Successful MDA .HCl synthesis from piperonal (with good yields)

[xoxo2.0]

Hey i was just looking around the threads and want to share my experience with this synthesis ( as i didn't find any report for this in moderate scale )

I HAVE DONE THIS PROCEDURE ABOUT 4 TIMES BY NOW AND WOULD LIKE TO SHARE SOME OF IT.

EQUIPMENT USED

• 500ML FLAT BOTTOM FLASK
• 500mm ALLIHN CONDENSER
• 300MM LIEBIG CONDENSER
• 500ML AND 250ML BEAKERS
• HOT PLATE WITH STIRRER
• STAND AND CLAMPS
• 250 ML CONICAL (WITH NECK)
• STEEL SEIVE
• WHATMANN FILTER NO. 40
• BUTCHNER APPARATUS (DIY)
• PUMP AND HOSES
• PETRI DISHES
• SEPARATORY FUNNEL
• SPATULAS, DROPPER, FUNNEL, PH PAPERS, thermometers.

CHEMICALS USED

• 45 G PIPERONAL (BOUGHT FROM PERFUMERY STORE ONLINE)
• 35 ml NITROETHANE (AR)
• ~350ML GAA
• 200-250 ML IPA
• ~550ML DCM
• DISTILLED WATER
• 40% NAOH SOL.
• 48 GM ALUMINIUM FOIL (18 MIC)
• HgCl2 (1.2 G)
• 25ml n-BUTYLAMINE
• ~50 g Na2SO4 anhy.

PROCEDURE:-

STEP 1 : PREPARATION OF MDP2NP

• In a flatbottom flask add 45g of piperonal followed by 200ml of glacial acetic acid stir it and piperonal will dissolve.
• Now add 35 ml of nitroethane in the flask followed by the addition of ~25ml of n-butylamine (carefully, as it fumes like hell and stinks)
• Attach your condenser and place the flask on a hot plate with temperature set to about 70-75 C (I have tried higher but didn't have any change in the yield) for 9-10 hours.
• THE HIGHEST YIELD OF MDP2P WAS ACHIVED WHEN THE REACTION MIXTURE WAS MIXED LIKE MENTIONED ABOVE AND KEPT FOR 4-5 DAYS COVERED WITH ALUMINIUM FOIL THEN HEATED TO 70-75 DEG C FOR 11-12 HOURS.
• Once the heating is completed the flask was allowed to cool (yellow crystals crashes out immediately) and put into fridge for 3 hours (can be more)
• The bright yellow crystals were vacuum filtered and washed with IPA ~80ml (PRODUCT IS QUITE PURE NO NEED TO RECRYSTALIZE)
• To the filtered mother liquor small amount of cold water was added some small crystals crash out and were filtered (They were of lower quality and with slight orangish hue to them). [Hence they were recrystallized from ipa and water 80:20] colour persisted but was lot less orange and more of dull yellow.
• The dried mass of crystals was 28.71 gm and the product recoverd from mother liquor was ~11 gm (after recrystallization)

THE TOTAL YIELD OF DRIED MDP2NP WAS ~39.5 G (THE YIELD OF 4-5 DAYS STANDING ONE)

IF THE MIXTURE WAS DIRECTLY HEATED THE YIELD DROPS TO ABOUT 27-28 G

NOTE : MDP2NP IS QUITE AN UNSTABLE COMPOUND AS IT DEGRADES EASILY IN SUNLIGHT AND ATMOSPHERIC OXYGEN AND GETS ORANGE-ISH. (RECOMENDED TO USE WITHIN 1-3 DAYS AFTER PREPARATION)


STEP 2 : REDUCTION OF MDP2NP VIA Al/Hg AMALGAM

[THE REDUCTION WAS DONE IN TWO PARTS EACH OF 20 G MDP2NP]

• 24 g of aluminum foil is added to a 2000ml round bottom flask followed by distilled water about 1 inch above aluminum foil.
• 0.6 g of HgCl2 was added to the flask and stirred for few minutes. the water turns greyish and tiny H2 bubbles come from the surface of foil, once the hydrogen bubbles are sustained and aluminum starts to float and sink on water your amalgam is ready. (~20-25 min)
• In a 500ml beaker add 20 g of MDP2NP and 100ml water 200ml IPA 100 ml GAA and heat on a hot plate with stirring the the MDP2NP whould dissolve after few minutes. (i recomend doing this just after adding HgCl2 as the amalgam prepares the MDP2NP solution is ready in about the same time).
• Drain the grey water and discard (using a seive really helps), please be quick as the amalgam is highly reactive and will react with oxygen.
• Wash the aluminum couple of times and add your MDP2NP solution the reaction is very vigorous and the addition should be done in parts (but the MDP2NP tends to crash out if you delay, mine crystallized out during addition 2 times).
• The allihn condenser was attached and the flask was given cold water bath (i didn't have any ice).
• Once the addition was completed the flask was shaken-stirred for about 30 min (till all the aluminum was gone and slurry was left).
• If the temperature raises the flask was again put under water bath till the reaction stabilizes itself and again stirred.
• Once the temperature is stabilized the flask was put on a magnetic stirrer and was stirred for 30 minutes.
• The slurry was then collected in a beaker (residues were washed with IPA) and NaOH solution was added and the pH was brought to ~12 the amalgam settles and a clear layer is formed, which was collected (if this separation doesn't happen no problem you can directly continue the extraction , i have found that the separation dosen't form is the pH is lower like 10 or 11, but be careful do not over basify ).
• DCM 100ml were added in the collected layer and placed in a separatory funnel shaken and lower DCM layer was collected again two more 75 ml extraction was done and DCM is pooled. The DCM was also added to the amalgam and collected ( i used a small tub and the DCM was mixed well with the amalgam and was pooled on side when tilted and was carefully decanted [you can also try vacuum filteration, i tried it once during amphetamine synthesis it didn't go as planed] ).
• The DCM was dried over a large amount of anhydrous Na2SO4.
• Now as i said the reduction was done in two parts 20 gm each, in one part the DCM was distilled off and only few ml were kept and in other one it was directly extracted with dilute HCl.
• The DCM was distilled off and collected till about 50 ml of dcm was left (colour turned to slight orange, previously it had a very slight yellow tint).
• To the DCM + MDA free base about 75-100ml of dilute (5-7%) HCl was added (honestly i don't remember) solution was placed in separatory funnel and shaken the pH of water was kept close to neutral ( in the thread of MDA prep from helional the pH was kept slight acidic to me this is is not the way to do it as when the solution is evaporated the pH decreases and the product over acidifies and turns to reddish pink and you have to purify further). [if the pH is kept close to neutral the product is more purer and much cleaner color with a slight yellowish tint or almost whitish]
• This was done few times and lower DCM layer was removed and the top layer with our product was saved and evaporated till the crystals starts forming. (i used multiple petri dishes)
• I suggest using a seed crystal to start the crystallization and once completing the crystallization the MDA.HCl was air dried.

MY TOTAL COMBINED MDA.HCl YIELD WAS ~20.5 G (STILL SOME PRODUCT IS STUCK TO PETRI DISHED)

Feel free to ask for any further details.
-Thanks.

The synthesis of mdp2np is a modification of pikhal
The reduction was followed from bbgate.com

 

[mycelium]

Xoxo2.0, thank you for sharing this with us!

 

[4mmc1]

Make video on this plz

 

[mycelium]

There are already videos on mda synth. This is well written, and we thannnyou

 

[4mmc1]

In that video bro use 10 liter dcm for 100gm
It's mens 100 liter for 1 kg