Reductive Amination of MDP2P to MDA

dr.crack · Sat Mar 12, 2005 4:31 am

Swim is trying to make some MDA and need some advice. In Methyl Man's "Reductive Amination of MDP2P with Al/Hg + Nitromethane he is careful with his methylamine and ammonium chloride because he says:
The problem is that the ammonium chloride will cheerfully react by the same mechanism as the MethylAmine.HCl with the MDP-2-P, but it will make MDA in place of MDMA.

Swim would like to run the Methyl Man's "Reductive Amination of MDP2P with Al/Hg + Nitromethane". with ammonium chloride instead of methylamine to get MDA.

Does this reaction sound good and does it make sense? thanks in advance.

java · Consumer

I found a thread from the old board that has some discussion of your planned experiment. You might want to replace the " I " with
SWIM in your post, to keep the conversation theoretical and annonymous......java

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the Hive BB

Methods Discourse

Re: Al/Hg amination using Nitromethane

APOPLEX

Junior Member
posted 11-07-1999 07:48 AM

In Rhodiums Chemistry Archive I found a way under the topic - Al/Hg

using Nitromethane - to make the honey without Methylamine.

http://rhodium.lycaeum.org/chemistry/index.html

The Method seems relatively simple:

For details look at Rhodiums Chem. Archive.

Prepare the Al/Hg using Methanole instead of wather as the solvent.

Then add a mixture of MDP-2-P, Nitromethane

and Methanole to the prepared Al/Hg dropwise.

In this Reaction the Nitromethane is reduced

to Methylamine and the MDP-2-P is also reduced in one Step !

If this works, you can save a lot of time

because you do not have to prepare the fucking MeAm.HCL !

Does this method work as described at Rhodiums Chem Archive ? Any

experiences ?

Hope you can help me
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Xerxes
Member
posted 11-07-1999 03:0 PM

yeesh...just to warn you, the old timers here will jump on ya and

tell you to use the search engine.

yours truly re-typed that writeup from Strike's book (with

permission) so it's safe to say it will run. but there are caveats.

SEARCH and ye shall find.
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APOPLEX
Junior Member
posted 11-07-1999 03:37 PM

To Xerxes:

Thank you for your B I G help !?!
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APOPLEX
Junior Member
posted 11-07-1999 03:48 PM

Ok, I will buy Total Synthesis II, so I can get the information

faster.

And BTW: I only asked if anyone has tried this synthesis in REAL,

not only theoretical.

I hope you do not misunderstand me.

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APOPLEX

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psychokitty
Member
posted 11-07-1999 07:21 PM

Use the search engine to locate posts by me, Methylman, Boingo X,

and many others. You'll find what you looking for.

--PK
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Scooby
Junior Member
posted 11-08-1999 01:36 AM

Have you checked out Bright Star's Compilation and Editorial ?

DEFINITELY worth a look.
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biltong
Member
posted 11-08-1999 11:10 AM

In the Ritter recipe for the Al-Hg rductive

amination using nitromethane instead of

methylamine HCl

http://rhodium.lycaeum.org/chemistry/ritter-alhg.txt

I guess it would be better- safer- to

do the HgCl2 this way:

Put the 50g of aluminum squares into the

2 necked 2L flask with 1 stopper,

add 0.3g HgCl2 and 1L H2O.

Let the bubbling start, it should take 10-20 min.

Then pour off the water, and rinse and shake twice more with 1 L

water each

time to get rid

of the Hg poison.

Do this quickly so the foil stays wet and

keeps reacting, then quickly

dump in 1 L methanol or until the foil is

covered then proceed to drip in the

ketone etc.

This way 90% of the mercury salt is removed

before the amination.

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K.C. Nicolaou
Member
posted 11-08-1999 11:43 AM

"This way 90% of the mercury salt is removed

before the amination."

