Turning black pepper into piperonal cause it smells better 

21:00 btw sodium periodate does the diol cleavage

The gigachad move would be: Making peperine from mdma

Are you going to turn the piperonal into mdma cause it parties better? Im excited for this one!!

That sweet sweet methylene dioxy bridge. Every time I see this structure bolted to a benze ring, I can't help but smile from ear to ear and nod to a faint memory of muffled techno. Cheers!

Ahh yes piperonal. Very interesting structure with some very interesting uses!

“No intent of further conversion into illicit substances” sure thing bud 😉

I am convinced that this channel is a social experience to test how fast you can get arrested by the DEA from making RU-vid videos

SWIM once made piperonal by dumping piperine into a jar with acetone and a little water, then blasting the solution inside said jar with ozone (about 800mg O3 per gram of piperonal). Afterwards he added ether, decomposed the solution by addition of water, seperated the ether layer, evaporated the ether layer and was left with an amber gooey substance with an incredibly seductive smell. The yields were around 40% by mass however he never bothered with recrystallization as he used the goo directly for further fragrance manufacture.

cant wait for this channel to turn out to just be chemplayers alt with a hired VA to do the voiceover instead of the TTS

Fell into the rabbit hole of RU-vid chemistry lately and I’ve been so excited to have found you my guy! Look forward to your videos every night and although I’m definetpy not a chemist you do a really good job of making it easy to follow along. Looking forward to learning some new stuff with every upload. Much love!

It's calming to see someone else doing it and going through the exact same ordeals in the prep (like the filtration of piperic acid) like I have. To improve yield, you can do the last reaction in two phases (DCM + water). BTW there is another cycloaddition product between periodate and the vicinal diol produced by permanganate (syn dihydroxylation) and this should give you three products: piperonal, glyoxal and glyoxylic acid (I think). The smaller aldehydes turn to soluble hydrates and stay in water while piperonal won't hydrate and go to the organic phase. You may not have to isolate the piperic acid - just filter off piperate after the amide hydrolysis and recrystallize it. Going throug piperic acid will get rid of more of the piperidine though as you can wash it as hydrochloride. Quenching the reaction mixture with ascorbic acid will reduce all the MnO2 into soluble manganese ascorbate and this will avoid another long filtration - excess ascorbic may also protect some of your aldehyde product from oxidation during workup. It would be nice if you made a video about purification of the product via bislfuite or oxime and maybe recrystallization from aq. 50-70% EtOH - it would be nice to see it done by someone as skillful as you! The video is professional quality as well as the 'Hamilton' witty undertones :D Thanks sir for all the inspiration and reviving the spirit of good ol' chemists like ChemPlayer on YT!

I love how you show the mechanism of the reaction, keep making fun chemicals

You should have porous paper timblets instead of the cotton plug. There's nothing wrong with the soxhlet. It's the cotton!

Ah now only a few steps away from synthesising my own mdma

This is one of the few seldom exclusion where yellow chemistry is not awful!

This was a dope experiment bro your chemistry channel is really a revival to this side of RU-vid keep it coming bro 👏🏼💯

You packed lower cotton ball too dense. That is why it was not syphoning.

mhm because it "smells better" 👀

An ozonolysis of the piperic acid would probably prove to be better than the permanganate to avoid side reactions. I think ozone generators are relatively cheap, so it may be worth a shot

As an Englishman, the solution at 15:09 looks like the most perfect cup of tea.

24:25 "However, i really didnt get that high" That because you didnt complete the full synthesis ; )

Great vid and dive into chemistry, bub. These keep getting better and better.

