Five Unexpected Reactions

[@ThatChemistOld]

Make sure you subscribe to the new channel where all the new videos will be posted! kzbin.info/door/0nEDA3uRd5YuvBfMwQNteg

[@Bobbias]

As a non-chemist, I could barely follow anything in this, but the structure of the unexpected result in reaction 4 looks cool.

[@pannekook2000]

having worked with bioremediation that octafluoro ring sets off all of the alarms. really really really glad nobody figured out something useful to do with that compound in the 60s cuz that kind of structure sticks around basically forever

[@maxmuenchow]

Very interesting watch. Especially the 4-ring structure I would've never expected to form there

[@ThatChemistOld]

A lot of reactions are intuitive after you figure out what happened - everything makes sense in retrospect

[@romanpolanski4928]

There is a simple mechanism for Reaction 2 which explains why the tetramethyl intermediate fails to undergo the S-methylation: base-induced elimination of cyanide gives a thioquinoid species which can S-methylate. Repeat for the other thiocyanate and only then N-methylate and you have your hexamethyl product.

[@ThatChemistOld]

This is an extremely reasonable rationale!

[@romanpolanski4928]

@@ThatChemistOld I spoke a little hastily in my first post. The intermediate after the first S-methylation is an ortho quinonediimine (not sure how you name the nitrogen equivalent of a quinone!). A nucleophile is needed to remove the second nitrile to give the thiol, which is then methylated, giving the final product.

[@showmeyahmoves]

@@romanpolanski4928 wow, award winning film maker, rapist, AND chemist???

[@romanpolanski4928]

@@showmeyahmoves It's a pseudonym!!

[@thomasalanine9801]

The third one is really cool. Its useful to note that because the carbon-sulfur bond is longer than a typical carbon-carbon bond, the ring strain is not as extreme as the 4-membered ring structure would make you think!

[@ThatChemistOld]

Yeah I’ve made a thietane from 1,3-dibromoacetone and the 4-membered ring formation is easier than you would think!

[@kalrbaum]

1, 4 and 5 are pretty reasonable. I have had the same side reaction as in 1, if i left it going for too long. 2 and 3 however are pretty funky :D

[@YoAddicts]

I love these types of videos. I work with per-fluorinated compounds in the laboratory for my PhD, and it's quite interesting of what un-expected reactions can do. I actually never used to like organic chemistry till I had a proper mentor.

[@hasanjebory6629]

Wow what a hidden gem of a channel. I’m so glad I stumbled across your channel since I really enjoyed ochem and can’t wait to go to grad school for chemistry, so this channel is such an awesome source of insight and entertainment! :)

[@ThatChemistOld]

I'm so glad to hear that :D!

[@ahmedaldoori6221]

I will suggest this channel to my supervisor, he would love to see all of your videos. My supervisor got so many unexpected compounds while he was working on his Ph.D. His work was mainly focused on tertiary phosphine complexes

[@mineovernutter]

reaction 3 is really unbieveable if you hadnt shown it experimentally. really quite a beautiful reaction. Kind of thing youd expect as a q "question 12" in a final exam.

[@ThatChemistOld]

I’m glad you liked it!

[@eleetfleet4506]

Subbed! Always love finding new chem channels!

[@ThatChemistOld]

Awesome! Thank you!

[@BlackPawn14]

Had to look up Reaction 3 in Wikipedia, since the 4-atom carbon/sulfur ring looked so bizarre... and apparently it's named 1,3-dithietane 1-oxide, and there's at least one mentioned reaction to make it (allegedly by reacting bis(chloromethyl) sulfoxide with sodium sulfide in the presence of quaternary ammonium). It's loosely related to the lachrimatory agent in onions, too, which is pretty interesting (that such a wild structure is actually found in nature).

[@AaronBlazeproductions]

That moment when you realize you actually understand the video 👀

[@JOpethNYC]

Chemistry and physics teacher here 👨‍🔬👨‍🏫Definitely cool, keep up the research! Just shared this with my chemistry PhD friend.

[@kashjpm2272]

Just started learning(middleschool) chemistry seems interesting, great video!

[@ThatChemistOld]

I'm glad to hear it! One of my biggest beefs with pre-university education is the complete lack of exposure to what being a scientist actually looks like. Even in high school, we barely got any sense of what a career in science could even look like.

