MDMA Revisited

[nshanin]

This correspondence is from the bullshit thread. I felt we were cluttering it up there and that this procedure may be a bit more than... bullshit.

Finally done with finals and had enough sleep to think rationally...

The bad news: After researching it with every spare minute I had, I discovered what many of you already know: iodosafrole is basically useless without azide and strong reducing agents (though with precursors this cheap even a 5% yield could be huge).

The good news: One of the steps for this process for iodosafrole that I have in mind requires reaction with a base, which will undoubtedly form isosafrole anyway. So I lied to you; no halosafrole, just isosafrole in 2 steps and still from OTC reagents. Not as good as I had hoped, but my hopes were based on an idealized reaction of iodosafrole with amines, which AFAIK, has yet to yield significant substitution product.

Of course, there are reactions where iodosafrole can turn into MDMA with ~50% yield (JACS? JOC? the ref is out there), but they take weeks and require pressure vessels. It may just be easier to do a peracid on the isosafrole.

A clever line from TSII that has stuck in my head since I read it is "[trans isosafrole] doesn't react the same way in the peracid oxidation and won't be recognized as MDMA in the brain cells of users" (or something to that effect). During long bus rides home when I had hours to think about this and no resources to verify ideas I always came back to this line whenever I admitted to myself that isosafrole will be a large if not major byproduct of this proposed reaction so continue trying to find alternatives to the reaction with base. Fortunately, this statement is wrong and the trans isomer can be utilized without issue.

Originally Posted by Ford

I've seen OTC one pots from catechol but I can't imagine that doing you a whole lot of good here.

Were they all F-Cs? I can't imagine formylation and a Henry in one pot.

I've seen an OTC FC, though that was at least three or four steps.

I had a thought about using the amine itself as the base catalyst in the ring-closing, which should remove one step from the procedure. But that just sounds like crazy talk.

I haven't seen any sort of reaction involving semi-sythetic derivatives such as piperonyl butoxide and the like, and although I suppose'd be possible, I wouldn't put money on it.

It's not looking good, I'll tell you that.

Also, the mention of iodination leads me to believe that maybe a halogenated nonsafrole intermediate is formed in the first step and iodosafrole in the second, skipping plain garden variety safrole entirely.

You got it.

Maybe eugenol is iodinated to stabilize the alkene

Told ya you'd get it. Fortunately in this prep this is the first step so polymerization shouldn't be a huge worry.

and then something drastic is done to methylenate in one step.

Drastic? Ring-closing has plenty of refs... provided that you have adjacent hydroxyl groups. When chemists used to boil their safrole in HX they never got ring cleavage; however, I've found a process that will supposedly cleave ANY aromatic ether--ring or otherwise.

But probably not. Whatever it is I'm definitely still in the dark! (Although very excited.)

Nah, you basically have it. But the reaction doesn't involve gasing with HI or some other dangerous nonsense.

---------------------------------
The above was written a few days ago and I just slightly edited it. Now to your other questions:

Originally Posted by Fra

I'm sure both HBr and HI have been used to demethylate methoxy to hydroxy over aromatic chemicals of our interest in the ring zone. On the other hand I have not found any direct reference so who knows.

Yes they have and there are many references for both HI and HBr, but they all involve gassing the ether with the strong acid. The ref I found doesn't require that.

Originally Posted by Ford

Aye, dihydroxymethamphetamine is very easily oxidized to the quinone, which will polymerize with the amine group.

That's not a huge concern of mine; any dihydroxy compound is easily oxidized to the quinone, you just have to work quickly with it. While there's no way you could get a one-pot demethylation/addition of HI with the bridge-closing, one should be able to remove the product from the solution rather quickly. My ref fractionally distilled the entire solution but in the case of aryl-alkyl ethers there was no side product and minimal side product in the case of terminal alkenes. Thus, the major product should be the dihydroxy 2-iodopropane. After reaction with base and DCM one should be able to get isosafrole, which can then be worked up as one wills. The problem with isolating the dihydroxy compound and taking it to the amine is the fact that you'll need an extra step where the compound could be oxidized to said quinone. This wouldn't be that big of a problem if the ideal amine substitution of that compound didn't take several weeks! I figure you'll get a bunch of tar and useless quinones at the end of your work.