Except for the fact that 99% of the mercury salt ends up as mercury

metal deposited on the Al. What does amalgam mean again?
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APOPLEX
Junior Member
posted 11-08-1999 03:21 PM

Thanks biltong

I will try the Al/Hg with water instead of methanole to remove most

of the mercury, but

I have to less time because of my work.....

.....so I will post results and yields as fast as possible.

(I`m a German bee - sorry for my bad english)

APOPLEX
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scwam
Member
posted 11-08-1999 09:30 PM

Herr APOPLEX,

Darf ich Ihnen behilflich sein?

FYI: Unless your an older hive member hiding behind a new name - in

such case you wouldn't ask this question, you will burn your self

showing up here as a smartass)

.....NOW, bitte bedienen Sie sich:

http://hive.lycaeum.org/ubb_board/Forum4/HTML/000518.html

You must let it react for +24hrs. I hypathetically let it go for

36hrs. The ketone -> imine takes 4-6hrs. And thats the fast part.

The imine->amine is the reduction, and the reason for the Al/Hg and

thats the slow part. Ketone->imine is a spontaneous condensation

rxn. Unbalanced rxn is:

(R)2-C=O + MeNH2 -> (R)2-C=N-Me + H2O

Useing a dean start trap, refluxing in a toluene solution (BP-110C)

is a great way to

divide this reaction..... if you so choose. But I don't, and I bet

most of you have never

seen a Dean/Stark trap. But I do this. (When I dream of such

illegalities)Note : divide the amount of EtOH you were going to use

for the whole reaction into 3 parts. The first portion is going to

go into the ketone flask, and it should be anhydrous. The second

goes in the beaker (next part), this can be denatured stuff. The

thrid part will be used to wash stuff into the reaction mix. In a

too large round bottom flask.... You'll need it much bigger than you

think for the next part. 1. ketone +

2. Absolute (100%) EtOH +

3. Massive OverKill of MeAm.HCl. I'm talking, 4x molewise overkill.

4. Add CONCENTRATED NaOH solution, so that you can neutralize half

(0.5) of the MeAm.HCl you put in. Drip it in SLOWLY over 2 hrs.

5. Stir, for 4 hours total. Doing it this way allows, a

semi-anhydrous environment for the condensation to take place.

Placing an overdose of MeAm.HCl does two wonderful things. First, it

supplies the ketone will an overabundance of Amine to react with.

Secondly, the Excess MeAm.HCl will suck any water produced out of

the solution. At the 4 hr mark...... IN A SEPARATE BEAKER....

1. Denatured EtOH +

2. Al chips/turnings/thick foil whatever +

3. Hg Salt. For a 80g ketone batch add 2g of the Hg Salt.

4. Wait for 10-15 minutes, while stirring.

The Al should start bubbling, And a grey sludge should begin. The Hg

salt is very

important. It is the electron transferring agent for this reaction.

You must add a little more than Osmium did. Trust me. While wearing

gloves....

5. Dump the contents for the Al beaker into the flask containing the

ketone-imine.

(R)2-C=NHMe + H2O + e- -> (R)-CH-NH-Me

Do you see that we've added H2 across the double bond? Well with out

a Hydride (H-)

source ... Its though.... However, H+'s are available everywhere.

So, thats where the

Hg salt comes in. The difference in Hg+1 and Hg+2 can be bridged

easily with refluxing!

But it still takes time. So a Hg+2 gets an electron, and then gives

it to the imine....

and then the imine is attacked by a H+ ion..... So you need Hg Salts

for this and it will prolly work better if you use a little more

than what Osmium recommended.

So, to continue....

6. Make sure the damn thing is stirring.

7. Heat solution to reflux.

8. Make sure the damn thing is stirring.

9. Go get something to drink.

10. Make sure the damn thing is stirring.

11. Talk to your wife/girl/significant other.

12. Make sure the damn thing is stirring.

13. GOTO 8 until (time>24hrs) or until all the Al is gone. If you

wait till all the Al is gone you're going to be waiting +72hrs.

