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Limonene Reactivity!

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T

Trips

Rising Star
I'm a big fan of the limonene extractions but a Chemist friend seemed quite disturbed that I was proceeding as such. I didn't understand why until I actually thought about it (After he gently pointed out the pi bonds). Limonene has two regions of concentrated electron density (the double bonds) both very ready to react. Now, already once its come into contact with the air, it will readily oxidize to form carveol and carvone. Now, these aren't so bad as it is, but we're already talking about three new compounds added to the mix, because d-limonene does not evaporate completely. So with these three compounds, we have a truly infinite number of reactions that could take place with the essentially infinite number of compounds in the plant. Many of these WILL migrate across to the acidic layer from which the spice is eventually collected after evaporation. Since no recrystallization takes place, all impurities that migrate to the vinegar or fumaric layer ARE going to be present in the final product.

His logic was that heptane is unreactive, it will always be unreactive and chemists work with it every day to no real harm. Even if some winds up in the final product, it will be very very very very minimal, and you know its not that bad. And It seems to me it would likely combust to very small amounts of carbon dioxide/water/carbon monoxide. These things are known.

With the limonene, it seems as though nobody has any CLUE what they are doing, simply because it is damn near impossible to gauge the degree to which any of these reactions would be taking place (though they most certainly would be taking place!).

Just something to bear in mind: Don't kid yourself into believing you're doing the healthy thing: It could be far from it!

Any comments from those more advanced in the chemistry, let me know!
 
It takes a while before those double bonds will be oxidized to any significant degree. Furthermore limonene is a very stable terpene and can be distilled at high temperatures without breaking down. In open air some will oxidize as you stated to carveol and carvone. However these themselves are not very reactive and thus even if some was to convert to carvone or other oxidized products this would be very unlikely to react with anything in the plant especially at room temp and such short contact time. Even if it did it would be unlikely to be significant.

It is VERY unlikely that using the conditions that people are that ANY significant oxidation occurs. Furthermore even if it did this would make little to no difference as these products are not very reactive themselves. Most things require high temperatures and/or time to react to any significant degree. It is possible maybe that very old samples open to the air have some degradation.
 
Trips, you are definitely right to question about this :) We should be informed about these kind of things and not fall for apparent labels of 'safe and natural' before we have actually made sure it IS safe and natural ..

But in any case, its reassuring to read what bufoman has to say..
 
Carveol has been found to have anti-cancer activity in certain tests. Both oxidized products are found in foods as is limonene. Carveol is used in the perfume industry. People for years have cleaned their houses with limonene which exposes it to the air and oxides without any noticeable problems. It is unlikely that using limonene would make any negative difference. That said using organic solvents makes NO health difference so long as it is properly evaporated and done properly in a hood. However environmentally, and with the ease of use (no hood) using limonene does make a significant difference.
 
Even if the products are JUST carvol, carvone and limonene (Which is impossible, obviously SOME reaction is going to take place. Acidic conditions will certainly cause some hyrdation of the double bonds, etc.) even if these products ARE anti-cancer orally (and I assume your info was pulled from wikipedia and not a peer-reviewed source), I would like to wager that not too many rats have been exposed to the combustion byproducts of these compounds. Limonene DOES wind up in the final product with many of these reactions, with a host of unknown chemicals (WTF is jungle spice?). These are heated to VERY high temperatures, VERY conducive to a reaction. Sure it can be distilled at high temperatures (well, 176 degress, since that is limonene's boiling point). The flame from a lighter burns above 1000 degrees, so that certainly qualifies as a high temperature.

Also, just because it can be distilled, WHEN RELATIVELY ISOLATED, does not mean that it could be heated to these temperatures when mixed with all sorts of strange chemicals and plant matter WITHOUT REACTING. Sure, lots would probably evaporate cleanly off. What about the remains that are left behind? I bet there is all kinds of nasty crap.

Breathing it in while cleaning is not the same as reacting it and ingesting its combustion by-products.

I know people think it is nice and easy and it doesn't stink, which is fine and dandy, but to do it under the guise of it being better for you; that's just straight up deception. People are fooling themselves if they truly believe that to be the case. It is at best as good for you as heptane extracted DMT. At worst, who knows?! Nobody.

I just think people should think about the dangers before blindly nodding and going "Yea! NATURAL!"
 