Love your descriptions and other commentary on "subjective" observations of various properties. This experiment is very a much a sensory experience. You should try a simpler and far higher yield of piperonal from piperine that can be done in a one step process. Dissolve piperine in a minimum amount of dry acetone. Bubble ozone gas through the solution for 8-12 hours. That's it. It is possible to get ~95% yield of piperonal. I have managed 92% personally. There is a ton of literature out there on it so I won't go into the details. I believe the paper I used was from 1972 or 76. If you need it, I can dig it up for you. You end up with a reddish orange oil that is yellow around the edges in the resulting solution. Once the acetone is evaporated off it is already fairly pure, as I do not believe there are many side reactions, but recrystallization is never a bad idea. It smells exactly like a cherry gummy candy with a hint of vanilla. Note that this must be done in a fume hood! Ozone is nothing to play around with. It is one of the most oxidizing oxidizers in chemistry. Breathing in any substantial amount is like breathing in bleach vapor. The same goes with any mucous membrane. Preferentially it should be neutralized with an activated carbon filter or by passing the excess ozone through a solution of potassium iodide or sodium thiosulfate. The ozonolysis reaction is endothermic so the acetone solution gets extremely cold but it will not get cold enough to freeze the acetone.

Wonderful synthesis after so long from you🎉

Thank you for putting your resource links up! I'm positively addicted to doing more irrelevant things to my chemistry in the lab when you're in the waiting phase of hurry up and wait.

Solid stuff: both the chemistry and the video production.

For filtering, nothing beats a Buckner funnel with celite on the paper. You’ve never seen solutions get so clear, and never get a slow filter. A vacuum or aspirator is necessary with b funnels though, to hold the paper in on first pour.

"I extracted the rest from Amazon, 100% yield."

usually periodate cleavage is done under acidic conditions - 2 min also sounds like a really short amount of time for the KMnO4 thing, but I don't know how long it should be run for (I haven't ever run a dihydroxylation before) - I would think if the dihydroxylation was done in a discrete step, the final periodate cleavage would be facile

This is so informative!!! Fantastic video; I love this kind of content!🌻🌼🐝

"smells better", yeah...

When you connect the joints of your funnel with those of the receiving flask, you can't filter with cotton because the joint forms a seal, and thus, the air in the flask has nowhere to go. Pressure buildup within the flask and the surface tension of the liquid prevent displacement of the air with the filtrate. The diameter to length ratio of 24/40 joints does contribute negatively aswell. Btw, the type of funnel you used, is called a "powder funnel" for this reason. It works fine with particulate matter in any case and only for fluid filtration when there's no seal around it. Try it out with a different funnel or an erlenmayer flask without ground joints as the receiving flask (same setup like with the coffee filters) and it will work.

"I seem to be cursed with orange chemistry." At least it's better than yellow chemistry.

If you add compressed air to the top of your condenser, you could force the solvent over the loop for drainage.

I know almost nothing about chemistry but thanks to you and others making informative videos like this I can safely say i could replicate this rather easily, and so I must say thank you. Thank you for making these processes/synthesises easy to access and easy to replicate.

Ah yes the wizardly swirl of the flash everyone's favorite thing to do to the flask

Hmm, I wonder what a certain Grignard reagent would do to this compound? 🤔

Nice extraction and synthesis, have you ever thought about making citrulline?

Cotton always pisses me off when it's time to filter protic solvents, even for IPA. When you add water to cellulose, you can usually observe a certain swelling of the fibers which is thought to take place due to the packing of water molecules into the matrix. I suspect that H-Bonding interactions of the alcoholic solvents with the hydroxyl groups on the cellulose of the cotton forms a similar matrix which considerably slows down the flow. Otherwise I never had trouble using cotton filtration with any organic solvent. On a sidenote, is there a specific reason why dyou decided to go with the base catalyzed hydrolysis instead of acid catalyzed hydrolysis of the amide to the acid? Usually, it's much less efficient to hydrolyze amides under basic conditions because of the poor leaving group ability of the amine's conjugate base so it requires harsher conditions and longer reflux times which could result in some degradation of your products or reactant

The reason for the low yield is because the rate of aldehyde oxidation to acid occurs far more quickly than the oxidation of the diol to the aldehyde. Using your current method you are essentially destroying the product as soon as you form it. I’m not sure where I heard this but apparently a much better way of doing it is to slowly drip permanganate over many hours into a huge volume of very dilute piperic acid (sodium salt) containing the periodate with extremely vigours stirring. The moment you start to visibly see the colour of permanganate you have ruined the reaction. After each addition the colour should vanish within a few seconds. If the colour lingers you added too much too quickly. You could also try doing a biphasic system where the DCM extracts the piperonal into the organic phase as soon as it forms thereby protecting it from oxidation.

