Ozonolysis Of Piperine To Piperonal...Kinda
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- Опубликовано: 20 фев 2024
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Yo, today we split piperine's cheeks and put our big ozone into it. This cleaves the double bond giving us piperonal or sorta piperonal. Just watch the video to see what I mean.
Sources:
-Paper I was talking about: chemistry.mdma.ch/hiveboard/p...
-Procedure:
www.sciencedirect.com/science...
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Наука
Brent over at Moore Analytical kindly ran a GCMS and FTIR for the final product. It seems only a VERY SMALL amount of piperonal was made. The majority of the product was still in fact piperine with phthalates from the ozone machine hosing. I will be doing further research and figuring out how to optimize this. Likely needs an oxygen source and a better ozone machine without tubing that will dissolve in acetone lol. Please make sure to thank Brent for this! He has a channel as well @mooreanalytical4105. Sad boi hours on this one. We will get em' next time.
You should try using an indicator in your reaction mixture (like Sudan Red III) and use pure O2.
This reaction worked for me for piperine and other styrenes in 95:5. The ozone generator I use is ridiculously strong so I feed the exhaust through a cold trap, combustion chamber, and ozone destruct catalyst inline. I also run the reaction at -30C to be safe.
Two things could be going wrong:
If you are using air as your feed, you will get NO radicals which will parasitize your ozone yield. And in some cases cause side reactions.
The ozone generator is falsely advertising the production rate by using some kind of analogy when representing the production rate, but not actually measuring ozone production directly.
My machine advertises 3000 mg/hr at 100%, but with optimal flow rate and pure O2, it ends up being closer to 8000mg. However a previous ozone generator I bought barely produced detectable amounts.
@@ryanfenimore4114 From your memory, do you recall what your end product looked like in solution? I used a strong ozone generator (7000mg/hr with oxygen infeed) Sudan Red III and it eventually turned into a clear yellow solution with a lighter, opaque substance floating in it. In a sep funnel, the opaque substance sunk to the bottom. Could it be still unreacted piperine, or is it the desired piperonal? Thanks.
Not sure if that would work but you could try a photochemical oxidation. You would just need a photosensitizer, oxygen input and light of course.
That benzodioxole ring would go really well together with a n-methylisopropylamine group.
Bathtub chemists unite. But you won’t get X by adding methylisopropylamine to this, dipshit. Glad I don’t live upstairs from your basement operation.
true
mdma
Depending on how pure your starting material is, a simple TLC might be helpful
что предложите в качестве чуствительной подложки и растворителя для ТСХ?
TLC is a requirement to understand what's in the mixture. Why don't more chemistry channels show this???
@@morningstarsci Because they are mostly amateurs and that takes extra knowledge, money and effort.
@@morningstarsciI am making a video that will go over this and the purification of it as well.
You need to overshoot the ozone to get good results, especially with such small generators. Also, unless its an oxygen fed generator then you are getting 79 percent nitrogen (and other gases) in your ozone blend, further reducing efficiency.
Additionally, a taller, thinner reaction vessel enables more contact with ozone.
DONT skip the ether step. You will still get layer separation. The ether step is important for purity.
totally agree with the tall thinner reaction vessel.
As I study the solubility tables for piperine and piperonal, it appears piperine is more soluble in acetone than ether and piperonal more in ether. I found blowing ozonized air for 8 hrs entrained out acetone in spite of an ice bath. This would reduce the solubility of piperonal and enhance it's solution with ether.
Haven't tried to prove this but will do so and RB. So far staying at 1gm amts. that I take to a solid paste, I did a number of these and combined.
I have not tried 10 or more gms piperine.
I love that 98% stuff from Amazon.
A simple test of purity would use Piperonal's melting point.
I think dissolving whatever you get into minimum warm ether followed by cooling. Leaving piperine suspended, while dissolving piperonal. Then stripping ether to crystalize.
I solemnly swear I will not use this knowledge for anything illegal…
just let him cook.....;)
I solemnly swear I am up to no good.
I solemnly swear to not be obedient to pharmaceutical abomination-craft legislation written by non experts in ordering the people's pharmacy to a higher accessibility and safety till justice do we part. Amen. Fidelity to the overriding Laws of biochemical function, with liberty and injustice to all.
