LabCoatz - 2023-05-25
I'm on a quest to sample all of the world's foulest-smelling chemicals, and the next ones on my list are the isocyanides. To make isocyanides, however, I'll need organic amines like the one I'm making in this video: tert-butylamine. By itself, it's already a pretty cool and useful chemical, and plus, it has fairly powerful odor of its own, so making it was kind of a no-brainer for me! Here is a link to the paper I followed: https://orgsyn.org/Content/pdfs/procedures/CV3P0148.pdf Want to support LabCoatz? Then feel free to join my Patreon page! It literally costs less that a cup of coffee: https://www.patreon.com/LabCoatz Don't want to pay monthly and just want to be a one-time supporter? Then follow this link to donate: https://www.paypal.com/paypalme/labcoatz Want quality glassware at an affordable price? Check out CELL Supplies! If you're into hobby or professional chemistry, I definitely recommend them: https://www.cell-supplies.com/ WARNING: the chemicals shown in this video are dangerous if mishandled. Sodium hydroxide and sulfuric acid are both highly corrosive. Tert-butylamine is also mildly toxic, and it tends to produce a lot of unpleasant fumes which may irritate the respiratory tract. Anyone who attempts this procedure does so at their own risk! 0:00 What're we making? 0:42 Ingredients 0:58 Making tert-butylurea 2:19 Recrystallizing the product 3:20 Making tert-butylamine 3:57 The smell 4:13 Distillation and yield 5:13 Subscribe for the isocyanides! 5:43 Outro
oh man the beaker just floats in the ice bath 💀
The laws of buoyancy unfortunately prevent me from refuting this claim, lol. Things were better once the reagents were loaded in though!
@@LabCoatz_Science they have these flexible beaker weights that sort of snake around your beaker for cases just like this
please never stop making videos! You are already a legend
if that chemist doesnt like selenols than they must really suck in terms or toxicity anyways excited for the upcoming carbylamine vid
They're incredibly toxic.
You and StyroPyro need to do a storm chase collab. Just some chemists out chasing tornadoes!
Though the alphabet boys may be tailing you the entire time. 🤣
Going for the isonitriles like a BOSS !
Forget about the thiols , it's time for the industrial strength stench machines .
actually he should also make butanethiols and thiophenol also.
4:01 "but I personally found it to be akin to fresh animal urine"
🙃
I am learning more about uses for urea and this one is so cool! I didn't know this was an option. Great video man!
Thanks man! And by the way...in that clip where I was gasping from the horrible stench, I was using your n-butylamine to make n-butyl isocyanide! Needless to say, your donation proved quite useful, lol. Just for fun, I also tried the ethanolamine you sent me, and it produced a very unique stench of its own...I'll definitely be shouting you out in the isocyanide video once it's done!
I've had my bupropion analogues project on hold for a while now, and this is sure to reignite my interest in that.
I wouldn't worry much about yield, especially when you repeat a reaction several times and obtain a yield lower than literature. I don't want to accuse anyone of anything, but I know showboating is a very human behavior and all chemists I know of are human. When I do a Fischer esterification (without any extra steps to increase yield) and obtain the purified product in 76% yield, that makes sense. I do a nucleophilic substitution, and I get a yield of 82%, and that makes sense. Another aromatic electrophilic substitution, and I get the expected yield. Some formylation, that's 45%, and I didn't expect better. Take something from the literature, and routinely obtain 10-20% yield, and they're claiming high 70%. Yeah, it must be literally all the rest of us who are trash at chemistry, let me tell you. We just gotta get gud, and stop being trash, kid. ...or more likely, the high percentage number is a misrepresentation of the robustness of these preparations.
You mean like the ones reported in the literature?
The procedure for coming up with a number for publication appears to be along the lines of "Yeah, we measured an 83% yield one of the 30 times we ran this reaction, and I don't recall whether we actually dried it before weighing."
@@davidfetter Exactly lol, nailed it. That one time was great, and the reaction is kinda finicky otherwise. I don't really mind a reaction that has low yields that has other good reasons to use, like ease of prep or workup, or use of cheap or common reagents. I'd just like to know that information before I spend three weeks repeating it again and again and wondering why I'm so terrible at the prep.
@@RobsMiscellania let's put it this way. One of the major problems with "the literature," which is to say with a significant part of the political economy, of synthetic chemistry, is that the review process does not include actually reproducing the results, very specifically including reproducing the alleged yield. This is due in no small part to the pressure to produce publications.
