Sciencemadness Discussion Board

Distilling Piperine

Actinium - 18-9-2014 at 10:25

Had a quick question about distilling piperine?
The 2-propanol coming over smells of pepper and in a not pleasant way. I tested a small portion by dropping drop by drop H20 into the alcohol. at first a cloudiness then a small little bit of white cotton candy looking insoluble settle. as I kept adding H20 it completely suspended in solution.
Did some of the piperine make it through?
I thought that the whole point of distillation was to say, remove solvents and purify?
Can substrates come over if they are miscible in such substance?
I wanted to recycle my alcohol and get it down to a concentrate before crashing it out of solution with H20.
Can Hydrolysis be performed with regular store bought muriatic acid or does concentrated 36% solution be required?

aga - 18-9-2014 at 11:23

It is essential to watch the thermometer in the still head to get a clue as to What is 'coming over'.

Miscible substances may come over as droplets, at various temperatures.

2 or more substances forming azeotropes will come over at their azeotrope BP.

Actinium - 18-9-2014 at 13:17

I know that 2-propanol has a B.P. 82.6c, my water bath was about 87c and stirring was at about 5.5-6 on my plate/stirrer and recorded the temp coming over at 78c-81c.
I know that thermometers can be off by +/- 1c and that placement in the still head is essential for good reading.
I understand the principle of Azeotropic distillation, i.e. steam distillation because the substance(s) are NOT miscible with eachother, however is it possible that the piperine formed an azeotrope with the Isopropyl?
Would omitting the stirring possibly help? Its coming out 1-2 drops per second.

2 or more substances forming azeotropes will come over at their azeotrope BP
I was wondering about that, that was something that I was wanting to know how to figure out as there is another analytical project that I'm working on and knowing how to calculate the B.P. of an azeotrope would help narrow my window on not only the distillation of the compound(s), but help in identification along with all the other data I have been collecting.
-Ac-

aga - 18-9-2014 at 14:30

From the spreadsheet of BP data collated just yesterday, a VT between 78 and 81 C could be any of 22 compounds or azeotropes of 2 compounds in your mix.

None of the known (to my database) 3 compound azeotropes matched.

All that means is that my data is very much limited, and identifying your distillate is difficult.

Calibrate your thermometers with Ice and Boiling water to get an accurate reading.

In the spreadsheet, the Green box is your Mean Vapour Temperature.
The Red box is how many C +/- you want to go.
Column K will say 'THIS' if it matches.

Attachment: Boiling Point Calculator.xlsx (38kB)
This file has been downloaded 324 times

with update

Actinium - 18-9-2014 at 16:26

thanks aga. :D
would it be better to reduce down then crash it out of solution to work on another day or should I distille to dryness and rework to gunk prior to hydrolysis?
I was thinking of using Dipropyl ether as suitable solvent. but one thing at a time no sense in rushing.

So tried steam distillation after reading this tasty piece, Here
Besides not being able to get my water bath over 100c, I havent sat down and figured the Azeotrope b.p. for Piperine and H2O. the only thing coming over was about 1ml of clear distillate that had a very pungent odor, incredibly volatile. Its probably the Ethers of Piperine. that and upon getting home just now, the 1ml-2.5ml had evaporated and the contents of the flask are as such.
250ml dH2O in 1,000ml 3-necked flask
the Piperine concetrate which looks more like tar at this point is sitting at the bottom and hardened up and is holding the stir bar firmly in place. the water ontop looks like a cup of tea with milk in it.
Im either going to filter and try distilling the saturated H2O or allowing to settle and filter out to try and recuperate the Piperine.
As far as the gunk, I'm going to wash with P.E., followed by disolving in suitable solvent, (I do have a pint of ether in fridge, a little worried about peroxides forming durring distilling), filter and at that point either try to get it to fall out of solution of just go with the hydrolysis, recuperate and store away for another day.

[Edited on 19-9-2014 by Actinium]

vmelkon - 19-9-2014 at 11:31

"I do have a pint of ether in fridge, a little worried about peroxides forming durring distilling"

Peroxides don't form during heating, they just get concentrated.
You should test it for presence of peroxide.

I have kept some diethyl ether in a freezer for 1 month without any KOH and BHT. No problem.

aga - 19-9-2014 at 11:46

Personally i've never touched Piperine, and am a complete noob to all chemistry, OC more so.