Originally Posted by Fra

Man what are you starting from? Eugenol? If you want to go through iodosafrole, mdp2p isn't an intermediate. Please give us some clue

Hah! Wanna bet? I went over it a few posts ago. Either one directly aminates iodosafrole in which case yields are shit because of the combined facts of 1) yields being shit in the first place, and 2) Oxidation to the quinone, especially under extreme conditions and long reaction times. When isosafrole is the main product the intermediate you'll have to go through to MDMA will be MDP2P. Unless you guys have other ideas...

Originally Posted by Formula409

Oh hi there!
http://www.pubmedcentral.nih.gov/art...?artid=1573171

Cool stuff. They make HHMA from the corresponding 3-MeO compound under a nitrogen atmosphere though, probably because of concerns mentioned above. It would be interesting to see just how much oxidation one would get just by performing the reaction under normal conditions (ref takes 6 hours maximum). In any case, the reaction wouldn't be difficult to cover in some sort of air blanket and CO2 should work well for this.

Have you guys read what PsychoKitty has said on the Hive in the Rhodium archive about MD(M)A from Eugenol?

Several times.

Basically he proposes the following route to avoid the shit yields obtained from demethylation/methylenation of eugenol.

Link:
http://www.erowid.org/archive/rhodiu...enol.mdma.html


Eugenol > isoeugenol > methyl vanillyl ketone > co-responding (meth)amphetamine > demethylation > methylenation > MD(M)A.

Unfortunately

Makes a lot of sense IMO, and I've just shown that demethylation of the respective amphetamine immediates works, along with reductive amination of methyl vanillyl ketone

But not the peracid with eugenol. I haven't seen evidence either way but I remember hearing that the peracid doesn't work on eugenol (though I've seen papers where exotic catalysts and O-substituted eugenols are used to do so). There's a lot of information on this on psychonaut where AlCl3/thiourea came up as a demethylating agent--eventually I'll read that thread again and come up with a final conclusion. Ultimately the best idea that came up there (again, IIRC) was to methylate eugenol, then to react the alkene to whatever stage desired and finally to demethylate twice.

Another thing I've always wanted an answer on is if someone has tried the demethylation/methylenation on ISOeugenol - PK says something in his rant about the double bond being on the end of the side chain being the main problem as it easily cyclises (sp)

Good question. I don't know but my intended route does not necessitate this knowledge. It's interesting stuff nonetheless though.

Will edit later.

[Fra]

are you sure that passing through isosafrole, peracid and reductive amination would yield more than a delepine rxn or equivalent with methylamine? Unluckily, halosafrole is poorly documented, but most of the problems come from the halogenation itself. http://www.erowid.org/archive/rhodiu...y/dmmda-2.html this isn't about safrole, but on a similar allylbenzene, yields aren't that bad.

[Fra]

yeah, but you can synth MDA. and you don't necessarily need a bomb to make mdma, you can reflux with methylamine.

[Ford]

Originally Posted by nshanin

The bad news: After researching it with every spare minute I had, I discovered what many of you already know: iodosafrole is basically useless without azide and strong reducing agents (though with precursors this cheap even a 5% yield could be huge).

I wouldn't be so quick to rule out iodosafrole. The reaction scheme is well documented, at least clandestinely. Historically it seems that most of the problems arose in the preparation of bromosafrole, not in getting acceptable yields from it and methylamine. But you're right, while clove oil is still $10-15 a pound, yields are not extremely important just so long as the product can be efficiently extracted. It is also my understanding that the pressure vessels are only needed if using bromosafrole as higher temps are needed.

"The iodosafrole method of producing MDMA and MDA is indeed viable; being one
of those multikilagram processes here in the Netherlands someone was asking
about.... Finally, amination is done at room temp with methylamine for MDMA or with
hexamine (via Delepine process) to get MDA or other analog." [1]

Sum refs:

Chem. Abs. 1961, col. 14350.
JACS 68, pages 1009-11.
JACS 68, page 1805.
JACS, part 2 1938, page 2005.