This is going to be awesome! 😂
I've used t-butylisonitrile as a ligand before (bought from Aldrich). Can confirm that it is fairly stinky, similar to trimethylphosphine. Used mostly in glove-boxes and high-vacuum lines, so exposure was very low, implying that its stench level was quite high.
2:46 comment on screen about the spill/splatter 😂
As a chemist with congenital anosmia (born without an olfactory system), I feel like it's my destiny to work with the stinkiest chemicals that no one else will work with.
holy shit the stinky chemistry never ends
ngl this series is awesome tho
How did I miss this video! Time to watch this while eating salt and vinegar potato chips!
Yasss now I can finish making my own bupropion, thankyouu
Stanks a lot for sharing this
I've heard rumors that 2-isocyanobenzoate esters smell pleasant (still unnatural and weird tho) like anthranilate esters.
The how to name a chemical book was quite interesting. Maths and computation at the time.
Very cool stinky compound.
It's awesome when you have a friend who agrees to sniff everything that you offer him, even knowing that you won't get him some wonderful aromas. :D
The bis-tertbutyl urea should have also give your desired amine with it's reacted with NaOH
" stop looking,
there is only pain"
🤣
Cool preparation what about converting isocyanides into isothiocyanates and isocyanates. Also I hope you'll make organophosphines and Me3As one day
Hmm
Ive made benzyl isonitriles on multigram scale and as a result did the most unpleasant purification of my life. Unpleasant is really an understatement. A week later, I forgot I had a small amount dissolved in CDCl3 in an NMR tube, and promptly opened it to dump in the waste. The fumes seemed to have built up, because I got hit with a smell so potent I could taste it. It triggered my asthma and I ended up in the ER, but ultimately I was fine.
Anyways, have fun.
Describe the smell
@@Esterified80 It is unlike anything I've ever smelled. I actually still work with it frequently as a part of my project. It does not have the typical sulfury egg/fart smell. Instead it is extremely sharp like cheese. Feels like being punched in the nose and is very chemical-y. Closest thing I can compare it to is ammonia, but it isn't really the same.
I made the infamous n-butyl isocyanide a few weeks ago, which is what I was distilling as I was gasping for air in that one scene. The smell isn't what I would call disgusting...to me, isocyanides smell very artificial, a lot like melting/burning plastic mixed with an assortment of other unpleasantries...but it was by far the most powerful thing I have ever inhaled that wasn't a corrosive/irritating chemical (like chlorine, HCl, etc). Like you said, you can taste it as it travels through your nose, and in the case of n-butyl isocyanide, it leaves a nasty bitter taste in your mouth as well. I also sampled phenyl, t-butyl, and 2-hydroxyethyl iscyanides (made from aniline, t-butylamine, and ethanolamine respectively), and they were all similar. The one made from ethanolamine, however, had an added vinegary note which made it probably the nastiest one.
@@LabCoatz_Science I'm also curious about benzyl and methyl isocyanide
@@LabCoatz_Science so they smell exactly the same or they still have some differences?
Does this also work the same for n-butyl amine from n-butyl alcohol? Also, please share the link to the paper you are following.
Nice, except for the yields. I suppose the Butylamine is the compound with the lowest bp in the last reaction and by far too. As there were obviously losses through the condenser I would thing using this to an advantage and to run the reflux condensner with hot water at 40 to 50 °C and to attach a second ice-cooled condenser at the outlet and collect the product there, minimizing losses and at the same time removing product from the reaction as it forms what in my experience is the best one can do provided its technically feasible.
Ladies and gentlemen he has done another stinky chemical
Any chance I can buy some of this also? :)
If you live in the United States, then yes (but not until the video is published). I tried shipping internationally last time, but every single sample got returned and I lost hundreds of dollars in the process, so I'll be sticking to US-only shipments from now on.
I've done multiple R-NH2 -> R-NC reactions in the past and believe me, "what's been smelled cannot be unsmelled" 😆. Go for it and see / smell for yourself. NB! I presume you'll take the :CCl2 way. The reaction is very fast and exothermic, quite prone to go POP! / splash / foam over. Use a reactor 10-15x the reaction volume + open Allihn / Liebig.
