Making ABNO: A New Stable Radical

[@Chemiolis]

For this video, at the end, I have added an insight in the price I pay for pretty much all the chemicals I use in this video. Also, I have added captions which I plan on doing for every future video to destroy the AIs. Enjoy and have a nice new year's!

[@prbmax]

An informative professional educational video. Thanks. Just found your content and channel.

[@trailblazingfive]

Thanks for the cost analysis. My question now is how many days/hours did this synthesis take - and how much does a chemist charge for an hour of his/her work while babysitting something like that - cause we assume your time isn't free (probably could be running few synthesis in parallel, but still).

[@hawkeyeplank]

I think if your yield was even marginally higher you would have beat the sigma price, if you could have gotten 2g it would have saved you 200 euro over buying it outeight

[@mitchellangelo6738]

😅🎉

[@dieSpinnt]

2:24 "When that is done, the mixture has turned to a piss-yellow". I love science! Thank you for the effort and the video, Chemiolis!:)))

[@andreasflensmark8616]

The constrast between complex chemistry and calling a solution "piss yellow" is awesome

[@Sniperboy5551]

Have you ever seen Explosions & Fire’s videos? lol

[@andreasflensmark8616]

@@Sniperboy5551 I certainly have, and I enjoy every moment of it

[@guyvandenbroeck8405]

Still the term has shades from mountain dew to coffee caramel....

[@firstmkb]

I got a laugh out of that too, and was going to comment!

[@nugboy420]

Ik I love these.

[@KakashiBallZ]

It warms my heart seeing this carry-over fest, rather than purifying every intermediate and reporting the yield for each. My grad school time would have doubled if I hadn't done it lmao.

[@Felixkeeg]

Keep and analytical sample and carry on the rest...

[@eaeis9879]

Some advice on hydrogenations: you can simply use a smaller amount of Pd/C. To recover the palladium, use a filter paper. This way, you don’t have to waste your precious and expensive catalyst. Don’t use a frit to remove Pd/C because in it can release palladium which will screw with NMR if you use this frit for drying agent removal and crude NMR measurements. You can alternatively use sand, not celite, to remove Pd/C if you don’t want to recover it. Wash catalyst with water, when you dispose Pd/C. New Pd can actually burn pretty easily when washed with MeOH and dichloromethane.

[@adrianpip2000]

Strictly speaking, it was Pd(OH)2/C (Pearlman's catalyst) in this case, but I think most of your points still are valid. And I was also really surprised by the large amount of cash money catalyst that was used.

[@treelineresearch3387]

When something turns black all I can think of now is party balloons and confetti "TAR!"

[@unexpected2475]

(2:27) Is this a scientific description I just haven't seen before?

[@Blakearmin]

This was one hell of a synthesis! Man, that was fun to watch. Also, I need to get me a short-path vacuum distillation apparatus.

[@AsmodeusMictian]

The guy blurs the lines between chemistry and alchemy lol.

[@jogandsp]

It's crazy how much work goes into making such a seemingly simple product! Thanks for showing us this cool chemistry

[@ZeroLuckMitchy]

Holy step count!!!! Amazing how patient you must remain through all of this process.

[@petevenuti7355]

That's enough short path vacuum distillation for this year! Happy new year! Someone has to get you free NMR service for your channel!

[@ChrisContin]

Very professional! ABNO is a mineral acetone, making it unreactive at strong stabilizations. High (or low) pH, high (or low) temperatures relative to burning point, and in the presence of a catalytic by-product (such as glucoses, firerands, or axiosed chemicals- strongly axled, like sugar, hetaramine, or other organic carbons). All sugars will burn in the presence of a mineral acetone in order to release some mixture- warning! But you already know! Thanks!

[@Matoro342]

I appreciate a man that isn't afraid to call out piss when he sees it. Looking forward to your description of my life

[@nilnull5457]

You may try anchoring this ABNO to a solid resin at the stage where you had that -OH functional group. Could be used as an easy-to-recover catalyst.

[@Felixkeeg]

That is a pretty nifty idea

[@oitthegroit1297]

The fact that a radical can be stable is cursed to me lol. Also, why is it that both ABNO and TEMPO are a deep red colour? Does the N-O• cause the deep red colour in both of them, or do they just happen to be red from something unrelated?

[@guisimoso5]

I guess the reason is because of its unpaired electron

[@martineli15]

An unpaired electron in a radical probably has a very high energy which usually causes the LUMO to have a rather low energy. This can cause a low energy needed for transition, hence the color.

[@redmadness265]

@@guisimoso5 Nitrogen dioxide is a radical and it has a deep reddish color

[@oitthegroit1297]

@@martineli15 Thank you! That's very interesting to know. So far, my chemistry knowledge is slightly more than high school knowledge, so I don't know a lot about things such as orbitals and reaction mechanisms. I only have a basic understanding of both of those so far.

