Ritter
(Stranger)
07-14-00 00:31
No 28473
      Urushibara Style Amphetamine
(Rated as: excellent)
 Bookmark   

Urushibura Style Amphetamine

First of all many thanks go to CHEM_GUY for his continuous urging of the Hive community to try Urushibara Nickel reduction on phenylnitropene.  This reduction turned out to be easier than any so far encountered.   This is not based on any of the excellent references pertaining to Urushibara that have been mentioned on the hive, only chem_guys postings!

Procedure:

Dissolve 4.0g Nickel Chloride hydrate (light green crystals) in 75 ml 95% ethanol w/ mag stirring and warming to 50'C.  After salt is dissolved remove stir bar and add 1ml water and 1ml conc. HCl. [1] While solution at 50'C slowly add 5g regular Reynolds wrap torn up into .25 x 1.0in strips in 1g portions with manual stirring.  The aluminum will SLOWLY react with the nickel salt forming the metal  Ni(s) through metathesis as a dark grey chunky powder which settles to the bottom.  A gentle effervescence of hydrogen occurs during reaction.  Add aluminum at a rate that maintains a steady effervescence and keeps temperature roughly in the 50' range.  Note this may take up to two hours!
At the end of Al addition all green color from nickel salt should be discharged.  If any color remains add another gram of aluminum and wait for soln to clear. 

At this point  Urishubara nickel catalyst is prepared and ready for reduction.  Dissolve 5g pure phenyl nitropropene in 50ml Ethanol and add to nickel soln. [2]  Now slowly add 3ml conc. HCl  [3] and 1 gram shredded aluminum w/ manual stirring.  Aluminum will slowly dissolve with a more vigorous effervescence of hydrogen than the first step.  Maintaining good stirring with a glass stirring rod is essential in beginning.  Attempted magnetic stirring will result in frustration because nickel is ferromagnetic and will stick to stirbar preventing surface area exposure necessary for reduction.  After aluminum is dissolved add three more milliliters HCl and one more gram Al.  Repeat adding acid and Al until 10 grams Al and about 30ml HCl  has been added.  Aluminum reacts slowly.  Expect addition to take about six hours, longer if temp falls below 50íC.  Constant stirring towards end is not necessary, just give mix a good stir occasionally.

After all aluminum is added and mostly decomposed slowly pour in a soln of 30g NaOH in 100ml H20 with careful stirring.  Wear goggles and be careful!  Base neutralization is highly exothermic!  In 30 minutes all aluminum sludge will solvate into bottom aqueous layer and a nice orange alcohol layer reeking of amine will settle out on top.  Nickel is not dissolved by the NaOH so it will remain floating around between the two layers but this does not present a major problem.  After all, itís not poisonous like mercury or anything!  Now decant off the top orange organic layer and distill off alcohol down to a orange stinky syrup completely different smelling than the P2NP.  Dissolve these goodies in acetone and slowly add sulfuric acid to precipitate the amine sulfate.  Voila!!!!!!  about 3 grams light yellow amphetamine sulfate.

[1]  Addition of water and acid found to be necessary to initiate rctn. btw NiCl2 and Al.

[2]  When nitropropene was added to NiCl2 soln before conversion to Ni powder was complete some polymerization occurred greatly reducing yield.  It seems essential to add P2NP to rxn after Ni is fully precipitated.

[3]  Use of Sulfuric acid produced inferior results causing polymerization of P2NP to red tar

Increasing Yield:  Use overhead mechanical stirring to keep nickel catalyst better suspended during reduction.  Re-extract aqueous NaOH/Al layer w/ toluene and work up in standard manner.  Use larger amount of  nickel catalyst and more aluminum for hydrogen generation.




 
 
 
 
    zooligan
(Hive Bee)
07-14-00 01:50
No 28493
      Re: Urushibara Style Amphetamine  Bookmark   

Thanks Ritter!  This great write-up right on the heels of Beaker's 2C-B is wonderful.  I wonder what the 2C-H yield using this method to directly reduce 2,5-DMNS would be???


Thanks too to CHEM_GUY for enlightening the Hive to the benefits of Urushibara, and for answering my dolt-like questions regarding same offline!
 
 
 
 
    Alphabeta121
(Hive Bee)
07-14-00 04:42
No 28556
      Re: Urushibara Style Amphetamine  Bookmark   

could you also increase yeilds by placing the beaker into an ultrasonic cleaner bath, thereby sonicating it as well?  see old hive for great ultrasonic info

 
 
 
 
    Antibody2
(Hive Bee)
07-14-00 16:17
No 28708
      Re: Urushibara Style Amphetamine  Bookmark   

Ritter! Antibody would like to kiss you!

