Elemicin -> Mescaline

[Daphuk_up]

Alright, this is about the 50th time SWID has sat down and tried to write this post.  Everytime he does, he ends up answering his own damn questions with a little bit of research, which would be cool if it weren't so fucking annoying.  >_<

Ok, so these questions remain:
   a.  Can the 3,4,5-TriMeoBenzaldehyde be made (from Elemicin) without KMnO4, or any other difficult to obtain ingredient?  What other chemical agents perform similiarly?
   b.  LAH and NaBH4 are out of the question.  What are some other possabilities for the reduction of the nitro group to an amine?
   c.  Finally, although SWID is pretty sure of the answer already, is there no way to exploit the double bond near the end of the aliaphatic chain in such a way as to add an amine group, thus creating the ethylamine directly?  SWID is guessing that either an N-methyl analogue (which PhIKAL says is highly biologically inactive) or an extended chain (propylamine?) would result.  Is there then no way, in the case of the N-methyl, to remove the methyl group?  (SWID is thinking not, since something which would break that particular carbon-carbon bond might reek havoc elsewhere.)

So, the only route to phenethylamine from elemicin is to first break the chain forming a benzaldehyde, then condensing with nitroethane, then reducing the nitro group to an amine group?  SWID supposes this is just how things work, although he does find it a bit annoying that one cannot simply swap CH2 group on the end chain with an amine group.  So close, yet so far away.

[cattleprodder]

Elemicin + ozone (g) + zinc followed by acid hydrolysis workup-->  3,4,5-trimethoxyphenyl-1-acetaldehyde + formaldehdye

3,4,5-tri-methoxyphenylacetaldehdye + NH4OAc+ NaCNBH3 in methanol at pH 7--> freebase mescaline

The first reaction can be carried out without ozonolysis if you use KMnO4 under mild conditions (look them up) to form a vicinal glycol out of the double bond, which can then be cleaved with HIO4 (periodic acid) to cleave the elemicin of its unwanted carbon leaving you with the desired 3,4,5-trimethoxyphenyl-1-CH2C(=0)H.

Also, if sodium cyanoborohydride is a problem, then the above acetaldehyde can be reduced to an alcohol with NaBH4, reacted with red P and Br2 to make a bromoalkane and then reacted with anhydrous ammonia in acetonitrile or dimethylformamide to yield mescaline.

So yes, you can if you so desire forget about LAH and nitromethane and still end up with mescaline from elemicin.

[Nick_J]

"...KMnO4, or any other difficult to obtain ingredient?  What other chemical agents perform similiarly?"

Living in England, I would not classify KMnO4 as difficult to obtain. Check larger garden centres, it is used as an algaecide for rain-water collection tanks. Might even be worth checking pet shops for small amounts, for cleaning aquariums perhaps. But, in larger quantities from garden centres, it can be obtained for £5/500gm.
I don't know specifically about using it for this purpose, but potassium dichromate, K2Cr2O7, can be made to work similarly to KMnO4 for many things. Check out photo chem suppliers for it. It's generally £5-10 for 500g.

"What are some other possabilities for the reduction of the nitro group to an amine?"

Again, I'm afraid I cannot be specific to this reaction, but (aromatic) nitro groups are easily reduced to amines wit Zn/Fe/Sn etc and HCl. Also by Na2Sx and other (poly)sulphides in basic environments. Na2Sx is easily made by mixing NaOH and excess sulphur and adding a drop of water or two with good ventilation, although there are side reactions so it is hard to predict exactly how much polysulphide you have without experimentation. I would think that these methods would work for alkyl nitro compounds too, but I do not know as I have never had reason to try. Actually, I do know that the metal/acid reduction can convert nitroalkanes into alkylamines, so unless it'd mess with other areas of your molecule then I think this could be used.

[foxy2]

Where can you get elemicin?
I haven't heard a single tale of its effective isolation.

[LiquidGaia]

Its suppose to be found in elemi oil in extremely low content around 12-20% and elemi oil is expensive. There is a plant found in Queensland is Australia referred to as the prickly leaf tea tree and the oil is suppose to contain elemicin and isoelemicin at around 80% and 5% respectively.
The name is Melaleuca squamophloia, I have been unable to locate any oil or seeds for that matter, but hopefully a break though in obtaining this plan could come along sometime in the future.