[@martineli15]

@@oitthegroit1297 Gotcha. It is basically about the electrons. They receive energy from the sun light and release this energy as (some times) visible light. Orbitals are the mathematical description we give them that allows us to make predictions and understand better atomic and molecular behavior.

[@elnombre91]

I may be wrong but it looks like you only used a single balloon for the hydrogenation? In future, I definitely recommend putting one balloon inside another for added security, then either electrical tape or parafilm (I prefer electrical tape or a jubilee/hose clip) the two balloons to the rubber tubing. Also worth noting that unhindered (and even some more hindered primary amines) can react rapidly with CO2, so that may not have helped. Great video though!

[@kaezaklimber3391]

Hi Chemi! You are such a hero. So much work done here omg

[@phizc]

When I saw the price of 411€/g, I went "Yikes - more than 5 times the price of gold!".. After watching the process it seemed quite reasonable, and that was *before* I saw the cost breakdown at the end. 😀

[@Chemiolis]

My yield was just bad ;(. If it was slightly higher it would have been cheaper. I still have most of the starting materials left over so might be cheaper depending how you look at it.

[@kieranodea771]

My god, so many distillations ! props for all the effort and time it must have taken to do this prep.

[@jcolinmizia9161]

Having watched a bunch of your videos, you should really invest in a rotovap and a Schlenk line. It would cut out a lot of distillation time and give you the chance to demonstrate more air-sensitive chemistry.

[@dasbuj]

One of your best Chemiolis, well done!

[@Xdreazsva]

I wanna see TEMPO synthesis too :)

[@nosmokingplz]

I was totally blown away by the end of the video that you called the patreons 'rotavaps' lol

[@midwestchem368]

Another interesting and great video man!

[@ZeroLuckMitchy]

I imagine that stabilizing ph levels could greatly preserve material and increase your yield drastically even. On the long run…I talk while you do. Great video

[@mcwolfbeast]

Wow, so many steps in this one!

[@kiloohm]

blown away here, congrats!

[@penroc3]

new here but I've been watching a few of your videos(love them and your flow) and i am shocked you are getting some of these reagents so easily, must not be in the US or Canada. Or a teacher or sticky fingered employee or student. The quest for getting some reagents and solvents is an education in it's self.

[@bdnugget]

Is the smell comparable to TEMPO? I always though it had this nice funky radical banana smell, slightly sweet and yeah like a very synthetic banana milkshake, very unique. A lot of people disagree and call it stinky. You call ABNO stinky like socks, but how does it compare to TEMPO? Is it similar in any way? Or do you think anyone would find it stinky?

[@Chemiolis]

I never smelled TEMPO. Maybe one day I can do a smell comparison (and taste test).

[@filiphabek271]

@@Chemiolis aren't radicals bad for health?

[@firstmkb]

@@filiphabek271 only free radicals are bad for you. Expensive radicals are harmless.

[@hansjorgkapeller6899]

must be a human who really cooked the whole "Organicum" / here in austria a book for chemists in organic chem. really fantastic what he does!

[@AnAcceptedName]

As someone who worked making chemicals using industrial scale specialty chemical hydrogenation, it's always wild to see how you lab chemists get some of this stuff worked out in such small scales. Its good to see that everyone still works with half broken equipment sometimes 😂

[@rehanmohammad5841]

M still wondering why that benzyl group left the nitrogen on hydrogenation ???

[@foc2241]

For Sigma products: if it has an expiry date or recommended retest then it is fine. If it has no date then I'd be a bit unsure too. You can also check with AS and CRMs (if available) to see what a good storage temperature and shelf life is ;)

[@aaronbarlow9616]

I'm here from extractions and ire. Instant sub.

[@guyvandenbroeck8405]

As my field is automation engineering I cannot say anything about the awesome physics and chemistry but I wonder about the hydrogen balloon. A) can a silicon oil be used as a sealant inside the balloon?(wet inside) B) If de hydrogen is needed multiple days, can it be produced locally with a tube to a electric dissociation device and match the production with the reagens speed? The production trigger can be a optical level switch in the electrolisis tube. I was duckshooting that this would give a good indication of how much the reagens consumes to protonate and thus give a intermediate result for yield or something.

[@lolroflpmsl]

This is a nuts synthesis!

[@chanheosican6636]

That is very cool never heard of ABNO until now. A neat alternative to more toxic chemicals hmm.

[@goryao]

Wonder what the mechanism looks like, that's pretty cool!

[@Eggman009]

This is so cool

[@martineli15]

Amazing video, amazing material!!