[@kashjpm2272]

@@ThatChemistOld Ah alright, I have an idea for a youtube video if that's something you might be interested in, you could make a video of how it is in the chemistry industry so people can see how it is. Would help me out big time to see if it's something I'd be interested in

[@ThatChemistOld]

@@kashjpm2272 There are a lot of different experiences at different levels - at the undergrad level, you kind of get to feel out what research is, and discover the world of what is possible. In a PhD you get a sense of who is doing what, and why (and you usually get to meet everyone who matters if you are diligent), but beyond that stage there are many different paths you can take

[@ThatChemistOld]

@@kashjpm2272 If you like chemistry, maybe try checking out NileRed - his videos are pretty approachable for non-experts

[@kashjpm2272]

@@ThatChemistOld I'm pretty sure I've watched all of his videos already haha, even the MrGreen parodies before the dude had like 1k subs, pretty sure I've watched most of the good chemistry content on KZbin so far

[@v.567]

Chad Kekulé line benzene instead of virgin circle benzene as a profile pic? Subscribed.

[@ThatChemistOld]

Kekulé for life

[@v.567]

@@ThatChemistOld My man.

[@benwhitehair5291]

Tbf who genuinely uses the circle nomenclature? Its entirely useless. Conjugation is best left interpreted. I only ever really saw it done at A level

[@BODYBUILDERS_AGAINST_FEMINISM]

I have zero chemist knowledge. Forbidden ice cream sandwich was nice though

[@ThatChemistOld]

Yay somebody liked the joke

[@Falco.]

I'm so glad I found this channel! I personally study pharmaceutical chemistry but I love Organic!❤️ Subscribed!

[@strangeanimations2518]

So glad I found this channel

[@ThatChemistOld]

So am I :D

[@ozonefreak2]

For reaction 2, it would be interesting to cyclize the tetramethyl starting material to see if it’s a function of ring electron density. Maybe all the methyls twist the anilines out of plane and reduce the sulfur’s nucleophilicity

[@ThatChemistOld]

Yeah and see effect of substituents on the outcome of the reaction

[@crabcrab2024]

Very interesting! Thank you.

[@ThatChemistOld]

Thanks!

[@joshuaalmonte8546]

Dude, this was an awesome video. Please make more like this. Would also love to see what other chem videos you could come up with.

[@ThatChemistOld]

Thanks!

[@ThatChemistOld]

I have another video like this scheduled for Tuesday

[@matheussales4861]

Awesome!

[@limmuquan4796]

As a student learning about chemistry in high school, this is really interesting!

[@ThatChemistOld]

Glad to hear it!

[@tolleyt8270]

starting undergrad chemistry this year and this is very intriguing

[@ThatChemistOld]

Glad to hear it!

[@kagamer21]

This was very cool, I would love to hear more!!!

[@ThatChemistOld]

glad you like it! I have some more good ones, and I will do another video like this in the future

[@wannatalkscience4136]

I think the third is the coolest and the forth looks pretty predictable. Thanks for awesome content!!!

[@jesse4202]

Just came across this channel. And glad I did! I hope you pursue a degree in chemistry or materials science down the line and this has really piqued my interest in it further. Keep it up

[@ThatChemistOld]

Thanks! I'm currently writing up my PhD in organic chem.

[@raffine_9705]

This is really interesting! Wanna hear more about it

[@ThatChemistOld]

I have another video about more reactions which is dropping Tuesday!

[@annunzarizzle]

reaction 3 was literally mustard gas reaction. cool product for sure, dam strained ring. That carbonyl is begging for some love.

[@ThatChemistOld]

the sulfur actually has pretty big orbitals, so the 4-membered ring isn't as bad as you would think

[@annunzarizzle]

@@ThatChemistOld Yeah I'm not perfectly sure about this one, definitely not made anything like this but you would think the orbital size mismatch does not lend well to stabilization of the carbonyl.

[@ThatChemistOld]

@@annunzarizzle it will definitely be electrophilic

[@slimp4644]

Very insightful! How do you handle or dispose of those mercury salts in the end? Also no Sigmatropic cyclization variants of the allyl species?

[@ThatChemistOld]

I followed a workup procedure for the specific compound - I believe that I did aqueous washes, followed by a filtration through celite, and the celite and any aqueous waste went into a mercury waste container for disposal; I did several DI washes of all of the glassware as well to be sure that I got all of it. It was the one and only time I have used mercury, so I was overly anxious and careful.