Also: sodium methylamide might be a decent reductant for this. I don't have anything to back up this claim... but it might be worth looking into anyways.

Were they all F-Cs? I can't imagine formylation and a Henry in one pot.

US7402709 describes the one pot to piperonal that I was suggesting to. Sorry if there was a misunderstanding, I said I didn't think it'd be a whole lotta use in this reaction because it produces piperonal not safrole. But it was awesome enough to need mentioning anyways.

I had a thought about using the amine itself as the base catalyst in the ring-closing, which should remove one step from the procedure. But that just sounds like crazy talk.

Hah. The one I was referring to used aluminum amalgum. Weird paper. It's in the hive archives somewhere but I can't seem to find it anymore.

You got it.

Proud of me?

[Ford]

Also, relevant bits for those interested:

...

The alkaline solution is prepared by prolonged stirring of 8.8 of KOH pellets in 30 ml of glycerol. The solution is placed in a round-bottom flask provided with a reflux condenser. Then 4.0g of eugenol is added and the solution heated under microwave for 3 min with a 98% yield.

Syn. Comm. 27 (24), 4335-4340 (1997) [1]

...

A solution of 30% aqueous hydrogen peroxide (9 ml, 85.6 mm) and formic acid (16 ml, 88%) is added to a soultion of isoeugenol (8.1 gm, 50 mm) in formic acid (4 ml). The reaction micture is stirred at 35-40C under nitrogen for 3 hours. The resulting 1-(4-hydroxy-3-methoxyphenyl)-propane-1,2,diol-monoformate is treated with 10% agueous sulfuric acid (125 ml) and toulene (15 ml). After refluxing with mixing for 6 hours, the reaction mixture is cooled to room temperature, and the toulene layer serparated. The aqueous layer is extracted with fresh toulene and the toulene layers are combined, washed with saturated aqueous sodium sulfate, dried over anhydrous sodium sulfate and concentrated to give methylvanillyl ketone is 48% yield.

US4337360

[sexualjesus]

i havnt been in the bullshit thread in a while, got a write up of the synth?

whats this wonderful revolutionary and cheap precursor? it isnt an oil is it...

[nshanin]

Disregard that, I suck cocks.

http://designer-drug.com/pte/12.162....etetramine.pdf

Reveiw of the use of HMTA as a reagent with (not surprisingly) much attention focused on the delepine, which apparently does work with secondary amines. WTF?

I had a long post typed up when the unthinkable happened--a Linux machine froze on me. I'll get back to you guys, promise.

[stateofhack]

Originally Posted by nshanin

I had a long post typed up when the unthinkable happened--a Linux machine froze on me. I'll get back to you guys, promise.

I call shenanigans

[Fra]

Is your work ready? I really can't wait. Please post it, if you have managed to get isosafrole from OTC, then your work is fine.

[nshanin]

Originally Posted by Fra

Is your work ready? I really can't wait. Please post it, if you have managed to get isosafrole from OTC, then your work is fine.

If by "work" you mean experimental results, then no because my supplier is out of stock of a crucial ingredient and so I won't be able to realistically work on this until winter break when I get back home. I'll post further thoughts next week when I actually get a break though. Promise. I'm telling you, this plan looks foolproof. Even if you manage to halogenate the benzylic carbon instead of the alpha carbon you'd still get isosafrole after treatment with base and DCM. I'll outline a full procedure, refs n' all, and hopefully one of you guys can try it out.

[stateofhack]

Originally Posted by Ford Prefect

Anything happen with this?

Is intrested. I don't mind giving this a shot, i think i might have the neccessary reagents, but i have not fully read into this.

[nshanin]

Hey guys, sorry for letting you down but I'm no longer into the whole illicit chemistry scene. I'll PM you the procedure in IRC, SoH. We'll see how things go from there.