Which is not a bad thing.....

Well thats it! At the end you let the contents of the flask settle,

decant. Put in 50mL of EtOH (Abs or denat), stir the contents for 30

min, repeat. The solution you get should be cherry red/black. Vacuum

off the solvent, wash with 2x NaCl soln., 2x H2O, make the contents

acidic, extract some by-product crap with MeCl2, make basic, extract

goodies 3x MeCl2. For a complete conversion of your oil.... I'd

vacuum distill at this point for pure shit. MDMA oil should come

over a little before the temperature that the ketone comes over.

So... Reflux for at least 24 hrs. More is better. Wear gloves! At

the 12 hr mark ...leave! Go get a beer. Pizza. Whatever. It will be

fine.

APOPLEX,

Now tell Mr. Bright Star "Thank you Mr. Bright Star"
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mean old man
Junior Member
posted 11-13-1999 09:16 AM

If you start the Al-Hg amalgamation with 50 g Al, 1g HgCl2 in 1.5

liter of water, and let

it start to amalgamate for 20-30 minutes,

then pour off water and rinse twice more with 1L each fresh water,

you are removing any left-over ultra-toxic HgCl2.

The Hg that's amalgamated onto the aluminum

isn't a toxic substance, it's not going to contaminate the product.

After the last wash, you quickly add the 1.5L

methanol and put your funnel with the

nitromethane, ketone and methanol on.

Of course you have to do these rinses pretty quickly, you can't let

the aluminum dry

off and stop amalgamating, but at least

your product is a lot less likely to be

contaminated with any HgCl2 crap.

It's a lot safer and I don't think it's any less workable.
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K.C. Nicolaou
Member
posted 11-13-1999 12:28 PM

My point is that if you allow enough time for the mercury solution

to fully react with the Al, the conversion of HgCl2 to Hg(0) is

nearly quantitative, meaning that basically ALL of the HgCl2 is

removed from the aqueous solution. Worry more about disposing the Hg

containing Al sludge than the water rinses from the amalgamation.

Basically no HgCl2 will make it through the rxn. It will all be

present as Hg(0), which is not soluble in water or organic solvents.

By the way, 1g HgCl2 to 50g Al is more than you really need if you

are using thick pieces of Al(thick Al works better).
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a taste of honey
Junior Member
posted 11-13-1999 03:00 PM

I checked this recipe in TS2, and it seems to me it would be more

effective to clean it up with the same acid-base as Strike uses

for the previous recipes in TS2...

OK, Ritter's recipe says after the nitro-ketone-methanol-al/hg is

finished, dump the

stuff into 1.5-2L of 35% NaOH.

Let separate into 2 layers.

Discard bottom.

Take top layer, evaporate off the methanol,

take the crude oil, dissolve it in a liter of toluene, wash with

water a few times,then with saturated NaCl.

Dry the toluene with MgSO4.

Chill toluene, then bubble HCl gas to crystallize.

Couldn't you also do it this way?

After the nitro-ketone etc is finished,

vacuum filter the stuff to remove the aluminum shit.

Then vacuum distill off the methanol.

Throw the crude oil remaining into 500 ml

of 3N HCl.

Wash with DCM.

Basify with 25% NaOH to pH 12.

Extract the freebase with DCM.

Vacuum distill off the DCM or crystallize.

Which method gives you a cleaner product?
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lexamillion
Junior Member
posted 11-15-1999 08:08 PM

am i just old-fashioned or is it really a good idea to be using

mercury anything. i can't think of any mercury compounds i would

feel comfortable ingesting. am i just paranoid?
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Methyl Man
Member
posted 11-16-1999 12:39 PM

a taste of honey: something you need to be aware of in advance is

that the Ritter writeup has one flaw: it doesn't tell you that in

all likelihood you WILL NOT get a separation of a methanol/product

layer (Ritter even admits this himself in a post somewhere buried in

these archives).