I was just going to say that haha
And I believe you.
this video bring so much memories... i was doing exact same synthesis when i was at the university... the difference was that i started with piperic acid and not piperine. the rest was preaty much the same as in your procedure. the think i have learned is that you cant overshoot the ammount of ozone and you can just keep it running. i was running my synthesis at the doubble the ammount of time needed. I also learned that the ozone generators produce a lot less than they state and it is best to make a iodometric titration to determine your generation in the first place. it also helps to hook up pure oxygen to the generator as the nitrogen is decreasing the ozone production. and for the purification i dont remember exactly but I think i just did an ethanol recrystalisation. anyway i have tested my sample without recrystalisation on 1H NMR and it was quite pure. also, i dont think that it matters but i have made the extraction with ethyl acetate. hope this information helps you.
I've used an ozone generator for other things, and yes if you are familiar with the strong smell of it, you can kinda guess how efficient it is. With that said, pretty much every chemistry channel that's used one has also said exactly the same thing, that they are not nearly as efficient as stated.
Anyway, something I've also wondered is if the atmospheric nitrogen is producing NO and NO2.
@@nunyabisnass1141 i like to breathe NO in my freetime
@@nunyabisnass1141- Attaching an oxygen tank at low pressure to the intake of the ozone machine might help reduce NO/NO2 production.
Ahh yes, good old H2O2 sideproduct in an acetone solution.
So both your life AND your lab can flash before your eyes ...
Just manage the pH and it will be fine.
ooof good catch
What could go wrong?
WIthout adding mineral acid TATP not producted
Hell fucking yeah, >100% chemistry is my favorite chemistry
I believe the standard procedure is to introduce ozone until a faint blue color persists. This is due to ozones sensitivity to decomposition and difficulty delivering a known amount into the reaction. And not to mention, I would imagine you arent getting anywhere near the specified amount of ozone on the generator.
Ozone output level of those cheap ozone generators can be very questionable unless you measure it. Sometimes the output level can be eg. given for oxygen feed instead of air or just have no connection to reality for one reason or another. For quantitative use measuring output level is a must I think.
For purification, recrystallizing is probably always the first thing to try. Something like ethanol probably works. (never done it, just an educated guess).
typical chinese crap
You are absolutely right. It's like those Chinese power banks on eBay that claim to produce 9000000 mA/h which is impossible to say the least.
what a surprise, a society of scammers producing scam products
You're such a sub for giving in to the goth girl
She told me it was alpha to give in😞
A bisulfite adduct will remove piperonal from the mix as well as the other aldehydes or ketones in the mix. That should make purification much easier!
Good job, my friend. You’re like halfway there!
HAHAHAHHAAHAHHAHA
6:14 regarding "extract with diethyl ether", the experimental sections of scientific papers can be extremely hit and miss, either due to lack of detail, poor drafting or deliberate obfuscation; my general approach is to take them as a starting point, and not as absolute gospel
it's definitely worthwhile checking out which papers, if any, have cited the original one, as they often contain refinements and improvements to the method
After thinking about this, it seems possible that addition of even small quantities of water to acetone could cause the solution to not mix with ether. Imagine the acetone molecules interacting with water; the polar side (carbonyl oxygen) will align/ form H bonds with the water molecules and the carbon chain will orient away. This could lead to non-polar shells of acetone surrounding water molecules. Without easy access to the polar regions, ether molecules may not be able to mix with the solution. This would be similar to fatty acids forming miscelles.
It's just a guess, but it seems plausible. If not, then ya probably just some crap that made it past edits.
@@awdswimmer2it's a lot more likely that you'd get a ternary mixture of solvents instead
for sure, there'd be composition ranges in which they'd form two separate phases, but the water fraction would have to be relatively large for that to occur
from my experience of surfactants (13 years working in toiletries and personal care manufacturing, which uses them extensively), surfactant properties rarely occur at carbon chain lengths below 10, and almost never below 6
@yorkshirechemist That makes sense. It felt like a stretch, but it was the only explanation I could think of beyond just bad work up procedure notes. I just know I've seen solvent mixtures be really sensitive to small changes (4 1/2 years in a lab focusing on high performance TLC for identification), so I try to find a plausible explanation when something in a paper/procedure seems wrong or odd.
1:46 100% Nice.
I did one extra step and hydrolyzed the piperine amide into piperic acid and piperidine, then separated the two as potassium piperate and piperidine hydrochloride, respectively.
Interestingly enough, the piperate is no longer spicy :)
The cleavage should then theoretically produce glyoxylic acid, glyoxal and piperonal. There are 3 products due to two double bonds. I think the simple aldehydes can be removed by heating with base as they disproportionate easily (unlike the non-enolizable aryl aldehyde). There might be other methods of separation the products, but perhaps liquid-liquid extraction will do (piperonal is more soluble in less polar solvents, while glyoxal and glyoxylic acid tend to stay in aqueous).
I support the idea of isolating the piperonal compound as an adduct upon interaction with NaHSO3. This is simple and gives good purity for piperonal after adduct breakdown and extraction.