When I was filming the isocyanides, I did notice that a few of them spontaneously boiled (ethanolamine was by far the most violent). Fortunately, the n-butylamine was fairly well-behaved, so I was able to reflux and distill a few milliliters of n-butyl isocyanide without trouble...well, until I broke the receiving flask on the pavement and released what is apparently the worst isocyanide (and I so far, I can confirm it is the most aggressive one in terms of smell).
@@LabCoatz_Science 😁
n-butyl and n-propyl are particularly vile, but PhNC doesn't fall behind either. I've never bothered separating the products though, the reaction conditions are just about right for the next step, a condensation reaction.
Does this amination work with all alcohols ?
Like isopropanol
I was discussing the same thing with That Chemist, actually! The biggest trouble area is the formation of the substituted urea. In theory, any substituted urea will reduce to the amine with sodium hydroxide and heat (this method can be used with plain urea to get ammonia), but it's hard to say how different alcohols would react with acidified urea...you could get anything from tetra-substituted ureas to branched alkenes, depending on the temperature and stability of intermediates. I think the best way to get organic amines (which I might test later on) is by reacting sulfamic acid with the alcohol: this yields the alkyl ammonium sulfate, which can sometimes be heated with NaOH to afford freebased alkyl amines (I know this trick works with methanol/methylamine, but idk if other alkyl groups work the same).
@@LabCoatz_Science Wikipedia says that sulfamic acid reacts with alcohols to get the ammonium alkylsulfate salts, not an amine sulfate. Is this incorrect?
@@grebulocities8225 No, I was just thinking of ammonium methyl sulfate, which can be heated to form methylamine sulfate. Looking back, I'm not totally sure if this would work with other alkylammonium sulfates, but it might be worth a shot! I was chatting with That Chemist, and he was interested in a similar route.
@@LabCoatz_Science Oh cool, I didn't know that ammonium methyl sulfate rearranged to methylamine sulfate after more heating - thanks! I looked it up and just watched Thy Labs' video on this. I can't think of why it wouldn't work for other alkylammonium sulfates - try it and let us know!
I wonder if you could synthesize other mono urea derivatives the same way with decent yield..?
Take care man, with isocyanide. Max Gergel report are seriously deadly.
I've heard most aren't all that toxic, although tert-butyl isocyanide seems to have a 4-hour inhalation LD50 lower than carbon monoxide, which is somewhat disturbing...I'll definitely be careful around them, but inhaling small doses shouldn't be too bad for my health (since only a few milligrams make into the air at a time).
@LabCoatz Is there any alternative synthesis route other than the carbylamine mechanism cuz. I had read from a reputable research paper that isocyanides made by the carbylamine mechanism are susceptible to rapid polymerization yeilding a quite odourless polymer kinda thing ???
There are ways, but they require chemicals that I don't have. What I did that worked well was distill out the isocyanides: I set up a flask with chloroform, NaOH in ethanol, and an amine, and did a short-path distillation. The first fraction is mostly unreacted chloroform and ethanol with some isocyanide, but the higher boiling fraction tends to be a mix of water and isocyanide (evident by a layer floating on the aqueous phase...isocyanides are less dense than water, while chloroform is more dense). My samples are somewhat yellow, but they still reek of isocyanide, and they don't seem to want to polymerize.
@@LabCoatz_Science Man u must be having a stiff nose and the guts to do a distillation of alkyl isocyanides. Cuz as far as people i have met they all are terrified of extremely debilitating smell of these compounds(including me). I wouldn't even think of concentrating this stuff due to the shear fear of its smell. Nice one dude 👍👍👍
@@mihirsanghvi9876 Thanks, I'm glad to have tried it! As far as the smell goes, it's basically a polar opposite to the thioacetone/selenols I previously tested. While thioacetone was natural-smelling (sulfury and oniony), far-reaching, and kinda nasty, isocyanides are mostly unnatural (having the acrid nature of burning plastic, adhesives, or exhaust fumes), unbearably offensive, and yet not excessively far-reaching. I don't find the smell all that gross in low doses, but if you get a good whiff of it, the effect is palpable: you can feel it travel through your nose, forcing you to gasp or cough, and it leaves a bitter taste in your mouth and throat.