[@Emil-cj6ey]

Amines can react with co2 to carbamates, could be possible it doesnt happen here but could be another step where the yield diminished

[@bromisovalum8417]

Acetonedicarboxylic acid can be made cheaply from anhydrous citric acid by oxidising with 100% sulfuric acid (or preferably oleum). And glutaraldehyde can be obtained much cheaper than Sigma-Aldrich prices, as it is used as algaecide, as a fixative (alternative to formol) and 10% solutions are even used to remove warts. So this brings ABNO well in the reach of the dedicated amateur chemist (next to 4-hydroxy-TEMPO made from triacetonamine).

[@stpeter1241]

Extremely well made video and quite insightful, but, the way you said “piss yellow” had me on the floor😂

[@k9man163]

crazy that people figure this stuff out.

[@Alexander_Sannikov]

doesn't this video have more steps than nilered has on his channel total? it seems weird that you don't analyze yield at each step though

[@nerd1000ify]

If you want to make an expensive reagent, might I request carbamoyl aspartate? Last I checked it cost $10000 per gram.

[@Oaisus]

lol I haven't seen this channel before and after a few minutes of professional commentary I was really caught off guard when he described the color as 'piss yellow'

[@pennychan323]

For chemoselective oxidizing alcohol to ketone or aldehyde, Dess-Martin reagent is a better choice as no metal catalyst is required. Besides alcohol oxidation, this kind of nitroxyl radical is not a strong electrophilic HAT reagent so it can only do HAT for some activated C-H like the alpha C-H of alcohol which is activated by hyperconjugation. For this reason, I am not that interested to use this in synthetic chemistry.

[@DXLabz]

Impressive stir bar

[@АндрейКириллов-ш1ч]

In Terent'ev lab, there are even "more" unhindered nitroxyl radical of acetylacetone. If you have any interest, check this out "Org. Chem. Front., 2017, 4, 1947" In this case radical can be purified by coloumn chromatography

[@hegedusmarton8485]

The ketone could have been removed just in one step by a Kischner-Wolff reduction. Then the deprotection of the amine.

[@foc2241]

It would be nice too see what the cost of the used chemicals are (e.g. buy 1000 g for 10000 € but only use 1 g -> 1 €) cuz like you said, reuse :)

[@petevenuti7355]

Sigma do sponsorships? You deserve it!

[@aber1237]

Hi, I was wondering how you know that the crystallized product at the end is actually ABNO?

[@LightPhoenix7000]

Amusing that this is the easier version of the synthesis. I imagine a lot of this could be automated for industrial production though.

[@adamrak7560]

This is a relatively easy synthesis in the first place. There are no "-40C for a month" steps, or "separate the intermediate products in a chromatography column" steps. Even the crystallization step at the end is an optional one!

[@Ewr42]

I really hope you're Australian, bc it'd be the first time I actually distinguish an Australian accent from American I like it

[@Chemiolis]

I'm not Australian 😪 (see channel info ;))

[@Ewr42]

@@Chemiolis thx for letting me know I'm just deaf(for accents at least, but I should know that already bc of all the times I discover someone's British midway through watching something, and I only notice it if something's mentioned, otherwise I'm clueless unless it's the most obvious accent ever, and that's just on American vs British, i would never guess which is Australian between examples of the 3) Great channel btw, you're really good at this

[@markb5249]

TIL you can just hydrogenate off benzyl amines to the amine and methyl arene. Also wild how much more convoluted it is to make the amine over the corresponding borane.

[@bdnugget]

Wait, why did you purge with CO2 at 9 minutes? Amines are used as "scrubbing" agents a lot because of their ability to take up CO2 and form carbamates. Ethanolamine is a great example of this but it works on any unhindered amine

[@Chemiolis]

Of course this is a thing that exists that I didnt know of 💀 I think in this case the contact with CO2 wasnt long and extensive enough to matter. I can imagine scrubbing is normally done with high surface area. Or maybe it did something, who knows 🤫

[@glieb]

love the professionalism until "the mixture has turned a piss yellow" lmaoooo 2:27

[@spurgu9769]

I have to convince the researcher i work for to let me make this because the process seems alot of fun

[@LyraLyraPantsOnFyra]

presumably this can be regenerated in the same way TEMPO can with bleach and peroxide?

[@taifulin3943]

Concusion: Order it rather than purchase😅 Thanks for filming, very smooth synthesis technique👍

[@firstmkb]

I wouldn’t have been impressed nearly as much watching a video of Chemiolis ordering from Sigma.

[@ottowalter2519]

@Chemiolis could you please share a link to the short path distillation head? I'm looking for ones with NS29 fittings and this seems to be the one!

[@Chemiolis]

www.fengtecex-laborglas.de/shop/en/products/distillation/?p=1 I use the ones from them

[@pjahamed]

Thank you so much

[@jopmens6960]

I dont get how its explained this is stable, what do these saturated ring structures do to the electronic state?