Methyl's friend has considerable experience with this procedure at

this point and has never seen this separation occur. What you will

have to do is, after basifying and shaking in a sep funnel, extract

the whole mess with a liter of toluene. Then you can proceed however

you want with that solution.

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O+O+O+O+O+O+O+O+O+O+O+O+O

"There's a methyl to my madness"
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Xerxes
Member
posted 11-18-1999 11:25 AM

MM -- you're saying you should do that just after dumping the slurry

into the NaOH solution? So now you've got about 3L of fluid on your

hands, and you should extract this with portions totalling 1L of

toluene?
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Modesty
Member
posted 11-18-1999 12:01 PM

Let it do its work & cool down first. A foaf has let it sit for 24

hrs, and still got the product without reduction in yields.

methyl_ethyl · Riedel De Haen

dr.crack · Mon Mar 14, 2005 8:07 pm

Sorry Methyl Ethyl. You are correct. There is not nitromethane used. it is methylamine used. thanks for clearing that up.

CycloKnight · Thu Mar 17, 2005 7:24 pm

Dr Crack,
since it seems you are interested in this procedure let me share a few words of wisdom about it.
You are referring to the Ritter writeup, I belive Dr Gonzo (or something similar, not sure) did a photo essay on that procedure, using a half-scale variation of the Ritter method using methanol/nitromethane for the red. amination.
If following the Ritter write up, for goodness sake do not, DO NOT use the NaOH "workup" detailed near the end of the Ritter procedure. Simply because it will not work.
Adding NaOH (or conc. NaOH solution, say 25%) to the finished grey solution will usually cause the mixture to separate, the grey gook goes to the bottom and the alcohol/freebase/byproduct solution on top - which can simply be poured off. It works for IPA, it doesn't work for methanol!!

You will end up with a grey, highly caustic mix of methanol, NaOH, and your valuable product. SWIM has personally lost hundreds of ml of 3,4-MD freebase due to failed repeated attempts at gettting the methanolic amalgam mixture to separate. It will sit for days and not separate.

And what's more, once NaOH is added - you have to be careful because if you heat it, your product will be entirely ruined. So you can't steam distill, unless under strong vacuum. DCM cannot be used, so if you try the NaOH separation and it doesn't work, use toluene of Xylene for the extraction.

A method that I've found to work is as follows:
Vacuum filter grey solution, to yield a yellow solution - this contains most of your product.
Mix IPA with the filter cake to dissolve out the goods, then add a small amount of 25% NaOH solution to your filter cake/IPA mixture, the garbage will settle at the botttom. Add more IPA and decant again, repeat until the IPA that pours off is clear (no longer yellow).

You product is now in the combined IPA decants. and the yellow methanol filtrate. I have found through much experience, that simply "evaporating" off the methanol (as it says to do in the Ritter method) is a serious mistake. The methanol will steam distill out alot of your freebase!!!!!!!!!!!!!!!!!!!!!!!
Solution? Extract the methanol and IPA with toluene or similar (xylene), do not use DCM as it will dissolve in the methanol.

Any questions about this procedure just say, SWIM has done it many times and has pretty much perfected it. I even have a procedure for doctoring the reaction mid-way when it peters out!
It will sometimes peter out for no apparent reason, meaning that all your work was for nothing1
This is not the case, simply stop the addition, pour off the solution from the Al/Hg, soak in very dilute NaOH solution for 10 min, rinse with dH2O, reamalgamate, rinse with dH20 one last time, rinse with methanol (to help remove water) and then add your original solution (reaction mixture) that you first poured off. Careful, if you continued the addition after the reaction stopped, then it might erupt when you add the reaction mix to the re-amalgamated (rejuvenated!) Al. So, you may need to add extra methanol to keep the temperature down long enough for you to add all of the reaction mix.
Happy reacting.

IndoleAmine · Dreamreader Deluxe