oh and to those wondering, i did not know a henry reaction would work on something aliphatic like cyclohexaldehyde, and either way no one sells that other than chemical supply companies
Even if labcoatz did a great video on similar chemistry you did an awesome route to the ketone, frankly! I recognize manganese iii acetate generation in situ here, something I saw a paper about a few years ago and "the poor man's chemist" actually attempted to do, so bravo. You succeeded where others showed it didn't work. So I think you might give yourself a break on same chemistry. I mean think about how many nitric acid videos are on here, and yeah, I've watched a substantial amount of those, regardless of if it's been done by someone else. Again, you proved this worked, which is just awesome!❤❤
looking at literature more closely this time yeah it seems to be manganese iii formation, me and a few others have hypothesized possible improvements but im not sure if ill try them anytime soon
@EdwardTriesToScience don't blame you, seriously. I was merely impressed you had success with it, as the other channel "proved" it was a false claim, a claim from a less than reputable website, though many chemists on yt refer to it (erowid). So you definitely had success, your description of the smell of the ketone is appreciated. I've always wondered what those ketones smell like, but no, don't need to know firsthand. Thanks for the instructional and very educational video, again ❤️ keep em coming!
Having watched a few videos, here's what I would do, assuming I had access to a steam distiller (entire glassware of a college would really be nice bc we gotta do all kinds of things): birch reduction of benzene to cyclohexane, while that's going on (or after you've made and cleaned the product), brominating acetone to bromoacetone, drying and cleaning, simply NaCO3 and then a drying agent, acid side (MgSO4 or CaCl etc). Add some (depends on your amount, I'm not sure how much to add, but it's a catalyst, assumed the chloride ions kick off the bromine from the acetone in some beautiful intermediate and then attacks the cyclohexane) aluminum chloride to the cleaned up cyclohexane in a water bath kept near 15c addition funnel charged with bromoacetone, dripdrip into the cyclohexane and alcl3, takes some 30 minutes give or take. Then this is allowed to stir for another 30 min. Then take this and steam distill for the ketone. Tada!!
@Ryan-lc4bl well.. I didn't know that, I figured it would work since what I just watched showed manganese iii acetate performing so well. I don't know how to make cylcohexene from the alkane, so idk. You killed the wind in my sail ⛵️ But wait... I got it! Benzene with the bromoacetone and then THAT ketone, treated with Pd/C and hydrogen balloon (of course purging the atmosphere of air first) and voila.. I'd make sure it fully hydrogenated before the next step as indicated at end of video here.
Very nice, I love the intro and everything really. This was a great video the whole way through. I appreciated the editing and showing the reaction on screen.
how would you do that? You need to oxidize non activated C-H bonds which are remote from the only activating functional group. The only methods I can think of to aromatize this would be to either make the enone via a 2-step process plus isomerization of the double bond into the ring, followed by oxidation all the way to the aromatic ring OR to use photochemistry to absract the gamma-H atom in order to generate a first unsaturation on the cycle which could then be exploited to aromatize the whole thing
In my experience with the aromatic form of this exact compound, it is prolonged heating in the presence of acidic aqueous conditions that leads to aldol condensation and that floor polish smelling brown tar. I've found that vacuum distillation produces a far cleaner product with these alliphatic/aromatic ketones, and oxygen is not a friend during purification... i would recommend dehydrating the salts and drying the acetic acid but still use an air bubbler with a calcium chloride dry tube inline
Your analysis on the reaction mixture causing aldol reactions is spot on, probably a bunch of acid catalyzed aldol side reactions making that tar. Trying it under kinetic control rather than thermodynamic would probably yield better results as it would theoretically minimize the chance of the product reacting further under the conditions.
You can't really say the analysis is spot on if you haven't analyzed the mixture yourself :P but I agree the aldol product is one of the most likely side-products. On the other hand, there is no typical kinetic/thermodynamic control for this reaction unlike aldol chemistry, although I agree that using a silyl enolate in neutral conditions might lead to an improvement of the reaction (for different reasons). Based off the use of Manganese and Cobalt complexes, this is likely a radical based mechanism going via Hydrogen atom abstraction and many other things can go wrong.