Was thinking 💭 your like Chem player and then you said it lol great videos am enjoying thanks 😊

I just read a paper about the synthesis of piperonal, so it was really cool seeing this video. The potassium permanganate method you mention at the end was one of the routes they examined, but they """only""" got a 65% yield. The other route from piperine in the paper involved ozonolysis, but you probably don't have access to an ozone generator so I don't know if you could pull that one off. In addition to the methods that started from piperine, a couple procedures that started from vanillin were described. Also, how much piperine did you recover? It isn't very useful, but I think a video about piperine synthesis would be worth making, simply because of how inaccessible it is. It also has a pretty chemical structure.

Would love to see the THF/KMnO4 method, also - great video! Love to see the chemplayer legacy get carried further - the knowledge and little tips from videos like these really helped me with all the O Chem I did so far

"I seem to always be cursed with orange chemistry" that reflection was so out of left field it LOL

awesome, keep up the work man.

Black pepper, as noted, is used to acquire Piperine, along with its isomer Chavicine, the compounds responsible for the pungency of black pepper. Piperidine, a cyclic amine that results from Piperine hydrolysis, is used with Cyclohexanone to make PCP.

Id be interessted in a video about turning piperonal into mdma but i think you cant do that on yt sadly. Awesome video bud hope it stays online

Putting a bit of filter paper down there in front of the hole before putting a little cotton in there can help. Basically the cotton was plugging the hole cus it was packed too tight. It happened to me a couple of times.

When using a Soxhlet extractor, coarser grinds usually work a tad better, esp. when it comes to draining the apparatus. I had mine clog with plant powder during first use, despite putting in cotton -.-

What was your reasoning behind using IPA and ethanol instead of chloroform which piperine is much more soluble in? Assuming you have some left from your hypochlorite to chloroform vid:)

This is a beautiful piece of content, I hope youtube plays nice!

This man oit uere doing gods work teaching children about the spiciest of chemistry. Never stop being the G that you are

Mmmm very interesting structure

14:00 you've got the condenser inlet and outlet messed up. The cold water should always be connected to the lower inlet. Otherwise you'll get an air bubble right at the hottest spot of the condenser at its entry, thus reducing the overal distilation effectivenes and even risking to break the condeser glass at the overheated spot with a random splash of cold water. But thank you for the interesting content of the homebrewed stuff anyway! Thinking about joining your Patreon club :)

You said I’m looking to get one of these. You say that coffee filters are the mainstay of home chemistry and I agree - they are REALLY USEFULL! looking good, which reflux condenser did you use on top of the sohlex extractor? Did it have a mad, huge joint. All the ones I been looking at are huge - like a #40 Joint and seems to be a spiral Graham condenser.

Ethylvanillin might be an interesting route

what is with this law and order sound effects 😂😂😂i fucking love it

In Terms of flavor chemistry..white pepper as it goes thru a fermentation step has slightly lower piperine. Additionally typical % content of piperine in black pepper hydrocarbon Extracts (acetone/hexane) ie. Is ~40% piperine. ...cool vid 😊!

The reason why the solution could not filter is most likely due to there being a fixed pressure in the flask because the joint was sealed. Lifting up the funnel would most likely fix this.

You could add saturated salt solution into the dcm/water exctraction to get little bit more product

I've wanted a soxhlet extractor for a while now but I have no other glassware or heating mantles or anything else. I just want to extract all the oils from my herbs in my herb garden. We have a rosemary plant that's probably about 100-150 square feet in size as well as many other herbs.

anyone else get bothered when he let both the other stir bars solutions B and C fall into the beaker with solution A in step 3? the thought of that chaotic tumbling had me stressin lol. great video though, lots of nice colors throughout and i'm sure it smells great. gotta love when chemistry safely satisfies multiple other senses

not seen this for years. you having fun? BEElieve and youll get there eventually! BTW in subsequent reactions you can take a shortcut and make the unmethylated amine if you decide to nitrate in a henry condensation then reductively animate from there.MDA. of course u can go the usual route, more steps to MDMA for academic research only of course. good luck!

