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martha_stewart
(Stranger)
08-23-03 03:18
No 455123
      MDA recipe

So I was sitting in my chair last night watching TV when the most
interesting Martha Stewart Living episode came on.

-----------------------------------------------------------------
"Good evening, and welcome to my show. Today I'd like to share
with you a very special family dessert that I like to call
Ecstasy. I find this to be the perfect dish to serve to
guests when the hot summer conversation turns to dull topics
like stocks, bonds, trading and long words such as 'indictment'.
Usually, after just a little bit of this dish the
conversation will correct itself onto happier topics rather
than simply circling around boring Wall St. subjects like a shark.
What follows is a simple recipe I like to use that can be
prepared with (mostly) common household chemicals and a little
bit of advance preperation. Make this in advance, and serve
the crystals in a decorative ice cream dish with a garnish of
mint for cheerful decoration! So without further ado
let's get started with this wonderful dish!

MDA synthesis using (mostly) common household chemicals and equipment
Synthesis route:
1. Freezing to obtain safrole.
2. Sulphuric acid to get MDP2Pol.
3. Household bleach to get MDP2P.
4. Ammonia solution + Zinc (dust or pennies) to get MDA.
5. Acid/base wash, freezing to crystalize product.

Ingredients: (suppliers in parentheses)
150ml pure sassafras oil (essential oil supplier, organic grocery store - essential oils section).
100ml 65-85% conc. sulphuric acid (drain cleaner at hardware store or chemical supply company).
300ml 30% hydrochloric acid (brick or driveway cleaner at hardware store, also called Muriatic acid at pool supply store).
1L household bleach (6%).
2L 5% vinegar (acetic acid 5%).
1L Sodium Hydroxide Solution = NaOH (drain cleaner / red-devil lye from hardware store)
Distilled water.
Pickling salt (NaCl).
pH paper or indicator (fish store, chemical supply company)
50g Zinc dust, or US pennies made after 1983 scrubbed down with steel wool to take off copper plating and expose zinc.
30% industrial strength ammonia (estimated at 17.6M - available at chemical supply company)
1L 70% Isopropyl alcohol (available from the pharmacy)
1L Xylene (paint stripper from hardware store)

Equipment:
Narrow mouthed flask.
Balance or kitchen scale with gram markings.
Industrial strength rubber gloves (hardware store).
Goggles (hardware store).
1L Glass seperatory funnel. (lab supply).

Optional Equipment:
Starch-KI paper. (lab supply)
Hydrometer. (fish store)
Labcoat.

Step 1 - Fractional Crystallization of Safrole: (~1-3 days, distillation is faster if you have the equipment)
[1] Post 400671 (Arsenic: "You don't have a clue, do you?", Methods Discourse)

[2] Post 220835 (menthol_man: "Safrole Crystals", Methods Discourse)

[3] Post 107751 (smokemouth: "DP Harma's Sassafras Freezing technique Modified - scwam", Methods Discourse)

Place jar of sassafras oil in freezer for 1-3 days. Allow to freeze, crystals will form at the bottom.
(You may want to create some seed crystals to help this freeze, this involves chilling an open
watchglass/jar in the freezer before you start, then adding a few drops of sassy to the cold surface
to obtain seed crystals. See [3] for details.).
While this is freezing place jar of sulphuric acid, a cup with 1000ml distilled water, 1600ml vinegar,
and a jar of bleach in the refrigerator in preperation for steps 2 & 3. (At this point you may also want to make some
distilled water ice cubes to add for water in step 2 if you really want to help keep the temperature cold).
Freezing point of safrole is 11.2 C.
Pour liquid from top off.
Warm slightly to dissolve crystals. Refreeze. Again pour off liquid from top.
Repeat until crystals are clear.
Pure safrole should have a density of 1.1000 which can be measured with a hydrometer.

The remaining discussion will assume 100ml of safrole as reactant for step 2.
This is 110g of safrole = 110/162.1878 = .6782 mol.