[Hydroponichronic]

Originally Posted by nshanin

Hey guys, sorry for letting you down but I'm no longer into the whole illicit chemistry scene.

Son,

[AdMech]

Originally Posted by nshanin

Hey guys, sorry for letting you down but I'm no longer into the whole illicit chemistry scene.

Really sad music came on just as I read this.

[Hydroponichronic]

Originally Posted by AdMech

Really sad music came on just as I read this.

I died a little inside.

[Ford Prefect]

Originally Posted by nshanin

If by "work" you mean experimental results, then no because my supplier is out of stock of a crucial ingredient and so I won't be able to realistically work on this until winter break when I get back home. I'll post further thoughts next week when I actually get a break though. Promise. I'm telling you, this plan looks foolproof. Even if you manage to halogenate the benzylic carbon instead of the alpha carbon you'd still get isosafrole after treatment with base and DCM. I'll outline a full procedure, refs n' all, and hopefully one of you guys can try it out.

HEY NSHANIN WHATS UP HOW ABOUT OUTLINING THE FULL PROCEDURE REFS AND ALL SO ONE OF US GUYS CAN TRY IT OUT? ...Sorry for bumping an ago old thread, but you got us (me) way to excited about this to leave this motherfucker unfinished.

Srsly.

[missingno]

[/quote]
Hah! Wanna bet? I went over it a few posts ago. Either one directly aminates iodosafrole in which case yields are shit because of the combined facts of 1) yields being shit in the first place, and 2) Oxidation to the quinone, especially under extreme conditions and long reaction times. When isosafrole is the main product the intermediate you'll have to go through to MDMA will be MDP2P. Unless you guys have other ideas...
[/quote]

swim's idea plans to 1)demethylation vanillin/engenol OR purchase a good amount of catechol from sigmaalrich 2)methylenate the catechol to piperonal/safrole......with piperonal 3) prepare it to a nitrostyrene 4)reduce it with a strong reducing agent to mda 5) enjoy the unknown yeild!

OR with 3,4 methylenedioxybenzaldehyde (piperonal), couldnt one just add ammonia to mda or add methylamine **thiers OTC ways to prepare it** to mdma????

[atara]

Why not the Wacker oxidation?

Useful sources of palladium include bullion, coins, wire, sheet, and rings -- Google gives plenty of hits for all the palladium you'll ever need. It's really not hard at all to get compared to many of the other chemicals involved -- if you look closely you'll find that you can get bullion by the gram for quite reasonable prices. Preparing the chloride isn't too bad either:

http://www.bromicacid.com/lonelychem...ons/081108.htm
http://www.erowid.org/archive/rhodiu...m.chloride.txt

I don't know of any refs for the Wacker on eugenol, but I see no reason it wouldn't work, same as safrole:

http://toxicopoeia.com/archives/rhod...acker.krv.html

Also, I'm going to tentatively recommend a Nalgene over a soda bottle, because it's impossible to destroy a Nalgene. The advantages (of wacker) are, of course, recoverable catalysts, no toxic volatiles, and cheap solvents.

to 3,4 methylenedioxybenzaldehyde (piperonal), couldnt one just add ammonia to mda or add methylamine

No. Piperonal is not MDP2P. Also, you'll get an imine from MDP2P, which you'll need to reduce.

[missingno]

those procedures are more OTC and reliable then reducing the piperonal with LAH..ha

[atara]

Oh, one thing: Upon further investigation I've determined that Wackers don't work well on eugenol. The reason is that the phenol moiety interferes with the catalyst. Peracids also don't work well on eugenol, for the same reason. If you attach a protecting group to the phenol (methyl would work fine), you should be able to Wacker or peracid.

The correct answer is to get some saffy. There are a number of plants that contain it. Demethylating eugenol is also a lot harder than it sounds, unfortunately.

[Aperson444]

Hm, I've been out of this scene for a while, so could someone tell me what's wrong with distilling safrole from the sassafras extract, doing a Wacker oxidation with PdCl2 and benzoquinone to form MDP2P, then using Al-Hg amalgam to form MDMA? Is it more costly?

