Why not use the method given on The Vesp or here:
https://chemistry.mdma.ch/index/mda.html it seems easier.
Helional or 3-(1,3-benzodioxol-5-yl)-2-methylpropanal to the Helionamide or MMDPPA or 3-(1,3-benzodioxol-5-yl)-2-methylpropanamide
This is a rough sketch from someone's post from The Vesp:
100g Heli run
Mix 400 ml DMSO and 36.93g Hydroxylamine HCL, then add 100g heli and the last 100ml of DMSO.
Heat for 90 minutes at 85-90°C on hotpate with good stirring.
Turn off heating and when temp has gone down to about 70°C, add 15% NaOH solution carefully until pH is about 10, try keep temp around 70-80°C.
Then at 65-70°C start dripping 600ml 30% H2O2 very carefully. The H2O2 is pre-basified to pH 7-7.5 with 15% NaOH, keep a ice-bath ready if temps rise fast to above 95°C and periodically measure the pH to confirm it stays between pH 8-10.
If pH falls below 8 add 15% NaOH till pH is about 10, the temps should be about 80-95°C during the H2O2 addition.
When all 600ml H2O2 has been added continue stir until gas evolution and exothermia had ceased.
When temps have decreased to about 50°C one have 2 choices,
One could pour the content into a large beaker/pyrex dish, put into refrigerator and let it sit overnight to form crystals,
or one could dump it into ice cold water and then immediately vacuum filter the crystals.
I think i go with slow crystallization overnight.
Then vacuum filter the crystals and wash them on the funnel with distilled water.
Re-crystallization from water if it seem needed.
Then a Hofmann rearrangement of Helionamide with NaDCC (sodium dichloroisocyanurate) to MDA freebase.
Here is someone else's outline also from The Vesp:
Chemicals:
7.28g NaDCC dihydrate (~29 mmol)
400ml 10% NaOH
10.90g helionamide (~53 mmol)
Procedure and observations:
The entire 7.28g of sodium dichloroisocyanurate dihydrate was added to 400ml of warm 10% NaOH. I made the mistake of not crushing the little granules into a powder as before. If you're going to attempt this, crush the NaDCC into a fine powder. After nearly an hour of heating there was still a cloud of very fine precipitate visible in the beaker.
Then the helionamide was added in portions (no exotherm was observed, so it would probably be possible to just dump it in).
The mixture was heated to 70C and then to 90C. Total heating time was about 2 hours. The reaction was monitored by TLC on silica (eluent: 7:3 ethyl acetate/hexane, visualized by permanganate. UV works very poorly here in my experience.).
There wasn't much CO2 evolution - I'd say none, really. Maybe it was all immediately absorbed by the hydroxide and that's why I couldn't see bubbles. TLC was helpful.
A decision was made to hold the RM off-heat, but on stirrer and with a watchglass on top for the entire night (~9h). After letting the mixture stand a thin layer of brown-yellow oil could be seen on coalescing on top. The reaction mixture had a characteristic smell of something trying to smell bad but not doing too good of a job at it
. I'd describe it as warm helional that had gone bad.
The reaction mixture was filtered to remove the fine precipitate and the yellow mother liquor was extracted using 3x40ml of DCM. The extracts were red/orange in color. The DCM extracts were extracted using 90ml of water to which 10ml of conc. HCl was added. This mixture was added in 4 portions and the extracts were yellow. This was then basified using first potassium carbonate and then sodium hydroxide. You could as well probably just use sodium hydroxide - the basicity created by the carbonate wasn't enough to fully precipitate the amine freebase.
The mixture was put in fridge and a couple large globules of red oil could be seen on the bottom. The basified mixture was extracted once again with 3x30ml DCM, dried over magnesium sulfate and the DCM was mostly stripped with help of some warm water and a fan.
When the mixture was concentrated to around 20ml it was poured into a 25ml RBF and heated up over a steam bath to draw off any remaining DCM.
Then the oil was vacuum distilled (140C, ~1mbar, remember - first vacuum, then heat! There will be a lot of bumping as some DCM will always remain and has to be first drawn off by the pump - use the gas ballast to remove it from the oil or it will kill your pump). The crude oil weighed 6g and after the distillation it was around 5g. Pure phenylethylamine freebases are colorless - and the distillate was indeed colorless. In the boiling flask there remained red goop that had a smell similar to that of the freebase.
The freebase was taken up in ~20ml of IPA, acidified using 3 pipettefuls of conc. HCl and the salt spontaneously precipitated out as thick crystals after addition of some anhydrous acetone.
The salt was filtered and washed with plenty of acetone. After drying the final yield of very pure (blindingly white!) MDA hydrochloride is around ~50%. The converesion to salt is nearly quantitative, but remember to collect the second crop from the washings (I forgot about it and lost ~500mg of the product).
I have not gotten around to MDA but I would for sure go with this method instead of the older "2 dogz" synth outlined here.
https://chemistry.mdma.ch/index/mda.html it seems easier.
