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stateofhack
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Pepper to Piperine problem
Hello,
I am new here so please put up with me 
Anyways, i have done this extraction numerous times at school but when done at home all i got was this:
A very sticky and spicy beaker, containing a green annoying residue 
I followed the following procedure and used fresh powdered black pepper:
place 15g of ground black pepper and 1g of powdered CaCO3 (1) in a 250mL
boiling flask, add 100mL of IPA, and, after fitting the flask with a reflux condenser,
boil the mixture for about 1h on the steam bath. at the end of the heating period,
filter the mixture by gravity into a 125mL erlenmeyer flask, clean the 250mL
boiling flask, and return the filtrate to the boiling flask. fit the boiling flask with a
distillation adapter and condenser, and boil off all but about 10mL of the IPA (2).
transfer the residual solution from the boiling flask to a 25mL erlenmeyer flask,
and set the flask aside to cool for crystallization of piperine (3,4). collect the product
by suction filtration, using small portions of MeOH to rinse the flask and wash
the product. yield: about 0.5g.
(1) the addition of CaCO3 should prevent the extraction of acidic
components of pepper
(2) IPA boils at 80°C, only a little below the maximum temperature attainable on
the steam bath. to make the distillation proceed quickly, clamp the boiling flask so
that it is well down in the rings of the steam bath, and drape a towel over the flask
and the steam bath to make a tent that will hold steam around the top of the flask.
(3) crystallization occurs slowly, and the flask must be allowed to stand for
at least 24h.
(4) alternatively, add 25mL of water to the IPA solution of piperine, allow the mixture
to stand for at least 24h so that precipitation will be complete, collect the solid by
sucction filtration, and recrystallize it from either IPA or acetone.
I repeated this twice and i really can't see where i have gone wrong
Anyone has an idea?
Thanks
edit: picture doesn't seem to be wanting to show up
http://img99.imageshack.us/img99/161/img0351tx8.jpg
[Edited on 17-6-2008 by stateofhack]
[Edited on 17-6-2008 by stateofhack]
[Edited on 6-18-2008 by Polverone]
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S.C. Wack
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http://www.sciencemadness.org/talk/viewthread.php?tid=4698
Using lime/limestone in the extraction is in the literature, as above. Doesn't prevent shit in my hands.
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Klute
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Maybe your product simply oiled out? Try redissolving and letting it cool very slowly again
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LSD25
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Looks a lot like what I got years ago when I based the green-yellow alcohol extract with NaOH - let me guess, did the whole thing stink there for
quite a while? I strongly suspect that you have a nice yellow precipitate of calcium piperinate there (same as I had the sodium salt). In order to get
it to crystallise you'll need to boil it dry, add water and then hydrochloric acid and collect the filtrate:
http://www.ias.ac.in/resonance/Sept1996/pdf/Sept1996p25-33.p...
In order to extract the piperine, you'll need to let the alcoholic extract sit COLD with the base (yeah, it seems that that is precisely what the
carbonate has done, go figure - at a guess, I'd say refluxing it might be the culprit - that is why I asked about the smell, piperidine is a lot of
things but as a fragrance, subtle or understated it ain't).
Then again, I'm often wrong - lets see what the more experienced readers think
Whhhoooppps, that sure didn't work
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stateofhack
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| Quote: | Originally posted by LSD25
Looks a lot like what I got years ago when I based the green-yellow alcohol extract with NaOH - let me guess, did the whole thing stink there for
quite a while? I strongly suspect that you have a nice yellow precipitate of calcium piperinate there (same as I had the sodium salt). In order to get
it to crystallise you'll need to boil it dry, add water and then hydrochloric acid and collect the filtrate:
http://www.ias.ac.in/resonance/Sept1996/pdf/Sept1996p25-33.p...
In order to extract the piperine, you'll need to let the alcoholic extract sit COLD with the base (yeah, it seems that that is precisely what the
carbonate has done, go figure - at a guess, I'd say refluxing it might be the culprit - that is why I asked about the smell, piperidine is a lot of
things but as a fragrance, subtle or understated it ain't).
Then again, I'm often wrong - lets see what the more experienced readers think |
This sounds promising! I will look into it!
Thanks!