Step 2 - Hydration of alkene to form the alcohol MDP2Pol: (~1 Hour, yield ~95%)

Hydration of safrole [3] https://www.rhodium.ws/chemistry/mdp2pol.html
General Theory - [4a] http://www-scf.usc.edu/~chem322a/ppt/Chapter_08/322a_Ch_8_06.pdf
General Practice - [4b] http://www.users.csbsju.edu/~kgraham/cps2.html

To the safrole in the ice bath slowly add 100ml 65%-85% conc. sulphuric stirring vigorously for 10 minutes
while keeping the temperature just warm enough so that the safrole does not freeze.
The reason for keeping the temperature low is that the reaction is subject to rearrangement and
may form MDP1Pol at higher temperatures (see [3]).
Wear goggles, gloves & preferentially do this in a flask pointed away from
you since there may be splattering as you add the sulphuric acid.
The mixture should become a homogenous reddish color.
(Be careful about letting this react too long, the sulphuric forms a
hyposulphate compound with the alkene and may start to polymerize).
Add 100ml of cold distilled water / distilled water ice cubes to the solution (watch for splattering)
and stir for an additional 15 minutes. Now add another 100ml cold distilled water,
200ml cold, dilute NaOH (slowly with plenty of stirring to keep the temperature cold!)
and salt. A greenish white alcohol
layer should form on top of the solution. Collect this oil by
using seperatory funnel to pour off the aqueous layer.

Step 3- Oxidation of MDP2Pol to form the ketone MDP2P: (~1.5 Hour, yield ~95% of step 2 = 90% of step 1)

[5] http://www.sonoma.edu/users/t/trowbrda/335a/labs/oxidation.html
[6] Journal of Chemical Education Volume 58, p. 824
Original and best reference - [7] Stevens, Chapman and Weller, J. Org. Chem., 45, 2030 (1980).

Place the oil from step 2 in a 2L flask in a bowl of ice water. We are going to use household bleach as an oxidizing
agent to form MDP2P at a cold temperature with minimum rearrangements.
Do this step in a well ventilated area as some chlorine gas may be released
as the bleach decomposes.
First add 1600mL of cold(5%) vinegar, then, slowly add
800ml of cold bleach a small amount at a time with stirring so that the temperature remains cold.
Here we are aiming for a roughly 10% molar excess of bleach.
(The bleach reacts with the acetic acid to form hypochlorous acid - an
oxidizing agent. We cannot simply add the bleach to the dilute sulphuric
acid solution in step 2 because the suphuric acid will decompose the bleach
to chlorine gas and water).
In [7] Stevens et. al. find that household bleach (6%) is approximately 0.9 - 1.0 M
concentration depending on how old it is.
You will know you have an excess of bleach since the solution should be faintly greenish yellow
and a drop of it should turn starch-KI paper blue. (It's OK if you don't have starch-KI paper
here since all you need to do is make sure you have excess bleach.
The starch-KI paper turning blue indicates the prescence of hypochlorous acid.).
Allow the solution to react for approximately 1 hour.
If the reaction is complete, as indicated by a positive starch-KI test,
add dilute sodium hydroxide a little bit at a time until until the solution is slightly basic.
The solution should no longer turn starch-KI paper blue.
Add a small amount of salt to flask. A reddish oil should fall out of the bottom - this
oil is your ketone MDP2P.
Pour the liquid off the top into a second flask and keep the oil. (This is most easily done
via a seperatory funnel).
To the second flask add cold brine water, again more oil should fall out, pour the liquid
off the top and combine the two parts of oil.

Step 5 Reductive Amination (~2.5 Hours, yield ~88% of step 4 = 80% of step 1)

- Formation of imine from MDP2P:
[7] L.G. Wade, "Organic Chemistry, 5th Edition," p. 808
[8] https://www.rhodium.ws/chemistry/alhg.osmium.html
[9] https://www.rhodium.ws/chemistry/znhg.alhg.reductions.txt
To the tune of "Margaritaville"
[10] http://cstl-cst.semo.edu/Hathaway/CH343/ChemSongs/Spring%202003/Hydrated%20Away%20in%20Organic%20Lab.doc

Reduction of imine to form MDA:
JACS is short for "Journal of the American Chemical Society"
Reductive amination with Zinc:
[10] Emerson, Dorf and Deutschman, "The Activation of Aromatic Halogen by Ortho Ammonium Salt Groups," JACS 62, 2159 (1940)
[11] Emerson, Dorf and Deutschman, "The Reductive Alkylation of Hindered Aromatic Primary Amines," JACS 63, 972, 2843 (1941)

Using Zn as a reducing agent - great overview and discussion of mechanisms - a must have:
[12] T. Nakabayashi, "Studies on the Mechanism of Clemmensen Reduction..." JACS 2, 3901 (1960)
[12b] http://www.umich.edu/~chemh215/W00HTML/SSG4/ssg2/anim.htm

