Author Topic: TMA-2 from calamus oil by psuedonitrosite and aluminum amalgam thread. (Read 693 times)

solidstone · « **Reply #20 on:** October 17, 2010, 01:03:45 AM »

Why not just halogenate the asarone, then do a simple pipe bomb reaction with methanol and ammonia? This would be Analogous to the bromosafrole MDA synthesis which is by far the easiest of the set.

director of sound · « **Reply #21 on:** October 17, 2010, 04:21:43 AM »

i dont like playing with anhydrous ammonia and most people cant get it or know how to properly handle it. if you have every been around it when there is a small leak it will clear a house and possibly give you chemical pulmonary edema. not something i wanna toy with or know that someone reading this put them selfs in the hospital because of what i wrote. though it would be as simple as HBr and acetic anhydride or glacial acetic acid to get the halogenated form but that would require a vacuum distillation setup to get pure asarone to use. or go about the way you would make 4-iodovanillin with a NaI:I3 complex on sodium vanillate. the way im trying to go about this is to have it as OTC as possible so anyone with some chemistry knowledge could accomplish the synth. id say its a good chance that 1 in 5 people or more that try a pipebomb synth from a halogenated form would blow something or them selfs up. as nasty as NO2 and anhydrous nitrous acid are it is much safer than sealing stuff in a stainless pipe and heating it. i may set aside a good portion of the B-nitro to try an electrochemical reduction on if the Hg/Al yields low. and the fact also that not many have easy access to HBr, acetic anhydride or GAA to even make the halogenated asarone. just about anyone can get H2SO4, NaNO2, ether, NaOH, HgCl, foil and glassware.

director of sound · « **Reply #22 on:** October 17, 2010, 04:25:51 AM »

Quote from: director of sound on October 10, 2010, 04:55:03 AM

the electro chemical reduction is pretty simple and uses stuff anyone can get, the only drawback is you have to watch your temps and it takes some time. this one is written for mescaline but it has worked in similar yields for many other phenethylamines and amphetamines, ones of note ate the TMA series, MDA/MDMA, lophonine and could presumably work for the 2C-x and DOx series as well; for a power source one could use a trickel charger that allows you to adjust the amperes.

iv. Mescaline. ( \ ) APPARATUS (Fig. 1) A cell of porous porcelain (PC)(exter-
nal dimensions: 75 X 160) with a glazed rim is placed in a glass jar of 500cc capacity (J)

(J), surrounded by a cooling bath (B). The anode (A) is a lead or carbon rod, surrounded
by a glass coil; the cooling water flows through the coil and is discharged into the cooling
bath. the cathode (C) is a sheet of lead (220X90X2mm), which previous to each experiment
is electrolytically coated with lead peroxide in a dilute bath of sulfuric acid.

(B) REDUCTION. The cathode liquor consist of 30g 3,4,5-trimethoxy-w-nitrostyrene in
100cc glacial acetic acid and 100cc alcohol , to which 50cc conc.
hydrochloric acid has been added. The anodic compartment is filled to the same level occu-
pied by the catholyte, with a solution of 25cc conc. sulferic acid in 175cc water.

The recudtion requires 12 hours, using a current of 5-6 amperes; the cathode current density
should be about 3 amperes (INS> .03A/cm2) per square centimeter. the temprature is regulated
by the flow of cooling water and the catholyte should be kept at 20*C for the first 6 hours. the tem-
prature is then allowed to rise until it reaches 40*C at the end of the reduction.

When the reduction is complete, the catholyte is filtered, evapurated in vacuum and the residue
taken up in 300cc water. Unreacted nitrostyrene is extracted successivly with ethyl acetate and ether.
the crude Mescaline Hydrochloride solution in a separatory funnel is then treated with a cold consentrated
solution of 100g sodium hydroxide and the liberated base exhaustivly extracted with ether. the somewhat
consentrated (evapurated) and dried (potassium carbonate(anhydrous)) is treated with a stream of dry hydrogen
chloride gas (acid gas) and the separated (precipitated) hydrochloride twice recrystaled from abs. alcohol.
the pure mescaline hydrochloride thus obtained in 77% yield forms white leaflets melting at 184*C

solidstone · « **Reply #23 on:** October 17, 2010, 04:49:24 AM »

In Strike II it says that an ammonia hydroxide solution of 18-25% is sufficient. Is there literature that suggests anhydrous ammonia. I've never heard of using anhydrous for this process. And also making the Bromide would just need the addition of HBr as I understand it, and I am fairly sure you can make HBr from its salt NaBr which is found in bulk at pool supply stores. I'm pretty sure you could use the chloro asarone as well just expecting a lower yield, or at least thats what I recall from the trends with safrole in this method.