That's what I was thinking, but I wonder if a second aldehyde forms from the second double bond breaking. Vac distillation always an option
Bro really wants us to become our own supplier XD
hey we studied this reaction last week in my Ochem class! It's great fun watching yourcontent and slowly knowing more and more of what youre doing :)
с изосафролом проходит следующая авантюра...., в субстрате из ацетона или метилэтилкетона с добавлением 5‰-ной перекиси водорода через капельную воронку, в качестве какталитика подходит бромноватистокислый калий! направленный жесткий ультрафиолет заменяет все страдания с озоном..., и главное разительно уверенный выход по гелиотропину и минимум отчисток! ☝️
That sounds like it wants to burn my face off.
Попроси у токаря сделать реактор высокого давления и синтезируй себе эксту всякую из мускатных орешков и солянки с метиламином
Really love your sense of humour! The videos aren't too bad either 😉 seriously though, I really enjoyed this one. Ty
Great video! First thing that comes to mind is to analyze the product by TLC. Otherwise maybe smaller diameter reaction flask of smaller diameter to make sure the ozone is more efficiently dispersed throughout the solution and follow the paper generator instructions precisely. Finally recrystallization can be used to seperate any residual starting material. Small alcohols are good for recryst of piperine so gotta find another solvent.
Is squarespace going to teach me how to make PCP from piperidine?
Bruh, Hamilton will 😉
International waters
I loved o Chem. You like synthesizing some interesting compounds, some using methods I haven't seen before, like ozonolysis
I love the smell of pepper, maybe I'll love this even more!
damn that production quality is sedative
Nice! The quality of you videos keeps getting better. Keep it up man! I’ve always wanted to do an ozonolysis on piperine, but never got around to doing it because the typical ozonolysis reactions always seemed like a dangerous pain in the ass. This however, is way too easy; it’s almost too good to be true. Are you going to document more experiments on this particular methodology? More data would be great like using different alkenes as substrates, and trying different methods of characterization. I’ll have to try it myself someday, so I can do some basic tests on the product since I have an old melting point apparatus. Trying some chemical other qualitative analytical methods would also be helpful.
On an unrelated note, how’s the diphenhydramine synthesis going? Any luck?
If you're into electronics or have a friend that is, it's probably pretty easy to change out the analog timer with something that is either digital or runs longer.
The timer is just a very very dumb switch, you can bypass it.
@@tiagoangelo3828 - The timer is probably for safety to prevent overheating of the ozone generator since it heats up quite a bit. Another solution is to use multiple units at once to increase the volume of ozone. ;)
Jeez - pushing the boundaries - good luck out there ICARUS !!
Seems like you got a new camera, it looks great!
One can supposedly use sudan III, a red dye, to get a visual indication for when the ozonolysis reaction is done😘 never tried it myself though
The Bezos extraction technique is very high yielding
I don't know what anything you say means but I like you style of talking :)
That doesn't look anything like your desired product, which after recrystallization should be waxy and not like a regular old ass powder.
You can extract aldehydes from mixtures by way of their NaHSO3 adduct.
well, thats an easy way to get onto a watchlist buddy;)
@@neffix6976 look at you scared little rodent
@@neffix6976 are you bored? i sure as heck am by your brainless comment
I would second purification through bisulfite adduct if he doesn't care too much about maximizing yield. The output of his ozone generator is probably much less than stated so he would have been better off leaving it to run for a few days or attaching an oxygen cylinder
@@zevkurtzman8108 true dat, yields aren't stellar but it works more than well enough.
FCK yeah dude this is awesome... you need a method of absorbing the ozone into the substrate efficiently enough.
❤ Thank you
i wonder if there’s an N-glycoloylpyridine and/or glyoxal byproduct in there as well. some glyoxal oligomers melt around 80 deg C. if that is the case, perhaps a base wash with aqueous ammonia would hydrolyze the amide and react with the glyoxal to form imidazoles.
I tried this with styrene to get benzaldehyde... It kinda worked. I should not get any side products, but product was ultra dirty and smelled strongly of both styrene and benzaldehyde. Not sure how aldehyde is not oxidized further to acid in these conditions for prolonged time periods.
But definitely super simple prep if you need obscure aldehyde with "whatever" purity.
Probably because you oxidize the acetone instead of the aldehyde with the formed peroxide and excess ozone making some fun oxidized acetone junk and explosives. We get over oxidation all the time in our lab if we do it in pure water.
there is no way that you're not on a list at this point
Ordering piperine is enough to be on the list, but combined with his other videos, I’m sure he’s been visited by the DEA before
I guess you haven't seen a channel called "Total Synthesis" yet.