Hey trips.. As I said, its an important point you bring up... but you talk as if its PROVEN that its NOT better for you, while what you are bringing is only the POSSIBILITY that it MIGHT not be good.. So if you say people think its better for them and that it is deception, well, you just dont know.. maybe it IS better for people.. So if you say its "Maybe" a deception, it makes more sense what you say :)
 
the thing is with the d-limo teks that use vinegar or water..how could an oil contaminate it? when you pull out the water or vinegar..and not the d-limo...and then filter it...its basically impossible for d-limo to even get in it...perhaps the acids do bring something over..but unless they are soluble in acetone or IPA you wont get them in your final freebase product
 
The fact that people eat d-limonene all the time in fruit is a clear indication that we have been designed to ingest it over the millions of years we've evolved. When you ingest d-limonene it goes through an A/B type of reaction in your body. First in the stomach it's bombarded with hydrochloric acid in a low pH environment, and then in the small intestines it's made alkaline.

We are biological A/B extractors:)

I wouldn't worry about d-Limonene at all. It's been part of our diet for millions of years.
 
Coca has been a natural part of the diets of many for years. That is not to say that when super concentrated and smoked it is good for you. I'm not saying the cases are similar, but this point still serves to nullify the "obvious safety" of the compound. Really though, when did you last smoke 40 orange peels? Or smoke 40 orange peels, for that matter. (Haha! Don't forget to let them go moldy in a brown paper bag first!).

I don't think it is harmful to you. As stated, it is by far my favorite solvent. But really, WTF is that nasty goo we wind up with? I don't know. Do you know? It's full of "jungle spice". ...great. What is jungle spice and why can its existence not be proven? Isn't it potentially much safer to yield pure DMT crystals, which are KNOWN to be safe, using known chemicals? This just seems stupid.

But I suppose I would not smoke anything that still smelled like xylene and people here do. It IS deceiving to tell yourself this substance is safe; Because you don't know.

That's like telling someone you have exactly $4.83 cents in your bank account. Is it deceitful? Yes, if you're not sure how much money you have, it is INDEED deceitful, even if you are right. Terpenes are much MUCH more reactive than saturated hydrocarbons, and to deny that is foolhardy. And to say you know exactly what you're creating and smoking is even more foolhardy.

Smoking ANYTHING is bad for you. Period. Only the byproducts of combustion determine HOW harmful to you it is.

Do you know what the byproducts are?

I'm not trying to be a prick (that's a lie, I totally am), but you've gotta consider these things.

It's not an urgent matter, just something to consider.
 
Trips said:
Do you know what the byproducts are?
Click to expand...

do you?
you asked for the more chemically-inclined members to chime in, and we did.
the byproducts would still be simple non-toxic terpenes, not potentially mutagenic epoxides


besides, who smokes dmt anyway? that's such a waste. :?
vaporization separates compounds by their boiling points, no combustion occurs. limonene, the 'jungle spice', and other insolubles vaporize at a much higher b.p.
 
Trips said:
Even if the products are JUST carvol, carvone and limonene (Which is impossible, obviously SOME reaction is going to take place. Acidic conditions will certainly cause some hyrdation of the double bonds, etc.) even if these products ARE anti-cancer orally (and I assume your info was pulled from wikipedia and not a peer-reviewed source), I would like to wager that not too many rats have been exposed to the combustion byproducts of these compounds. Limonene DOES wind up in the final product with many of these reactions, with a host of unknown chemicals (WTF is jungle spice?). These are heated to VERY high temperatures, VERY conducive to a reaction. Sure it can be distilled at high temperatures (well, 176 degress, since that is limonene's boiling point). The flame from a lighter burns above 1000 degrees, so that certainly qualifies as a high temperature.

Also, just because it can be distilled, WHEN RELATIVELY ISOLATED, does not mean that it could be heated to these temperatures when mixed with all sorts of strange chemicals and plant matter WITHOUT REACTING. Sure, lots would probably evaporate cleanly off. What about the remains that are left behind? I bet there is all kinds of nasty crap.

Breathing it in while cleaning is not the same as reacting it and ingesting its combustion by-products.

I know people think it is nice and easy and it doesn't stink, which is fine and dandy, but to do it under the guise of it being better for you; that's just straight up deception. People are fooling themselves if they truly believe that to be the case. It is at best as good for you as heptane extracted DMT. At worst, who knows?! Nobody.

I just think people should think about the dangers before blindly nodding and going "Yea! NATURAL!"
Click to expand...

