Author Topic: Review: S_S (SM) "high-yielding one-pot" reduction of ALIPHATIC NITRO  (Read 344 times)

Electro´S

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Review: S_S (SM) "high-yielding one-pot" reduction of ALIPHATIC NITRO
« on: January 07, 2013, 05:33:32 PM »
Yep!  :)
I Had read a lot of times this thread on SM, And I have found some numbers on the work of Stoichiometric_Steve.  8)
http://www.sciencemadness.org/talk/viewthread.php?tid=4965
Items:
15L. Plastic Box.
Small water pump
5L Beaker.
Motor head from a 12V Drill.
Variable power supply for the drill.
Stirrer rod made with a computer fan.
Hot Plate.

Reagents:
25gr -P2NP (Recovered from a "Dungeon Waters Bottle"
12,5gr NaBH4.
250 ml Denatured ethanol bottle.
Some water.
Some Acetic Acid
Some concentrated HCl
100 gr Zinc Dust "activated"
45 gr Ammonium Formate.

The 5L beaker is place in the plastic box with cold water and the small pump recirculating it around the glass. Then a 250 ml Ethanol bottle is open with the mouth and the liquid is place in the beaker with 50-100 ml H2O and 12,5 gr NaBH4 with vigorous stirring.
Then the 25 gr of P2NP is added in 3 portions in less than ONE MINUTE. High hydrogen evolution is observed but the flask is big enough. The solution is stirrer for half hour around.
At this point, some Acetic acid is used to kill borohydride and made the precipitate a little soluble in the liquid phase.
While 100gr of zinc was activated and it was just drain off and added to the nitroalkane mixture. Reaction start a this point for the acid traces on the zinc, and the ammonium formate is drop down in 3 portions in less than one minute. All was stirrer for 15 minutes.
Now water bath and stirrer is removed and the beaker is place on the hot plate and 200 ml of concentrated HCl is added in portions. The beaker was heated and stirred with a glass rod for 30-40 minutes. And the reaction was finished at this point.
After basification, extraction, boiling out the ammonia, drying the solvent y neutralization... 24 grams of the  propylamine sulfate was obtained.  ;D

So looks like the Stoichiometric_Steve procedure works perfectly for Nitropropene even if you make it with not too much attention.





« Last Edit: January 07, 2013, 11:08:32 PM by Electro´S »

antibody2

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Re: Review: S_S (SM) "high-yielding one-pot" reduction of ALIPHATIC NITRO
« Reply #1 on: January 08, 2013, 11:53:17 PM »
Nice post Electro, glad you got it work so well for you  8)

Electro´S

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Re: Review: S_S (SM) "high-yielding one-pot" reduction of ALIPHATIC NITRO
« Reply #2 on: January 13, 2013, 03:41:26 PM »
Thanks for the kind of words Ant!!!
This route works fine, just needs to be sure of kill borohydrides before the nitro reduction.
In other paper, i read the same workup  scaled x4 , and the yield was like 70% with a good amount of P2P-bisulfite recovered as a side product.
Any suggest about P2P => Phenylpropylamine ?
Can sodium borohydride with ammonium acetate do the work??

lomg john

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Re: Review: S_S (SM) "high-yielding one-pot" reduction of ALIPHATIC NITRO
« Reply #3 on: January 13, 2013, 09:37:18 PM »
Its great to come to this site and read of the slight modifications being given to Stoichiometric_Steve original method.
niobium2,5-dm-benzaldehyde Jan 2006 is another example, using Formic and Potassium Hydroxide.


Anyway, my mate uses niobium's way and always adds his P2NP slowly and never let the temperature rise above 25oC.

Any advise on the best way to recover the nitroalkane after step one (after the acetic, before the zinc) would be appreciated.
He wants to try and improve yield, now that he has got the whole original method and niobiums working on a 100 - 200 mmol scale without intermediate separation, just to see if in fact it is worth dividing this methods into a two stage for better yield.
« Last Edit: January 14, 2013, 06:59:57 AM by lomg john »

antibody2

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Re: Review: S_S (SM) "high-yielding one-pot" reduction of ALIPHATIC NITRO
« Reply #4 on: January 14, 2013, 09:03:43 PM »
why do you want to go from p2p >> phenylpropylamine? Its a step in the wrong direction ...

using P2P + NaBH4 + ammonium acetate will give you amphetamine,
but Ab2 would instead form the oxime of p2p with hydroxylamine and then reduce it with acidic Al/Hg to yield amphetamine

using P2P + methylamine +Al/Hg will give you methamphetamine

Electro´S

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Re: Review: S_S (SM) "high-yielding one-pot" reduction of ALIPHATIC NITRO
« Reply #5 on: January 17, 2013, 10:11:46 AM »
Just because it's recovered as a side product in this route to amph (I know than you know but just to be sure... I said Propylamine not propanolamine).
And yes, i know a lot of references to Antibody works with Oximes... But This "Expensive" route is the choice to avoid the limitations of amalgams for reducing the Nitropropenes. So the oxime synth with the P2P from a P2NP reduction while tin salts are in hands, sounds like I'm miss in a maze!!!. : :)
The best point would be avoid the p2p formation, But in what moment or condition ketone is the product instead of the amine???
And the second (or the first ) choice, will be isolation of the nitroalkane before nitro reduction.
« Last Edit: January 27, 2013, 06:08:20 AM by Electro´S »

lomg john

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Re: Review: S_S (SM) "high-yielding one-pot" reduction of ALIPHATIC NITRO
« Reply #6 on: February 10, 2013, 06:35:29 AM »
The intermediate product after borohydride double bond reduction is AFAIK 1-Phenyl 2-Nitropropane.
What is the best method to separate and recover it from the mix.

Electro´S

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Re: Review: S_S (SM) "high-yielding one-pot" reduction of ALIPHATIC NITRO
« Reply #7 on: February 11, 2013, 10:27:16 AM »
The best method at the moment is with IPA as the solvent and plenty of salt after acid addition to the borohydride. The Brine Mix will separate the Ipa top layer with the nitroalkane.

But Separation of the nitroalkane is not recommend (At less with plain P2NP), With one gram of P2NP, one gram of Amine sulfate was recovered.
May be you can get the perfect yields, But you will spend a couple of hours for a little bit more...
« Last Edit: February 11, 2013, 09:44:19 PM by Electro´S »

lomg john

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Re: Review: S_S (SM) "high-yielding one-pot" reduction of ALIPHATIC NITRO
« Reply #8 on: February 12, 2013, 08:35:04 PM »
Thanks Elec for that.
Stoichiometric_Steve in the original SM page said that at 1 mol scale the nitro alkane separates naturally, kind of oils out of the ethanol.

Do you use super high speed stirring when adding the p2np to the Na-boro alcohol,  I have seen the dreaded white slime appear a couple of times, but that was using stir bar and beaker.
I dont understand how you get that much in there so quickly.

Electro´S

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Re: Review: S_S (SM) "high-yielding one-pot" reduction of ALIPHATIC NITRO
« Reply #9 on: February 14, 2013, 04:07:54 PM »
Stirring is vital in Yields in all the stage, even more when the Formic Acid... But you don't need crazy stirring, just make it at homogeneous as possible.
And the secret is the reaction vessel. IN a 50 Liters CardBoy HDPE Container with 3 Female 29/32 joints in the top (Yes, Survival Style!!!) for reflux and additions, And internal SS coil for cooling and heating, this reaction runs smooth inside a hood.
  ::)