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Fleaker
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I'd still like to see some pictures or a design of Picric/Saber's contact plant. As far as I know, I'm the only one here on SMDB to have built and
documented a miniature version of this (and if anyone else has done it, please let them speak up).
Why all the interest in piperine? This is an extraction done in most freshman or sophomore organic chemistry laboratories.
Neither flask nor beaker.
"Kid, you don't even know just what you don't know. "
--The Dark Lord Sauron
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Bot0nist
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Black Pepper to Piperine 91%IPA small scale
This little extraction was a lot of fun. I learned a great deal about recrystallizations, which is a very valuable skill. It was also challenging and
results in a beautiful crystalline and harmless end product.
I have some pictures of the process and some good notes, but I will try again on a larger scale and take pictures at every step to post with a
writeup.
Here is how it happened.
Materials:
500ml RBF
30cm Fredrick's reflux condenser
assorted beakers
filters
eye droppers
Bottle of 91% IPA
Fresh ground black pepper
<a href="http://s1207.photobucket.com/albums/bb475/TheBot0nist/?action=view&current=IPAandPepper-1.jpg" target="_blank"><img
src="http://i1207.photobucket.com/albums/bb475/TheBot0nist/IPAandPepper-1.jpg" border="0" alt="Photobucket"></a>
Note - I thought that maybe if I used freshly ground, aromatic black pepper that I may yield more piperine. While I have not yet done a comparative
run, It may not be worth all the effort. Next I will try on bulk ground restaurant pepper.
The extraction:
A stir bar and 25 grams of finely ground black pepper were funneled into the RBF. 100ml of 91% IPA was added to the round bottom flask and I then set
up for reflux using a Fredrick's and a boiling brine bath for heat. The pepper was stirred and refluxed for 2 hours and then hot filtered. The result
was about 75ml of a dark solution.
This was reduced to a thick dark oil of about 15ml in a hot water bath. I then dissolved .1g of NaHO into 20ml of hot IPA and added this solution to
the 'oil.' After about 30min a small bottom layer of oil had separated out and the dark solution was decanted off of it.
This solution was evaporated to 15ml and 30ml of ice water was stirred into it. Resulting in a yellow, milky solution.
<a href="http://s1207.photobucket.com/albums/bb475/TheBot0nist/?action=view&current=PercipitatewithdH2O.jpg" target="_blank"><img
src="http://i1207.photobucket.com/albums/bb475/TheBot0nist/PercipitatewithdH2O.jpg" border="0" alt="Photobucket"></a>
This was allowed to stand in the fridge overnight and then filtered, leaving 1.2 grams of a waxy mass about the color of brown mustard. This mass was
crumbled when dry. This waxy mass was added to 50ml of boiling water and pulverized and stirred. The 0.9grams of insoluble were filtered out and kept.
<a href="http://s1207.photobucket.com/albums/bb475/TheBot0nist/?action=view&current=WetFilteredpercipitate.jpg" target="_blank"><img
src="http://i1207.photobucket.com/albums/bb475/TheBot0nist/WetFilteredpercipitate.jpg" border="0" alt="Photobucket"></a>
The resulting golden waxy substance was dissolved into 20ml of boiling 91% IPA and allowed to slowly evaporate and cool to room temperature. Here are
some shots of the recrystallization over the course of a night.
<a href="http://s1207.photobucket.com/albums/bb475/TheBot0nist/?action=view&current=Recrystalize1.jpg" target="_blank"><img
src="http://i1207.photobucket.com/albums/bb475/TheBot0nist/Recrystalize1.jpg" border="0" alt="Photobucket"></a>
<a href="http://s1207.photobucket.com/albums/bb475/TheBot0nist/?action=view&current=Recrystalize2.jpg" target="_blank"><img
src="http://i1207.photobucket.com/albums/bb475/TheBot0nist/Recrystalize2.jpg" border="0" alt="Photobucket"></a>
In the morning the remaining few ml of golden oil was poured off the crystal mass.
<a href="http://s1207.photobucket.com/albums/bb475/TheBot0nist/?action=view&current=Recrystalize3.jpg" target="_blank"><img
src="http://i1207.photobucket.com/albums/bb475/TheBot0nist/Recrystalize3.jpg" border="0" alt="Photobucket"></a>
The crystalls were washed with a few ml of IPA that sat in the freezer all night, and then dried, leaving 0.3g of pretty little needles from the first
crop.
<a href="http://s1207.photobucket.com/albums/bb475/TheBot0nist/?action=view&current=Washedanddriedpiperine.jpg" target="_blank"><img
src="http://i1207.photobucket.com/albums/bb475/TheBot0nist/Washedanddriedpiperine.jpg" border="0" alt="Photobucket"></a>
U.T.F.S.E. and learn the joys of autodidacticism!
