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Author: Subject: Pepper to Piperine problem
Fleaker
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[*] posted on 18-7-2010 at 13:31


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.




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[*] posted on 24-9-2011 at 11:15
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&amp;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&amp;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&amp;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&amp;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&amp;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&amp;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&amp;current=Washedanddriedpiperine.jpg" target="_blank"><img src="http://i1207.photobucket.com/albums/bb475/TheBot0nist/Washedanddriedpiperine.jpg" border="0" alt="Photobucket"></a>





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[*] posted on 24-9-2011 at 11:44


wow, impressive...beautiful crystals you got there...going for piperonal now? If so, keep us updated. :)
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[*] posted on 24-9-2011 at 12:40


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.



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[*] posted on 3-10-2011 at 21:15


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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[*] posted on 3-10-2011 at 21:21


Also.. Has anyone here ever ate this stuff? I ate some and all it did was make me STARVING. lol
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[*] posted on 13-3-2012 at 19:53


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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[*] posted on 14-3-2012 at 05:51


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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[*] posted on 6-6-2012 at 05:51


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.



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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[*] posted on 6-6-2012 at 16:00


No, there was no organic layer. Sorry for being unclear. By "oil" I meant the thick, dirty, super-saturated extract.



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[*] posted on 7-2-2013 at 00:28


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.




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[*] posted on 23-6-2015 at 20:58
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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[*] posted on 4-12-2017 at 04:22


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.




~25 drops = 1mL @dH2O viscocity - STP
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https://en.wikipedia.org/wiki/Solubility_table
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[*] posted on 2-4-2018 at 23:53


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.




~25 drops = 1mL @dH2O viscocity - STP
Truth is ever growing - but without context theres barely any such.

https://en.wikipedia.org/wiki/Solubility_table
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[*] posted on 3-4-2018 at 04:03


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]




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[*] posted on 12-4-2018 at 08:49


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





~25 drops = 1mL @dH2O viscocity - STP
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https://en.wikipedia.org/wiki/Solubility_table
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[*] posted on 5-5-2018 at 08:16


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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[*] posted on 5-5-2018 at 09:18


Just posting to mark this thread so I can find it later.
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[*] posted on 6-7-2018 at 14:59


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.




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[*] posted on 7-7-2018 at 19:34


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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[*] posted on 7-7-2018 at 19:42


I'm only interested because its a cool extraction for my students to do.



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