[idontlie]

Originally Posted by Aperson444

Hm, I've been out of this scene for a while, so could someone tell me what's wrong with distilling safrole from the sassafras extract, doing a Wacker oxidation with PdCl2 and benzoquinone to form MDP2P, then using Al-Hg amalgam to form MDMA? Is it more costly?

Getting Sassafras oil is the problem.

[Aperson444]

Ah, I see. How difficult are the syntheses from piperonal? Also, with regards to sassafras oil, isn't it available as a flavoring agent or something for aromatherapy? There is a plant called Hoja santa, which can be grown in Mexico-like climates that containes 80% safrole, and is relatively unwatched.

Anyways, I took a look at designer-drugs synthesis information for piperonal. It looks as though converting piperonal to isosafrole is quite equipment heavy.... It requires BuLi and ethyldiphenylphosphine oxide.... Not very OTC at all. Anyways, I'm up for any synthesis that's had good results.

[BungHole]

Originally Posted by Aperson444

Anyways, I took a look at designer-drugs synthesis information for piperonal. It looks as though converting piperonal to isosafrole is quite equipment heavy.... It requires BuLi and ethyldiphenylphosphine oxide.... Not very OTC at all. Anyways, I'm up for any synthesis that's had good results.

Methylenedioxyphenyl 2-nitropropene to MDP2P.....

[idontlie]

Originally Posted by Aperson444

Ah, I see. How difficult are the syntheses from piperonal? Also, with regards to sassafras oil, isn't it available as a flavoring agent or something for aromatherapy? There is a plant called Hoja santa, which can be grown in Mexico-like climates that containes 80% safrole, and is relatively unwatched.

Anyways, I took a look at designer-drugs synthesis information for piperonal. It looks as though converting piperonal to isosafrole is quite equipment heavy.... It requires BuLi and ethyldiphenylphosphine oxide.... Not very OTC at all. Anyways, I'm up for any synthesis that's had good results.

Getting to piperonal from piperine is shitty yielding and not a bulk production method in any way. Hoja santa steam distillation is rather disapointing but yes it does work. The cook friendly version is steam extract gives a bilayer in your collection strainer. distill under vacume, isomerize via koh, do buffered peroxic to mdp2p animate. (pinky didnt do from p2p to amphetamine she chose to oxime to mda to use a a reference sample for her helional adventures.)
Piperonal to iso is a waste of time while mr. henry with nitroethane (readily available via ethyl bromide, rhodium has info. neither pinky nor I have tried it as we are not interested in piperonal.)
Helional -> MDA via twodogs on psychonaut is very do-able something he doesnt mention is you want to put you bleech, your beckman product and lye water in the fridge.

Titrate and shake works well for small runs, Pinky liked to pool her results and gas them in toluene.

I as an ex meth user prefer MDA over mdma and pinky as a next gen cook prefers mda as well. Dont use the first perfumist bitches aldehyde, when you get it and not the smell against a fresh from her sources aldehyde (its really cheap, they accept prepaids dunno about po boxes pinky used a friends friends friend's appartment then took a long drive to pick it up) you can figure out why the yields are so extra ordinarily low. Replacing bromine and additional lye in the hoffman gave a slight increase in yield (about 5%). Not significant to warrant the effort for only a few dollars more of product. Expecially if you are considering piperonal as a starting source.

Dont buy shit you dont need. Thats my advice. Plan plan plan plan then get only exacally what you need. Overseas glass is cheaper and more than able to do anything youd like it too. Pinkies glass nor mine shows any signs or wear damage.

