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amalgum
(Hive Bee)
06-23-04 08:07
No 514935
      determined

SWIM knows this has been posted on before, but nobody tries it.
Well, homeslice contacted me a while ago via PM about some post where I had mentioned playing with eugenol as MDMA precursor in the past. Back then, my technique was nowhere near good enough, I wasn't knowledgeable enough, and I was too caught up in other stuff at the time to get serious in chemistry. Even though he spent a pretty penny on glassware.

Well, now it's time to do what SWIM wanted to do from the get go (before meth). Back when he bought the glassware, he also purchased two 16oz bottles of clove oil for a very good price (considering thats a few kilos of eugenol to play with), and only used a little bit. He still has it.

These are his ideas so far. This is just a copy of my last reply to one of homeslices recent PM's, so it doesn't go to much in depth. But it covers some basics of my ideas.
I need opinions on their feasibility, both good and bad. Don't hold back either, SWIMS not deterred. He is very confident something can be worked out to utilize eugenol to make MDMA.

Here:

SWIM heard of this search engine strictly for chemistry and shit like that, it even searches for patents and shit. SWIM did some searching there and found a lot of good info (after going through an ass of bullshit of course).

When using HBr or HI, you only need 5x molar excess to eugenol, so that of course is way better than 50x molar excess (for HCl). Plus since those acids are in higher concentration they would take up so much less volume.
SWIM found out from several basic sites on organic chemistry that the method most popular for cleaving ethers on a ring or chain was the use of either HBr or HI. The mechanism is like this:
R-O-Ar + HX-----> RX + HO-Ar
If the Ar group was a benzene ring, the R is a methyl, and X is Br, then our example is like this:
Me-O-Ar + HBr------>MeBr + HO-Ar

It's a simple Sn2 mechanism. Now obviously, that mechanism also applies to hydroxy groups whether alcohols or phenols. So the rxn has the potential to run further, like this:
HO-Ar + HBr----->H2O + Br-Ar

However, most info that when into depth a little more about reaction of ethers, claim that using equal molar amounts of HX to R-O-Ar, then HO-Ar will be the sole product (law of mass action I suppose).

However, I also found this little nifty mechanism for X-Ar groups when X is a halogen, lets use our example:
1 Me-O-Ar + 2HBr -----> 1MeBr + 1H2O + 1Br-Ar
Now above thats if double molar amount of HX was used, but SWIM is sure some of the X-Ar will be a product from side rxn's. Plus in eugenols case, it already has a hydroxyl that can be attacked, attatching the halogen in it's place. So this is where this comes in:
Br-Ar ---(Na2CO3)---> NaO-Ar
Now thats all they said, they didn't give any details. SWIM thinks the Na2CO3 gives one of it's sodiums to the halogen forming NaBr, the CO3 gives an oxygen to the remaining sodium becoming CO2 gas, and the NaO attatches in the halogens place to give you the sodium salt of the phenol. Of course the next step is hydrolysis:
NaO-Ar + H+ (acid, HCl, H2SO4) ---> HO-Ar + sodium salt of the acid.

Ok, before SWIM wanted to use that on eugenol to get the halocatechol. SWIMs still going to do that, but not first. With the halocatechol, the first thing SWIM was going to do next was to try converting the halogen to an alcohol. Then he'd make a sodium salt with both the hydroxy's on the ring to protect them, and use a simple method like using bleach or chromic acid or something like that (cause he has those things on hand mainly) to oxidise the alcohol to ketone. Then go ahead and react the sodium salt in the methylenation rxn to give 3,4-MD-P2P and proceed from there.
Just for shits and grins, he wants to see if the delepine can be put to use on the halocatechol, reacting it with methylamine like you would with halosafrole to get 3,4-HO-MA, then methylate that to get MDMA. Three easy steps, but we all know how sucky the delepine is for safrole, which is why SWIM wants to toy with this last.