Im just learning chemistry.wanted to try one of these extractors.have found out coffee filters suck. they are about 30 microns ive read.nothing goes through them.never imagìned them that fine.gonna save and try this video sometime...thanku!

Im so glad to see that im not the only degenerate in this thread.... keep up the good work guys

As other have suggested, a paper thimble for the soxhlet would have worked much better. You don’t have to buy the expensive analytical thimbles made for soxhlets, you can fold a couple coffee filters into a cone and it works very well. Also, it helps to pre-wet very dry powders with solvent to prevent air pockets.

You should do a lysergic acid amide extraction and (if possible?) crystallization from woodrose seeds.

Which hot plate do you use? I have the eBay classic blue one but I put an oil bath and it took ages to get to temperature - I was only distilling alcohol using a vigreux collumn (I don’t know why really -mother than I needed it to separate some yellow DMT infused solvent…anyway I refluxed using my hob as a heat source and got some stuff coming over but then the RB flask cracked - I think because it was covered with foil, I took a peak and I think the cool air cracked it! 😢 literally got it that day!

Lower cotton packed too dense for sure. Might even try something like inert glass or ceramic beads that are bigger than the tube opening as a support for the bottom cotton. That way you have a much lower chance of the tube plugging. Source: I’m a chemical engineer and this is what we do for our catalytic reactors to retain the catalyst but let the liquids go on through on an industrial scale.

The MnO2 is easily cleaned with Ascorbic acid. Just rinse with Vitamin C solution.

Do you know if methanol is a suitable solvent for the ozonolysis? I just completed a successful run with acetone, however I elected to purify the piperinal via sodium bisulfite adduct; this worked really well, actually, and my product seems quite pure. My only complaint is that the acetone has to be removed and replaced with methanol after the ozonolysis in order to do the bisulfite adduct workup because sodium bisulfite also creates an adduct with acetone. Seeing as methanol is actually the solvent of choice for most ozonolysis reactions of alkenes, I think it should work as a solvent and allow me to do my bisulfite adduct workup without the extra step of drying and re-dissolving the reaction mixture. Btw, I ran cables and tubing into my freezer that averages -14 C and did constant, vigorous stirring that created a spray inside the flask. I used the measurements you gave in the video, but put everything into a 2 L 3-neck RBF. Ozone was pumped in on one side via a gas addition adapter and a check valve was used on the other side to make sure gas could exit but air could not enter. The middle neck had a thermometer adapter. Effectively, it was a constant spray under ozone atmosphere at -10 to -20 C (depending on the caprice of my freezer). I could smell delicious cherry candy from the gas outlet tube after the first couple hours.

Still waiting for part two of this synthesis! Maybe on Nebula or less strict streaming service.

Welcome to the watch list boys and girls!

Hello sir, how did you calculate the yield of piperic acid and piperonal. Which reaction is taking place. Please answer.

the cotton in the funnel doesnt work because the space in the collectorflask is closed. it would build up pressure if the liquid drops down

14:16 Of course, stirring doesn't help against bumping in your case. Your magnetic stirrer is much too small for that. That is also the reason why you burned parts of your product. There was no stirring on the edge. Another small but perhaps helpful note: If you want to isolate natural products you shouldn't work with small quantities, at least if you want a pure product. Experience shows that such natural products have to recrystallize several times in order to get the product to some extent pure. Of course, you fall in love with some product. Therefore better more than less.

Brown Camphor oil smells great too

The soxhlet effect is caused by a syphon. In order for ot to work well you need to have a gap between the filter and the wall. That way there is enough fluid to start the syphoning and flush the tube. 🤓❤

can you extract the good smell from ponderosa pine?

Can you use something less toxic and carcinogen instead of DCM?

Bro you out here doin the lords work. Im joining your patreon and i wanna learn some more in the discord lol. Nobody else has the balls to post these vids. I bought gen chem and organic chem courses on udemy and it sucks to learn this alone. Im getting wrecked and im a software engineer.