Here is the link to the article I got the anti-cancer properties from:

Chemoprevention of mammary carcinogenesis by hydroxylated derivatives of d-limonene

carcin.oxfordjournals.org

Chemoprevention of mammary carcinogenesis by hydroxylated derivatives of d-limonene

Abstract. The monoterpene d-limonene has been shown to an effective, non-toxic chemopreventive agent in mammary and other rodent tumor models. The studies repor
carcin.oxfordjournals.org carcin.oxfordjournals.org

Natural does not mean safe. No one is saying that. There are environmental advantages to using this solvent. It is green chemistry which the entire chemical industry is moving towards by the way. In addition from many peoples stand point Limonene is easier to use as it does not stink up your entire place of work. Also if you do not have access to a hood you do not have to breath in potentially dangerous and harmful fumes. Additionally it is environmentally friendly as the waste is bio-degradable and non-hazardous.

Look into the reactivity of limonene and terpenes in general it requires much stronger acidic conditions to react and catalysts. The acidic conditions of probably pH 3-4 for 10 minutes are not going to have any significant effect.

Also SWIM has seen the HPLC and MS of products extracted with limonene and they are clean and pure just alkaloids.

Heptane is not the best solvent for an alkaloid extraction. As a significantly larger amount of solvent will be required as most alkaloids are only partially soluble in heptane (This is why it is a good recrystalization solvent). Slightly polar solvents (aromatic and halogenated are the best non-water soluble organic)

There are potential carcinogenic break down products to any thing that is combusted. This means nothing. The amount of limonene left in a final product is miniscule same with solvents like toluene there will always be minor amounts remaining. If a recrystalization is performed or better yet a freebase of the alkaloids from the salts (with an organic solvent like naptha) there will be almost none of any of these terpene like components left.
 
Jungle spice is a small amount of unknown alkaloids in MHRB. It is what is left after all of the DMT is extracted with hexanes. JS is usually classified as an orange-red colored oil. No one knows what they are although many believe they potentiate the effects of DMT. There is evidence that it does. However any attempts to determine what JS is have resulted in the sample consisting of mostly DMT with a few minor components of high MW unknowns. Maybe a possible MAOI type carboline compound in one case. People have looked by TLC, HPLC, MS, and in all cases it is mostly just residual DMT. Many people claim they have JS when in fact they just have no removed all of the DMT effectively.
 
I think that some people feel that what is better for the earth, and the environment they live in, is also better for them, and as far as limonene is derived from an agricultural waste product (orange peels), it lives up to these standards. Limonene is less toxic than all other solvents that can be used for these sorts of processes, both in the production stage of limonene, and its household use. This brings me to another strong point of limo, how often do you dilute some heptane and wash your counters, floors, or clean stains with it? I hope never, but it makes limonene that much more useful, and I have done this many times with limo, and it works very well and smells wonderful.

Limo is cool, if all you can get is heptane, that's cool too, you can make some very sick spice with that, but don't get so caught up in settling on one solvent, many of them have far more than just one use, and heck, it's fun to try out new things, I'd even like to get my hands on some heptane, but that doesn't mean I'm gonna get rid of the limo, will probably utilize both!

Try to accept some of the knowledge that's being sent back to you as a response to your thread.
 
lol. Y'all think I'm a closed minded prick. Just playing devil's advocate to see what you have to say on the subject.

*Cooooool*
 
Once you go green with d-limonene, it's hard to go back.

The advantages it has over many other solvents are:

1 - 100% natural. It's simply pressed from orange peels. This process is environmentally friendly.
2 - The smell is WONDERFUL. It clearly smells better than all the other solvents out there. It smells like oranges. Who doesn't love the smell of oranges?
3 - It's been part of ALL human diet around the entire world for millions of years.
4 - It's been shown to potentially help fight cancer.
5 - It's non-toxic. It's actually edible.
6 - It's fumes are non-toxic and non irritating. You don't need to worry about breathing it in. With most other solvents this is an issue.
7 - It's just polar enough to work well for most A/B extractions without being too polar. It's more polar than heptane, but less polar than chloroform.
8 - It's 100% biodegradable.

I could go on and on and on. There's simply no other solvent, other than water, that I like as much as d-limonene. I only wished it evaporated faster and boiled at a lower temperature.
 
GreenTerpene is now selling terpenes from other sources- tangerines, grapefruit, limes, lemons, eucalyptus, and cloves. Does anyone have any information on these? Could they possibly be used as a solvent like d-limonene? Would be nice to have an array of similar solvents that have different properties with regard to spice.
 
^^It depends. Many of these products may be mixtures with varying components. There is only one way to find out and that is to test the solubility of spice in those mixtures. Also be aware of what kinds of essential oils are in some of these mixtures. Concentrated essential oils are toxic at certain doses (well above residual amounts left after evaporation or that in which you injest with food) and some are neuro-toxins like alpha-thujene so you want to make sure the plant sources don't contain significant amounts of thujene.

When doing chemistry its best to work with a more pure solvent. That way your results are reproducible.
 
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