SWIM is finding it more pratical to sidestep the problem of the chain getting halogenated by the HX (and hindering the demethylation some). Instead, SWIM might leave the ether intact till the very end. The ethers of different amphetamine compounds and those similar HAVE been well documented, and works in much higher yeilds (claims of 80% to almost quantitative, like 98%). Plus, if you use HBr to make a salt of the amine instead of HCl before cleavage, you don't have to protect the amine group, and you also do not need a PTC to get higher yeilds as the salt is water/acid soluable.
Plus, SWIM is also finding out that pretty excellent yeilds of isoeugenol can be made using only KOH as the reagent. Thats not so when making isosafrole. Yeah you could do it with only KOH on isosafrole (and no solvent), but the yeilds will be lower than if you were using eugenol instead.
In some literature he found (I guess I need to start keeping track of references), they claimed that if using KOH and water to convert the eugenol's phenol group to the potassium salt first (so it doesn't use some KOH in your isomerization), good yeilds of isoeugenol can be had in 5 minutes. You have to use 1100g of KOH to every 100g eugenol, and heat to 220C. If you want to slack on the KOH usage, it also claimed using 800g at 220C for 40minutes had the same effect.
After that, he'll use any of the obvious methods to make the glycol. Probably at first he'll try oxone or somethinf to make the glycol. He has no problem making formic acid (or getting GAA), but he'd have trouble acquiring 30% H2O2, so other methods are being sought. He was also looking at some shit that claimed using very dilute (like 2%) solutions of KMnO4 will form the glycol in good yeilds from a propenylbenzene. That's cool as hell. They said using more conc. KMnO4 will go to far and form the aldehyde (of course). Of course the HO on isoeugenol will probably just be left the potassium salt so it doesn't get oxidised. It'll be hydrolized at the same time you do the hydrolysis of the glycol to get methylvanillylketone. Instead of adding the 15% H2SO4 solution, he'd add the amount of water needed to make it to the glycol first (but without the acid). And then using a rough estimate based on weight of glycol, add just enough acid to hydrolize all the sodium salts (of course it won't be perfect, unless you isolate the glycol, so you can be accurate on stoichiometry, but that would be impractical). Then add the amount of acid needed to make the water present a 15% solution, and carry on.

The formed MVK, will be reacted with methylamine and reduced in any popular fashion (Al/Hg, and when SWIM gets more $$$, NaBH4) to get 3-HO-4-MeO-methylamphetamine. Isolate as HBr salt, reflux in conc. HBr, and get the 3,4-HO-methylamphetamine-HBr in high yeilds. Then, of course isolate that as freebase, and perform the methylenation step, getting MDMA.
SWIM should have all the materials to begin by the end of this week. Can't wait. He is determined to make this work.

So what'll you all think? He thinks the MVK route to be the most promising out of the ones mentioned above, so he'll try that route first. A quick rundown:
eugenol----(isomerization)---->isoeugenol (A)
(A)-----(oxidation)--->MVK (B)
(B)---(red. amin.)--->3-HO-4-MeO-MA (C)
(C)----(ether cleavage)--->3,4-diHO-MA (D)
(D)---(methylenation)---->MDMA

bbinsq
(Stranger)
07-06-04 02:19
No 517675
      Anticipating a write up on Eugenol to MDMA Synth

SWIM is sitting on several liters of 99.99% Eugenol eager to hear first hand accounts of the Eugenol to MDMA Synthesis.

SWIM has delved deeply into the 'FSE' and referenced materials in the Eugenol threads and has yet to find a definite go/no-go on this synthesis for small scale OTC Bee's.

Bateman

Bandil
(The Archetypical "Good Guy")
07-06-04 07:04
No 517719
      Last step

I'd think that the last step could cause some trouble. You are attempting to methylenate two hydroxy groups, but what prevents the secondary nitrogen from being methylated in the same reaction? The methylenation reaction is not much different from a methylation reaction with MeX (X=halogen). If this is the case, you'd get alot of ugly side products.

I'm not sure where the methylenation step would be safer to perform.

Good luck, regards
Bandil

Nuke the whales!

Rhodium
(Chief Bee)
07-06-04 07:54
No 517727
User Picture       O- vs. N-alkylation selectivities

Read here for O- vs. N-alkylation selectivities: Post 506741 (Rhodium: "O-Methylation of Phenolic Phenethylamine", Chemistry Discourse)

^{The Hive - Clandestine Chemists Without Borders}

Bandil
(The Archetypical "Good Guy")
07-06-04 08:26
No 517732
      Seems it was a correct assumption

Great find Rhodium smile

If the methylenation reaction follow the same ratios as given in the article, you are sure to end up with some serious goo! You'll most likely methylenate the -OH groups, but the secondary amine will also be methylated causing all sorts of trouble.