Microwave Chemistry Reductive Amination and Related:
[13] André Loupy (Ed), "Microwaves in Organic Synthesis", p. 81, p. 202
[14] Brittany Hayes, "Microwave Synthesis: Chemistry at the Speed of Light"
   -- see review at http://www.iscpubs.com/articles/al/a0306how.pdf (Microwave Clemmensen Reduction? )
[15] https://www.rhodium.ws/chemistry/mw.carbonyl-red.txt

To the ketone from step 4, add a 10x molar excess of NH4OH.
So, .6782 mol / 17.6 * 100 = 385ml --> 400ml of 30% ammonia.
Add conc. HCl in parts to get the pH of the solution to 4.5 (~600ml HCl).
This will favor optimal speed of formation of the intermediate imine - from [7].
Add the HCl in a well ventilated area or under a fume hood as this will
give off copious white ammonium chloride fumes. If you have a large flask with an
addition funnel this would be the way to go.
Add 25g of zinc, 25g of NaCl and 200ml of 91% Isopropyl Alcohol to help solvate
the ketone. Allow the reaction to proceed at room termperature for two hours at which time
90% of the ketone should have reacted and gone into solution as an amine.
This could also be likely speeded up by refluxing, heating in the microwave [14],
or using a Zn/Hg amalgam as per [12]. Here, a fairly good reaction rate is obtained as is
so additional speedups were not attempted. Also, if one wanted to make MDMA
at this step simply use MeNH3 rather than NH4OH.

Theory:

NH4OH <--> NH3 + H2O
R=O + NH3 --> R=NH + H2O (imine formation)
R=NH + Zn + Cl + H+ --> R-NH2 + ZnCl

We are driving the reaction to favor amine formation by:
1. Using excess NH4OH.
2. Using an optimal pH to favor intermediate imine formation.
3. Reducing intermediate imines to amines so they cannot easily revert to the ketone.
4. Using relatively anhydrous conditions to favor the removal of water
(this can be increased by boiling the reaction and distilling
off water as it proceeds).
5. Adding NaCl to maintain a high Cl concentration -- see [12] for details.

This combination seems to give a faster and higher yield than reported in [10] and [11]
where the amount of HCl used likely created strongly acidic conditions that actually
inhibited fast amine formation.

Step 6 - Acid/base wash to remove product and crystallize. (1 Hour)
[16] https://www.rhodium.ws/chemistry/brightstar.mdma.html step 6 and preceding paragraphs.

Pour off unreacted organic layer via sep funnel using a filter so that your zinc and
crystals at the bottom of the reaction mix don't clog the funnel.
Add any crystals back to the seperated aqueous layer. Add NaOH solution until pH test shows mixture is slightly
basic, zinc sludge should fall to the bottom and any crystals should redissolve.
(Most likely these crystals are largely NH4Cl but they may also contain some product).
Add the liquid to the sep funnel through a filter along with 300ml IPA.
A yellow organic top layer should form and the bottom layer should be clear.
IF THE BOTTOM/AQUEOUS LAYER IS NOT CLEAR ADD MORE IPA AND SHAKE - OTHERWISE YOUR AQUEOUS LAYER WILL
CONTAIN PRODUCT THAT YOU WILL BE DISCARDING!!

Take the yellow orgainc layer you have obtained and add 300ml xylene then slowly drip in dilute (~0.5M) HcL
until the pH of the solution is 5-6 - or just barely acidic. Now remove the oil/Xylene
layer via a seperatory funnel and keep the aqueous layer that contains your product.
Allow the aqueous layer to dry with mild heating to obtain your final product."

------------------------------------------------------------------

After the show ended, I realized that I must have eaten something that agreed with me since
the TV was still off!! Being a curious chemist, I decided to test the above synthesis route
using 50ml of D-limonene (an inexpensive and widely available alkene). This gave the estimated
yields shown above, the yield in step 5 was estimated using the fact that the ketone is highly insoluble
so at the end of the amination reaction the amount of ketone/insoluble organic residue was measured to
obtain an estimate for how much of the reagent had dissolved as an amine. These early tests show
promise for this synthesis route but more work is needed to see how subject the alcohol and ketone
are to rearrangement even under cold conditions and with the mild oxidising agent of bleach.

madprosr
(Hive Bee)
08-24-03 07:17
No 455364
      i can't say i'd trust the research of anyone...

i can't say i'd trust the research of anyone pretending to be an educated chemist who suggests making MDMA using MeNH3.

i suppose this falls into the "hypothetical synths i'm trying to trick other bees into testing out for me" category...

or did somebee finally get ketone from the secondary alcohol while i was away?

Vitus_Verdegast
(Hive Bee)
08-24-03 07:19
No 455366
User Picture       Well Martha Steward,

You should go back to cooking cornflakes-encrusted chicken, 'cause with chemistry it just ain't tasting so good.