[@ThatChemistOld]

For your second question, could you be more specific? I never attempted to do an allylic rearrangement, although I am familiar with the reaction that you are talking about. At one point in time I tried to make mono-allyl catechol to make 3-allylcatechol as a substrate for my paper involving catechols, but I got a bunch of bis-allylated product, and my undergrad didn't feel like purifying it lol

[@ThatChemistOld]

the sigmatropic rearrangement of allyl aryl ethers required higher temps typically - the alkylation reaction was done at rt

[@vevenaneathna]

been a long time since ochem. still remember how to make meth from pseduo though. really good summary of most 200 level ochem reactions. SN1 haloalk formation (i think thats the first rxn everyone learns), E2 w/ strong base (i think thats the 2nd set of rxns u learn), H2 across double bond (that was somewhere in the first semester too) cool vid

[@ThatChemistOld]

Did you base that synthesis on WKUK “the never song” - it’s much simpler than that

[@vevenaneathna]

​@@ThatChemistOld oh no thats the red phosph method which i think has better yield and is the old way to do it in bulk but awhile ago they banned the iodine source, or atleast made it much harder to get (i think it was like tin iodine as a gardening ingredient or a wood stain? not sure). I also think that method used diethyl ether which smelled really loud and would cause labs to make the evening news every now n then lol so everyone switch to the poor man "shake n bake" during the late 2000s. 1 [s] + "something that contains a stomach juice compound", altered 4 youtube rules 2 Li -> LiOH 3 H2, delta T (Li metal as catalytic surface?) really kind of an elegant 3 step reaction that happens simultaneously. crap yield but you can do in one vessel (soda bottle) and by exploiting the buoyancy of Li, and maybe an interface between a lipid layer on top like napth and an aqueous layer on bottom, you can both shake it to control LiOH formation and burp the bottle to control hydrogenation. people on forum boards used to talk about doing it while walking down the street in public which i think the complexity is underappreciated lol lets see if this comment gets me banned

[@giovannipelissero1886]

This was very interesting. I'm currently studying chemistry in uni for a bachelor and planning to get a master and eventually a PhD and this video was particularly entertaining to watch. I would love to do stuff like this in the future. Thank you again for sharing your work!

[@ThatChemistOld]

Thanks!

[@annunzarizzle]

In the first example. The elimination is kinetic. Once Kcarb deprotonates, thats it. Its non reversible. These types of products are quite expected, in reactions that let off a gaseous product such as CO2. A lot of chemistry is driven by the release of a small molecule or gas that is then captured or lost to the atmosphere. Its the final product that is being eliminated due in small part to the phenoxy ether withdrawing effect, but more likely due to the chelating effect of the ether oxygen with the potassium of the Kcarb(or 2) and maybe a DMF(or 2), directing the elimination and stabilizing the transition state for that to occur. Otherwise no, your not getting elimination in the absence of heat in DMF on a dibromo alkane.

[@ThatChemistOld]

Yeah but E2 eliminations are concerted, not discrete two step processes - the K2CO3 deprotonates as the bromide is eliminated; typically HCO3- won't give off CO2, unless it is heated, which wasn't the case in my scenario

[@annunzarizzle]

@@ThatChemistOld I agree its E2, every condition you have is setup for that. My only point was you could easily draw a six membered transition state between that ether oxygen and a single Kcarb molecule. Once you see that its no longer a mystery how that transition state proceeds to afford the product you observed. Which is why I said it was kinetic. Its quick, not energetically favored, but there's just a perfect setup and once that collapses, its non-reversible.

[@ThatChemistOld]

@@annunzarizzle Oh I see, I didn't gather that from your initial comment

[@spiderdude2099]

I would assume for the one with the methylated thiosulfates here’s what’s going on: Iodomethane can pretty much be thought of as a source of free CH3 + carbocations. The C-I bond is weak and some amount easily forms in a lot of reactions. The bond of the CN to the sulfur in the thiocyanate group is also a bit weak. So you have a CH3 + cation come in and attack the sulfur and pop off cyanogen iodide. Granted this isn’t the whole picture because it doesn’t explain you not forming it when the pre-methylated amine was used, but I think maybe in the first case having free primary amines in the first reaction condition may have more greatly favored the production of CH3 + species. Whereas the tertiary amines in the second set of rxn conditions could not facilitate it. Also, the same rationale could be used to explain that the main mechanism comes from one of the conditions facilitating the elimination of the CN from the SCN. Either that or the formation of CH3 + cations could explain this.

