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Author: Subject: Cold extraction of piperine from black pepper
ParanoidAndroid
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[*] posted on 12-12-2011 at 14:12
Cold extraction of piperine from black pepper


My current method for extracting piperine is:

  1. 1000 mL of 91% isopropanol is brought to about pH 8 using NaOH.
  2. To this solution is added 100g black pepper.
  3. The mixture is heated to 70C, removed from heat, and then allowed to sit for one week.
  4. The pepper is strained out. This pepper contains more piperine and should not be discarded.
  5. The filtered liquid is mixed with 2000mL distilled H2O, causing the piperine to crash out.
  6. The liquid is filtered. Piperine on the filter is kept and the liquid is discarded.
  7. Yield is about 3.5g (impure) piperine. A second extraction on the same pepper yields about 1g piperine, for a total of about 4.5g. Can be scaled easily.


I like this method because it requires little human attention and can be scaled easily. However, I'm seeing a lot of waste there; the isopropanol is lost in each extraction and some of the piperine is lost in filtration.

I would like to perform a layered extraction similar to the DMT extraction found here as I think that will reduce waste (since the isopropanol isn't consumed by each extraction, and the piperine can be crystallized instead of filtered). I'm guessing that the first few steps of my original technique are fine (put the pepper in basified isopropanol). What I'm not sure is what solvent to use for the extraction. Naphtha is used for extracting the DMT but I think that might not work for the piperine because it's more polar, so I'm thinking I might need a more polar solvent. My understanding of the chemistry gets shaky at this point, though, so I'm not sure.

My question is: what solvent should I use for the extraction, and why? Knowing a solvent would be nice, but I'd actually prefer an explanation of how to tell what solvents would work in this sort of situation.

[Edited on 12-12-2011 by ParanoidAndroid]
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zoombafu
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[*] posted on 12-12-2011 at 14:49


I'm no expert on solvents, however here is a paper written on it that uses DCM http://pubs.acs.org/doi/abs/10.1021/ed070p598 . (You have to be a member of the ACS to read it though)

[Edited on 12-12-2011 by zoombafu]




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[*] posted on 12-12-2011 at 15:25



http://www.sciencemadness.org/talk/viewthread.php?tid=10676&...

Had some luck here. Can be a tricky isolation.

[Edited on 12-12-2011 by Bot0nist]




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[*] posted on 12-12-2011 at 16:34


Quote: Originally posted by zoombafu  
I'm no expert on solvents, however here is a paper written on it that uses DCM http://pubs.acs.org/doi/abs/10.1021/ed070p598 . (You have to be a member of the ACS to read it though)

http://www.megaupload.com/?d=5K970H8U
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TheNaKLaB
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[*] posted on 18-12-2011 at 04:51


Dichloromethane is great because it can be used to extract many things. I made a video on the extraction of Cinnamaldehyde from Cinnamon and used DCM as the solvent.



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[*] posted on 18-12-2011 at 08:49


Have you tried the DCM extraction? I had trouble with the resins when using IPA. If you could do a successful run I would love to read a writeup or see a vid on your channel.



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Nicodem
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18-12-2011 at 10:18
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[*] posted on 21-12-2011 at 13:46


The DCM extraction as described in that paper doesn't make my extraction easier; it introduces more complications, requires more equipment, and creates more waste. The only thing that improves is the speed.

As I said before, I'm specifically looking for a solvent to do a layered extraction like the DMT extraction that I linked.

If you're saying that DCM would work as the top layer solvent, I'd like to hear some reasoning or see a source for that. DCM is hard enough to procure that I'm not going to do it for something that might work.
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[*] posted on 21-12-2011 at 15:01


Why not try the IPA and KOH route in larger scale if needed. It's tricky, but its not that hard to yield piperine crystals of relative purity ( Don't know about chavicine content). I bet if you get a soxhlet extractor it could be done pretty efficiently with 91% IPA and bulk ground black pepper.



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allchemy
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[*] posted on 24-12-2011 at 08:04


Piperine from pepper:

http://www.erowid.org/archive/rhodium/chemistry/3base/pipero...
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[*] posted on 29-12-2011 at 10:28


Quote: Originally posted by ParanoidAndroid  

I would like to perform a layered extraction similar to the DMT extraction found here as I think that will reduce waste (since the isopropanol isn't consumed by each extraction, and the piperine can be crystallized instead of filtered). I'm guessing that the first few steps of my original technique are fine (put the pepper in basified isopropanol). What I'm not sure is what solvent to use for the extraction. Naphtha is used for extracting the DMT but I think that might not work for the piperine because it's more polar, so I'm thinking I might need a more polar solvent. My understanding of the chemistry gets shaky at this point, though, so I'm not sure.