Don't judge each day only by the harvest you reap, but also by the seeds you sow.
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simba
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wow, impressive...beautiful crystals you got there...going for piperonal now? If so, keep us updated. 
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Bot0nist
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I am not really interested in piperonal. Just trying to brush up on my technique. This was a gratifying and challenging project. Going to try with 10
oz of fine ground black aromatic pepper this weekend, with a few tweaks to hopefully improve. I will use my camera instead of my phone and capture
every step.
U.T.F.S.E. and learn the joys of autodidacticism!
Don't judge each day only by the harvest you reap, but also by the seeds you sow.
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MeSynth
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Quote: Originally posted by Bot0nist  | | I am not really interested in piperonal. Just trying to brush up on my technique. This was a gratifying and challenging project. Going to try with 10
oz of fine ground black aromatic pepper this weekend, with a few tweaks to hopefully improve. I will use my camera instead of my phone and capture
every step. |
I tried this before too but used the ethanol / potassium hydroxide method which resulted in a small yield. Your pictures were great and motivational.
Next time I do this I'm going to try it with IPA. If that doesn't work I'm buying new pepper.
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MeSynth
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Also.. Has anyone here ever ate this stuff? I ate some and all it did was make me STARVING. lol
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SWilkin676
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WTF no one's ever heard of steam distillation via microwave? The author was incorrect in using the term solubility in regards to pepper and water
because steam distillation works when what's being distilled is insoluble in water.
Not saying this is the best way to extract pepper but it's pretty basic chemistry and doesn't rise to the level of misinformation to say heating
pepper and water in a microwave will extract stuff.
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S.C. Wack
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There's a level of misinformation there all right; it's true, the author does not say piperine is steam volatile.
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david101
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| Quote: Originally posted by Bot0nist |
The extraction:
A stir bar and 25 grams of finely ground black pepper were funneled into the RBF. 100ml of 91% IPA was added to the round bottom flask and I then set
up for reflux using a Fredrick's and a boiling brine bath for heat. The pepper was stirred and refluxed for 2 hours and then hot filtered. The result
was about 75ml of a dark solution.
This was reduced to a thick dark oil of about 15ml in a hot water bath. I then dissolved .1g of NaHO into 20ml of hot IPA and added this solution to
the 'oil.' After about 30min a small bottom layer of oil had separated out and the dark solution was decanted off of it.
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Ok so you add the solution of NaOH + IPA to the oil. Then after 30 min, the oil seperates into 2 layers.
But, just to clarify, are the piperine crystals extracted from the top or bottom layer?
Can anyone help pls? Thank you kindly.
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Bot0nist
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No, there was no organic layer. Sorry for being unclear. By "oil" I meant the thick, dirty, super-saturated extract.
U.T.F.S.E. and learn the joys of autodidacticism!
Don't judge each day only by the harvest you reap, but also by the seeds you sow.
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zenosx
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| Quote: Originally posted by idontlie | Oh the gunk.
Tried this earlier this year.
The cold acetone shake n stir method gives you shitty grey gunk that smells stronger, rather spicy, than the original pepper. Unfortunately the grey
gunk simply clogs my filter paper and I gave up on it. Maybe I need a vacuum filtration flask.
Alcohol Reflux attempts:
Traditional Reflux (denatured alcohol) stirring strong before adding your pepper is important fyi unless you don't want anything to move. Brown
liquid, filtered, brown grey residue left on beaker scraped w/ razor blade smelled fowl, kind of made my eyes water. Decided that was bad,
accidentally spilled some and stepped in it. left sticky shit on my shoe that left nasty grey track marks on the floor. Got pissed and threw it away.
Microwave Alcohol extraction (191 proof grain alcohol) turned dark black, filtered hot. Filtrate is still black, leaves thick grey tinged green shit
on your collection beaker as it cools. Second filtration left only dark alcohol. Left this for two months to dry ended up with grey shit resembling
the stuff collected on the sides of the beaker.
Alcohol (Methanol, w/ possible NitroMe azeotrope) Thick black and nasty clogged the filter. Very sticky, smelled terrible, scraping w. razor blade got
it off.
Pepper corns where ground in a food processor until about the thickness of a broken off pencil lead.
Setup for reflux was microwave, 1l rbf hanging in from top at about middle, 200mm viggy (used to give separation from the microwave for the true
condenser), 400mm west running ice water toped w/ balloon when the balloon got bigger than my fat head I unplug the microwave. Yes I melted a kleck
clamp in the microwave, I don't want to talk about it.