ISTR that arkoma recently distilled some Piperine.

U2U him.

Actinium - 19-9-2014 at 13:02

Quote: Originally posted by vmelkon  
"I do have a pint of ether in fridge, a little worried about peroxides forming durring distilling"

Peroxides don't form during heating, they just get concentrated.
You should test it for presence of peroxide.

I have kept some diethyl ether in a freezer for 1 month without any KOH and BHT. No problem.


the way I understand it is that the peroxides are heavier than air and accumulate in the pot and this is where the danger lies.
I've had this either for a little over a year, also if memory serves me right from what I have read Cu will neutralize the peroxides?

unionised - 19-9-2014 at 15:16

Why are people talking about what the distillate smells like?
Piperine has no odour.

The smell of pepper is largely due to this stuff.
http://en.wikipedia.org/wiki/Rotundone

Actinium - 19-9-2014 at 19:44

Quote: Originally posted by unionised  
Why are people talking about what the distillate smells like?
Piperine has no odour.

The smell of pepper is largely due to this stuff.
http://en.wikipedia.org/wiki/Rotundone


Because I had pointed out that I was trying to steam distill the extract which yields the ethereal of piperine, which the Merck report I had posted 4 post up it explains that both the oil and ethereal oil are solvents for the piperine. so Unless I'm not understanding correctly, it would seem that had I separated the piperine from it, it should be clear and have a faint to no smell of such compound which it also explains.
Here is the article again just incase you feel like looking it over. :cool:

the water from the failed steam distillation was decanted and seems to have tons of minut crystals suspended in solution. the black oily gunk at the bottom of the flask was stuck with my stir bar smack in the middle. I added enough 70% 2-propanol to cover, a little swirling was done. as I was boiling water to add to a pan where the flask was waiting to my surprise was the gunk dissolved and fat plates that had the appearence of "desert rose" stones and the color of pyrite. The alcohol is realy greasy and oily as are the crystals. as soon as its dry I'll do a m.p. test

[Edited on 20-9-2014 by Actinium]

S.C. Wack - 20-9-2014 at 04:02

Quote: Originally posted by Actinium  

Can substrates come over if they are miscible in such substance?


You should not be expecting piperine to be distilling over with IPA, no. I would expect a rather clean separation.
Quote: Originally posted by unionised  
Piperine has no odour.


True of course but BTW years ago I mentioned large amounts having a very faint and pleasant odor...aka slightest trace of IPA.
Quote: Originally posted by Actinium  
Unless I'm not understanding correctly


Ding! If you want to isolate piperine, follow piperine isolation procedure. It would be wise to use the best one. If you want to distill piperine, start with asking "how does distillation work" followed by "can piperine be distilled"...start at the piperine wiki for the latter.

Actinium - 20-9-2014 at 11:42

@ S.C. Wack
may be extracted from black pepper using dichloromethane.[2] Aqueous hydrotopes can also be used in the extraction to result in high yield and selectivity. taken from Wiki
I understand the principal of steam distillation which is a great way to separate a compound or mixture of such compounds either liquid or solid.
Besides trying to isolate the piperine the point of the experiment was to also isolate the other compounds away from it. I think there are alot of interesting things in there not just piperine. There is no substitue for experience and no experience without failure.
Following a set of direction is important especially if you are unsure or don't understand, but if you bake a cake and you think you might of botched it, might as well experiment at that point. no sense in throwing thinks away.
As far as the smell that carried over with the IPA was most likely the Ethereal of piperine. I managed to get a very small amount by steam distillation.

Question? If I where to say make a solution of H2O and NaHCO3 and dripped set solution into an alcoholic extract to precipitate out the piperine, wouldn't it form the carbonate salt of piperine?

Nicodem - 20-9-2014 at 13:09

Quote: Originally posted by Actinium  
Question? If I where to say make a solution of H2O and NaHCO3 and dripped set solution into an alcoholic extract to precipitate out the piperine, wouldn't it form the carbonate salt of piperine?

How can a neutral compound form a carbonate salt?

As for the rest of your questions, it is pointless to comment as you gave no reference to the procedure you are using. I can only give one comment - based on your questions about piperine distilling and forming a carbonate salt - that you obviously did not even bother looking at the molecular structure of piperine.

