Chemiolis - 2022-12-24
Support my channel with patreon: https://www.patreon.com/chemiolis Literature: Procedure for synthesis of alkysbis(catecholato)silicates: http://www.orgsyn.org/demo.aspx?prep=v94p0016 NiCl2(dme) procedure: https://doi.org/10.1002/9780470132449.ch30 Photoredox literature and procedure: https://doi.org/10.1021/jacs.5b10963 (contains followed procedure in supporting info) https://doi.org/10.1021/acs.orglett.6b00024 https://doi.org/10.1021/acs.orglett.6b00208 - 00:00 - 00:59 - Introduction 01:00 - 03:46 - Cyclohexyltrimethoxysilane synthesis 03:47 - 06:30 - Alkylbis(catecholato)silicate synthesis 06:31 - 08:54 - Preparation of catalysts 08:55 - 13:32 - Photoredox reaction and workup - In this video, I'll show an innovative photoredox technique with blue LEDs and alkylbis(catecholato)silicates. This technique has many potential uses in organic chemistry and this is how it is done.
The YouTube channel Extractions&Ire has been tring to make cubane, its interesting to see other kinds of photochemistry
This is some out of control complicated catalysis. Amazing job carrying it out, let alone filming the whole thing. Glad it worked!
Just a heads up.
I have once also a PTFE piece stuck but destroying was no option.
I put it in the freezer at ca. -10 Celsius for a few hours and it came off like a charm!! Seriously, it was likeglued on, like night/day.
Yeah, PTFE has a thermal expansion coefficient roughly 5x that of borosilicate glass, so cooling it down will shrink the teflon tap more relative to the glass joint. This is also why one should be very careful if heating a flask with a teflon stopper (or glass stopper with teflon tape/sleeve), as the teflon will expand relatively more and might cause the glass to break.
I really enjoy your videos, especially because you show advanced organic chemistry and not the typical reactions you find on YouTube. I might be able to help you out with proper product analysis. If you’re interested, let me know how to contact you.
Agreed. Every chem creator has their own little niche and I love the more advanced nature of his work.
Does that offer apply to other YouTube chemists?
I hypothesize the leftover tar from most of them is more interesting than the product!
What kind of tests do you perform?
@@petevenuti7355 Not necessarily. This way, I would like to support Chemiolis high quality work + location wise, it’s feasible.
@@EthnobotanikFAQ I hope it works out! It sounds like it would be a very good thing.
@@petevenuti7355 We will see 😄
Finishing a PhD in photoredox methodology here. Your yields are low for likely 2 reasons: 1. the lack of inert atmosphere (O2 will quench the photocatalyst rather than the substrates) and 2. the flask surface area to volume ratio. By Beer's law, only the very surface mm or few of the solution will receive photons due to the high molar absorptivity of the Ru(bpy). Thinner reaction vessels, or ones with higher surface area to volume ratios, tend to work better (dram vials or even a flow setup in PFTE tubing).
I think inert gas is the key. air always mess up radical reactions.
Yes, unfortunately I ran out of N2 and Argon b4 doing this lol
3:25 cooling tube is so smol!
So pocket and tiny! He's such a good boi! Very smol
This was awesome. And more than a little complex.
Really well done. Thanks for sharing.
Great job fixing your prior issue with the column. I did my undergrad research with The author of this work, Gary Molander. Amazing chemist who has reinvented himself multiple times and come up with super useful chemistry from samarium iodide reactions, to trifluoroborates pd-couplings to this work
The low yield is very probably the reaction is not carried out in an inert atmosphere. As the Ru(bpy)3 as your photocatalyst, it generates triplet excited state via intersystem crossing since Ru has effective spin-orbit coupling for this spin-forbiddened transition. This triplet excited state can be quenched by dioxygen as it is also triplet in its ground state. This causes the single electron transfer from your photocatalyst not that efficient
You could've done it with a soxhlet with sieves in the thimble. It would've saved some steps and solvents
The most likely explanation why the NiCl2.DME yield was so low is because it turned yellow....