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LSD25
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I think the majority of the problem with this extraction comes from the names of the various compounds - here is a couple of 'PIPERINE' extractions:
| Quote: | Isolation of Natural Piperine (I)
Grind fresh peppercorns (25 g) to a fine powder, place in a Soxhlet thimble, and extract with ethanol (100 mL) for at least 90 minutes. At the end of
the extraction, the ethanol should be pale yellow to colourless. Cool the resulting solution, filter if necessary, and concentrate on the rotary
evaporator. Keep the water bath below 60 °C during the concentration. Dissolve the residue in 10 % alcoholic potassium hydroxide (25 mL). Decant the
solution if any residue remains. Cool the solution in an ice bath, and add water dropwise (about 30 ml will be required) to precipitate the piperine.
Collect the piperine on a sintered glass funnel, and dry it on the vacuum pump. If time allows, a recrystallization from acetone:hexanes (3:2) will
produce cleaner material. Record the mp, ir and 1H nmr spectrum of piperine.
From page 3/4 of this paper: http://web.uvic.ca/~pmarrs/chem465/465e03piperine.pdf |
Note that they cool the extract before letting it come into contact with the base. A very similar approach (but using much more expensive solvents) is
used here: http://courses.chem.psu.edu/chem36/Chem36H/IndivExpt1/874%20... and here (and a lot more places on the web): http://www.wiu.edu/users/mftkv/Chem332/Experiment3.html.
It seems (well at least to me), that what most people here have got in their attempts to extract piperine is the piperinate (the salt of
piperinic/piperonic acid), which is here:
| Quote: | Hydrolysis of Piperine – Isolation of Piperic Acid
Reflux a solution of 1 g of piperine in 10 ml of 10% ethanolic KOH for 90 minutes. Evaporate the solution to dryness by distillation under reduced
pressure, the receiver being cooled in an ice-salt bath. Suspend the solid potassium piperinate remaining in the distillation flask in hot water and
add concentrated HCl. Collect the yellow precipitate, wash it with ice-cold water and recrystallise it from ethanol. Pure piperic acid is obtained as
yellow needles, m.p. 216 – 217°C. Saturate the distillate (in the receiver) with HCl and evaporate it to dryness when piperidine hydrochloride
separates out. Re-crystallise it from ethanol. Pure piperidine hydrochloride has a m.p. 244°C.
Pages 8-9/9: http://www.ias.ac.in/resonance/Sept1996/pdf/Sept1996p25-33.p... |
Now, given that what you have (and what others have described) from the refluxing of the ethanolic piperine extract with the calcium carbonate looks
for all the world more like what others have gotten from cleaving the alkaloid with ethanolic base, then I'd suggest that the cleavage is done with
the carbonate under reflux. Easy way to find out, collect the yellow-green precipitate and hit it with HCl - see if you get crystals corresponding to
piperic acid (ie. see if you get precipitation, if so, collect it and recrystalise from ethanol).
Whhhoooppps, that sure didn't work
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Nicodem
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No, CaCO3 can not hydrolyze any such amide. It is probably added to catch various carboxylic acids in the peper (fatty acids, etc.) which would
otherwise interfere with the crystallization and final recrystallization. Similarly as petroleum ether is often used to remove lipids from plant
material in many extraction processes.
I would suggest to try the recrystallization on the resin directly even if you can't get it to crystallize. Alternatively crystallizations can often
be nicely induced by removing the interfering impurities with trituration in solvents in which your product has low solubility. Since you don't know
the nature of the impurities I would suggest to use both, a heavily hydrophobic solvent (petroleum ether) followed by a hydrophilic one (methanol). I
think piperine should not be particularly soluble in either petroleum ether or methanol, but I'm not sure. Do not loose patience and triturate for
some time before giving up, perhaps also by warming up.
…there is a human touch of the cultist “believer” in every theorist that he must struggle against as being
unworthy of the scientist. Some of the greatest men of science have publicly repudiated a theory which earlier they hotly defended. In this lies their
scientific temper, not in the scientific defense of the theory. - Weston La Barre (Ghost Dance, 1972)
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stateofhack
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| Quote: | Originally posted by Nicodem
No, CaCO3 can not hydrolyze any such amide. It is probably added to catch various carboxylic acids in the peper (fatty acids, etc.) which would
otherwise interfere with the crystallization and final recrystallization. Similarly as petroleum ether is often used to remove lipids from plant
material in many extraction processes.