Looks like you and labcoatz are right on the same page. One of my first chemistry projects ever was extracting the API from those nasty lil buggers. I did most of it while on the clock using my workplaces solvents lol
If by Ac2O you mean Dakin-West type reaction, I highly doubt it would work as is after hydrogenating the aromatic ring, since you need the benzylic carbon to efficiently generate the anhydride enoate with a weak base, namely 1-methylimidazole or the acetate ion present in solution. It also helps to differentiate this C-H bond from all the other Ac2O alpha C-H which could also be deprotonated. You would need to tweak the reaction conditions quite a bit for it to work, and even then, it would be very hard to selectively deprotonate the cyclohexylacetic acid selectively over Ac2O (actually there should be a preference for Ac2O vs cyclohexylacetic acid due to the CH3 being less hindered and lacking alkyl substituent which would provide hyperconjugative destabilization of the resulting anion) so you would probably make a lot of aceto-acetic acid side product with your cyclohexylacetone.
I remember seeing some notes stuck to your fume hood with this suspicious-looking motif, actually thought you were trolling us at the time having that in the background.. I know you're working on this way back then.
yeah i dont even know where one could buy cyclohexaldehyde, much less for a reasonable price. then again hes all buddy buddy with the owner of chemical supplier sooooooooo (the chemicals he showed in his video are about $500 by my estimate... LAH goes for $200 per can from carolina, cyclohexylamine $30 a bottle, etc, and ive only spent $100 or so ignoring the boro which was $200 for half a kilo which will last a year or more even)
@EdwardTriesToScience ahah. I dunno about his supplier, but I know you can ask Chinese companies for WHATEVER you want... as long as you're willing to pay
@@fmdjthat's 100% true but many only do bulk orders. Like industrial scale amounts. Though you can often talk them into a free sample if you pay the shipping....
@@chemistryofquestionablequa6252 a bunch of them have 1kg as a minimal quantity, but yes it's not the most common and for small quantities shipping fees will be higher than the product costs lol. It can still be useful. But what I had in mind was what some of them call "custom synthesis". Entries which, *for some reason*, are not listed in the catalogue ;)
as mentioned sink is always within arms reach and the things here wouldn't do much on skin, stuff thats more nasty would warrant gloves for sure but acetone and acetic acid are rather benign (though the acid supposedly burns skin like hell but i never experienced that) and the cyclohexene while it isn't healthy whatever on my hand would evaporate too rapidly due to the fumehood and at most it would probably only dry skin out
@EdwardTriesToScience You didn't have to post this, and making the video was work. We're all here because we love watching chemistry videos. So I really appreciate you showing this reaction. Don't worry about the music, there are royalty free music selections. I can't remember the name. But videos without background music are totally okay too.
first
I sent you a DM on discord.
oh and to those wondering, i did not know a henry reaction would work on something aliphatic like cyclohexaldehyde, and either way no one sells that other than chemical supply companies
Really 😮🤓
Ho did you make the cyclohexane?
Even if labcoatz did a great video on similar chemistry you did an awesome route to the ketone, frankly! I recognize manganese iii acetate generation in situ here, something I saw a paper about a few years ago and "the poor man's chemist" actually attempted to do, so bravo. You succeeded where others showed it didn't work. So I think you might give yourself a break on same chemistry. I mean think about how many nitric acid videos are on here, and yeah, I've watched a substantial amount of those, regardless of if it's been done by someone else. Again, you proved this worked, which is just awesome!❤❤
looking at literature more closely this time yeah it seems to be manganese iii formation, me and a few others have hypothesized possible improvements but im not sure if ill try them anytime soon
@EdwardTriesToScience don't blame you, seriously. I was merely impressed you had success with it, as the other channel "proved" it was a false claim, a claim from a less than reputable website, though many chemists on yt refer to it (erowid). So you definitely had success, your description of the smell of the ketone is appreciated. I've always wondered what those ketones smell like, but no, don't need to know firsthand. Thanks for the instructional and very educational video, again ❤️ keep em coming!
