Pseudonitrosite MDA Synthesis??? maybe

amenselah · Thu Sep 08, 2005 12:00 am

Pseudonitrosite MDA Synthesis

SWIM was dreaming about using NaNO2 to make MDA...

This is the plan:
1- Isomerization of Safrole:
Reflux good quality sassafras oil in KOH until Isomerization is achieved.
Isosafrole.

2- A solution of 1 mole of sodium nitrite in 100 ml (200ml and less ether-hexane) water was prepared in a 500 ml flask, and a solution of 0.1 moles of propenylbenzene (16.2g isosafrole) in 150 ml of ether-hexane (starting fluid). Maybe less???…
Was added. During a period of 3-4 hours, a 20% solution of H2SO4 (prepared by cautiously adding 0.5 moles of conc. sulfuric acid to 200 ml of H2O was added dropwise with magnetic stirring, preferably through a pressure- equalized addition funnel. Watch the addition rate so that the temperature of the two-phase solution doesn't rise over room temp and this solution can preferably be cooled during the addition In the beginning of the addition of acid, monomeric pseudonitrosite can be seen in the etheral layer. The monomer derived from isosafrole is yellow. If oxygen gets into the system during the addition, formed NO oxidizes to brown NO2 gas, which can lower the yield of pseudonitrosite. After the addition, the solution was allowed to stir for an hour or two.

If all you get is goo, drain out the unwanted solution as the goo will stick to the sides of the container, and then wash with water. If you get nice crystals, wash with water and then cool alcohol.

3- The Ungoo-ing:
Make certain the main reaction container has been rid of any ether and place it in a boiling water bath. Remember ether and nearby flames will be your death sentence. After a short period it will turn blue or green and start to bubble. Continue heating for several minutes after the bubbling starts. Some brown NO2 may be formed and is a good sign. Evidently this step increases yield by turning unreacted monomers in to the pseudonitrosite dimer. While it’s hot, add 4 oz or so of ethanol. White crystals of the pseudonitrosite dimer separate out. Filter the hot mixture and wash the crystals with more ethanol.

Pseudonitrosites cannot be stored, as they begin to decompose within hours at room temperature with the evolution of nitrogen oxides, and should be further processed to for example the very useful phenyl-2-nitropropenes, which upon reduction can yield phenylacetones and amphetamine derivatives.

MDA!!! maybe

4- sassafrass oil process:
In a quart jar, add several grams of Na2Co3 (washing soda) and the absolute minimum amount of water to fully dissolve it. Then add enough ethanol to fill container to within inch of top. Then add 5-10g of the pseudonitrosite crystals. Let sit for several days. The pseudonitrosite crystals should slowly be digested with the solution becoming yellow. Then filter solution and add ice to chill to within freezing. Then add just enough HCl to make the solution slightly acidic. It should turn Day-glo yellow-green under a fluorescent light. If you're lucky, the beta-nitro compound will just crystallize out- then just filter and wash it. More than likely though, you will have to extract it with 1,1,1 trichloroethane (flux remover for electronics) and then let the solvent evaporate to get crystals. Recrystalization can be done in the minimum volume of boiling methanol ("Heat" auto gas treatment) that will dissolve the product. Then cool to get pure well formed crystals that can be filtered out.

Or

0.1 mole of the corresponding propenylbenzene pseudonitrosites ( 23.8g isosafrole e) was dissolved in 150ml 8% alcoholic KOH with shaking, and possibly light heating (not over 30?C, there is a risk of decomposition (to the aldehyde, amongst other things).
0.2 Caution: Foaming with evolution of N2O will occur. The cloudy solution was suction filtered, and the filtrate was poured onto 100 grams of crushed ice. The solution was acidified with dilute HCl and was stirred occasionally until the ice had melted. The precipitate of nitropropene was filtered off, washed with a little cold water and air dried.