[@spqrjack2941]

Can I still make this synthesis even if I don't have a broken flask for the drying step?

[@billyma6]

just curious, so at 3:50 you distill to dryness but in my undergrad classes we were told to never distill to dryness at risk of forming volatile peroxides. is this untrue in this situation? is the difference the presence of solid in the distillation flask?

[@Chemiolis]

It is only a problem if you would use unstabilized ethers

[@talamioros]

I did not understand the words. But colourful solutions and stirrers go brrr. I like.

[@viorp5267]

that's pretty cool

[@darkmann12]

That is one sexy stir plate!

[@koukouzee2923]

8:20 jointed funnels work perfectly for this

[@knallpistol]

What would this be used for? Nitroxy radicals?

[@chrisjones-fp5vd]

Hey I read this paper the other day on orgsyn. Awesome!

[@icebluscorpion]

how do you get this specific catalyst back once used in a reaction?

[@Kanal-ns4sq]

What is the reason behind its stability?

[@michaelryan3731]

Stability is related to the fact that nitroxyl radical decomposition has to do with alpha hydrogen abstraction and elimination. ABNO’s alpha hydrogens are bridgehead hydrogens that if eliminated to a double bond would form an extremely strained imine.

[@Kanal-ns4sq]

@@michaelryan3731 Thank you :)

[@andrewproudfoot3426]

Some chill tunes underneatth would be sick. Like ratatat.

[@vincentguttmann2231]

Needs more shortpath vacuum destillation imo

[@douro20]

Rotavaps are not only very expensive, they are also high-maintenance...

[@jansenart0]

Sodium tungstate is a fuckin sexy molecular compound.

[@spiderdude2099]

Honey, wake up, new stable radical just dropped!

[@luladrgn9155]

you should do a nilered collab!

[@marcopolo8584]

Could this be used to oxidize ephedrine and psuedoephedrine to methcathinone?

[@Chemiolis]

It won't work on most amine bearing substrates. It can work on molecules with a pyridine moiety, but amines like in ephedrine need to be protected.

[@Issveinn]

Great video and synthesis...BUT can you please try to speak more slowly or make some "silent" scenes? I felt running a marathon 😅.

[@oneofthechannelsofalltime]

I think it's missing an ester and phenyl group.

[@kingnotail3838]

Where did you buy the three way adaptor?

[@firstmkb]

All in all, this was a pretty intuitive process. I wondered why they bothered to write it up as a paper when it was so obvious? How long on the calendar do you think you worked on this? Not trying to subtract days for other work & life, just start to end. I wish I could follow your chemistry, but I never took organic, and my general Chem last class was in 1980. The yield sucked, but your product was BEAUTIFUL, and the rest is just tuning the process. Thanks for making the video, and providing some inspiration with your aspirations, skill, and most importantly - determination.

[@papasmokyy]

Why are you adding heptane to remove DCM?! The boiling point of DCM is at 40°C and the boiling point of n-haptane is almost at 100°C

[@Chemiolis]

When it boils they will distill off together, it helps in removing all of the DCM from the mixture. At the same time it will precipitate the ABNO. Since the ABNO sublimes easily it was better to not distill it to dryness and instead use heptane. Their method was more suitable for larger scale. For lab scale it would probably be more useful to completely skip this step, distill it and dry it, then do vacuum sublimation on the residue.

[@alext552]

only disappointing thing is that you weren't wearing gloves around the 4:00 mark! please be safe!

[@wissen5410]

do you need na2wo4 or can i use differend chemicals

[@Chemiolis]

It seems in literature of different procedures for ABNO and also procedures for other nitroxyl radicals they all use the combo of sodium tungstate + urea h2o2 to do the final step, so yes it is necessary

[@janefkrbtt]

After watching this I now understand why it's so damn expensive to buy in bulk.

[@douro20]

How about AZADO?

[@arminkappp]

Are you the new nile red?

[@adamdude]

If it's a stable radical, is it realllyy a radical?

[@isaacm1929]

Stable radicals are cool! -Immediately starts making yellow chemistry.

[@ProfaneGod]

You can easily see why it costs so much per gram the time and labour and multiple chemicals and steps wow!

[@asensniper]

AZADO's little cousin!

[@y.a.46]

As soon as I saw the amount of Pd catalyst used, I knew this was going over 500 euros.

[@HMan2828]

Jesus how many ingredients are in this cake?

[@nRADRUS]

Главное что катализаторы дорогие.

[@dillboticus9563]

As a stable unhindered radical, I approve

[@koreaface]

I just wanted to know like, where did you get this Glasware? Did you amass it over time? Is this a university’s lab? Thanks

[@Chemiolis]

I amassed it all over time, everything is my personal property

[@ashypharaoh8407]

What happens if you eat it?