S.C. Wack - 20-9-2014 at 13:54

Quote: Originally posted by Actinium  
I understand the principal of steam distillation which is a great way to separate a compound or mixture of such compounds either liquid or solid.


Not when the solid in question melts at 130C and is hardly volatile at that point.

Actinium - 20-9-2014 at 22:45

Quote: Originally posted by S.C. Wack  
Quote: Originally posted by Actinium  
I understand the principal of steam distillation which is a great way to separate a compound or mixture of such compounds either liquid or solid.


Not when the solid in question melts at 130C and is hardly volatile at that point.

I whent back and read steam distillation and it was defined as solids "sublime", so if the solid can't evaporate on its own at a lower temp does that disqualify it as a candidate for Steam distillation?

@ Nicodem britannica says its classified with lipids and alkaloids, another reference said carboxylic acid, another vanilloid. my lack of knowledge in Chemistry makes it hard to UTSF and find what I need and what I would be looking for, if you could please explain I would be so grateful?

Little_Ghost_again - 21-9-2014 at 02:15

Quote: Originally posted by Nicodem  
Quote: Originally posted by Actinium  
Question? If I where to say make a solution of H2O and NaHCO3 and dripped set solution into an alcoholic extract to precipitate out the piperine, wouldn't it form the carbonate salt of piperine?

How can a neutral compound form a carbonate salt?

As for the rest of your questions, it is pointless to comment as you gave no reference to the procedure you are using. I can only give one comment - based on your questions about piperine distilling and forming a carbonate salt - that you obviously did not even bother looking at the molecular structure of piperine.


I shouldnt say this as I am a new member etc, but I have had a similar comment recently.
This is the beginners section, some of us like me are 14, some have NO chemistry experience at any level (again like me). We ask on here because there are very experienced and knowledgeable members. Most give great guidance and so slowly and gradually we learn.
In my own case looking at the molecular structure would be a bit like someone with zero electronic experience looking at a circuit diagram. Ok google and search engine are great IF you know can sort the crud from the good./
This is why we ask here, while learning we need the experience and expertise of others.
I am at School but I dont get taught Chemistry, I have brought books that I read, but some times I dont understand. So who exactly should we ask when things we dont understand crop up?
Sorry but some times I think too much is expected of complete beginners.

That said in my case I have received very good help and much patience. But Like aspergers people I have a thing about injustice (google it) :D

aga - 21-9-2014 at 02:49

It is probably very hard for seriously experienced chemists to avoid frustration when us noobies ask (what seem to them) really basic questions, or make really basic mistakes.

Also, as it's all Text communication, much intended information is lost, such as nuances like Humour.

Essentially we're asking for Free info, so you got to accept that any Info given out might not arrive in the format requested, or with the attitude expected.

Personally i'm really grateful that i get any assistance at all.
The occasional slating i get for being a dumb-ass is a very small price to pay.

[Edited on 21-9-2014 by aga]

S.C. Wack - 21-9-2014 at 06:08

The missing phrase is vapor pressure. Lab manuals speak of this in the distillation part. The vapor pressure of piperine is low, and the temperature required for a distillable vapor pressure apparently polymerizes or isomerizes it or something. If you're going to distill something, shouldn't the first piece of information you search for be the boiling point? What's frustrating is this being one of so many threads over so many years and it's getting worse. At some point we say fine, flush your drug precursor, detonate at the wrong time and place, and burn down your neighborhood.

If optimized piperine extractions posted here are ignored and several historically widely read lab manuals scanned for you are ignored, you risk being ignorant. I spoke out having done some of that scanning and optimizing, and ignorant things. Piperine extraction, and chemistry and its hazards is not intuitive at 14 like throwing rocks, so it would not be unwise to figure out how to end an experiment with a fair chance of (casualty-free) success, before experimenting.

Actinium - 21-9-2014 at 09:24

See I had no idea that it polymerized or isomerized, everything I looked at never mentioned any of those things. and after providing the reference 2-3 times above which states you can S.D.
as a beginner seeing this in the Merck Report none the less you would think that it would hold some validity. Since its clear that it is wrong this would be a perfect example to demonstrate that not all literature is accurate and really explaine how and why.
I'm really interested in azeotropic distillation, but guess I don't fully understand solid distillation, and if I could understand how to calculate the some of both the V.P. im assuming you would be able to tell if its feasible or not, unless you are an experienced chemist and can just look at the compound and determine wheather of not.

