MDA by Al Amalgam reduction tips?

[biffman]

SWIM is thinking about the MDA method using Ammonium Chloride with the Al amalgam reduction.  Not wishing to waste any valuble ketone for R&D is looking for any response or pointers from anyone who has thought about this before.  The NaCNBH method has been used before by SWIM with success and no problem but now would like to avoid sourcing the borohydride if possible again.
  Anything SWIM should be aware of before thinking about the method taken from Rhodium's site?  Pointers, omissions etc?  Seems pretty straightforward.  Thanks in advance.

[biffman]

SWIM decided after UTFSE that the yields would be way to low to bother using that method.  As suspected. TGTBT (too good to be true)

[Bandil]

If you can get sodiumcyanoborohydride, surely hydroxylamine chloride/sulfate can't be hard to obtain? That will boost the yields quite a bunch!

Make the oxime like

this

(https://www.thevespiary.org/rhodium/Rhodium/chemistry/mdaoxime.html) and reduce it via the amalgamated Al, as described on rhodiums site!

Regards
Bandil

[biffman]

Thanks for the reference.  Yea, it's not really a probelm to get the borohydrate it's just that it's fairly expensive and the yields are rather low.  However this referenced method looks interesting if those yields are obtainable.  Never had to get elemental sodium before but that shouldn't be a problem I wouldn't think.

[DiMethyl]

There really is not much detail on the amalgamated Al reduction of the mda oxime.
Questions such as the type of Al are rarely answered.
Absoloute et-oh is hard to come by and $$$ if you find it.
I have yet to find any info on producing it in a reasonable time with readily available materials.
I saw a reference to Mg and I2 once for producing it but I am relutant to buy the I2 although the Mg is easy to get.
I have 8 grams of the mda oxime that I just made about an hour ago (in a country where it is legal to do so) so I will be pursuing the amalgamated Al reduction and I will let you know how that turns out.
I also have over 28 grams of Na metal so if I come up with something on getting the absolute et-oh I would probably pursue that route.

DiMethyl

[Midi]

If you cant get sodium cyanoborohydride, but can get sodium borohydride, then ANHYDROUS ammonia acetate and NaBH4 may be worth your while.

Just a fyi, Ammonia acetate purchased from a chem supplier appeared to be pretty anhydrous and was used in this rxn. Yields were horrific, returning 7g from 40g of ketone.

Make sure everything is anhydrous and I bet you will have better results.

[Bandil]

midi>
No, i doub't you'll be able to tweak the reaction with the ketone and some ammonia salt to higher yeilds. Ammonia is simply a horrible compound to use with these kinds of reactions. You really NEED to use hydroxylamine to get useable yields.

I have successfully reduced the oxime using denaturated ethanol, so that shouldn't be a problem. The oxime/immine formation is what's tricky here!

Regards
Bandil

[cublium]

Hi dimethyl,i was wondering about using some other alcohol in place of EtOH.IPA should work fine(in theory).Raf will try this out in near future.You might to want to check out this thread:

Post 465769

(cublium: "Alternative to ethanol in oxime reduction with Na", Newbee Forum)

[moo]

Those in need of absolute ethanol can dry the 96% stuff with calcium oxide, as described in Vogel if I remember correctly.

[SPISSHAK]

Copper sulfate pentahydrate from the hardware store can be dehydrated and used to make absolute EtOH.
UTFSE.

[cublium]

Cub was present when following took place:
10 grams of oxime was dissolved in 250 mls of pure for analysis grade IPA and 12 grs of Fluka sodium was added over period of 1 hour.Sodium reacted with IPA just fine,just cub was worried because it floated on top the IPA and lots of hydrogen evolved as sodium dissolved.When reaction was over cub was sure he could smell some unreacted oxime.Yield wasn't ok too,after extraction and washing was about 2,75 grams(round 30% or so,molar) of some snow white powder that tasted more bitter than MDMA but was still consumable dissolved in water and it dissolved very easily.110 mg of said powder was consumed and onset was around 1 hour after drinking the solution.30 minutes later cub felt pretty funny and also experienced some mild but pleasant hallucinations in a dark room.Overall it was pretty fun even though cub was very tired at the moment of bioassay.No hangover or crash whatsoever.Will try some 130 mgs or so next weekend and maybe in combination with MDMA.Cub thinks low yield was because there was no stirring used,just mild reflux,will try with magnetic stirring next time,he has some 30 grams of oxime and nearly 90 grams of sodium left to test with.If stirring doesn't improve yields considerably will try lower temperatures for slower reaction along with heavy magnetic stirring.IPA seems react with sodium just fine.White powder is suspected to be MDA or MDOH(it really doesn't matter,both should work equally good) and mp test is also in order to make sure what it really is or mixture of both.If cub will get this reaction work with IPA he will post some pics also and maybe detailed write-up

[Antibody2]

There really is not much detail on the amalgamated Al reduction of the mda oxime.
read this

https://www.thevespiary.org/rhodium/Rhodium/chemistry/alhg.oxime.html

Questions such as the type of Al are rarely answered.

regular reynnolds wrap will do

Absoloute et-oh is hard to come by and $$$ if you find it. then use 95% EtOH, IPA or MeOH, they all work

[madprosr]

swim found that yields are fine with AcOH/al/hg reduction of the oxime in MeOH (1/4 of AB2's scale). but after basifying and adding toluene the MeOH separated out with the toluene. several emulsions were formed as a good amount of brine was used to bust the toluene out of the MeOH. eventually the emulsions were broken and a number of back-extractions performed.

swim has forced himself into retirement by acting like a dumbass. without a doubt he'll spin it again someday when he is old and wise. we have a severe dmt and mescaline shortage in this quadrant!

[Antibody2]

IPA and EtOH are both much less soluble than MeOH in saturated aqueous solutions