@@LabCoatz_Science Yeah actually some selected alkyl isocyanides in very very low concentrations kind of smell decent like for example smelling it from the outside of a air tight reagent storage bottle with the lid screwed real tight but as the bottle is opened eventually the smell becomes damn offensive very fast. Oh and second of all these are way less volatile than thioacetones and selenoketones as we examine the resonating structures of alkyl isocyanides we see formal charges of +ve on N and -ve on C so mutual coloumbic attraction makes them less volatile. Correct me if you find something incorrect as this is my hypothesis 🙂🙂
@@mihirsanghvi9876 I also found that at least one isocyanide smelled alright when dilute, and surprisingly, it was the t-butyl isocyanide! Assuming there isn't some wild contamination in my sample, the dilute t-butyl isocyanide smells almost exactly like green tea (although slightly more artificial). The dilute phenyl and n-butyl isocyanides still just smell like various mixtures of burning or melting plastic though.
Nile_Red is going to be on this next haha
I've been trying to convince him to try isocyanides, lol. Not sure if he will or not!
Cool video, you do realize that tert-butyl isocyanide is quite toxic though...
Yeah, it's worse than carbon monoxide in terms of a 4-hour inhalation LD50, but it's also not excessively volatile, so there isn't a lot of it in the air at a given time. I've already smelled it, and experienced no ill effects.
Everything is better if you use a torch!
4:12 you dont say... 😂😂
2:20 government: what is that white substance?
LabCoatz: just a precursor to a stinky compound, I swear
Government: oh, okay then. Carry on
😂😂
I remember Eastman Kodak many years ago, used t-butylamine borane as a component for one of their film processes. If I recall correctly it was used for E-4 color films. VERY toxic stuff.
I worked in a quality control lab and for the mobile phase to analyse a particular drug, we needed to use trimethylamine. Smells horrible too. If you have smelled it, how does it compare to t-butylamine?
T-butylamine and most primary amines are typically more ammonia-like, but slightly fishy. Secondary and tertiary amines (like dimethylamine and trimethylamine) smell a lot more fishy, biological, and gross imo. I've heard that Bradford pear trees smell because of trimethylamine, and if that's the case, it smells WAY more horrible than t-butylamine.
@@LabCoatz_Science interesting. Thanks for the reply. Maybe you could also make it and we could get a comparison between all the smelly substances you have made?
Can smaller alkyl amines be made this way too?
Maybe, although to my knowledge, there are no records of this method being tested on other alcohols. The bit that is uncertain is how different alcohols would react with urea in sulfuric acid...depending on the conditions, you could form multi-substituted ureas, branched alkenes, or even nothing at all. It COULD work, but there would need to be a testing to see if it would.
Is this the same or a different chemical that Nile red made?
If you are talking about tert-butylamine, I think NileRed only ever made trimethylamine and methylamine (in a video which was taken down). If you are talking about isocyanides, then no, the chemical he made was very different and far less offensive. For reference, I made the chemical that he did (thioacetone), and everyone I shared it with thought it was tolerable (one friend of mine even liked the smell, describing it as "burnt garlic"). Isocyanides, on the other hand, were deemed completely intolerable by everyone I shared them with!
Thought the thumbnail said stinky anime 💀💀💀
I’m studying OChem and I’m questioning why you wanna remove the ditert-butyl urea despite it’s a tert-butyl group bound to a nitrogen.
Not really sure, I was just following the procedure!
@@LabCoatz_Science So let’s try extracting the anime from the ditert-butyl stuff and make more isocyanide (unless you really had enough of it)
👀
With the carbon, hydrogen, and nitrogen, I'm kind of curious how flammable and or explosive this is
It's mildly flammable, similar to alcohol, but not nearly as much as you'd expect given its low boiling point. But, then again, my sample did have some water in it, so it could be more flammable when pure!
@@LabCoatz_Science fun
could you make Grapefruit mercaptan?
Maybe someday. I've thought about it, but I'd need alpha-terpineol first. I could buy it on Amazon for pretty cheap, but I'd much rather make it from limonene so I can call the video something like "Making Lemons Smell Like Grapefruit With Sulfur Chemistry", lol!
@@LabCoatz_Science dont forget that that stuff smell really Bad and has Like 0.1ppm smell
Turd-Butylamine
you and @NileRed would probably be best friends.
I chat with him every once in a while, and he's a pretty solid dude!
@chemdelic - 2023-05-27
Bro is on a journey to destroy his olfactory receptors. Good video brother!
@abivise7756 - 2024-06-17
Oh look...ADHD! And a smidge of the 'Tism