So instead of doing it as you suggested, try this scheme:

1: Demethylate the eugenol
2: Methylenate to get safrole

Its described throughly here (https://www.rhodium.ws/chemistry/methylenation.html)

The experimental section suggest using DMF as a solvent in the methylenation reaction... But a bit further down in the article there is a description of a DMSO solvated reaction looking really easy, giving super yields. It should be applicable in your case aswell. Worth a shot IMO!

Use any standard route from there...

Good luck, regards
Bandil

Nuke the whales!

homeslice
(Hive Bee)
07-06-04 17:31
No 517767
      This is just an excerpt from a PM from ...

This is just an excerpt from a PM from amalgum. Swims almost done gathering materials for the demethylation/remethylation using the SIBX method to demethylate, but has recently put it on hold according to how amalgum does. What do yas think about this?

Auto-Oxidation of Propenyl-Benzenes to Aldehydes and Ketones

SWIM found this awesome little tidbit last night. It seems that propenylbenzenes can be oxidised by refluxing in DMSO. The oxygen comes from the air, and yeilds can be maximised by passing a stream of air into the mix. It was originally found using isosafrole, but it will work with isoeugenol and shit too.

propenylbenzene -----(O2/DMSO 120C)----> ketone

propenylbenzene ---(O2/DMF or AcNMe2 120C)---->benzaldehyde

SWIM has some patents he still needs to work through pertaining to this, but this looks like a good OTC procedure for acquiring MVK, MDP2P, and vanillin. It's been cited that isosafrole was added to DMSO, and refluxed for 26h. This yeilded 60% 3,4-MD-P2P. They also refluxed isosafrole in DMI for 8h and got 56% 3,4-MD-P2P.

So for our purposes, we can do the isomerization with KOH on eugenol getting isoeugenol. Then we can add it to some DMSO and reflux 26h. Viola, MVK. You can't get too much more otc than that.

1. eugenol -----(KOH)---> isoeugenol
2. isoeugenol ----(DMSO/O2)---> MVK
3. MVK + CH2NH2 ----(NaBH4 or Al/Hg)---> 3-HO-4-MeO-MA
4. 3-HO-4-MeO-MA ----(47% HBr)----> 3,4-HO-MA
5. 3,4-HO-MA + MeBr ----(DMSO/K2CO3)---->MDMA

"Drugs and akahol have ruiinnned my life..." -Tyrone Biggums

homeslice
07-06-04 17:33
      This is just an excerpt from a PM from ...
(Rated as: redundant)

Rhodium
(Chief Bee)
07-06-04 19:05
No 517781
User Picture       cautionary notes

Just a couple of cautionary notes regarding Post 451720 (Rhodium: "Isosafrole to MDP2P by auto-oxidation!", Novel Discourse)

* The japanese article has yet to be translated to a western language.
* Noone at the Hive has tried out the featured DMSO oxidation yet.

I just feel it is a little early to base a multi-step synthesis partly on reactions which has not been fully worked out. This is not to discourage you from trying it out, but rather that you should make a few small-scale test runs with the procedure before deciding to use it in your synthetic pathway.

^{The Hive - Clandestine Chemists Without Borders}

amalgum
(Hive Bee)
07-10-04 16:05
No 518556
      Re: This is not to discourage you from trying...

This is not to discourage you from trying it out, but rather that you should make a few small-scale test runs with the procedure before deciding to use it in your synthetic pathway.

Of course tongue

I thought I have gotten this one pdf file from Rhodiums site, but I guess not. It's mainly about oxidation with t-BuOH in DMSO.

I think the rest of the info was from the link Rhodium posted above. Of course some testing is in order, as well as more research.

Rhodium
(Chief Bee)
07-10-04 16:39
No 518561
User Picture       Hmm...

I thought I have gotten this one pdf file from Rhodiums site, but I guess not. I think the rest of the info was from the link Rhodium posted above.

