Piperine from Pepper, CaCO3, IPA, MeOH

MistaMiyagi · Dream Team

Swiped from 3base's page at Rhodium's old site:

Isolation of piperine from black pepper
Piperine, a very weakly basic substance, can be isolated from a variety of peppers by extraction with alcohol. Piperine, along with a small amount of its Z,E isomer, accounts for about 10% of the weight of black pepper.

Procedure

Place 15g of ground black pepper and 1g of powdered CaCO3 (a) 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 (b).
Transfer the residual solution from the boiling flask to a 25mL erlenmeyer flask.
Set the flask aside to cool for crystallization of piperine (c,d).
Collect the product by suction filtration, using small portions of MeOH to rinse the flask and wash the product.

Yield: about 0.5g

Notes

The addition of CaCO3 should prevent the extraction of acidic
components of pepper.
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.
Crystallization occurs slowly, and the flask must be allowed to stand for
at least 24h.
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 suction filtration, and recrystallize it from either IPA or acetone.

Reference: Pgs 340-341 of "Techniques and Experiments for Organic Chemistry," 6th edition, 1998; Addison Ault of Cornell College; UniversityScience Books, Sausalito, California; ISBN 0-935702-76-8

monkichi · Sat Feb 26, 2005 7:41 am

Methanol might be more efficient due to its increased permeability through the plant cell structure.

ApprenticeCook · DILLIGAF

What about an ethanol/methanol extraction of black pepper resin?
Its easy to order and contains ~40% (in most) piperine.
Either way depending on your resources....

-AC

java · Consumer

Here is an interesting thread on the extraction of peperonal from pepper, that was translated from german..........java
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S.C. Wack
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posted on 10-3-2005 at 01:33 AM Reply With Quote Report Post to Administrator
I posted the full article before - http://www.sciencemadness.org/talk/viewthread.php?tid=1369
but no one has yet taken advantage of this opportunity to gain good karma in this life, or a seat at the right hand of God should you get another. I've heard many times that German has changed a bit more than English has since 1869. This is interesting regardless of the yield.

Die geeignetste Methode, um das Piperonal in gröfseren
Quantitäten darzustellen, ist folgende:

Man löst 1 Th. piperinsaures Kalium in 40 Th. heifsem
Wasser und fügt unter beständigem Umrühren in langsamem
Strome eine Lösung von 2 Th. krystallisirtem übermangansaurem
Kalium in 40 Th. Wasser hinzu. Der entstehende
schwarzbraune Brei läfst sich wegen des unvermeidlichen
Stofsens und Ueberschäumens weder aus Glasgefäfsen noch
aus einer kupfernen Blase destilliren. Man bringt ihn deshalb
heifs auf ein Seihtuch und wascht den Rückstand mit
dem vier- bis fünffachen Volumen siedenden Wassers aus.(1)
Die gesammte Flüssigkeit wird dann der Destillation unterworfen.
Die ersten Destillate sind sehr reich an Piperonal.
Sie gehen milchig über und scheiden häufig schon im Kühler
Krystalle ab. Man läfst das in verschiedenen Portionen aufgefangene
Destillat 24 Stunden an einem kühlen Orte stehen
und filtrirt die abgeschiedenen grofsen Kryslalle ab. Sie sind
chemisch-reines Piperonal. Die wässerigen Mutterlaugen
davon werden wiederholt mit Aether durchgeschüttelt. Die
ätherische Lösung hinterläfst bei der Destillation im Wasserbade
von 40 bis 50° noch eine ansehnliche Menge von Anfangs
flüssigem, aber sehr bald krystallinisch erstarrendem
Piperonal.

Das Piperonal krystallisirt aus Wasser in zollangen und
linienbreiten dünnen, stark glänzenden, völlig farblosen und
durchsichtigen Kryslallen. Es ist schwer löslich in kaltem
Wasser (in ungefähr 500 bis 600 Th.), leichter löslich in
heifsem Wasser und läfst sich aus letzterem umkrystallisiren.
In kaltem Alkohol ist es leicht, In heifsem und in Aether in
jedem Verhaltnifs löslich. Aus sehr concentrirter, unter
Wasser befindlicher ätherischer Lösung krystallisirt es allmälig
in derben schiefwinkeligen Tafeln. Es riecht sehr
angenehm, dem Cumarin sehr ähnlich, schmilzt genau bei 37°
und siedet bei 263° ohne Zersetzung.