Helional or 3-(1,3-benzodioxol-5-yl)-2-methylpropanal to the Helionamide or MMDPPA or 3-(1,3-benzodioxol-5-yl)-2-methylpropanamide
This is a rough sketch from someone's post from The Vesp:
100g Heli run
Mix 400 ml DMSO and 36.93g Hydroxylamine HCL, then add 100g heli and the last 100ml of DMSO.
Heat for 90 minutes at 85-90°C on hotpate with good stirring.
Turn off heating and when temp has gone down to about 70°C, add 15% NaOH solution carefully until pH is about 10, try keep temp around 70-80°C.
Then at 65-70°C start dripping 600ml 30% H2O2 very carefully. The H2O2 is pre-basified to pH 7-7.5 with 15% NaOH, keep a ice-bath ready if temps rise fast to above 95°C and periodically measure the pH to confirm it stays between pH 8-10.
If pH falls below 8 add 15% NaOH till pH is about 10, the temps should be about 80-95°C during the H2O2 addition.
When all 600ml H2O2 has been added continue stir until gas evolution and exothermia had ceased.
When temps have decreased to about 50°C one have 2 choices,
One could pour the content into a large beaker/pyrex dish, put into refrigerator and let it sit overnight to form crystals,
or one could dump it into ice cold water and then immediately vacuum filter the crystals.
I think i go with slow crystallization overnight.
Then vacuum filter the crystals and wash them on the funnel with distilled water.
Re-crystallization from water if it seem needed.
Then a Hofmann rearrangement of Helionamide with NaDCC (sodium dichloroisocyanurate) to MDA freebase.
Here is someone else's outline also from The Vesp:
Chemicals:
7.28g NaDCC dihydrate (~29 mmol)
400ml 10% NaOH
10.90g helionamide (~53 mmol)
Procedure and observations:
The entire 7.28g of sodium dichloroisocyanurate dihydrate was added to 400ml of warm 10% NaOH. I made the mistake of not crushing the little granules into a powder as before. If you're going to attempt this, crush the NaDCC into a fine powder. After nearly an hour of heating there was still a cloud of very fine precipitate visible in the beaker.
Then the helionamide was added in portions (no exotherm was observed, so it would probably be possible to just dump it in).
The mixture was heated to 70C and then to 90C. Total heating time was about 2 hours. The reaction was monitored by TLC on silica (eluent: 7:3 ethyl acetate/hexane, visualized by permanganate. UV works very poorly here in my experience.).
There wasn't much CO2 evolution - I'd say none, really. Maybe it was all immediately absorbed by the hydroxide and that's why I couldn't see bubbles. TLC was helpful.
A decision was made to hold the RM off-heat, but on stirrer and with a watchglass on top for the entire night (~9h). After letting the mixture stand a thin layer of brown-yellow oil could be seen on coalescing on top. The reaction mixture had a characteristic smell of something trying to smell bad but not doing too good of a job at it
The reaction mixture was filtered to remove the fine precipitate and the yellow mother liquor was extracted using 3x40ml of DCM. The extracts were red/orange in color. The DCM extracts were extracted using 90ml of water to which 10ml of conc. HCl was added. This mixture was added in 4 portions and the extracts were yellow. This was then basified using first potassium carbonate and then sodium hydroxide. You could as well probably just use sodium hydroxide - the basicity created by the carbonate wasn't enough to fully precipitate the amine freebase.
The mixture was put in fridge and a couple large globules of red oil could be seen on the bottom. The basified mixture was extracted once again with 3x30ml DCM, dried over magnesium sulfate and the DCM was mostly stripped with help of some warm water and a fan.
When the mixture was concentrated to around 20ml it was poured into a 25ml RBF and heated up over a steam bath to draw off any remaining DCM.
Then the oil was vacuum distilled (140C, ~1mbar, remember - first vacuum, then heat! There will be a lot of bumping as some DCM will always remain and has to be first drawn off by the pump - use the gas ballast to remove it from the oil or it will kill your pump). The crude oil weighed 6g and after the distillation it was around 5g. Pure phenylethylamine freebases are colorless - and the distillate was indeed colorless. In the boiling flask there remained red goop that had a smell similar to that of the freebase.
The freebase was taken up in ~20ml of IPA, acidified using 3 pipettefuls of conc. HCl and the salt spontaneously precipitated out as thick crystals after addition of some anhydrous acetone.
The salt was filtered and washed with plenty of acetone. After drying the final yield of very pure (blindingly white!) MDA hydrochloride is around ~50%. The converesion to salt is nearly quantitative, but remember to collect the second crop from the washings (I forgot about it and lost ~500mg of the product).
I have not gotten around to MDA but I would for sure go with this method instead of the older "2 dogz" synth outlined here.
- By GhostChemist
You can use any method what do you want
Our team published only methods that were tested in our labs
Our team published only methods that were tested in our labs