Well, it is linked in my DMSO auto-oxidation post you are referring to...

^{The Hive - Clandestine Chemists Without Borders}

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		amalgum (Hive Bee) 06-23-04 08:07 No 514935				determined
						SWIM knows this has been posted on before, but nobody tries it. Well, homeslice contacted me a while ago via PM about some post where I had mentioned playing with eugenol as MDMA precursor in the past. Back then, my technique was nowhere near good enough, I wasn't knowledgeable enough, and I was too caught up in other stuff at the time to get serious in chemistry. Even though he spent a pretty penny on glassware. Well, now it's time to do what SWIM wanted to do from the get go (before meth). Back when he bought the glassware, he also purchased two 16oz bottles of clove oil for a very good price (considering thats a few kilos of eugenol to play with), and only used a little bit. He still has it. These are his ideas so far. This is just a copy of my last reply to one of homeslices recent PM's, so it doesn't go to much in depth. But it covers some basics of my ideas. I need opinions on their feasibility, both good and bad. Don't hold back either, SWIMS not deterred. He is very confident something can be worked out to utilize eugenol to make MDMA. Here: SWIM heard of this search engine strictly for chemistry and shit like that, it even searches for patents and shit. SWIM did some searching there and found a lot of good info (after going through an ass of bullshit of course). When using HBr or HI, you only need 5x molar excess to eugenol, so that of course is way better than 50x molar excess (for HCl). Plus since those acids are in higher concentration they would take up so much less volume. SWIM found out from several basic sites on organic chemistry that the method most popular for cleaving ethers on a ring or chain was the use of either HBr or HI. The mechanism is like this: R-O-Ar + HX-----> RX + HO-Ar If the Ar group was a benzene ring, the R is a methyl, and X is Br, then our example is like this: Me-O-Ar + HBr------>MeBr + HO-Ar It's a simple Sn2 mechanism. Now obviously, that mechanism also applies to hydroxy groups whether alcohols or phenols. So the rxn has the potential to run further, like this: HO-Ar + HBr----->H2O + Br-Ar However, most info that when into depth a little more about reaction of ethers, claim that using equal molar amounts of HX to R-O-Ar, then HO-Ar will be the sole product (law of mass action I suppose). However, I also found this little nifty mechanism for X-Ar groups when X is a halogen, lets use our example: 1 Me-O-Ar + 2HBr -----> 1MeBr + 1H2O + 1Br-Ar Now above thats if double molar amount of HX was used, but SWIM is sure some of the X-Ar will be a product from side rxn's. Plus in eugenols case, it already has a hydroxyl that can be attacked, attatching the halogen in it's place. So this is where this comes in: Br-Ar ---(Na2CO3)---> NaO-Ar Now thats all they said, they didn't give any details. SWIM thinks the Na2CO3 gives one of it's sodiums to the halogen forming NaBr, the CO3 gives an oxygen to the remaining sodium becoming CO2 gas, and the NaO attatches in the halogens place to give you the sodium salt of the phenol. Of course the next step is hydrolysis: NaO-Ar + H+ (acid, HCl, H2SO4) ---> HO-Ar + sodium salt of the acid. Ok, before SWIM wanted to use that on eugenol to get the halocatechol. SWIMs still going to do that, but not first. With the halocatechol, the first thing SWIM was going to do next was to try converting the halogen to an alcohol. Then he'd make a sodium salt with both the hydroxy's on the ring to protect them, and use a simple method like using bleach or chromic acid or something like that (cause he has those things on hand mainly) to oxidise the alcohol to