[Edited on 12-12-2011 by ParanoidAndroid]


Soak black pepper in basified IPA

We will have a quantity of non-polar, ie freebase, piperine dissolved in the IPA (since we are removing polarity via basification with hydroxide)

In theory, this piperine should now be vastly more soluble in a non-polar solvent, so: mix non-polar solvent of choice into IPA then separate the polar and non-polar layers (separatory funnel makes this a breeze, but cheaper/more readily available devices can be constructed for this purpose

Now we have non-polar, freebase, piperine dissolved in our non-polar solvent. We could simply evaporate the solvent, but this will waste the solvent unless you want to construct a solvent recovery setup which, while possible, would be a phenomal waste of time since it would be easier, imo, to:

Lower the pH, iow acidify, our solution via acid of choice, causing the now polar piperine to precipitate from the non-polar solvent. This can now be filtered then dried, OR:

Mix the non-polar solvent / piperine precipitate with distilled water in order to dissolve the precipitate, then separate the non-polar solvent from the water.

Evaporate water with heat. This should leave a salt form of (most likely impure) piperine.

I am not sure if this is feasible for piperine extraction, but it works for alkaloid extraction fairly efficiently, and allows us to reuse our expensive solvents. I apologize for not researching before posting, however, I will do you one better and start this process myself this afternoon and keep you updated on my yield. Worst case scenario: I am out $.50 of black pepper!

I will use IPA for the first step, obviously, then base with NaOH; non-polar solvent I will use limonene. For acidification I will use HCl.

Critiques: ime, using a less polar substance for the first step would increase yield, however, I will try IPA since that seems to be a rather common extraction method. Also, the fact that we have peeps pulling piperine from black pepper with basified IPA leads me to believe that it is possible that based piperine isn't as non-polar as I am assuming (IPA is rather polar) but only experience can tell me for sure...

As I mentioned, I will post back in a few days!
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[*] posted on 29-12-2011 at 10:34


IPA, limonene, NaOH, and HCl are all cheap and readily available

One could probably even substitute CaOH for NaOH, aka Pickling Lime, which is available @ most grocery stores. Possibly even use acetic acid, aka vinegar, for acification, rather than HCl, but ime, this could lead to a sticky end product (at least this has been the case with several alkaloid extractions I have performed).

Limonene is available for cheap on E-Bay, and I know it is used as a natural cleaning product (limonene is extracted from orange rhind), however one could use naptha as well which is available at any hardware store if you can't find limonene.
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[*] posted on 29-12-2011 at 10:42


Ack, I finally got around to doing some research on the subject instead of just making assumptions, and the common consensus seems to be that piperine is insoluble in water, so my entire theory may be fundamentally flawed... I will try it anyway!
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[*] posted on 29-12-2011 at 13:05


Ketamatic, that looks promising. I'm about to perform a similar liquid-liquid extraction, using xylene as my non-polar solvent. Instead of acidifying I'm going to cool the xylene to crystallize out the piperine and recycle the xylene (with some piperine still in it). This will result in a loss of piperine in the short term but a much larger savings of solvent.

One thing I'd like to point out: your HCl is going to acidify the piperine salt into piperic acid. Depending on your goals for extracting piperine this may or may not be a problem.

[Edited on 29-12-2011 by ParanoidAndroid]
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[*] posted on 29-12-2011 at 13:12


Also watch out, as the acidification releases gaseous piperidine (not good for you).
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[*] posted on 29-12-2011 at 14:30


I think your making this harder than it needs to be, but give it some runs and post a write up.



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[*] posted on 20-3-2012 at 13:46


I do hate to ask, but why is the piperidine gaseous? From my recollection, it forms a dark, oil liquid (impure as hell) amongst the piperic acid crystals if you base the crude ethanol extract and refrigerate it. You can certainly smell it, but it ain't gaseous.



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[*] posted on 20-3-2012 at 14:01


I've attached the paper for extraction from pepper using DCM, since Megaupload seems to be going through some legal troubles at the moment.

[Edited on 20-3-2012 by Rich_Insane]
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