[director of sound]

look into electrochemical reduction, super easy to go from piperonal from black pepper to MDA then formyl MDA via formic acid and benzene then another electrochemical reduction to MDMA. just a thought. i got a pic of the electrochemical cell in my profile album. the catholyte is 100ml HCL, 100ml glacial acetic acid and 30g of the coresponding nitrostyrene. the anode compartment is filled with a solution of 25ml conc. H2SO4 in 175ml water. this will work for anything really TMA-2, Mescaline, MDA, MDMA, DMMDA, really any phenethylamine or amphetamine as long as you can make a nitrostyrene from it or if it can be reduced by LAH. current runns 5-6 ampres for 12 hr, 20*C for the first six then let it warm to 40*C over the last six. yeilds the crude phenethylamine or amphetamine in HCL form. just workup from there to a pure product. usually around a 70-75% yield. for instance from 30g of 3,4,5-trimethoxy-b-nitrosytrene (via gallic acid to 3,4,5-trimethoxybendaldehyde) yielded 27.3g mescaline HCL

[BungHole]

Originally Posted by director of sound

look into electrochemical reduction, super easy to go from piperonal from black pepper to MDA then formyl MDA via formic acid and benzene then another electrochemical reduction to MDMA. just a thought. i got a pic of the electrochemical cell in my profile album. the catholyte is 100ml HCL, 100ml glacial acetic acid and 30g of the coresponding nitrostyrene. the anode compartment is filled with a solution of 25ml conc. H2SO4 in 175ml water. this will work for anything really TMA-2, Mescaline, MDA, MDMA, DMMDA, really any phemethylamine or amphetamine as long as you can make a nitrostyrene from it or if it can be reduced by LAH. current runns 5-6 ampres for 12 hr, 20*C for the first six then let it warm to 40*C over the last six. yeilds the crude phenethylamine or amphetamine in HCL form. just workup from there to a pure product. usually around a 70-75% yield. for instance from 30g of 3,4,5-trimethoxy-b-nitrosytrene (via gallic acid to 3,4,5-trimethoxybendaldehyde) yielded 27.3g mescaline HCL

What method of reduction was used to reduce the gallic acid to the aldehyde? Electrolytic also?

And I'm assuming the nitrostyrene still required a nitroalkane for the procedure? You kind of skipped right to the reduction, so I'm not sure.

Honestly the reduction isn't really the hard part in my opinion, I'm just trying to figure out how to get decent quality nitroalkanes without distilling. Some people say they've done it, some people say good luck doing it without the stuff combusting/detonating in the apparatus. Not to mention my elf friends don't even have a vacuum pump. I really don't know, people say alkyl halide--->alkyl nitrite--->nitro alkane isn't so bad, but I say fuck alkyl nitrites. Nitromethane wouldn't be as bad to distill from OTC sources, but I hear it's hard to separate from methanol if you're using the hobby grade, so it still might be better to make it yourself. I know people laugh at the idea, but I really think one should try oxidation of alkyl amines, maybe as the hydrochloride, although acidity might cause excessive oxidation depending on the oxidizer used.

But I've been really wanting to get into electrochemical reduction, and this looks like a good place to start, as it doesn't need any hard to get catalysts.

[nshanin]

Originally Posted by BungHole

I know people laugh at the idea, but I really think one should try oxidation of alkyl amines, maybe as the hydrochloride, although acidity might cause excessive oxidation depending on the oxidizer used.

In a typical reaction, n-butylamine (.7mmol) in 5ml of acetone is treated with 95ml of DMDO in acetone solution (.05M). The solution is kept at room temperature for 30 min with the exclusion of light. DMDO is prepared by the action of oxone on a buffered acetone solution.

80-90% yield.

Refs:
Murray, R.W., R. Jeyaraman, L. Mohan. Tetrahedron Lett., 27, 2335 (1986)
Murray, R.W., R. Jeyaraman, J. Org. Chem., 50, 2847 (1985).
Zbrowski, D.L., A.E. Moorman, and K.R. Beck, Jr. Tetrahedron Lett., 29, 4501 (1988)

Taken from "The nitro group in organic synthesis" by Noboru Ono. Google some of what I've typed above and it'll come up in google books.

Also: Method 8 from here

[BungHole]

Originally Posted by nshanin

In a typical reaction, n-butylamine (.7mmol) in 5ml of acetone is treated with 95ml of DMDO in acetone solution (.05M). The solution is kept at room temperature for 30 min with the exclusion of light. DMDO is prepared by the action of oxone on a buffered acetone solution.