ketone. Then go ahead and react the sodium salt in the methylenation rxn to give 3,4-MD-P2P and proceed from there. Just for shits and grins, he wants to see if the delepine can be put to use on the halocatechol, reacting it with methylamine like you would with halosafrole to get 3,4-HO-MA, then methylate that to get MDMA. Three easy steps, but we all know how sucky the delepine is for safrole, which is why SWIM wants to toy with this last. SWIM is finding it more pratical to sidestep the problem of the chain getting halogenated by the HX (and hindering the demethylation some). Instead, SWIM might leave the ether intact till the very end. The ethers of different amphetamine compounds and those similar HAVE been well documented, and works in much higher yeilds (claims of 80% to almost quantitative, like 98%). Plus, if you use HBr to make a salt of the amine instead of HCl before cleavage, you don't have to protect the amine group, and you also do not need a PTC to get higher yeilds as the salt is water/acid soluable. Plus, SWIM is also finding out that pretty excellent yeilds of isoeugenol can be made using only KOH as the reagent. Thats not so when making isosafrole. Yeah you could do it with only KOH on isosafrole (and no solvent), but the yeilds will be lower than if you were using eugenol instead. In some literature he found (I guess I need to start keeping track of references), they claimed that if using KOH and water to convert the eugenol's phenol group to the potassium salt first (so it doesn't use some KOH in your isomerization), good yeilds of isoeugenol can be had in 5 minutes. You have to use 1100g of KOH to every 100g eugenol, and heat to 220C. If you want to slack on the KOH usage, it also claimed using 800g at 220C for 40minutes had the same effect. After that, he'll use any of the obvious methods to make the glycol. Probably at first he'll try oxone or somethinf to make the glycol. He has no problem making formic acid (or getting GAA), but he'd have trouble acquiring 30% H2O2, so other methods are being sought. He was also looking at some shit that claimed using very dilute (like 2%) solutions of KMnO4 will form the glycol in good yeilds from a propenylbenzene. That's cool as hell. They said using more conc. KMnO4 will go to far and form the aldehyde (of course). Of course the HO on isoeugenol will probably just be left the potassium salt so it doesn't get oxidised. It'll be hydrolized at the same time you do the hydrolysis of the glycol to get methylvanillylketone. Instead of adding the 15% H2SO4 solution, he'd add the amount of water needed to make it to the glycol first (but without the acid). And then using a rough estimate based on weight of glycol, add just enough acid to hydrolize all the sodium salts (of course it won't be perfect, unless you isolate the glycol, so you can be accurate on stoichiometry, but that would be impractical). Then add the amount of acid needed to make the water present a 15% solution, and carry on. The formed MVK, will be reacted with methylamine and reduced in any popular fashion (Al/Hg, and when SWIM gets more $$$, NaBH4) to get 3-HO-4-MeO-methylamphetamine. Isolate as HBr salt, reflux in conc. HBr, and get the 3,4-HO-methylamphetamine-HBr in high yeilds. Then, of course isolate that as freebase, and perform the methylenation step, getting MDMA. SWIM should have all the materials to begin by the end of this week. Can't wait. He is determined to make this work. So what'll you all think? He thinks the MVK route to be the most promising out of the ones mentioned above, so he'll try that route first. A quick rundown: eugenol----(isomerization)---->isoeugenol (A) (A)-----(oxidation)--->MVK (B) (B)---(red. amin.)--->3-HO-4-MeO-MA (C) (C)----(ether cleavage)--->3,4-diHO-MA (D) (D)---(methylenation)---->MDMA