Originally started with the soda bottle method. Don't do that at all, the bottle warps, the cap blows off and burning hot irritating pepper blows into
the microwave and if your unlucky the roof the walls and just fucking everywhere, leaving yellow stains on everything. They come up with scrubbing but
take some paint with em. sucks. Tried deflatting the soda bottle, keeping a cup of water in the microwave with it, yada yada same result.
Traditional reflux was 500ml 400mm west, oil bath, stirring. |
I'm sorry but I LMAO at this post for at least 10 minutes. I can only imagine if OrgSyn had posts like this for syntheses.
A question that sometimes drives me hazy: am I or are the others crazy?
Albert Einstein
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ChemPlayer_
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Piperine extraction (and to piperidine) using ethanol
I worked on this recently with good results. Some tips:
1. Microwave extraction is awesome and magic.
2. Use white pepper if you can (less nasty gunk to separate).
3. If you use black pepper then filtering after alcoholic KOH addition is really important to help remove black tarry gunk - otherwise the quality of
product is terrible.
4. Lots of reviews say that the extraction of piperidine from the subsequent hydrolysis of piperine isn't worth it, but I didn't find it too difficult
(gas the alcoholic distillate with HCl, then evaporate).
I got 3.6% piperine from black pepper (in the video) and 4-5% from white.
Video here: https://www.youtube.com/watch?v=FdFEEwon6nI
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Fantasma4500
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http://puu.sh/yz8G6.png
xlogp3 of piperine is 3.4, naptha is approx 4. i have had some slight success with naptha. the procedure was to boil white pepper with ethanol, then
let that evaporate off slowly - let it catch some foul smelling fungi and thereafter scrape the horror into a small flask with some naptha, about 3
times the volume naptha. eventually with heating the goop seperated and piperine crystals magically grew ontop of the goop. these yellow puffy looking
crystals were scraped out, they werent sticky at all and i included them in the picture above.
i have noticed a bunch of times now that a yellowish ppt forms when a hot naptha-pepper extract is stashed in the freezer, however it seems to turn
brown when you let it heat up to room temperature, and it also turns out to be a sticky mess once the naptha is out from the ppt.
seemingly piperine and a bit of other stuff has quite low solubility in -17*C naptha, but doable solubility at higher temperature, this could make for
quick seperation if one were to acquire a vacuum filtration device to continously use the same solvent.
i tested the yellow crystals by first carefully melting and it would seem to be about 200*C melting point, also stings your tongue greatly. the yellow
crystals dissolves easily in ethanol. they crumble apart easily so seemingly at room temperature naptha keeps the greasy stuff seperated from the
piperine itself.
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Fantasma4500
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i was suggested by a fellow chemist to try precipitating the piperine from alcohol solution with water
at the point where it precipitates the solution is then heated up to redissolve the piperine, and its then left to slowly cool down
i stashed it in freezer straight from 60*C, 800 mL. next morning i found a gelatinous precipitate of glittering piperine crystals, quite small, but
big enough to partially settle to the bottom and make filtration a whole lot easier
i realize on inspecting the filter how much easier this makes the seperation method, the piperine flakes off dry! struggled so far to get just
somewhat dry piperine
on top of that i could let the piperine-alcohol mix slowly cool down to form bigger crystals instead of stashing it in freezer immediatedly, i found
practically zero insolubles in the filtrate which again suggests larger than usual particle size of the piperine
http://puu.sh/zVeSk.jpg
another thing: when you take it straight from freezer and pour into filter its adviced to add a bit of cold water to make sure the polarity maintains
and the solution doesnt redissolve piperine as it heats up from sorrounding atmosphere
actually i added too much water and added a bit of ethanol again until i precipitate was gone while solution was hot, havent worked out water-ethanol
ratios yet.
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LearnedAmateur
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I’ve had a go at the extraction before, and precipitating with cold water (until it no longer becomes cloudy when water is added dropwise) is the
best way to go about it. Albeit, I never had any issues with filtering the piperine through a Büchner funnel without reheating and then hot
isopropanol was poured in to dissolve it where the filtrate went onto being evaporatively crystallised, got a nice mass of sparkly crystals that way.
If you want to avoid reheating then freezing, I recommend letting the precipitate sit for a couple of hours so the micro particles can pick up more
piperine thus making them easier to filter. Just my suggestion to make it more efficient, but if that works (only way or is better) then stick to that
- also if you notice that the filtrate is still cloudy I’ve read that it is due to a negligible amount of piperine in suspension and there is really
no point in trying to extract the rest out, would probably total a few milligrams if that.