I would suggest to try the recrystallization on the resin directly even if you can't get it to crystallize. Alternatively crystallizations can often
be nicely induced by removing the interfering impurities with trituration in solvents in which your product has low solubility. Since you don't know
the nature of the impurities I would suggest to use both, a heavily hydrophobic solvent (petroleum ether) followed by a hydrophilic one (methanol). I
think piperine should not be particularly soluble in either petroleum ether or methanol, but I'm not sure. Do not loose patience and triturate for
some time before giving up, perhaps also by warming up. |
Thanks, unfortunately I have disposed of the “product” but I will be trying it again and I will be trying what you said!
Anyone know any “quicker” and less involved methods to extract piperine? (soxhelt??)
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not_important
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From several articles on the subject, including some referenced in the old thread on the topic such as "Microwave-Assisted Extraction of Piperine", it
looks as if pet ether is the way to go if you're specifically after piperine.
If you want it as raw material for one or another of its constituents, then use alcohol, acetone, or DMC, followed by hydrolysis, isolation, and
purificationof the desired component. For those cases going for pure piperine is wasted effort, as several of the impurities will yield one or another
of the desired compounds too. The major components of extracts besides oleoresins are listed as piperine, piperidine, piperettine, piperanine, and
chavicine; check their structures to see what I mean.
Useful references you might want to chase down:
Separation and identification of piperine and chavicine in black pepper by TLC and GC-MS
Constantin Maărutoiu, Ioan Gogoasa, Ioan Oprean, Olivia-Florena Maărutoiu, Maria-Ioana Moise, Cristian Tigae, Maria Rada
JPC - Journal of Planar Chromatography - Modern TLC
Volume 19, Number 109/June 2006
Pages 250-252
DOI 10.1556/JPC.19.2006.3.16
Kinetics of Light-Induced Cis-Trans Isomerization of Four Piperines and Their Levels in Ground Black Peppers as Determined by HPLC and LC/MS
Nobuyuki Kozukue, Mal-Sun Park, Suk-Hyun Choi, Seung-Un Lee, Mayumi Ohnishi-Kameyama, Carol E. Levin, and Mendel Friedman
J. Agric. Food Chem., 55 (17), 2007
Pages 7131-7139
DOI 10.1021/jf070831p
Black Pepper: Piper Nigrum
By P. N. Ravindran
Published 2000 by CRC Press
ISBN:9057024535
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MagicJigPipe
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| Quote: |
Thanks, unfortunately I have disposed of the “product”
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Why did you do that before you could run more tests etc... ?
"There must be no barriers to freedom of inquiry ... There is no place for dogma in science. The scientist is free, and must be free to ask any
question, to doubt any assertion, to seek for any evidence, to correct any errors. ... We know that the only way to avoid error is to detect it and
that the only way to detect it is to be free to inquire. And we know that as long as men are free to ask what they must, free to say what they think,
free to think what they will, freedom can never be lost, and science can never regress." -J. Robert Oppenheimer
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stateofhack
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| Quote: | Originally posted by MagicJigPipe
| Quote: |
Thanks, unfortunately I have disposed of the “product”
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Why did you do that before you could run more tests etc... ? |
Well it was such a bitch to remove! You have no clue! Soaked in acetone, warm water, dilute hcl took for ever!
But i will be running some more test soon and i will post a full pictorial (with appropriate sized pictures  )
But yes, i should have tried to run some test
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S.C. Wack
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| Quote: | Originally posted by not_important
Black Pepper: Piper Nigrum
By P. N. Ravindran
Published 2000 by CRC Press
ISBN:9057024535 |
It's a good book but it has nothing useful on isolation of piperine or anything else. Lots of information as to the chemicals present in there.
Not much of a surprise that water and HCl did not do much to the oleoresin.
Toluene and xylene are great for cleaning resinated glassware.
Everyone else here seems to think that the earlier thread is worthless, but that really is the best that can be done with old-fashioned organic
solvent extraction.
Since 3base sadly no longer has a website that I know about, here is a link to the same files that I linked to before, should this thread come up in someone's search.