[Daphuk_up]

SWID is beginning to see why the "Natural amphetamine precursors (with pictures)" (aka "YaDontSay") is a broken link.  That thing contains a rather large amount of misinformation.  SWID was under the impression that elemi oil had elemicin as its main constituent.  SWID obviously should have dug deeper and verified the information.   

On a seperate note, SWID believes that currently Elemicin -> Mescaline is beyond his equipment, resources, and capabilities.  However, TMA looks to be of some interest.  Is SWID correct in thinking that a wacker oxidation followed by al/hg amalgam with ammonium chloride (or Delepine in sealed stainless steel pipe?) would produce TMA from elemicin? (assuming he can find a source at all)

Also, SWID lives in a place where KMnO4 is (so far) impossible to find, and sodium cyanoborohydride is most definetly out of the question, thus does he believe he has not the resources to perform this synthesis.  Patience will have to be his friend for a few years.

Thanks for the help bees.  As always, SWID is very grateful.  

[foxy2]

Its suppose to be found in elemi oil in extremely low content around 12-20% and elemi oil is expensive.

If its 12-20% thats ok, there is cheaper Elemi Oil out there.  Swif found some for a reasonable price, don't know how much but not to expensive because swif definately wouldn't have bought it if it was expensive.  I'd guess ~$25/500ml but alas I forgot.

[LiquidGaia]

I'd guess ~$25/500ml but alas I forgot.

If u can get it at that price its a steal. Its enough to test to see if the allybenzene could be convered to the aldahyde.  I am looking futhur into the Prickly Leaf Tea Tree, trying to see what I could dig up.

Oh as for the reduction, Look up sunlights Zn/Hcl techniques that he has used to make 2ch.  You can successfully make it in 10g batchs (small scale) but otherwise the only other way I'd go with a PtO2 catalyst and perform a CTH.

Don't give up on mesc, the progress so far is good, don't be afraid to buy reagents from chem houses, just dress appropriately.

http://fins.actwin.com/aquatic-plants/month.200008/msg00615.html

http://www.koi.com.my/ubb/Forum9/HTML/000021.html

Gives you an idea why an avg joe might want KMnO4.

Anyway good luck, sorry for the rambling.

[Vitus_Verdegast]

I can get a liter of elemi oil for $87.50 and there are places that sell it much cheaper.

Do you got some refs on the elemicin content of elemi oil?
I've never saw it listed as a constituent of it, thought it was only present in the elemi resin.

[LiquidGaia]

Look at

Post 341470 (missing)

(alchemy_bee: "Elemicin content", Chemicals & Equipment) and

Post 406358

(acid_egg: "Asarum heterotropoides(one of two forms of the", Chemicals & Equipment)
these are not published references, but I would respect them as valid.

[Daphuk_up]

Perhaps mescaline isnt quite as far away as SWID thought.  If SWID can obtain some commercial oxidizing agent (KMnO4 or similiar), then it ought to be possible.  A thread around here somewhere states a feasable method for producing nitroethane, and after a bit of research on Rhodiums page SWID found a method for producing Sodiumcyanoborohydride that is within his grasp.  Well, almost...

SWID needs some input on the idea of taking boric acid and removing the oxygens from it to form borohydride gas.  (At least, SWID would guess it is a gas, since his 12th edition Merck doesnt seem to have an entry for it.)  SWID hasnt had much of a chance to brainstorm on this one, but the idea of heating the boric acid initmately mixed with activated charcoal crossed his mind.  Any ideas on this one?

As for the elemicin content of elemi oil, it has been SWID's expierence that most suppliers state that the oil is made from the gum(resin) by steam distillation.  That would probably account then for the elemicin content.

[hypo]

read a highschool chem book. come back. ok?

[Aurelius]

for saying it before I did.

[Daphuk_up]

SWID is guessing that you are refering to the second paragraph.  Undoubtably one of his greatest weaknesses is laziness and expecting others to answer questions he could probably solve on his own.  Nevertheless, please humor him regarding the following ideas, as he knows very little of the chemistry of boron.