Having watched a few videos, here's what I would do, assuming I had access to a steam distiller (entire glassware of a college would really be nice bc we gotta do all kinds of things): birch reduction of benzene to cyclohexane, while that's going on (or after you've made and cleaned the product), brominating acetone to bromoacetone, drying and cleaning, simply NaCO3 and then a drying agent, acid side (MgSO4 or CaCl etc). Add some (depends on your amount, I'm not sure how much to add, but it's a catalyst, assumed the chloride ions kick off the bromine from the acetone in some beautiful intermediate and then attacks the cyclohexane) aluminum chloride to the cleaned up cyclohexane in a water bath kept near 15c addition funnel charged with bromoacetone, dripdrip into the cyclohexane and alcl3, takes some 30 minutes give or take. Then this is allowed to stir for another 30 min. Then take this and steam distill for the ketone. Tada!!
@ iirc friedel crafts does not work on non aromatic compounds
@Ryan-lc4bl well.. I didn't know that, I figured it would work since what I just watched showed manganese iii acetate performing so well. I don't know how to make cylcohexene from the alkane, so idk. You killed the wind in my sail ⛵️
But wait... I got it! Benzene with the bromoacetone and then THAT ketone, treated with Pd/C and hydrogen balloon (of course purging the atmosphere of air first) and voila.. I'd make sure it fully hydrogenated before the next step as indicated at end of video here.
Very nice, I love the intro and everything really. This was a great video the whole way through. I appreciated the editing and showing the reaction on screen.
next up in editing: SbCl5
One time I had to balance the formula for cellular respiration and now I’m now In business school
You absolutely could aromatize that, but no tweaker would be able to afford the catalyst
The average tweaker is able to do things we can only imagine
They already steal catalytic converters, they have more catalyst than they'd be able to use.
how would you do that? You need to oxidize non activated C-H bonds which are remote from the only activating functional group. The only methods I can think of to aromatize this would be to either make the enone via a 2-step process plus isomerization of the double bond into the ring, followed by oxidation all the way to the aromatic ring OR to use photochemistry to absract the gamma-H atom in order to generate a first unsaturation on the cycle which could then be exploited to aromatize the whole thing
In my experience with the aromatic form of this exact compound, it is prolonged heating in the presence of acidic aqueous conditions that leads to aldol condensation and that floor polish smelling brown tar. I've found that vacuum distillation produces a far cleaner product with these alliphatic/aromatic ketones, and oxygen is not a friend during purification... i would recommend dehydrating the salts and drying the acetic acid but still use an air bubbler with a calcium chloride dry tube inline
Your analysis on the reaction mixture causing aldol reactions is spot on, probably a bunch of acid catalyzed aldol side reactions making that tar. Trying it under kinetic control rather than thermodynamic would probably yield better results as it would theoretically minimize the chance of the product reacting further under the conditions.
You can't really say the analysis is spot on if you haven't analyzed the mixture yourself :P but I agree the aldol product is one of the most likely side-products. On the other hand, there is no typical kinetic/thermodynamic control for this reaction unlike aldol chemistry, although I agree that using a silyl enolate in neutral conditions might lead to an improvement of the reaction (for different reasons). Based off the use of Manganese and Cobalt complexes, this is likely a radical based mechanism going via Hydrogen atom abstraction and many other things can go wrong.
Some patents are absolute goldmines for synthesis. Except when I want to do a synthesis then they are garbage💀
I see, you too dig deep into chem youtube. As i would have expected haha
Looks like you and labcoatz are right on the same page. One of my first chemistry projects ever was extracting the API from those nasty lil buggers. I did most of it while on the clock using my workplaces solvents lol
It recrystallizes beautifully in acetone. The smell of lavender still makes me gag. Odd choice for a nasal inhaler.