I find your post somewhat misinforming.
MDP2Pol cannot be made via H2SO4, at most MDP1Pol can, so your end-product will be the less potent ALPHA instead of MDA. Also I don't think that grinded up pennies will be very effective where Zn dust is needed. And the most important thing, you don't mention cleaning MDP2P even by the bisulfite route. You should at least distill the ketone if you're not distilling safrole or MDMA base.

I hope no-one will waste sassafras oil on this one.

But hey, Martha, try your proposed reaction scheme, i'll bet ya you will not get a single gram of MDA out of it.

A Dream Within A Dream (http://www.poedecoder.com/Qrisse/works/dreamw.html)

martha_stewart
(Stranger)
08-24-03 19:48
No 455432
User Picture       > Vitus wrote: > I find your post ...

> Vitus wrote:
> I find your post somewhat misinforming.
> MDP2Pol cannot be made via H2SO4, at most MDP1Pol can...

OK. See the link provided with the intial post:
https://www.rhodium.ws/chemistry/mdp2pol.html
The product formed is in fact MDP2Pol since this is Markovnikov orientation for the hydration. The problem
is that this tends to rearrange after a few hours at room temperature. Previous attempts to turn the MDP2Pol into the ketone have used oxidizing agents that require refluxing which will hasten rearrangement. It is my belief that the refluxing used in previous attempts is largely responsible for the rearrangement and hence low yields. As mentioned in the link:

"What is needed is a gentle, high-yielding oxidation procedure, which is to be performed immediately after the formation of the MDP2Pol, so that it's converted to MDP2P before it has a possibility to decompose."

Here I propose bleach for this oxidation. It is a gentle, high-yielding oxidation agent that can form the ketone quickly at cold temperatures as described above which should minimize rearrangements. In the writeup posted above, the oxidation is carried out immediately, and quickly in an ice bath.

Having said this, I agree that it will require actual experimentation to determine the degree of rearrangement. I also mention this at the end of the original post. Any suggestions on simple ways to measure the amount of rearrangement would be welcome.

yellium
(I'm Yust a Typo)
08-24-03 19:53
No 455435
      Although your post might appear as a good idea

Although your post might appear as a good idea at first sight, since it uses common household chemicals, have you any idea why this route wasn't already worked out and tried before?

martha_stewart
(Stranger)
08-24-03 20:01
No 455438
User Picture       >i can't say i'd trust the research of...

>i can't say i'd trust the research of anyone pretending to be an educated chemist who suggests making MDMA using MeNH3

Oops, meant to say MeNH2. In the above post, in principle a smaller molar ratio of MeNH2 would be needed than is required for aqueous ammonia since the literature claims that aqueous ammonia is less reactive in ammination than MeNH2. Here, I have not tried this reaction with MeNH2, only with aqueous ammonia and using D-limonene as a starting material to do an initial run through as a feasability study as mentioned in the original post.

martha_stewart
(Stranger)
08-24-03 20:22
No 455443
User Picture       I think there are two things that are novel in

> Yellium wrote:
> Although your post might appear as a good idea at first sight, since it uses common household chemicals, have you any idea why this route wasn't already worked out and tried before?

I think there are two things that are novel in this approach that have not been properly investigated (from what I could tell on searching the forum).

The first is the alcohol MDP2Pol. Here I think this path was abandoned prematurely since the original methods used required refluxing which degraded the product as explained earlier. Maybe the original investigators were not aware of using bleach as an oxidizing agent since this was published at the end of 1979 and may not have been widely disseminated.

The second novel idea is to try using zinc as a reducing agent since this is a commonly available material. This is well known as a reducing agent in the Clemmensen reaction, but is not much investigated for amine reduction since non-clandestine laboratories have easy access to NaBH4 etc. Here the original papers [10] and [11] give yields ranging from 50%-80% with refluxing 24 hours. However, as I mentioned in my post, the problem with their method from 1940 was that they used strongly acidic conditions which modern chemists now know actually inhibits the intermediate imine formation and likely was a big part of the problem. What is different in the method proposed above is that the pH was controlled to be 4.5 thereby favoring optimal intermediate imine formation. Also the 10:1 molar ratio of NH4OH to ketone and the addition of salt to give a high Cl concentration should help drive the reaction to completion quickly. Initial experiments with cheap D-limonene bear this out since about 88% of the ketone had reacted within two hours at room temperature. Here, I actually like the idea of being able to do the reaction at room temperature since again, this should help guard against rearrangement of the ketone.

abolt
(Hive Addict)
08-25-03 05:49
No 455506
User Picture       The chief has spoken

Post 378681 (Rhodium: "NB!", Methods Discourse) and Post 378788 (Rhodium: "Safrole -> MDP2Pol", Methods Discourse)

In fact, read the whole thread. Maybe Overclock could help?