80-90% yield.

Refs:
Murray, R.W., R. Jeyaraman, L. Mohan. Tetrahedron Lett., 27, 2335 (1986)
Murray, R.W., R. Jeyaraman, J. Org. Chem., 50, 2847 (1985).
Zbrowski, D.L., A.E. Moorman, and K.R. Beck, Jr. Tetrahedron Lett., 29, 4501 (1988)

Taken from "The nitro group in organic synthesis" by Noboru Ono. Google some of what I've typed above and it'll come up in google books.

Mmmm, ozone, yummy...

It's a lead though, so thanks.

EDIT: The designer-drugs page was where I originally got the idea. I really need to look into it more though, haven't bothered looking up any of the references.

[director of sound]

gallic acid in DMF/ potassium carbonate suspension @20*C adding dimethyl sulfate dropwise gets you methyl-3,4,5-trimethoxybenzoate, the methylbenzoate in benzene is reduced to the benzyl alcohol via red-Al ( i am testing out other reducing agents that are easier to get, i will update when i can) the benzyl alcohol is desolved in methanol and cooled to 0*C bromine is added(made from isopropal alcohol and bromine hot tub tablets condensed with acetone/dry ice or ice/HCL) allowed to react converting the alcohol to the aldehyde, the excess bromine is decomposed with a saturated sodium thiosulfate/water solution and the crystals of 3,4,5-trimethoxybenzaldehyde are filtered out and recrystalized from benzene.

as for the nitrostyrene use an excess of nitromethane with ammonium acetate as the catalyst and reflux for 4hr, quench with water and the nitrostyrene is filtered out and recrystalized from from boiling methanol. the nitromethane/ammonium acetate method of nitrostyrene production should work for piperonal, isosafrole or asarone (2,4,5-trimethoxypropenylbenzene) probally many others as well. you can use a palladium catalyst if you can get your hands on one or make it from a lump of palladium you get as a 'element sample'. there are vendors dedicated to RC cars/boats or whatever online that sell 100% nitromethane by the gallon undiluted by methanol and castor oil like the rest of the stuff.

[nshanin]

Originally Posted by BungHole

Mmmm, ozone, yummy...

Oxone, not ozone. SM has stuff on ozone oxidation but it's tricky and you're workin' with ozone for chrissakes!

Oxone is sold as non-chlorine pool shock.

[BungHole]

Originally Posted by nshanin

Oxone, not ozone. SM has stuff on ozone oxidation but it's tricky and you're workin' with ozone for chrissakes!

Oxone is sold as non-chlorine pool shock.

Hmmm, wtf. Why did I assume you were talking about ozone gas? I thought you misspelled it or something. I should know by now, Mr. nshanin doesn't misspell words.

I'm very glad you pointed that out though. Maybe ethyl amine to nitroethane wont be too difficult afterall.

[JoePedo]

Originally Posted by BungHole

I'm very glad you pointed that out though. Maybe ethyl amine to nitroethane wont be too difficult afterall.

Look into perborate/ethoxime.

Your cheap cooking sherry may be good for something after all. Add NH3, catch snowflake, throw in washing machine...

Originally Posted by BungHole

I should know by now, Mr. nshanin doesn't misspell words.

o.O

LT doesn't misspell chemical names, nigga. Err, much...

O3->oxone, however, does have a certain interest in the preperation of methylenedioxyphenethaldehyde. Y'know, for people with a raging aversion to, I dunno, isomerizing things.

It's the most ghetto-ass OTC concept I've ever had the pleasure of looking at and saying "hoshite." Right around the time I found the concept of ozonolysis.

...and alkylzinchalide reductions.

[BungHole]

Originally Posted by JoePedo

Look into perborate/ethoxime.

Your cheap cooking sherry may be good for something after all. Add NH3, catch snowflake, throw in washing machine...

I looked into this once, as per your recommendation. I forgot what I found. Looks like it needs another look....