@@Sniperboy5551I haven’t been visited once! As long as you don’t have illegal intentions, it’s legal to own and make.
Maybe the ether extraction leaves behind some of the water insoluble impurities. Food for thought.
Nice of you to make a substance used in cosmetics
преоксид сафрола слишком экзотичное взрычатое впщество, безусловно ❤
I'm not super familiar with ozonolysis, but I'd use a massive excess of ozone. I'd be skeptical first of 600mg/hr, but also that it's actually dissolving and reacting, not just bubbling out. The group at my university gets beautiful blue colors running in an acetone/dry ice bath. A hot water bath with a thermometer in the bath would make a better MP apparatus than the thermometer in the tube.
Recrystallize or a silica chromathography. The product is probably more soluble so dissolve in ether/hexane and filter of any impurities, evaporate
😂😂😂😂😂 the incredibles edit was funny af
Does the ozone generator also produce nitrogen byproducts? I know the corona based converters make something like nitrogen oxide or dioxide. If this would cause interference then perhaps increase available oxygen for the ozone converter so it can provide a higher percentage of ozone.
Extraction of guineesine from black pepper any ideas on solvent great next video
A flame closed capillary tube in the same test tube filled with glycerin works as a mp apparatus
It might be interesting to prepare solutions w/ heat and then cool in the fridge, great vid nonetheless, as usual
Doesn't water react with the aldehyde to give the hemiacetal of piperonal?
i made a ozone generator for like 30$. its only 3 parts and a box to build it in. you can even buy it as a diy kit or like 50$
Make the bisulfite adduct and filter it off, usually very poorly soluble. After that you can easily convert it to the free aldehyde again with some dilute acid. All your other impurities and starting material shouldn't react with bisulfite unless they're also aldehydes or ketones.
For the product.
A simple recrystallisation and recheck the m.p.
I'm super new to this, but can you crystallize an oil? I've got either a waxy filtrate or a yellow oil after vacuum evaporation. I don't imagine I could test the melting point on either easily without recrystallizing.
An easier and much more accurate method for determining melting point of your product would be to use an oil bath, that way you monitor the temp of the bath itself while having a small test tube of your product sitting inside. In school we used silicone oil because it had a really high smoke point.
I did that as well and had a similar melting point :)
I love to recrystallise from cyclohexane as my first solvent of choice. However, piperine is more polar than piperonal therefore I would try something like ethyl acetate. Or maybe a mixture of both solvents.
I'm just curious. Did you use a fish air tank pump to pump through the ozone machine or pure oxygen? Cause if you used just environmental gas theirs going to be a lot nitrogen oxides mixed in there. And did you use a inline dryer before feeding it into the ozone machine? Cause if the humidity is high your producing small amounts of nitric acid. I'm asking cause that could be a reason why your yield was a little low
Were you feeding the ozone generator dessicated oxygen? If not, the ozone product from the generator will be quite lower than expected or advertised.
Love your videos. Could you please talk about your experiences as a chem major sometime? How hard do you find it? What interesting stories do you have and what are your future academic goals?
Purification through the bisulfite adduct?
My thoughts exactly.
Interesting looking molecule that certainly doesn't look close to any other molecules that could be pressed into pills
I wonder if feeding the output of a medical oxygen concentrator to the ozone generator would help, because then you don't have any nitrogen compounds present. Also perhaps getting a hyuge capacity ozone generator because chinese companies on amazon lie about the stats of the equipment.
They say you can get asthma like symptoms for years after large ammounts have been contacted.
Hey, ChemD. I wanted to thank you for your videos. I have no notable background or understanding of chemistry, and so most, if not the entirety of your content basically goes right over my head. It's not an excuse; it's a reason. I went the whole, Good-Enough-Diploma, some community college, military, then the trades, kinda route. I'm fine with that.
Anyway, specifically: you, That Chemist, Nile Red, Extractions&Ire/Extractions&Fire, ... I'm sure I'm forgetting a bunch of others ... have taught me so much. I will, just as one of those things I want to do one of these days, take some remedial math, chem, physics; because you guys are freaking cool and I want, now, to know more. Which necessitates more school. I'm not exactly in a place to do that right now, so you will educate me.
I had never even heard of ozonolysis until I read the video descriptor.
Thank you. Now I have something to lose myself in for however long. I mean this in no way ironically...you're a rock star. Good work, brother.
I also enjoy living vicariously through chemtubers. I have a passion for chemistry, but my math and physics knowledge isn’t there, at least not any more.