I give you respect for the thought you have put in.

keep it up. smile

This space for rent

suttleila
08-26-03 06:01
      i applaud u!!!
(Rated as: incomprehensible)

Vitus_Verdegast
(Hive Bee)
08-26-03 07:07
No 455737
User Picture       You don't have a clue, do you?

they also say its not possible to make mdma from meth even tho i personally know a chemist that says its possible..he said that is why you roll on meth because a few more steps and you would have it..i think he told me mdma is an 13 step program or 11 i can't remember.

You're chemist friend is obviously bullshitting.
Why don't you read up some more on pharmacology, before you try to make such statements on this issue.

Suppose it is possible to dihydroxylate the benzene ring of meth, and you are able to isolate it, and methylenate with CH2I2, your yield would be shit. Maybe after your alleged 13 step process you would start with 1 kg meth and end up with maybe a gram of MDMA ??

You must back up your ramblings with references, or a procedure, or else you better stop whining.

BTW you're not the first one with the completely OTC MDMA idea, but unfortunately the MDP2Pol route has already been proven not to work years ago. Do you want to waste sassafras oil on it? Be my guest, but don't come complaining.

A Dream Within A Dream (http://www.poedecoder.com/Qrisse/works/dreamw.html)

Sunlight
(Pioneer Researcher)
08-26-03 13:30
No 455771
      Zn reduction

I've personally tried months ago to make MDA with ammonium acetate or ammonium formate and Zn dust 97 %, the reaction yielded a curious absolutely white gum, I wonder what the hell it is. Interesting, but not psychedelic at all.

martha_stewart
(Stranger)
08-26-03 20:45
No 455830
User Picture       Zn reduction

>Sunlight wrote:
> I've personally tried months ago to make MDA with ammonium acetate or ammonium formate and Zn dust 97 %, the reaction yielded a curious absolutely white gum, I wonder what the hell it is. Interesting, but not psychedelic at all.

Unless you had some hydrochloric acid in there as well, this sounds like a Leuckart type reaction with Zn to help accelerate it rather than a Zn reduction. I tried running a regular Leuckart without Zn but gave up on this method since it was taking more than 24 hours and not seeming to reduce my test ketone much at all. If you like the Leuckart type reaction you should be sure to check out the published papers on running this reaction anhydrously on a clay medium using microwaves where they claim a high (>95%) yield in 30 minutes -- likely you have already seen these already on this site.

Not sure about the gum. Maybe you refluxed it at a high temperature for a while and the ketone started to polymerize then react?

Sunlight
(Pioneer Researcher)
08-27-03 03:33
No 455901
      Ammonium salts for imine

Ammonum acetate is commonly used to make primary amines, it provides the NH3 and keeps the pH ok for imine formation. MDA and amphetamine are made with ammonium acetate through hydrogenation with Raney Nickel and the like.
Ammonium formate works fine for MDA with Pd/C, it provides NH3 and H2 from the decomposition with the catalyst for the reduction of the intermediate hemiaminal (the rxn is carried in 9:1 methanol:water). I explored it (from papers published here in the Hive by Foxy2) and I found that a 20-30 w/w catalyst yields 80 % of MDA, and a 10 % about a 65 %. Catalyst works fine at least 3 times. Even ammonium acetate works in this rxn, but obviously it is necessary some ammonium formate for the reduction of the intermediate.
My idea was that ammonium acetate would form the imine or the hemiaminal and then it could be reduced with the H2 released from the rxn of Zn and the acetic (or formic) acid present in the solution. It was carried at rt, but it didn't work at all.
We could try it also with plain NH3 (alcoholic or aqueous+alcohol) and Zn, it's said it produces for example a 60 % of benzylamine, but having the very low yields of MDA with plain NH3 and Al/Hg we did not make the effort to test it.
The best way to make MDA at home is with ammonium formate and Pd/C if you can get good commercial Pd/C. UTFSE.

The MDP2Pol has been discussed extensively and I personally doubt that it works, although someone reported a possible succes oxidyzing it immediatly with a nitrate and cupric acetate, I don't remember it exactly. Why don't you try it and then tell us what you got ? It will be better than argue about theoretical stuff.

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