 in the peak of summer
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!
Lack-rim-eightor
more organic chem, yo!
Lol i can drive 5 minutes down the road and get dry ice from my local ice cream shop
0:36 "I soy butene" eh?
Soy Nick. ¿Donde esta la biblioteca?
where do you buy dry ice and what are the prices/volumes like?
nickt place called BOC and online it was $10 a kilo, but when I get to the store I asked for 4kg and he said $20 and then gave me 6kg because he was like 'whatever' so I think the price I paid was alright
Lachrymator = La cri mator (Le cry maker)
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
my bet is on Di-tert-butyl ether on that first run. Although I would have thought it would have distilled over at those temps.(B.P. 107C) There isn't a lot of info on it without digging so it may form some sort of azeotrope. Great chemistry and perseverance though!
Daniel Coleman yeah that totally explains it! Great thinking
Daniel Coleman not likely. SN2s don’t work well with tertiary alcohols. E1 is much more likely. Phase separation is a mystery to me though.
mrmax35 perhaps tert-butanol isn't very soluble in conc. Sulfuric? Still don't know why I could take the temp so high though without anything coming over
Typically the reaction doesnt happen until 140-150c But thats going by diethyl ether
O haych .... Haych + O haych2 .... Not sure if that's the aussie accent or just how he says it lol
that is a female Badumna insignis (black house spider). bloody good bastards to have living in your lights, any bug that fly's to the light is fucked.
Hache
oh-haitch group
OH2 lmao
seeing that u like pyrotechnical chems and other fun things, I have an interesting chemical challenge for you: Cubane, and then perhaps if you won't get in trouble hexanitrocubane or octanitrocubane... Here: www.chm.bris.ac.uk/webprojects2004/hook/synthesis/index.html#
Love everything about your videos but what the fuck is the deal with this "haitch" nonsense? It seems to have started up in university educated Australians in the late 80s or early 90s. Was there a mass introduction of Irish professors into the Australian tertiary education system? Its such a weird linguistic development.
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