[@onbekende07]

Guess the formation of HI when methylating the amine's helped. You needed the free iodide's to help it along I'd guess.

[@waterunderthebridge7950]

It’s kinda interstate to think that we’re probably constantly making molecules that have never existed in that constellation (and/or in that amount) in the known universe

[@ThatChemistOld]

most of space is too unhospitable for molecules in general!

[@waterunderthebridge7950]

@@ThatChemistOld Yeah, most of the universe is just a big nothing with a sprinkle of simple molecules. Also just realized interesting was somehow auto-corrected to interstate lol

[@MrYuchiang]

I'd like to see some analytical data to support all those claims. they all seem possible but I'd get convinced with an NMR and a HRMS

[@ThatChemistOld]

I fully agree, you should take everything with a grain of salt unless you have full characterization data

[@ThatChemistOld]

I reviewed a manuscript last week, and the authors weren’t even willing to include 1H or 13C NMR for their standards, even though they were previously reported - all they would report was 19F-NMR

[@carterbrz2]

That indole vinylation might actually be quite useful… acetylene is pretty hard to work with in an academic setting (unless you have any suggestions??) and other indole vinylations are inconsistent at best in my experience. Not sure I wanna touch mercury anytime soon, but cool reaction!

[@ThatChemistOld]

yeah you just use calcium carbide in water as your source and connect the gas to your vessel

[@ThatChemistOld]

if you look around I think there is a paper discussing it

[@flaplaya]

Actually a compound I've made, the 2-chloropropane. Ultra flammable. My condenser wasn't efficient enough so only gas passed immediately igniting from the open flame 20 inches away. The bromo version is easily condensed. 2-propanol + H2SO4 + NaBr or NaCl ---> reflux = 2 Halopropane. Wonder if sodium fluoride would make the fluorinated molecule? I'm a scaredy cat with fluorine.. Really enjoy these videos thank you for interesting content.. 2-Methyl Aziridine synth available?

[@ThatChemistOld]

It is a lot harder to do the reaction with fluorine - you would need to take the chloride or the bromide and do a halogen exchange, but you could definitely find conditions on scifinder

[@ThatChemistOld]

What were you wondering about aziridines?

[@Autepify]

#4 looks like a spider

[@nbonasoro]

I feel like I was shown something interesting only I couldn't understand any of it.

[@briang.valentine4311]

Reaction 4: I cannot understand how a free radical mechanism could account for the perfluoro ring cyclization on the benzene ring. Free radicals don't interact with benzene (e.g., UV light + chlorine + toluene -> alpha chloro toluene, no chlorinated toluenes are seen)

[@ThatChemistOld]

There is established literature on this chemistry - it is possible that an aryl radical from BPO reacts with the Rf radical, but the likelihood of having two radical terminate each other is really unlikely; the copper catalyst helps oxidize the C-H of the arene to H+, reducing the Cu(II) to Cu(I), and the resulting Cu(I) is oxidized by another BPO to make benzoate, a benzoyl/aryl radical, and Cu(II)

[@briang.valentine4311]

@@ThatChemistOld Hmm. But if that's true, any of the 5 remaining arene protons are equally susceptible, and you would have a wide variety of products, I think.

[@xmgBv]

Reaction 1, I think this is Neighbouring Group Participation, the oxygen lone pair can react at the carbon bearing the bromide (4-exo-tet, baldwin rule allowed). Leading to a 4 membered ring with a positively charged oxygen, elimination of beta-hydrogen forms the minor product.

[@ThatChemistOld]

3-membered ring - come join the discussion in the discord! I’ve drawn out a possible mechanism in the video discussions channel

[@bobgill4069]

What does the slash R on the benzene ring represent in the first reaction? I'm embarrassed to say but I have a BS in Biochemistry and I'm honestly not sure if I ever got an answer to that.

[@ThatChemistOld]

It just means some group, in some various position

[@bobgill4069]

@@ThatChemistOld Oh ok. So whether it's an alkyl group, or carbonyl, or even just an H?