[Edited on 3-4-2018 by LearnedAmateur]
In chemistry, sometimes the solution is the problem.
It’s been a while, but I’m not dead! Updated 7/1/2020. Shout out to Aga, we got along well.
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Fantasma4500
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i believe you mean vacuum filtration when you say buchner funnel - this is what i dont have so far and as such ppt particle size is critical to avoid
multiple days for filtration to go through and ending up with a thick slurry in the filter, after redissolving the crystalline mass left in the filter
and letting it crystallize out i was left with this, or well i threw in a bit of acetone and poured it into another beaker, just to get as many
impurities out as possible, as a beautiful crystalline product is my goal with piperine im quite satisfied
http://puu.sh/A1Hyi.jpg
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eesakiwi
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If using the 'soda bottle method' squeeze air out of the before microwaving.
as the solvent heats up you can hear the bottle 'popping' as it expands.
when it stops popping. STOP!
Its expanded as much as it should...
If using the alcohol/water idea, dissolve the brown toffe leftover lump in boiling Hexane.
as it cools down clean crystals will drop out, once enough have, pour it into another beaker and reheat.
Pick the crystals out of the first beaker, or dissolve in alcohol while the 2 nd beakers reheating.
keep doing this till you have all the crystals & a ceramic like lump of the brown toffee.
hexane dissolves piperine well when its boiling, but not well when its warm.
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PhenethylamineMachine
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Just posting to mark this thread so I can find it later.
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DraconicAcid
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Yesterday, I was playing with this. I've got several different versions of this experiment- some extract with alcohol, some extract with
dichloromethane, some purify the compound by chromatography, some call for washing with potassium hydroxide.....
The little chromatography columns I have suck, and I'm trying to reduce the amount of dichloromethane we use.
One thing that I did try was adding petroleum ether to the extract after rotovaping off most of the dichloromethane. That gave me a golden yellow
solution, with some black oil at the bottom. Removing the yellow solution with a pipette, and allowing it to stand, gave me some really nice crystals
of piperine. I'll be testing their purity later.
Please remember: "Filtrate" is not a verb.
Write up your lab reports the way your instructor wants them, not the way your ex-instructor wants them.
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Gl3n
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Maybe it’s been said or not... things change dramatically over time. Piperine is freely available on eBay etc atm. I acknowledge people’s desire
to reach a molecule BUT if said molecule was a step along a chain. I’ll take extreme help when it makes sense in every way
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DraconicAcid
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I'm only interested because its a cool extraction for my students to do.
Please remember: "Filtrate" is not a verb.
Write up your lab reports the way your instructor wants them, not the way your ex-instructor wants them.
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Fantasma4500
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i was looking for some stuff on hexane and piperine and instead ended up on ethyl formate
did 500g extraction, 500mL EtOH maybe 700, 25g NaOH in the ethanol, mixed that with maybe 2L water, fridged it for hm- 3 days
on the bottom i find a bunch of piperine sludge, filtering this through a very simple cotton cloth filter i get some not very greasy piperine, some
water in that, i scoop that into 50mL vial with screwlid, add in a bunch of EtForm, piperine is already half gone, lid on, shake- now its 2 liquids in
there
EtForm is about 4g/100mL water iirc of solubility- easily recoverable and easily made.
https://patents.google.com/patent/CA2040284A1/en
the hexane boiling/cooling method is also very interesting, sounds more promising than using IPA to crash it out, crucial step is to use the right
amount of hydroxide to remove all the acid fats- i only heated the EtOH/NaOH mix with pepper extract on stove at like 50*C or lower even, maybe
overnight- NaOH can react with piperine right?
whats really interesting with EtFormate is that- one can dunk in the EtForm to clear out even the suspended piperine, nilered claims this is only a
very small fraction of the yield in suspension, .. now we can put this to the test. long dissolution time not advised as EtForm can react with NaOH to
make EtOH and NaForm
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Mateo_swe
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If the end goal of piperine extraction is to make piperonal maybe another route is easier.
De-methylate vanillin to protocatechuic aldehyde using AlI3 in DMSO and then methylenate this using DCM to piperonal.
Piperonal must be one of the best smelling aromatic compounds and is a component of some perfumes.
The extraction of piperine from white/black pepper is a nice experiment though.
I tried it long ago and got decent results.
I first tried extracting using a soxhlet extractor and isopropanol but found out that just heating/refluxing the ground up pepper in isopropanol works
just as well and is easier.
There is a ton of papers and videos preforming the extraction so check YT if you want some examples.
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