Ok, so if someone would, please comment on the following pathway:
1.  B(OH)3 + heat -> B2O3
    B2O3 + 3Mg -> 2B + 3MgO
    2B + 3(H2) -> 2(BH3) (Anybody got the reaction rate constant for this?  I bet it is pretty slow.   )

SWID hasnt been able to put together a second path yet, but he has some ideas.  Reactions such as:
  2B + 2Al + 3(H2SO4) -> 2(BH3) + Al2(SO4)3

Anyways, any help or input would be appreciated. Thanks.

[cattleprodder]

According to Strike's book, _Sources_, the elemicin content of elemi oil ranges from 3.4 to 10.6% (page 123).

[MarleyBob]

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[MarleyBob]

[Nick_J]

Daphuk_up: I think borane could be made in a method similar to that used to produce silane - heat B2O3 with Mg, then add HCl.

B2O3 + 6 Mg --> 3 MgO + B2Mg3
B2Mg3 + 6 HCl --> 3 MgCl2 + 2 BH3
+ side reactions.

[LiquidGaia]

317548On a seperate note, SWID believes that currently Elemicin -> Mescaline is beyond his equipment, resources, and capabilities.  However, TMA looks to be of some interest.  Is SWID correct in thinking that a wacker oxidation followed by al/hg amalgam with ammonium chloride (or Delepine in sealed stainless steel pipe?) would produce TMA from elemicin? (assuming he can find a source at all)

Why not go with TMA-2, its suppose to be more potent and the asarone is easy to obtain fron parsley leaf oil. (I believe)
it would be interested to play with this oil and convert it to the benz. its a 2,4,5tmba. I'm sure a proceedure would also work for isoelemicin. The elemicin could be converted via reflux or at higher temp for a longer period.

Post 317548

(3base: "vanillin from 3-methoxy-4-hydroxy-propenylbenzene", Chemistry Discourse) seems interesting for the conversion of the propylbenzene to the aldahyde. Also,

Post 412020

(Aurelius: "Synthesis of TriMeO-Ph-propenylbenzenes (Shulgin)", Methods Discourse) seems interesting for converting the allybenzene to the propylbenzene, I'm assuming the KOH does work.

Here is my theorical proposal.

1. Elemicin ---> IsoElemicin
    a. KOH and Elemicin @ 140C for 48h.
2. IsoElemicin ---> 3,4,5-TM-BA
    a. KMnO4 + Acidic Alumina + Amberlite 120
    b. Ozone + GAA
    c. Oxygen + GAA
    d. Electrolysis

I would opt for b,c, or d. Since the Amberlite is somewhat pricey.

Does anyone have the specifics on either of those oxidation/ozonation methods?

The primary sources are listed in

Post 317548

(3base: "vanillin from 3-methoxy-4-hydroxy-propenylbenzene", Chemistry Discourse) however they are out of my reach and apparently in german.

[GC_MS]

Why not go with TMA-2, its suppose to be more potent and the asarone is easy to obtain fron parsley leaf oil. (I believe)
it would be interested to play with this oil and convert it to the benz. its a 2,4,5tmba. I'm sure a proceedure would also work for isoelemicin. The elemicin could be converted via reflux or at higher temp for a longer period.

Wrong. Asarone can only be obtained in high yield from Asian calamus oils. There are some other plants with a high asarone content, but as we speak, their essential oils aren't yet commercially available.

[amine]

[amine]

Post 233837

(Bwiti: "Aldehydes From Ozone", Chemistry Discourse)and

Post 426991 (missing)

(ylid: "DIY ozone generator", Chemicals & Equipment) are helpful for ozonolysis.

The acetic acid + ozone method works best as by

this patent

(http://l2.espacenet.com/espacenet/viewer?PN=US2916499&CY=gb&LG=en&DB=EPD)
apparently MeOH could also be used as the solvent.

[amine]

http://www.iisr.org/varieties/viswashree.htm

According to that website elemicin is found at 13.65% in Mace Oil. Currently I found Mace oil for $70/16oz. I'm sure theres cheaper out there.

also, any other bees care to share what the think about the theorized synthesis on top?

thx.

[armageddon]

Google rulez!!
GOOGLE FOR PRESIDENT!  