BEAST
what the john is cyclohexylacetone
how about hydrogenating phenylacetic acid and then doing the Ac2O thing?
lmao perhaps but that would be spicy for yt
Sounds doable
If by Ac2O you mean Dakin-West type reaction, I highly doubt it would work as is after hydrogenating the aromatic ring, since you need the benzylic carbon to efficiently generate the anhydride enoate with a weak base, namely 1-methylimidazole or the acetate ion present in solution. It also helps to differentiate this C-H bond from all the other Ac2O alpha C-H which could also be deprotonated. You would need to tweak the reaction conditions quite a bit for it to work, and even then, it would be very hard to selectively deprotonate the cyclohexylacetic acid selectively over Ac2O (actually there should be a preference for Ac2O vs cyclohexylacetic acid due to the CH3 being less hindered and lacking alkyl substituent which would provide hyperconjugative destabilization of the resulting anion) so you would probably make a lot of aceto-acetic acid side product with your cyclohexylacetone.
Thank you Dr. K, this was sick
nicely done, the yield was ass, but the video was well made and its probably the patent's fault
nicely done! still a cool experient with that yield. have you considered doing some TLC?
i have but i dont have a stock of pure solvents and still dont have the hang of choosing eluants
u could have tried to make the sulfite ketone adduct to purify it, would that work?
did think of that but am lazy
The phenylacetone equivalent precursor to propylhexedrine, nice! If you do a reductive amination that would pretty cool to see. Labcoatz comp lol.
I remember seeing some notes stuck to your fume hood with this suspicious-looking motif, actually thought you were trolling us at the time having that in the background.. I know you're working on this way back then.
Niiice, I much prefer this one to... the other one, you know... at least you're not cheating by starting from one step away ;)
yeah i dont even know where one could buy cyclohexaldehyde, much less for a reasonable price. then again hes all buddy buddy with the owner of chemical supplier sooooooooo (the chemicals he showed in his video are about $500 by my estimate... LAH goes for $200 per can from carolina, cyclohexylamine $30 a bottle, etc, and ive only spent $100 or so ignoring the boro which was $200 for half a kilo which will last a year or more even)
@EdwardTriesToScience ahah. I dunno about his supplier, but I know you can ask Chinese companies for WHATEVER you want... as long as you're willing to pay
@@fmdjthat's 100% true but many only do bulk orders. Like industrial scale amounts. Though you can often talk them into a free sample if you pay the shipping....
@@chemistryofquestionablequa6252 a bunch of them have 1kg as a minimal quantity, but yes it's not the most common and for small quantities shipping fees will be higher than the product costs lol. It can still be useful.
But what I had in mind was what some of them call "custom synthesis". Entries which, *for some reason*, are not listed in the catalogue ;)
Gloves man!
as mentioned sink is always within arms reach and the things here wouldn't do much on skin, stuff thats more nasty would warrant gloves for sure but acetone and acetic acid are rather benign (though the acid supposedly burns skin like hell but i never experienced that) and the cyclohexene while it isn't healthy whatever on my hand would evaporate too rapidly due to the fumehood and at most it would probably only dry skin out
You're welcome!
Nice music tho
if youre wondering its c418 - mall but slowed 802% using paulxstretch, its posted somewhere on youtube
I loved seeing this, but next time can you leave out the creepy music, thanks.
perhaps, idk just didn't have anything better on hand
@EdwardTriesToScience You didn't have to post this, and making the video was work. We're all here because we love watching chemistry videos. So I really appreciate you showing this reaction.
Don't worry about the music, there are royalty free music selections. I can't remember the name. But videos without background music are totally okay too.
First 🎉
blasphemy
@@EdwardTriesToSciencehuh 🤔
1:51 bro wear ppe please
a sink is barely a foot right next to me (its next to the hopd) lmao and these aren't acute poisons, for stuff that truly is nasty i wear gloves