If I haven't already mentioned it somewhere else: some brands of pepper contain very little piperine. it is not necessarily related to price: the
inexpensive Gel Spice Co. product gives at least the same yield as familiar McCormick. But the cheapest brands do tend to give little product.
[Edited on 19-6-2008 by S.C. Wack]
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LSD25
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| Quote: | Originally posted by Nicodem
No, CaCO3 can not hydrolyze any such amide. It is probably added to catch various carboxylic acids in the peper (fatty acids, etc.) which would
otherwise interfere with the crystallization and final recrystallization. Similarly as petroleum ether is often used to remove lipids from plant
material in many extraction processes.
I would suggest to try the recrystallization on the resin directly even if you can't get it to crystallize. Alternatively crystallizations can often
be nicely induced by removing the interfering impurities with trituration in solvents in which your product has low solubility. Since you don't know
the nature of the impurities I would suggest to use both, a heavily hydrophobic solvent (petroleum ether) followed by a hydrophilic one (methanol). I
think piperine should not be particularly soluble in either petroleum ether or methanol, but I'm not sure. Do not loose patience and triturate for
some time before giving up, perhaps also by warming up. |
I figured that it probably 'shouldn't' be capable of doing so, yet the material in the photo - made up of at least 80% salt and less than 20% oil
(after removal of solvent) suggests strongly otherwise. It is either that, or the particular brand of pepper used is degraded and contains an
unusually high level of carboxylic acid(s), because the piperine is an oil and only crystallizes when purified to some extent and then allowed to cool
(ie. the stuff in that photo ain't piperine - it is quite seriously exactly what I remember the piperinate to look like - ).
Dunno, maybe extract the water soluble salt (probably even better if you filter it and then wash the filter cake through the funnel with water) and
then cool the filtrate to give the piperine a chance?
Whhhoooppps, that sure didn't work
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S.C. Wack
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| Quote: | Originally posted by LSD25
the material in the photo - made up of at least 80% salt and less than 20% oil (after removal of solvent) suggests strongly otherwise.
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Where did you pull that out of?
| Quote: | Originally posted by LSD25
the stuff in that photo ain't piperine - it is quite seriously exactly what I remember the piperinate to look like - ). |
I don't see how you or anyone else can tell what is in that photo, or what it looks like - other than not white or black.
I don't see how CaCO3 could hydrolyze this amide or anything else, regardless of its base strength, with the handicap of being fairly insoluble in
this and perhaps all other organic solvents, and water.
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LSD25
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Have a look at the photo - do you see the solvent level - where the precipitated crud is about halfway up the wall? & where it is now? Do you see
the yellowish-green precipitate? Is it extremely finely divided and in a dark-ish oil? Does it look like the entirety of the alcoholic extract is in
that beaker?
You've done this too, what stage does it look like? What does it sound like from the description? The piperine is still in the oil, when it comes out
it does not look like that crud. As the precipitated material can only be one of two things - the alkaloid(s) or the acid salt(s), there really is not
a lot of guesswork that has to be entered into - is the precipitated material the alkaloid(s)? I think not (based upon days of fucking around with
this before and looking at working out precisely what happened) thus for mine the precipitate is piperinate, while there is so much of it there there
is no chance of the piperine crystallizing.
As to whether the carbonate could hydrolyze the amide, I cannot work it out, but in order for the precipitated material to be the piperinate something
has happened, either the amide has been hydrolyzed or the pepper contained a LOT of carboxylic acid - perhaps this is the result of degradation, I
dunno. All I know is that from the description and the photo, I am willing to bet that that is the salt not the alkaloid(s), in order for that to be
the case, something unusual has to have occured. Alternatively, nothing of the sort has happened and the precipitated crap is the alkaloids and they
have simply acted somewhat unusually? It certainly ain't the carbonate, the fact it ain't white (something you also must have seen?) tells me that.
Then again, this is all somewhat subjective - noone has run any conclusive tests on the material, it has not been identified (and now cannot be). That
said, I don't regard the suggestions above as unnecessarily speculative, it is based upon what I see in the photo and what I have seen in person. I
certainly don't think that is beyond the pale, it is simple deductive reasoning, what do I see, what could it be and what needs to have happened in
order for that to be? Given the fact that this is the alcoholic extract of pepper, there really ain't that many alternatives.