It's looking like a reductive amination of acetaldehyde, but with an OTC oxime route. I was thinking reductive amination of acetaldehyde with excess ammonium chloride, and whatever hydrogenation method I use that would favor low pH. But oximes supposedly do yield primary amines more efficiently.

[director of sound]

how do you propose to get the actealdehyde out of the cooking sherry, mabey peppermint oil would be a better source for that. it boils around 20*C so i guess a fractional distillation could work but i cant see getting more than a few ml from 1L of sherry. its not like acetaldehyde is watched im sure someone could pick it up rather easy. what about a wacker oxidation of ethylene to get your acetaldehyde?

i do find it easier to work with nitrostyrenes than phenylacetones but... there is another electrochemical route to the P2P through the epoxide. set up a regular electrochemical cell with 2 graphite anodes (combined around 70cm2) and a stainless steel cathode (should be around 100cm2) seperated by 1cm. now desolve 25g or so of sodium bromide in 100ml water and 500ml acetonitrile along with 20g of isosafrole, apiole, asarone or whatever propylbenzene you want to use. under heavy stirring run a current of roughly 3.5 ampres through the solution for 2 hours keeping it between 10-30*C then pour into your sep funnel and let it sit for about an hour or so. the water in there will have become more polar due to the NaBr and has settled on the bottom leaving the acetonitrile containing your epoxide product on top. remove the acetonitrile by vacuum and desolve the epoxide residue in 150ml ethyl acetate pour in a 500ml flask flushed with N2 and add 1.5g lithium iodide. reflux it for 5hr and the LiI catalytically transforms the epoxide into the phenylacetone. just wash the ethyl acetate solution with water to recover the LiI then dry the ethyl acetate over sodium sulfate and evap to get right around 20g of the phenylacetone. like baking a cake its so easy, NaBr and LiI are easy to get, acetonitrile is moderatly easy to get and it would be no prob to get the electrodes and glasware.

[atara]

Over at WD they're thinking dithionite might work better than Al/Hg, both for safety and cost reasons. I don't know if it'll reduce nitros so you'll probably need to pre-prepare methylamine (Fe + MeNO2 or AcNH2 + NaOCl)if you go that route.

[BungHole]

Originally Posted by atara

Over at WD they're thinking dithionite might work better than Al/Hg, both for safety and cost reasons. I don't know if it'll reduce nitros so you'll probably need to pre-prepare methylamine (Fe + MeNO2 or AcNH2 + NaOCl)if you go that route.

Whoa, whatcha doin' with that nitromethane reduction silly?!?!

[Flex0r]

Catchol (1,2-dihydroxybenzene) reacts with methylene chloride to form 1,2-methylenedioxybenzene (1,3-benzodioxole). Somehow they have managed to go from there and arrive at alpha-methyl-1,3-benzodioxole-5-propanal

Thoughts from the clever guys out there?

[idontlie]

Originally Posted by Flex0r

Catchol (1,2-dihydroxybenzene) reacts with methylene chloride to form 1,2-methylenedioxybenzene (1,3-benzodioxole). Somehow they have managed to go from there and arrive at alpha-methyl-1,3-benzodioxole-5-propanal

Thoughts from the clever guys out there?

JUST BUY HELIONAL. Pinky bought 25kg at 35$/kg, can you beat that? No. Its cheap as fuck and its legal kids. It maybe watched by the officers but its not enough to be probably cause yet. Hell look at how long sassy stayed legal. Just get a "friend" who will "let" you mail things to their houses. If you are worried.

If you're hell bent on making your own go do a pattent search or read the two dogs thread some 'tards wrote a bit about it in there.

[atara]

Originally Posted by BungHole

Whoa, whatcha doin' with that nitromethane reduction silly?!?!

http://designer-drugs.com/pte/12.162...l#Nitromethane

Fe + RNO2 + [acids] ---> RNH2 + byproducts.

An old favorite. Apparently refluxing acetic acid works well, according to a 1948 paper cited on Wikipedia.

In other bad news, piperonal is List I.

http://en.wikipedia.org/wiki/Piperonal