I work with HPLC machines, and I really liked your manual column setup
As for the lights, I noticed that the blue (30w?) Kessil aquarium lamps are used. Those are expensive (150€/$) but not neccessary. Just plough through data sheets and stuff but I think a 60-100w led COB (chip on board) + maybe a lens to concentrating the light would be ok.
Rotovap? Just do a vacuum short path and have a bowl of warm water on a jack to raise and lower onto the distillation flask. It doesn't spin but it's sure a helluva lot cheaper.
These videos are super, well done!
An advice. To prevent stuck something at the flask use a layer af the soft PTFE tape for waterproof connection of the pipes.
I think the way to optimization of the reaction of catechol and that trimethoxysilane is trying to swap the solvent for 1,4-dioxane. THF and methanol have really close boiling points hence all the pain with restarting the rection. Dioxane however boils around 101 C, so technically we can try to distill the methanol over by controlling the temperature of the rextion mixture. Of course there are many factors that can go wrong but I feel like this is the first step at least.
Could be. I wonder if it’s possible to just add 4A sieves in the reaction
@@Chemiolis maybe, but those are usually zeolites and can go ham in the mixture and catalyze everything into madness.
Pretty colors!
Amazing video, amazing explanation, you have great skills in the lab.
You MUST make a video tutorial on how to make your beginner lab
I read a paper recently about using a photochemical reaction to add acetone to the double bonds on an unsaturated fatty acid, making an oxetane ring, which lets it be cleaved in MS/MS and allows the location of the double bond to be revealed in MS. They literally just put a lamp by the electrospray, no actual machine modification necessary
Do you have link of the paper?
Standard video of this guy:
First I start with [fill in super complex molecule]. Then I add [a molecule I've never heard of]. This will then react to [molecule I wasn't aware is even possible].
My yield is a bit lower than in the literature, probably because they used [fill in some advanced 500 million dollar machinery].
I love it.
I would have liked to see you characterize it with something more accessible than an NMR. Use a plain IR Spec or get the refraction angle or check for light rotation or mp/bp etc etc.
THis channel is a total GEM! That LED strip you used LOL hahhaa! Org chem synthesis hacking. This is hacking mate. Your channel deservers way more subs. I would love to include more detailed reaction schematics of the electron flows for further learning of the basics of organic chemistry. Maybe for Patreon or donors? I would subscribe right away.
Nice stuff!
Another good video, with excellent solutions! Light is an entire field of study, so using a light source is not only simple. In trying to make light do work it must be offered no other option— and, it must find the work easier than not. I recommend creating a similar chamber of light-in-an-insulated-box then aiming the light towards a hole in the ceiling for convenience while placing the reactives in the way. This is similar to how a solar power cell works! Good luck.
Can you elaborate more on why the orientation matters? Not sure I get the difference
When light orients itself is towards less effort, since that is not productive. All work makes less effort needed. So the light will travel through a hole in the ceiling otherwise in all directions evenly. If light travels along all paths evenly it is least likely to find the work you want also! Light from the sun is this way by finding simply “the earth” and your solar panel atop!
As someone who regularly does synthesis on 10-20mg scale its so funny to hear 0.4g being called "such small amounts", lol
A potential reason why the yield was low for the photo reaction is that many of them are reversible reactions. Exposing to UV supplies the correct energy for a reaction but if it is also exposed to white light through lighting in the rooms and transporting out of the photo reaction vessel it may reverse.
Why not wrap the flask in the led strip? Even though someone mentioned cooling may be an issue, it seems like a solid wrap would give you more light in the right place? Maybe do it in a grad cylinder to make it easier to wrap.
This would definitely up yields.
That coupling reaction between the cyclohexyl and the benzene ring is very interesting, it's not that easy to couple an alkyl fragment and an aryl fragment like that, you can do that with Gilman reagents and other organocuprates, but I would prefer this photochemical pathway over handling cuprates.
Chemistry micro-photonics chips, get on it, TSMC!
TSMC: "Bb..b..but.... you're kidding... we just got everything in place for EUV by the skin of our teeth... ; - ; "
Application of the tiniest glob of clear vaseline on the stopper have saved me from stopper-related fits of fury on many occasions. 😅
Would be nice to see some photooxidation syntheses, some photo chemistry for us mere mortals, maybe the synthesis of ascaridole starting from α-Pinene?