Little_Ghost_again - 21-9-2014 at 09:36

I shouldnt have commented, something else got to me I guess. Sorry guys I am not sure why I wrote what I did. It seems I am also a bit stupid, It never occurs to me that people ask questions that relate to making drugs. I am lucky, my entire life has been lived in VERY rural locations. My current School is in what seems to me a huge town, but to most its little more than a village.
The house I live in is not remote but (not to me anyway) but very Rural (google map DG80LG) That post code places a arrow directly above our house! As you can see I live in the middle of nowhere and always have. The place I lived in before was remote even for me :D.
So I dont or rather so far I havnt had ANY contact with drugs or people that sell,use or make them. I wouldnt know drug precursor if I fell over it. The search function is good, but I kind of think if you only use the search function then eventually all the questions get answered and no more threads are ever posted.
Then you get the other situation, I am a member of three of other forums, all electronics related and all of them insist on starting your own threads and not resurrecting old threads. Different forums have different preferences and etiquette, it takes time to kind of fit in and understand.
I also ask alot of very basic questions because at the moment I cant even balance an equation, I am working on learning this stuff but have to balance that with the need for answers. This isnt just a learning exercise for me, I am trying to make and sell a product. I dont want to cause anyone harm so my product has to be safe. Also I am very aware how dangerous chemistry can be, so again I ask before doing. I understand old hands getting peed off, but certainly in my case I dont ask because I am lazy, I ask because I trust the information given on here.
Anyway Sorry for the outburst earlier, it happens sometimes with me. I get funny over things that most people dont.
LG

aga - 21-9-2014 at 09:39

Quote: Originally posted by Actinium  
as a beginner seeing this in the Merck Report none the less you would think that it would hold some validity. Since its clear that it is wrong this would be a perfect example to demonstrate that not all literature is accurate

Definitely.

There is quite a lot of literature that Assumes that the information they have is True, and print it. Especially so on the Internet.

Hold everything you learn in the 'Might be right' box until you have experimented with it and proven it's validity for yourself.

Experimentation is how it all got discovered in the first place, and there is no substitute for sheer experience, so get distilling, fiddle with the parameters and take load of measurements.

arkoma - 21-9-2014 at 09:55

This post is EXCELLENT. Second entry down,by bot0nist.

Melting point of piperine:130C--well above B.P. of isopropyl alcohol (2-propanol).

When I did this, only reason I distilled was to recover my solvent.

S.C. Wack - 21-9-2014 at 11:51

Quote: Originally posted by Actinium  
seeing this in the Merck Report none the less you would think that it would hold some validity. Since its clear that it is wrong this would be a perfect example to demonstrate that not all literature is accurate and really explaine how and why.


It may be a better demonstration of misreading the literature and the accuracy of your interpretation.

aga - 21-9-2014 at 12:31

Quote: Originally posted by arkoma  
This post is EXCELLENT. Second entry down,by bot0nist.

Fantastic post by bot0nist. Inspiring.

So inspiring that i got a Soxhlet running full of black pepper and ethanol now, and it's just done it's first cycle.

What does one do with Piperine if the extraction succeeds ?

Little_Ghost_again - 21-9-2014 at 13:14

Quote: Originally posted by aga  
Quote: Originally posted by arkoma  
This post is EXCELLENT. Second entry down,by bot0nist.

Fantastic post by bot0nist. Inspiring.



What does one do with Piperine if the extraction succeeds ?


Kill bugs or make brandy taste funny apparently (Merck Index 13th ed)

Actinium - 21-9-2014 at 20:46

Quote: Originally posted by aga  
Quote: Originally posted by Actinium  
as a beginner seeing this in the Merck Report none the less you would think that it would hold some validity. Since its clear that it is wrong this would be a perfect example to demonstrate that not all literature is accurate

Definitely.

There is quite a lot of literature that Assumes that the information they have is True, and print it. Especially so on the Internet.

Hold everything you learn in the 'Might be right' box until you have experimented with it and proven it's validity for yourself.

Experimentation is how it all got discovered in the first place, and there is no substitute for sheer experience, so get distilling, fiddle with the parameters and take load of measurements.
That sums up what I'm trying to do. I think we are all here to share in learning and fondness for Chemistry.

@ Arkoma that was my original intent was to recover the solvent, but when I started to smell pepper in the IPA it made me wonder, and was wondering if you had a similar account and if so why? I don't have boiling chips I use my stirbar set on 300 rpm's.