осталось проверить растворимость в нитроалканах и на предмет конденсации с таковыми тоже неплохо протестить Ваш тетраозонид 1,3-бензодиоксаля
I suggest TLC. Also you could react your product with hydroxylamine to make the oxime, the melting Point should be known
Loving your editting lol
Why the video stops here ? There are a few more steps 💊💊
Extract Thorium from thoriated welding welding rods
Sep funnel for the ether step? Idk, thats what I would try. Or shake the living hell out of it, create an emulsion, and centrifuge.
do you by any chance wanna show us how to add a n-methylisopropylamine group to that molecule? i have a feeling it would get a lot of views... just saying
recristallize it in ethanol for purification
hypothetically if one had an ozone generator that just lets ozone out in the air, how should he capture it to pump into the solution?
Will this work ? Piperonal + MEK --hcl-->B. Then B + Peracetic acid (Glacial Acetic acid and H202) = C. Then C + NaOH = p2p
Recrystallization, my dude. Also more ozone (those generators are pretty much never up to spec). Could maybe also do some washes in a sep funnel.
For the melting point, at least get some mineral/silicone oil and put your compound in an inner tube or capillary. Having your thermometer just touching the bottom of a test tube is not gonna provide adequate heat transfer.
I did that melting point test as well. It came out around the same! Others mentioned doing a bisulfite adduct, so likely I’ll do that first before recrystallization
A Baeyer test would reveal alkene impurity
You can also take the mother liquor and make TATP👍
LIKE VERY NICE VIDEO
I think you need more ozone and maybe better temperature control.
Maybe 5C instead of OC.
I 100% need more ozone and an oxygen supply too. I had a GCMS run on it and it came out to a terrible conversion 😂
Piperonal has a melting point of 37 °C and a boiling point of 263 °C so I would think you could just melt it and filter off anything solid 45 °C or lower as you dare, then heat up to 250 °C to boil off anything with a low boiling point, then let it become solid. then I would think you could just do normal recrystallization let it dissolve in small amount of hot water(solvent) cool it then filter when solid. ruclips.net/video/04HWovMzkAk/видео.html
Why is chemdelic breaking bads all of the sudden
Chemdelic is Breaking Good. ;D
Writing down these procedures like cooking recipes and not understanding them… I no longer feel safe but I must push on!
where recrystallization
Salt and ice is very cold? You were raised in SoCal, weren't you? 🤣
The smell of this stuff has been described by so many things. I Still have no idea what it smells like.
It smells just amazing...
Ectric trains in the 70s
Ayo did that goth girl’s name happen to be Molly by chance?
I swear i would not use this to make MDMA 😭
Send me your samples and I will analyze them.
Send me an email Chemdelic@gmail.com
make the ketone using iron, zinc or tin and I will let you know how to properly do it :)
Amozone
amazine
I think using a sep funnel extraction and then doing a simple recrys would give you pretty pure compound. Organic chem never comes out pure the first time and tbh you’re lucky if it works with just a sep funnel or recrys. Often times you gotta resort to column chromatography for complex structures.
I'm not a chemist, but amazon ozone generator specs are full of shit and it wouldn't surprise me at all if you needed 10x as much gas as calculated
I swear dude, this channel is che player number 2. It has every vid indirectly related to precursors of drugs. Very nive and useful, but will get deleted feom youtube soon I am sure of that
Everything is legal and I just like the smell of what I make! No plans to make anything “special”
@@chemdelic dont get me wrong. I really enjoy these vids, just like I did chemplayers. But although techically legal to synthesize, they could report to youtube, since they are precursors. Thats what happened to chemplayer.
Anyway I agree to the odour part. Many of these had mindblowing smells, when I made them myself. Especially the piperonal for me.
Keep up the splendid work.
use column chromatography
You do, actually, have the equipment to do that.
TLC and other ones yes. Which I will be doing in another video. However, NMR, I do not have.
@@chemdelic even oxime precipitation with dollar store ammonia would detect unreacted piperine... But it's a thin line between "tinfoil art" and "mass spectrometer"
@@jtmediaholdings7877I was thinking of doing Tollen’s test for the video and TLC, but I wanted to put all of those into a new video.
@@chemdelic tollens under tlc would be an absolutely beautiful developing method, and contaminants would likely themselves be aldehydes.
You should wash your product with a sodium bicarbonate solution to remove any piperonylic acid, which inevitably is made in an oxidating solution
If you liquefied the ozone would it make a difference? Super concentrate it. I will never perform this reaction for the record. Piperine is good medicine by itself!
...So "100%" yield" is a euphemism for "bought it on Amazon"?
Man, imagine this would end up in an anise smelling HCL.
Wouldnt that be crazy?
yo, uh... column chromatography?
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