Quick note. My TA always told me to use an erlyn for loading the silica. Its easier to keep suspended
This is some next level cursed chemistry, I’m gonna have trauma from this. It radiates the same energy as tetramethylammonium auride.
Nice video! I Remember making a similar ruthenium complex myself for some photooxidation...
If you are using oil pump, i would never use its out air for column: oil contamination
As for photochem, for good yields you want to maximise surface for light irradiation (tubes/test tubes are better than flask, small ones are better than big ones). and second, you want to kee mixture cool or better cold (cold finger inside reaction vessel works nice).
As for light box, metal kitchen ot works nicely, led strip glues good and it works as radiator for them
I just use a membrane pump, the oil pump is way too powerful and has no exhaust connection
@@Chemiolis Thanks Mendeleev beard....
Membrane pumps are awesome XD
I see that making nice photochem setup (i am talking about you Explosion&Fire XD) is not so easy, especially to make it work efficiently. Do you plan any more photochem? Or it is end for now?
For now I have no plans for more photochem like this, but maybe I will try UV in the future
@@Chemiolis Ok, good to know :)
Then making better photochem reactor is no needed for you. Keep on great work with videos!
I might not be the only one who left speechless after this video. wow
Sometimes inert atmosphere is not needed. When you have inert atmosphere you remove the possibility of oxidation (or reactions with nitrogen that are more rate). When I did research I used inert atmosphere just to make things sure (although probably it was needed often).
I haven't read the synthesis instructions, but actually a certain wavelength is always required for this kind of photoreaction. RGB LEDs may appear to emit only light of a specific wavelength. But this is not the case. In fact, RGB LEDs only mix the colors using red, green and blue LEDs that emit different levels of intensity. Nevertheless, this does not result in monochromatic light of a specific wavelength, which is often required in such syntheses. It would have been better to choose LEDs of a specific wavelength.
Ah, time for my daily short path vacuum distillation video.
give this man a tabletop nmr!
4:37
My brain: excuse me whut???
😂
Great stuff. I'm not sure about the chemistry here, but O2 can definitely act as an electron scavenger to throw off yields. But I also think the setup is a big culprit for the low yield. RBFs generally aren't the best photo reaction containers because the curved surface will cause a large portion of photons to be reflected and never reach the solution. Remember, any photons reaching your eyes are photons that don't reach the reaction.
Also a good idea to use quartz glass for any photochem
@@wingl5841 Not true in this case, the blue light is not absorbed by the glass. UV would be, but not visible light.
I'm curious what the product was, aside from just being a "clear liquid" as you described it.
Photochemistry! Gonna try biphenyl acetylene?
I have to wonder how many takes it was to get Diisopropylammonium bis(catecholato)cyclehexylsilicate out without tripping over the 37 consonants 😀
Awesome video, you're always a pleasure to watch even if you sometimes lose me with the chemistry
Do you have any idea what that pink compound was? Also, what was the point of using tri(m)ethyl orthoformate? Great video!
my guess is that it's some quinone complex; no idea about the orthoformate though
@@That_Chemist the orthoformate sequesters the water present in the starting nickel salt. Triethyl and Trimethyl orthoformate should both work equally well for that.
I've used old catechol in the past that was slightly pinkish brown, can't think of anything other than a quinone that it would be - they're often quite strongly coloured.
This pink stuff is most likely oxidized catehol, orthoformate is used probably to remove water from the reaction mixture
very cool!
@longnguyenhoang9608 - 2022-12-24
Im a professional Synthetic chemist and i'm working on this type of methodology, I'm glad that you can conduct these experiement in advance and modern synthetic chemistry !! KEEP IT GOING
@PotionsMaster666 - 2023-01-23
Hey, I am an undergraduate and want to be a synthetic chemist ahead. I really don't know the resources and opportunities and paths ahead that will lead to this. Can you help plz... I wanted to know your journey of becoming a professional synthetic chemist, so that I can take some notes 🥲
@zzzluvsk - 2024-03-08
@@PotionsMaster666 Hows the degree going? Still on track?