@ S.C. Can you take a look at the link I had posted and give me your interpretation? The part I was talking about is one page back, right column middle of the page.:)

I really want to invest in a soxlet extractor, Laboy has them fairly cheap, but for now would loading the pot and refluxing work the same?

S.C. Wack - 22-9-2014 at 13:15

My interpretation is that it's a vague abstract of some observations on white pepper extracts. It's not about piperine extraction, it includes it, and if I was going to go through the steps I'd just copy/paste them.

It's obvious that piperine is not distilled in any way.

There is a mention of using petroleum ether to remove oil from the piperine...this is the only part that really interested me; the recrystallization in water would be interesting if it could be easily done on a large scale, but the filtration is too potentially horrible to contemplate.

In the oldest piperine thread IIRC I mentioned that if you leave denatured alcohol extracts to evaporate for a long time, the piperine crystallizes out not badly, but then it gets crapped on by the oil suddenly precipitating, and like the Merck thingy said as well as I did then, it dissolves piperine. So if you go that route it might be worthwhile to evaporate to whichever point and wash with pet. ether.

But I disavowed that later after trying base precipitation followed by washing with boiling hot water, instead of pet. ether, so it's moot...all I can say is, after a couple IPA crystallizations, 3%, 134C.

Pepper does not float or stay suspended in alcohol without overhead stirring. Therefore, the Soxhlet.

aga - 22-9-2014 at 14:10

White pepper ?!?!
Damn. I tried it with black pepper corns.

Got 1.38g of black pepper-smelling oil drying with some (what i hope is) CaCl2 in a bag.

Messing with the watery light brown top layer for a while, some of it dissolves in toluene.

It separated a little in NaCl and a bit more so in NaOH, but not much.

With Ammonia it went slightly darker, but nothing special.

Mixed all that together to see if it did anything, but no, so dumped it all.

Just the Black Oil and some residue from filtering.

OC smells a lot better than IC.

Edit:

Pepper corns being made by one of the most complex and amazing chemists ever living, strange and unexpected results when a monkey steals it's seeds and 'extracts' things from said seeds should be expected, by the monkey.

[Edited on 22-9-2014 by aga]

Actinium - 23-9-2014 at 10:31

Quote: Originally posted by S.C. Wack  
My interpretation is that it's a vague abstract of some observations on white pepper extracts. It's not about piperine extraction, it includes it, and if I was going to go through the steps I'd just copy/paste them.

It's obvious that piperine is not distilled in any way.

There is a mention of using petroleum ether to remove oil from the piperine...this is the only part that really interested me; the recrystallization in water would be interesting if it could be easily done on a large scale, but the filtration is too potentially horrible to contemplate.

In the oldest piperine thread IIRC I mentioned that if you leave denatured alcohol extracts to evaporate for a long time, the piperine crystallizes out not badly, but then it gets crapped on by the oil suddenly precipitating, and like the Merck thingy said as well as I did then, it dissolves piperine. So if you go that route it might be worthwhile to evaporate to whichever point and wash with pet. ether.

But I disavowed that later after trying base precipitation followed by washing with boiling hot water, instead of pet. ether, so it's moot...all I can say is, after a couple IPA crystallizations, 3%, 134C.

Pepper does not float or stay suspended in alcohol without overhead stirring. Therefore, the Soxhlet.

thanks for taking the time to kindly answer. Is there anyway to makeshift a soxlet with a chromatography flask between the pot and the condenser?

@ aga Wiki pepper and it gives you the definition of white pepper. So no need to throw your project away.

so the left over gunk I had used to 70% IPA on to remove from the flask after my failed steam distillation, had formed plates which I believe to be fats, i left the IPA in a beaker and have watched it evaporate very slowly over the course of a week. the bottom has the same plates, but in the oil surface of the IPA are tons of sparkles, on further inspection revealed small clear needles.


[Edited on 23-9-2014 by Actinium]

S.C. Wack - 23-9-2014 at 16:14

Quote: Originally posted by Actinium  
Is there anyway to makeshift a soxlet with a chromatography flask between the pot and the condenser?


The only recommended improvised Soxhlet is the one attached to one of my posts in the thread my piperine posting is in.

[Edited on 24-9-2014 by S.C. Wack]