Also. Heliotropine or just shortened to helio. Is used alot in marshmallow type flavors.. as well as the obvious cherry-garcia-esque vanilla icecream almond vibe... and perhaps even more commonly used in womans fragrance.

Piperine is crashed out and in the fridge! I got worried for a moment as my isopropyl was a deep black but yellow when in a thin layer, very strange color (I let it reflux quite a long time with the pepper so it probably dissolved some of the dyes too). Then I didn't distill enough of the solvent to be able to crash the piperine out in the flask I wanted to use, so I had to split the liquid into 5 other containers to have enough room for the amount of water needed but it ended up precipitating exactly like in the video! Filtering will be fun. Hopefully vacuum filtration won't be too painful.

I think a lot of yield was lost with the extraction. Seemed like the aqueous layer was a fair volume and usually when adding in solvent to extract you want to use about 70-100% of the aqueous volume. Usually also extract three times, maybe more if you really want some extra stuff (although if you pull in 90% of your desired compound into the organic layer you should have 99.9% of it after 3 extractions)

I wonder why you have to convert the amide to the acid if you are going to cleave off the entire side chain anyway

btw. i tend to use glass wool instead of cotton because working on a small scale. when i use cotton I tend to pack it very lightly in the stem and have a small mushroom ish part above the stem.

Hello, another user mentioned a similar process here in the comments I think, but what about washing the product with non-polar to remove the byproducts intead of distillation?

What's the purpose of it though?

The problem with the soxhlet was the particle size of the pepper + very tight packing. You can use coffee filters closed with a paper clips and larger particle size, also adding solvent through the soxhlet until it siphons will help getting the right amount in and verifying if the flow is ok through the apparatus. Great video nonetheless

Using sodium bisulfite solution works well for cleaning manganese dioxide off glassware

I think your cotton filtration isn't working because you are using a jointed funnel and it is making too good of a seal. Try breaking the seal at the joint and see if it starts flow next time you run into issues. Fun video!

Hey man, could you tell me what kind of filter you used to get the piperine out of the solution? Everything I tried just clogs and takes like hours to get through 200ml. I tried glas filters with G3 and G4 and filter paper "blue". The filtrate is still pretty much cloudy, so I doubt I can go with looser filters, but man, I don't know if my pump really likes to work 24h constantly to get through 1000ml of liquid. How did you do it?

If you use an extraction thimble, the siphon will work properly.

I once played around with pepper chemistry and made what I am pretty sure was 3,4-methylenedioxy-phenyl-aceticacid. It smelled super sweet but it was not very pleasent(possibly due to me burning a bit of it) it was either a very viscous liquid or a very waxy solid. I only made it so I could glout to my friends about mdma synthesis but I made the carboxylic acid because you can just halogenate it methylate the halide after whitch you just do a reductive amination to the ketone with methylamine HCL.

I think it would be better to recristalize piperine using isopropyl alcohol, but once you had disolved it you should add water until its not soluble anymore, and then add a bit of alcohol in order to dissolve all the pyperine. This way you will be sure that you would barely loose pyperine

i somewhere saw an prep where Mg/MeOH reduced the double bond of an piperine derivate on the 3,4 position, oxidizing this alkene would lead to the phenylacetic acid, if you want try it out :P

You have packed the shoxlet with to fine powder, thats why its not working correctly. A more coarse grind would have worked, also the exit hole must be clear from any blockage. But you can just mix the ground pepper and isopropanol in the boiling flask with stirring and heat for a while, that works too.

Sorry if others have said this, did you try not using cotton to plug up the tube? It's typical to put the extracted material in a little package made of filter paper wrapped up and secured with copper or stainless steel wire.

In case of soxhlet and filtration cotton is packed (depending on cotton you push very slightly or even not at all), and first case too much, this broke siphoning. Also from what i remember from literature, diethyl ether gives pure compound directly. And also all this could be done directly in one step ozonolysis reaction, with high yield.

You could try and make the acetate as it smells and tastes like cherries.