Whhhoooppps, that sure didn't work
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McLovin382
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Pretty sure that piperine can be obtained from black pepper by heating in the microwave in dH2O for about a minute, followed by a filtration of the
now empty peppercorns and evaporation/boiling off of the water.
http://www.erowid.org/archive/rhodium/chemistry/3base/pipero...
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stoichiometric_steve
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| Quote: | Originally posted by McLovin382
Pretty sure that piperine can be obtained from black pepper by heating in the microwave in dH2O for about a minute |
like piperine is water soluble or what
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DJF90
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Googling "piperine" reveals that it can apparently be extracted from black peppercorns (if so wished) using DCM.
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Nicodem
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I can not find anything like this in the page you referred to. Please avoid spreading misinformation whenever possible. Piperine is not water soluble,
at least not to any useful level. Even if it was water soluble, just extracting pepper with water would also extract all kind of water soluble sugars,
proteins and other plant products. So just evaporating the water would give you a mixture of all kind of stuff.
…there is a human touch of the cultist “believer” in every theorist that he must struggle against as being
unworthy of the scientist. Some of the greatest men of science have publicly repudiated a theory which earlier they hotly defended. In this lies their
scientific temper, not in the scientific defense of the theory. - Weston La Barre (Ghost Dance, 1972)
Read the The ScienceMadness Guidelines!
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Baphomet
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Try this:
- soak overnight in a closed glass container, filled with acetone to match the level of the pepper. or excess acetone - hardly matters
- filter through coffee paper or some other fine mesh. if you are careful it is possible to keep the water soluble solids separate from the pepper
grinds (using coarse-grind pepper). though not particularly useful
- allow the acetone to evaporate.. takes a day or two
- there was thick oleoresin after evaporation, with lots of little rhombic crystals embedded in it
I tried the above, for shits & giggles last week. Did not bother to separate it but the following might work:
- dissolve the lot in EtOH or IPA, put it in the freezer to dewax
- base wash if you like
- evaporate the alcohol
- recrystallise
[Edited on 2-10-2008 by Baphomet]
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Bander
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I have always failed in purification of the alcoholic black pepper extract by active means. This is something I attribute to the crude nature of my
attempts and not the methods themselves. I have ended up with an oily mess most times trying to recrystalize from acetone (picture). If you are willing to wait and have a stable location; store a closed container of the unpurified alcoholic extract at room temperature
with little physical disturbance for about a year. I have done this twice with ~1 liter amounts and twice I have ended up with centimeter scale
multiple crystal formations of piperine. It's not novel, efficient, or fast, but it works.
[Edited on by Bander]
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Ephoton
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wow there huge.
I've never had prob with this extraction. I used a continuous extraction setup so the pepper never gets hot alcohol on it. this way most of the tar
stays in the pepper.
I just add a little water to extract when finished and let sit over night. the more water the quicker the crystals form (though much smalller).
I never get any brown in the extract and hydrolisis is very smooth afterwards  .
e3500 console login: root
bash-2.05#
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McLovin382
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| Quote: | | [quote=stoichiometric_steve]like piperine is water soluble or what |
Not usually, no - and when normal heating is applied, piperine is very insoluble in water.
However, the microwave radiation for whatever reason does a very good job at drawing the piperine out of the pepper and into the hot water. You then
can filter it while it's hot to get the peppercorns out, then cool it and filter out the piperine.
Try it if ya don't believe me.
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starman
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| Quote: | | Quote: | Originally posted by McLovin382
[quote=stoichiometric_steve]like piperine is water soluble or what |
Not usually, no - and when normal heating is applied, piperine is very insoluble in water.
However, the microwave radiation for whatever reason does a very good job at drawing the piperine out of the pepper and into the hot water. You then
can filter it while it's hot to get the peppercorns out, then cool it and filter out the piperine.
Try it if ya don't believe me. |
If you don't have results of your own experiments or literature references to offer in support of your assertions,I would suggest you pay attention to
Nicodem's warning about misinformation.Steve will also tear you a new one if he thinks your talking crap.
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stoichiometric_steve
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| Quote: | Originally posted by starman
Steve will also tear you a new one if he thinks your talking crap. |
DAMN RIGHT!!!
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