		bbinsq (Stranger) 07-06-04 02:19 No 517675				Anticipating a write up on Eugenol to MDMA Synth
						SWIM is sitting on several liters of 99.99% Eugenol eager to hear first hand accounts of the Eugenol to MDMA Synthesis. SWIM has delved deeply into the 'FSE' and referenced materials in the Eugenol threads and has yet to find a definite go/no-go on this synthesis for small scale OTC Bee's. Bateman



		Bandil (The Archetypical "Good Guy") 07-06-04 07:04 No 517719				Last step
						I'd think that the last step could cause some trouble. You are attempting to methylenate two hydroxy groups, but what prevents the secondary nitrogen from being methylated in the same reaction? The methylenation reaction is not much different from a methylation reaction with MeX (X=halogen). If this is the case, you'd get alot of ugly side products. I'm not sure where the methylenation step would be safer to perform. Good luck, regards Bandil Nuke the whales!



		Rhodium (Chief Bee) 07-06-04 07:54 No 517727				O- vs. N-alkylation selectivities
						Read here for O- vs. N-alkylation selectivities: Post 506741 (Rhodium: "O-Methylation of Phenolic Phenethylamine", Chemistry Discourse) ^{The Hive - Clandestine Chemists Without Borders}



		Bandil (The Archetypical "Good Guy") 07-06-04 08:26 No 517732				Seems it was a correct assumption
						Great find Rhodium If the methylenation reaction follow the same ratios as given in the article, you are sure to end up with some serious goo! You'll most likely methylenate the -OH groups, but the secondary amine will also be methylated causing all sorts of trouble. So instead of doing it as you suggested, try this scheme: 1: Demethylate the eugenol 2: Methylenate to get safrole Its described throughly here (https://www.rhodium.ws/chemistry/methylenation.html) The experimental section suggest using DMF as a solvent in the methylenation reaction... But a bit further down in the article there is a description of a DMSO solvated reaction looking really easy, giving super yields. It should be applicable in your case aswell. Worth a shot IMO! Use any standard route from there... Good luck, regards Bandil Nuke the whales!



		homeslice (Hive Bee) 07-06-04 17:31 No 517767				This is just an excerpt from a PM from ...
						This is just an excerpt from a PM from amalgum. Swims almost done gathering materials for the demethylation/remethylation using the SIBX method to demethylate, but has recently put it on hold according to how amalgum does. What do yas think about this? Auto-Oxidation of Propenyl-Benzenes to Aldehydes and Ketones SWIM found this awesome little tidbit last night. It seems that propenylbenzenes can be oxidised by refluxing in DMSO. The oxygen comes from the air, and yeilds can be maximised by passing a stream of air into the mix. It was originally found using isosafrole, but it will work with isoeugenol and shit too. propenylbenzene -----(O2/DMSO 120C)----> ketone propenylbenzene ---(O2/DMF or AcNMe2 120C)---->benzaldehyde SWIM has some patents he still needs to work through pertaining to this, but this looks like a good OTC procedure for acquiring MVK, MDP2P, and vanillin. It's been cited that isosafrole was added to DMSO, and refluxed for 26h. This yeilded 60% 3,4-MD-P2P. They also refluxed isosafrole in DMI for 8h and got 56% 3,4-MD-P2P. So for our purposes, we can do the isomerization with KOH on eugenol getting isoeugenol. Then we can add it to some DMSO and reflux 26h. Viola, MVK. You can't get too much more otc than that. 1. eugenol -----(KOH)---> isoeugenol 2. isoeugenol ----(DMSO/O2)---> MVK 3. MVK + CH2NH2 ----(NaBH4 or Al/Hg)---> 3-HO-4-MeO-MA 4. 3-HO-4-MeO-MA ----(47% HBr)----> 3,4-HO-MA 5. 3,4-HO-MA + MeBr ----(DMSO/K2CO3)---->MDMA "Drugs and akahol have ruiinnned my life..." -Tyrone Biggums



		homeslice 07-06-04 17:33				This is just an excerpt from a PM from ... (Rated as: redundant)



		Rhodium (Chief Bee) 07-06-04 19:05 No 517781				cautionary notes
						Just a couple of cautionary notes regarding Post 451720 (Rhodium: "Isosafrole to MDP2P by auto-oxidation!", Novel Discourse) * The japanese article has yet to be translated to a western language. * Noone at the Hive has tried out the featured DMSO oxidation yet. I just feel it is a little early to base a multi-step synthesis partly on reactions which has not been fully worked out. This is not to discourage you from trying it out, but rather that you should make a few small-scale test runs with the procedure before deciding to use it in your synthetic pathway. ^{The Hive - Clandestine Chemists Without Borders}



		amalgum (Hive Bee) 07-10-04 16:05 No 518556				Re: This is not to discourage you from trying...
						This is not to discourage you from trying it out, but rather that you should make a few small-scale test runs with the procedure before deciding to use it in your synthetic pathway. Of course I thought I have gotten this one pdf file from Rhodiums site, but I guess not. It's mainly about oxidation with t-BuOH in DMSO. I think the rest of the info was from the link Rhodium posted above. Of course some testing is in order, as well as more research.



		Rhodium (Chief Bee) 07-10-04 16:39 No 518561				Hmm...
						I thought I have gotten this one pdf file from Rhodiums site, but I guess not. I think the rest of the info was from the link Rhodium posted above. Well, it is linked in my DMSO auto-oxidation post you are referring to... ^{The Hive - Clandestine Chemists Without Borders}

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