And I'd take my luck with a thick steal pipe. You can even weld it shut if one felt the need. If your terrified of the thing just do the reaction in the woods and keep your distance till its over. I don't think theres to much risk if you take a little precaution. He also notes the procedure does not have to be done in a pipe bomb, it can more simply be done in a stoppered flask left to react 3-7 days.

The issue with this method of course is a low yield. If we were talking about safrole this would be alarming, but were talking about dirt cheap calamus oil. I also read you can recycle the brominated compound and take it for another run once you've removed your desired product, since you have shifted the equilibrium back.

I think this method would be interesting just for its simplicity, not the most involved procedure but if it could be applied to get shulgins 10 essential amphetamines that would be pretty neat, as I would never otherwise try to synthesize them.

Anyhow I guess I'll pick up some calamus oil and give it a go in a few weeks time.

As for the electro chemical reduction, I am doing a research project on electro chemical reduction and oxidation for university, I'll of course provide detailed plans as well as my research upon completion of my project

by the way you can use a shopvac for a weak vacuum source.

director of sound · « **Reply #24 on:** October 17, 2010, 08:38:06 AM »

i have a large industrial aspirator setup but done have the space to run it plus a burnt out pump... i dont think a shopvac would produce a strong enough vacuum to lower the boiling point appreciably. as for the pipebomb i was under the impression that anhydrous conditions were necessary or am i thinking about diethylamine and methyl amine.... its worth a try on a small scale before loading up 100g.....

akcom · « **Reply #25 on:** October 17, 2010, 01:18:29 PM »

I'd love to see some pictures of an user friendly electro-reduction set up. My last experience with electro chem was my gen chem 2 class. I think I have a lot of reading to do. I'm familiar with the theory, but it's the application I'm foggy on. What kind of vessels are appropriate, what can be used for a membrane, how to choose anode and cathode material.

Sedit · « **Reply #26 on:** October 17, 2010, 02:02:32 PM »

I would love to see someone pull off an amination of a haloalkane using (aq)NH₃ since I have little faith that it will produce nothing more then an alcohol and very little if any amine. Anhydrous NH₃ however in this sence is not as horrible as pure Ammonia since you are dealing with a solution in MeOH. Its still nothing I would feel good about heating in a pipebomb.

Crazyboy, try not to eat any sluge you ever form esp after performing an Al/Hg because your product is far from pure and you are dealing with bioactive compounds meaning something unforseen could have happened and you are now ingesting a toxin of some sorts. Take care is all I ask.

heisenberg · « **Reply #27 on:** October 18, 2010, 03:14:02 AM »

According to rhodium:

Quote

Upon storage, pseudonitrosites soon decompose with discoloration, releasing nitrogen oxides and hydrogen cyanide. At around 40°C decomposition takes place in less than one day.

Could the HCN be a health concern during the filtering, drying, etc, processes?

director of sound · « **Reply #28 on:** October 18, 2010, 07:47:34 AM »

i dont think the amounts would be appreciable as i would proceed directly to the B-nitro. the pseudonitrosite would only be in existence for an hour or less...

Sydenhams chorea · « **Reply #29 on:** November 28, 2012, 10:39:26 AM »

Quote from: crazyboy on October 17, 2010, 12:37:10 AM

I tried the proposed reactions scheme several months ago and I seem to have failed. Everything went well, I made the pseudonitorsite bith calamus oil, EtO and sodium nitrite, I made the nitropropene by decomposing the pseudonitrosite with NaOH (yielding a bright yellow product), and I attempted Al/Hg reduction on the nitropropene. However when I tried to isolate the TMA-2 as the hydrochloride salt by bubbling HCl gas through my nonpolar solvent (xylene) the xylene turned a reddish color and a black/red gummy precipitate formed.

For what it's worth (sorry for waking up the dead) this is where this guy did wrong. TMA-2 is very sensitive to strong acids and will become tars when a non-polar solution of TMA-2 freebase is gassed with HCl. It's best to use Shulgin's method, dissolving the freebase in a bit of IPA, carefully neutralizing with conc. aq. HCl, and flooding with ether.

antibody2 · « **Reply #30 on:** December 06, 2012, 11:21:13 PM »

Quote from: jon on October 13, 2010, 12:25:04 AM

it works but not as well as diethyl ether ether holds the no2/no3 gas complex very well.

