Bwiti (Hive Addict)
10-03-01 10:36
No 219895
      Reduction of P2Ps - From T.S.2, method 7  Bookmark   



Why not replace the sodium amalgam with Al/Hg made from something less suspicious than mercuric chloride like mercuric nitrate? Wouldn't one get better yields than with the more common Al/Hg reduction that doesn't use hydroxylamine? Peace!cool

  I'm going to help all of you cleanse this diseased planet.
 
 
 
 
    hypo
(Hive Bee)
10-03-01 11:20
No 219912
      Re: Reduction of P2Ps - From T.S.2, method 7  Bookmark   

don't understand question, but Al/Hg reduction of P2P-ketoximes has been brought to work (allthough yields are not enormous): Post 189985 (Antibody2: "Re: MDA via oxime", Methods Discourse)
 
 
 
 
    Bwiti
(Hive Addict)
10-03-01 14:00
No 219964
      Re: Reduction of P2Ps - From T.S.2, method 7  Bookmark   

"10% aqeous MeOH with 4 equiv HOAc (w/ lewis acid *) 62%!!!"

  That's not too bad, because it's not that exothermic and MDOH is active. I'm guessing this could be easily scaled up, but it requires more chemicals than one would need to do a reduction of a plain old p2p. I'm thinking that one would have more "luck" with the more common p2p reduction, because there's more literature covering it. Maybe I should search patents for zinc-amalgam reductions? I was just wondering what options an evil chemist has for reductions. Thanks for that link! How about using borohydride/nickel boride on a ketoxime? Peace!cool

  I'm going to help all of you cleanse this diseased planet.
 
 
 
 
    hypo
(Hive Bee)
10-04-01 11:14
No 220297
      Re: Reduction of P2Ps - From T.S.2, method 7  Bookmark   

no idea about borohydride/Ni. but according to this little treasure i found on rhodium's, urushibara should work: ../rhodium/chemistry /znhg.alhg.reductions.txt

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Piglet

NH2OH.HCl is readily available from photography supply. And a better reduction
using the Zn/Ni couple has been posted by labrat. Claims to reduce imines to
amines (ketone in 80% methanol saturated with NH3 at about 60-70%, yields higher
from oxime, the side-product being hydroxylamine (boo hoo!), the freebase of
which is a solid. It's active as MDA. If you really want MDA, put it right back
into the next batch being reduced!

Search for Labrats post (it IS there, I just havn't got the time) and then here
are some details. (I use the sulphate).

NiSO4 + 6NH3 --> Ni(NH3)6SO4.
Zn + H2O --> ZnO + H2.
ZnO + 4NH3 --> Zn(NH3)4(OH)2.

Pour off the NH3 solution, add your oxime in 80% v/v Methanol solution, add
3 moles of NaOH and slowly add the Zn in portions (if it overheats, cool under
running water) until it's all added, heat for 90 minutes, cool, filter (wash
filtrate into mother liquor). Neutralize, extract, remove solvent (yielding the
hydroxylamine as solid) or simply make salt as you see fit (IE a mix of MDA/MDOH).

2NaOH + Zn -->Na2[ZnO2] + 2H

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and Antibody2 says so smile