Yesterday I found a supplier of essential oils who sells PURE essential oil of the australian "Prickly Leaf Tea Tree" (melaleuca squamophloia), which has an essential oil containing mostly elemicin (followed by Linalool, alpha-Pinen, Bicyclogermacren, Paracymen in that order, at least their certificate of analysis says so, and I believe them..)

Unfortunately the price of this essential oil is quite high, something like 290 $ per 100ml....

But considering that at least approx. 50% of this oil could bee converted to something like 3,4,5-triMeO-benzaldehyde or the like, that's 300 bucks for 50 grams of a very valuable precursor, hm...
...starting from here, mesc would be still something very expensive to make!

Let's see what other valuable oils they have and what their analysis say:

ELEMI resin/oil main constituents are (in that order)
"Limonene, Elemicin, Elemol, Elemene, Phellandrene" but other sources say the elemicin fraction is only up to 10% of the oil, probably NOT enough for our needs

Nutmeg oil contains a small percentage of elemicin along with some myristicin (probably also not worth the work of separation, but somewhat cheaper than "m. squamoploia" oil):
"Pinene, Myrcene, Sabinene, alpha- & beta-Terpinene, Terpinene 1-0l-4, Myristicin, Elemicin"

...and a nepalese herb named "wintergreen" (gaultheria fragrantissima; wow, sounds like if it has a *lot* of strong fragrance ) has the following main constituents in its essential oil: Methyl-Salicylates, Benzyl-Benzoate, Menthyl-Azetate, beta-ASARONE, Hexanal

But I'm a little confused about their calamus rhizome oil analysis, 'cuz it says "Calamenene, alpha-Cadinol, Shyobunone, 6-Epishyobunone, Acorone, Acorenone, cis-Isoasarol", but no asarone at all, and that's the asian acorus calamus species, not the european variety (they contain more beta-asarone than the european species, due to having multiple chromosomes, being tetraploid (4 chr. sets) in contrast to russian/european varieties that are triploid (triple chromosomes, my botanical book says "sterile" species?!) and american calamus, being "only" diploid and containing almost no asarone at all. It seems as the number of chromosome sets is directly related to the asarone content of the essential oil (more chromosomes = more alpha/beta-asarone)!)
The essential oil asarone content may be determined by checking the refraction index: if its less than 1,500, there are less than 3% asarone present; if its more between 1,500 to 1,5545 the asarone content will be "something between 4 - 96%", not very precise, but as a first test...

..who knows better methods of estimating the asarone (or other essential oil goodies) content of herb oils? I'm all ears...

 
Not to forget Ho LEAF oil, not to confuse with the also available wood oil (cinnamomum camphora, a chinese herb called Ho-Sho): "Sassafrol, Linalol, SAFROLE, Borneon, Pinene" are the main constituents...


Hope this helps!  

http://tlf.cx/dearpenis.swf

[methymouse]

If you're referring to the supplier that I think you're referring to (the only one I found which sells that particular elimicin-rich oil), then they're out of the business.  The reason their website is still up is a mystery to me, but emails to the proprietor of the site indicated that he was unable to make any money in the specialty essential oils business...

If not (which is also possible, since the supplier I emailed had no prices listed), then $290/100ml seems outrageously expensive for something which you can make much more cheaply out of vanillin.

[armageddon]

Well, I ordered their catalogue and it arrived just today, seems they're still in the business...

But you're probably right about the price being far too high for our special purposes, the vanillin route looks a lot more promising.
I just posted the information about prickly leaf tea tree oil cuz I wanted to show that although the oil CAN be obtained, it is probably too expensive to make ANYTHING from it, and that there are other oils out there which are far more compromising in terms of use as a phenethylamine/amphetamine precursor...


And for the sake of completeness: after having read a bit about cinnamomum species, I doubt that the chinese camphor oil commonly sold as "Ho oil" or white camphor oil will contain anything useful, the literature says the white oil is the first of three fractions obtained by steam distillation of the wood of said plant, and it will contain almost no safrole at all, in contrast to the toxic, carcinogenic (and therefore NOT available) yellow 2nd fraction (40-50% safrole) and the (even more toxic) brown camphor oil (also known as "chinese sassafras") with a safrole content of up tp 80%. Unfortunately brown camphor oil (and perhaps yellow oil too) are considered List I precursors, thx pigs...        ;(

http://tlf.cx/dearpenis.swf