NO! Your major product using hexane/ pet ether or naptha will be cyclized asarone. This was experimented with ad nauseum back in the hive days. Your yield of pseudonitrosites in that solvent will be abysmal. (.) period. No ifs and or buts about it.

Other propenylbenzenes are much less subject to cyclization, but asarone even in diethyl ether has much much lower yeilds than iso safrole , iso apiole, iso dill apiole.

Initially it was thought that asarone being acid sensitive was being cyclized by the H2SO4, but even when a pipette was used to add the H2SO4 directly to the aqueous NaNO2 layer and stirring was reduced to the lowest possible rpm to minimize the contact of the two phases the yeilds were marginally better, but still way below what was achievable with other propenylbenzenes

Diethyl ether is readily available and is is your best bet, and it is very available as cold weather starting fluid , so why cut corners?

FYI - the rxn was successfully run, back in the day, with other ethers, but hexane and pet ether are not ethers at all.

Baba_McKensey · « **Reply #31 on:** December 08, 2012, 02:23:03 PM »

https://www.hyperlab.info/inv/index.php?s=&act=ST&f=17&t=28700&st=0&

https://www.hyperlab.info/inv/index.php?s=&act=ST&f=17&t=28922&st=160&

Baba_McKensey · « **Reply #32 on:** December 08, 2012, 02:30:45 PM »

See attachment

jon · « **Reply #33 on:** December 08, 2012, 10:02:53 PM »

what about using iodine and sodium nitrite?
forming the iodo nitrosate that adds across the double bond that would be much easier.

antibody2 · « **Reply #34 on:** December 08, 2012, 10:42:26 PM »

That may work with ethylvinylenzene or divinylbenzene, but not with asarone. Sorry.

jon · « **Reply #35 on:** December 09, 2012, 08:25:57 AM »

what would be the problem? it's not a lewis acid, the next step would be treatment with a base i don't forsee any problems of course i never worked with asarone.

antibody2 · « **Reply #36 on:** December 09, 2012, 02:29:26 PM »

Not 100% sure why it doesn't work with asarone in pet ether or hexane, Jon, but it doesn't. The isolated yield was always so pathetic as to make the effort a complete waste of time. But when ether is used the rxn becomes viable.

It may be that asarone reacts slower in hexane than in ether, making it more prone to acid catalyzed cyclization. NO2 is acidic, as is H2SO4. In ether the rxn is faster so once the pseudonitrosite is formed it is no longer prone cyclization thus the higher yield. But with asarone in ether the yield is still much lower (ca 50%)than with other propenylbenzenes like iso-safrole (100%) or iso-dillapiole (85%). So even with ether as the solvent asarone is still subject to some cyclization. Its a delicate acid sensitive molecule.

Asarone will not survive a performic oxidation either, due to its acidic conditions.

jon · « **Reply #37 on:** December 10, 2012, 12:16:27 AM »

but i was talking about a different route.
http://www.erowid.org/archive/rhodium/chemistry/nitryliodide.html

Sol Invictus · « **Reply #38 on:** December 20, 2012, 04:19:58 AM »

Nitryl iodide does work w Asarone (never tried w straight Calamus oil). Yields increase under inert atmosphere (Argon). Be careful when reducing the EtOAc post-rxn- use a water bath & keep the RB flask a few inches above the heat source because even just a small focused point of overheating at the bottom of the RB can fuck yr yields hard. This is especially pertinent when the volume gets down to the last 10% or so. I2 can be recycled from the Na Thiosulfate washes in a similar manner to how it is extracted from sol'ns of KI or Povidone. Cold alcohol (MeOH) washes seemed to render the nitropropene clean enough for the Al/Hg, however qualitative comparisons between washed & rextallized product were never conducted. I2 should be rendered as clean as possible before the rxn though (cold water washes followed by thorough wringing then desiccation seemed to be sufficient but sublimation is probably best).
The process has not been attempted utilizing any other propenylbenzene other that Asarone.

--Sol

Author Topic: TMA-2 from calamus oil by psuedonitrosite and aluminum amalgam thread. (Read 693 times)

solidstone

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director of sound

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director of sound

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solidstone

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director of sound

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akcom

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Sedit

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heisenberg

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director of sound

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Sydenhams chorea

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antibody2

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Baba_McKensey

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Baba_McKensey

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jon

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antibody2

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jon

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antibody2

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jon

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Sol Invictus

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