(1) Es ist zu empfehlen, das Auswaschen sehr lange fortzusetzen und
die letzten verdünnteren Waschflüssigkeiten nicht mehr auf
Piperonal, sondern anf die nachher zu beschreibende Piperonylsäure
zu verarbeiten.
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posted on 10-3-2005 at 03:52 PM Reply With Quote Report Post to Administrator
The best method of making piperonal in larger quantities:

You solve 1 part "piperin acidic potassium" ("piperinsaures Kalium" -> don't know how to translate) in 40 parts hot water and slowly and stirring add a solution of 2 parts krystallic potassium permanganate in 40 parts water. The resulting black-brown mash can neither be distilled in glass vessels nor in copper ones due to the inevitable bubbles and foam.
Therefore you put it on a filter cloth and wash the residue with 4 to 5 times its volume of boiling water. (1)
All of the liquid is then distilled. The first distillates are rich on piperonal. They become milky and often already crystallises in the cooler. You let the distillate you aquired in various portions sit in a cool place for 24 hours and then filter the crystals. They consist of chamicaly pure piperonal. The aqueous mother liquors are shaken repeatedly with aether. If you distill this aether in a water quench at 40 to 50 ° Centigrade you will obtain a considerable amount of piperonal, which is liquid at first, but will soon crystallise.
The piperonal crystallises from water in uncolored, shiny, clear crystalls which are about an inch long and needle-shaped.
It is hardly soluble in cold water (in about 500 to 600 parts(?)), better soluble in hot water and can be recrystallised from this. In cold alcohol it is readily soluble, in hot one and in ether in any proportion. From highly concentrated solution in ether under water it crystallises slowly in rough plates. It smells very good, similar to coumarin, melts exactly at 37 ° centigrade and boils at 263° without decomposing.

(1) It is advisable to continue washing quite some time and using the last, more diluted washing liquids not to make piperonal but piperoyl acid, which should be described later.

Not much for getting useful information, is it?

Kanem
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solo
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posted on 10-3-2005 at 04:00 PM Edit Post Reply With Quote Report Post to Administrator
Re: Piperonal article......

Translation software version...........
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The geeignetste method, around the Piperonal in gröfseren
To show quantities, is the following:

One solves 1 Th. piperinsaures potassium in 40 Th. heifsem
Water and adds under continual stirring in slow one
To stream a solution of 2 Th. krystallisirtem übermangansaurem
Potassium in 40 Th. Water, there. The coming into being one
brownish black mash läfst to itself because of the inevitable one
Stofsens and ebullience neither from Glasgefäfsen nor
from a copper bubble destilliren. One brings him, therefore
heifs on a Seihtuch and wash the remains with
to 4 waters boiling to fünffachen volumes from. (1)
Then the gesammte liquid is subjected to the distillation.
The first distillates are very rich in Piperonal.
They go over milky and part often already in the cooler
Krystalle from. One läfst in different servings of caught ones
Distillate 24 hours at a chill place stand
and filtrirt produced grofsen Kryslalle from. They are
chemical-pure Piperonal.

It's better to die on your feet, than live on your knees....Emiliano Zapata
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posted on 10-3-2005 at 04:46 PM Reply With Quote Report Post to Administrator
Danke!

Potassium piperate. What you get when you cleave piperine with alcoholic KOH.

That and the Berichte article that I mentioned in the other thread are the only references that I know of on the cleavage of piperic acid to piperonal with just KMnO4. Preparation of piperonal in this manner is mentioned every now and then on various international boards, yet this is the only translation/actual experimental that I've ever seen! And that's something. The most detailed translation I've ever seen before was the other article, and that was something like: "2% KMnO4 @ 3C". But then, that article itself seems to say little more.

So this is a historic event, you have much good karma from here, and yours may go down as the only surviving translation known to English-speakers of the future!

Because it really is useful, even if the copper or other methods are found to work better. There is a surprising amount of black pepper out there. I've personally been to a warehouse in St. Louis that just happened to have 90,000 pounds of Indonesian black pepper in big, white woven-plastic, neatly stacked bags on hand. Been sitting there for well over a year and making the whole place smell. Apparently it is inexpensive in bulk.