[@nicklashees7312]

Luckily it got fixed in the last update

[@ThatChemistOld]

Hey this isn't a tierlist video - no TierZoo jokes allowed >:(

[@johanneslam8594]

Ex-computationalist passing by. Need my brain for the chem party?

[@ThatChemistOld]

We always need computational people!

[@johanneslam8594]

Great! Have been a mechanism fan since undergraduate days. Are you interested in MOs, especially HOMO-LUMO stuff or solvent fields? I played Gaussian and a little CP2K for AIMD (molecular dynamics).

[@ThatChemistOld]

@@johanneslam8594 i am not well-versed enough with Computational work

[@paologuerini9339]

No disubstituted product formed on 1 at all? that's also weird

[@mylanremon4204]

Nice video :)

[@ThatChemistOld]

Thanks!

[@jeremiahbeavers9133]

I can't be the only one who thinks he's speaking Greek.

[@ElectronicMusicDaemon]

Hello, I wanted to ask you something. I have a bottle with potassium dichromate that I made for myself as a birthday present and I always eat next to it. Yesterday I discovered that the compound is carcinogenic. Is something bad going to happen to me?

[@ThatChemistOld]

I am not a doctor, nor do I know the extent to which you could have spilled it - it is a good idea to keep toxic chemicals away from where you eat

[@sexton_hale24verinaud66]

I love cursed chemistry lol

[@royaniv]

how do you know what the product is? do you test in in a mass spec or what? how do you know the exact structure?

[@ThatChemistOld]

Combination of NMR & mass spec depending on the compound

[@beka4080]

I only study at school and probably don’t understand something, but wasn’t that obvious that in the fourth reaction dicycle was going to form? I mean if one iodine is attacking the ring, why did you expect that another one would not?

[@ThatChemistOld]

Equivalents of initiator/equivalents of starting material; it didn’t happen with a two carbon dihalide, but if it did happen, a four membered ring would form so 🤷

[@Vexins]

Yellow chemistry is bad, didn’t you know that before deciding to pursue research involving sulfur

[@ThatChemistOld]

unfortunately Explosions&Fire made that video after it was far too late

[@justinedward9243]

i think theres always competition between E2 and SN2?

[@ThatChemistOld]

depends on conditions - most of the time in a research context you can selectively get one vs the other

[@radwanalnajjar9374]

Do you any experimental data such as NMR or MS? We can do theoretical investigation

[@lyrimetacurl0]

Thiocarbon eel?

[@cooleslaw]

Nice

[@ThatChemistOld]

🙃

[@stephenjacks8196]

If the O=CS2CH2 "enolized" would that four member ring be aromatic?

[@ThatChemistOld]

it would still disobey Huckel's Rule

[@Roedygr]

How did you identify the unexpected products?

[@ThatChemistOld]

hard work, prior experience, skill, patience, ADHD

[@Qwayta]

Is this weird 4-membered ring a solid? If yes, is it crystalline?

[@ThatChemistOld]

oil

[@ThatChemistOld]

it might not have crystallized from the 2-chloropropane though

[@thenightdriverofdeoli9258]

In the 2nd reaction scheme was CNI (Cyanogen Iodide) a side pdt?

[@ThatChemistOld]

In theory, but I never confirmed it’s identity

[@thenightdriverofdeoli9258]

@@ThatChemistOld Anyone this video is awsome, opens the doors of fascination of OrgChem.

[@ben_yeates]

are any of the bi-products useful? would it be useful to further study them?

[@ThatChemistOld]

Perhaps

[@htomerif]

Huh. Am I pronouncing "phenol" wrong? Or are you just messing with people...

[@ThatChemistOld]

Fenol vs feenol

[@htomerif]

@@ThatChemistOld I'm conflicted because google agrees with me about how to pronounce "phenol" but agrees with you about how to pronounce "acrolein".

[@tissuepaper9962]

Come on, I can't *not* laugh at "unexpected cleavage".

[@ThatChemistOld]

the funny thing is I could see people searched "cleavage" into youtube and arrived at my video about periodate cleavage of 1,2-diols

[@tissuepaper9962]

@@ThatChemistOld now *that* is some "unexpected cleavage", lol

[@remember6303]

How old r u?

[@ThatChemistOld]

somewhere between 0-100

[@KennardAlfredLim]

Edited.

[@ThatChemistOld]

sounds cool, I hope it goes well for you!!

[@charted8015]

Not helpful at all.

[@ThatChemistOld]

:(