5-
Reduction:
Small pieces of foil are stuffed into a bottle with a few grams of mercury liquid. The bottle is then shaken for about 10 minutes and the aluminum will amalgamate with the mercury forming a grayish black mass with the more liquid portion coating the bottle like a mirror. (get mercury from electrical relays or from mineralogical supply store) Take 5g or so of the beta-nitro compound and add to 8oz of ethanol. Then add 1oz of HCl. Dump the amalgam contents into the HCl-alcohol mixture. It should start bubbling and after 20 minutes to 1 hour the solution will go from yellow to clear. If it doesn't by the time the amalgam is used up you need to make more. If the solution overheats, add an icecube. When the step is complete decant the solution from the jar, leaving the now liquid (again) mercury. The mercury can be reused by leaving it or a few days with conc. HCl over top it in a bottle. When it’s needed again simply wash away the HCl and dry the mercury off with tissue paper. Take the solution and slowly add NaOH in water beyond the neutral point until the aluminum hydroxide gel that is formed breaks up. Then filter the solution and add water until the solution becomes cloudy. Extract with 1,1,1 TCE. You can also extract the filtrate. Evaporate the TCE-amine solution to get an oil, which is then added to 2oz of acetone. Conc. H2SO4 is added drop by drop to precipitate out the amine sulfate. Note that if you are storing the product, you will want to recrystalize it with methanol, since small amounts of H2SO4 remaining will ruin the product in a few weeks unless this is done.

Product maybe MDA..

Questions

1- what is the yield of this???
2- Maybe SWIM can use the Al, HgCl amalgam to do the reduction..??
3- Step 1- Try to keep it simple with no distillation.???

all this info is in Rhodium Archive

Before SWIM embarks on this journey are any issues or hidden dangers that SWIM should look out for?

icecool · Insistent Chemist

Am I correct when saying that going via the pseudonitrosite method and then converting to the nitrostyrene is easier then making MDP2P via the peracid method?
Since it uses a lot of GAA and so on it needs time to become a peracid etc.
So this would seem much better...
And if you would reductively aminate the nitrostyrene you get MDMA Smile

The pseudonitrosite that is formed and then turned into the nitrostyrene with this method is MDP2P right?

Concerning your question about yield.
When starting with 5g of nitrostyrene count on around 2g of MDMA.HCl
SWIM never got over a 19% yield on reduction of amphetamines.
5g also gave around 2g of sulphate, and around ~3ml impure freebase.

anime · Thu Sep 08, 2005 7:22 am

The peracid/formic oxidation is extremely easy...add the ingredients, drip slowly, go to bed... The hcl hydrolysis works pretty well. What is nice is once you have your MDP2P you can make the oxime which is readily reduced to the amine via Pd/C/Raney/Urushibara in either a hydrogenation or a transfer hydrogenation.

Or you could go with a Mg/formic acid reduction if you do this, be sure to use IPA as the solvent. It is near impossible to filter out the Mg(OH)2 crap that forms upon basification.

edit: I don't think you can reductively aminate the nitrostyrene, you can reduce it using Fe/HCl to the ketone and then reductively aminate that.

icecool · Insistent Chemist

That's what I forgot first Fe/HCl method and then reductively aminating it.
Anyway if SWIM would ever perform this he would chose for the peracetic acid method to make the glycol and then via HCl 15% (IIRC) make the MDP2P.
Then reductively aminating it with Al/Hg/MeNO2.
Although plain Al/Hg reductions never give SWIM over 20% yield out of 5g P2NP --> 2g amphetamine is this normal?

icecool · Insistent Chemist

That's what I forgot first Fe/HCl method and then reductively aminating it.
Anyway if SWIM would ever perform this he would chose for the peracetic acid method to make the glycol and then via HCl 15% (IIRC) make the MDP2P.
Then reductively aminating it with Al/Hg/MeNO2.
Although plain Al/Hg reductions never give SWIM over 20% yield out of 5g P2NP --> 2g amphetamine is this normal?

anime · Thu Sep 08, 2005 11:27 pm

The reductive aminations are generally higher yielding than nitroalkene reductions.

Swim doesn't like Al/Hg very much, its extremely messy to work with. Swim is looking into other methods for reduction, Urushibara seems promising, and NaBH4 works well, the only problem in these reactions is that the MeAm has to be made prior.

amenselah · Fri Sep 09, 2005 11:49 pm

Thanks for mentioning the periacid method..
icecool the direct reduction of phenyl-2-nitropropenes in this method gives MDA.hcl..??

both methods look pretty straight forward...
looking for some empirical knowledge into which should be easier..
SWIM has all the required equit. and chemicals..
about the reduction of the ketone ..SWIM will try the Al/Hg for now..

any input is welcome..

anime · Sat Sep 10, 2005 3:16 am

reduction of the nitropropene should yield the amine which in this case would be MDA Smile

amenselah · Mon Sep 12, 2005 10:39 pm

nothing wrong with MDA... Very Happy