Antibody was also urged by Chem_Guy to look into Urusibara catalysts, but being no chemist antibody wasnít up to blazing a new trail, but with a proceedure such you have gifted the hive with . . . who knows

See antibody doing a happy dance. Hugs for Chem_guy too!

Life is a dream (until someonew wakes you up)
 
 
 
 
    CHEM_GUY
(Hive Bee)
07-14-00 21:04
No 28801
      Re: Urushibara Style Amphetamine
(Rated as: excellent)
 Bookmark   

I'm glad it worked for you Ritter and thanks for the props!  The write up is excellent, and the commentary worth while.  Great job.

That Ultrasonic crap:


From "The Journal of the American Chemical Soceity", yr 1987, Vol 109,
 pages 3459-3461

"Hetrogeneous Sonocatalysis with Nickel Powder

We have discovered that ultrasonic irradition of Ni powder increases
 it's activity as a hydrogenation catalyst by >10^5.  ...

The use of high-intensity ultrasound to initiate or enhance both
 homogeneous and hetrogeneous chemical reactions has been under
 intense investigation [1-7],...

Simple Ni powder is an extremely inactive catalyst for hydrogenation of
 alkenes.  Even after 2 X 10^4 min, no alkanes are deteacted with rapid
 stirring under 1 atm of H2 at 273 K (i.e., <10 nM/min).  In comparison
 under the same conditions, if the nickel was first irradiated with
 ultrasound [12], 1-nonene is hydrogenated at millimolar per min rates,
 as shown on Figure 1.  Ultrasonic pretreatment of ~1 h gives optimal
activity, which decreases with longer irradiation.  The hydrogenation
activity is quite general and shows little dependance on the choice of
 alkene... ;  no reduction of ketones or aldehydes was observed.

Other methods of creating active Ni catalysts exsist [13].  The thermal
 hydrogenation rates at 1 atm of H2 and 273 K with high surface area Ni
 sponge (Raney Ni [13a], Aldrich Chemicals, grade W-2) are comparable
to those obtained eith ultrasoniclly activated Ni powder.  Compared to
 Raney Ni, however, our activaed Ni powder is more selective
(C-O double bonds are untouched), much easier to produce, and much
 simpler to handle (nonpryophoric).  Activation of Ni powders by H2 at
 150 C and 10 atm will also generate reactive catalysts [13b], which
rapidily lose activity upon exposure to O2.

..."

[1] Adv, Organomet. Chem. 1986, 25, 73. (b) Modern Syth. Methods 1986,
 4, 1. (c) Ultrasound:  Its Chemical, Physical and Boilogical Effects
 1987. (d) J Chem. Ed. 1986, 63, 427. (e) Ultrasonics 1985, 23, 157.

[2] J. Am. Chem. Soc. 1983, 105, 5781. (b)  J. Am. Chem. Soc. 1983,
105, 6042. (c)  High Energy Processes in Organomettalic Chemistry,
American Chemical Society 1987, p 191.

[3] High Energy Processes in Organomettalic Chemistry, American
Chemical Society 1987, pp 209-222. (b)  Organometallics 1986, 5, 1257.
 (c) Nachr. Chem. Tech. Lab. 1983, 31, 797. (d)  J Org. Chem. 1982,
5030.

[4] Ultrsonics 1987, 25, 40. (b)  Tetrahedron Lett. 1986, 27, 3149.
(c)  J. Org. Chem. 1985, 50, 910, 5761. (d)  J. Amer. Chem. Soc. 1980,
102, 7926.

[5] Angew. Chem., Intl. Ed. Engl. 1983, 22, 728. (b)  J. Am. Chem. Soc.
 1984, 106, 6856.

[6] Ultrasonics 1987, 25, 45. (b) J. Lab. Pract. 1984, 33, 13 and
references therein.

[7] Tetrahedron Lett. 1986, 27, 415. (b)  J. Am. Oil Chem. Soc. 1983,
60, 1257. (c)  Chim. Ind. (Milan 1968, 50, 314.

[12] All sonications were performed with a Heat Systems-Ultrasonics
W375 cell disruptor with a titanium immersion horn at acoustic
 intensties of ~50 W/cm^2 at 20KHz, as described elesewher in
detail [2].  Irradiation in a low-intenstity ultrasonic cleaning bath
 does give hydrogenation, but at greatly reduced rates.  Hydrogenation
 reactions were carried out at 273 K under 1 atm of H2.  In a typical
 reaction, 1 g of Ni powder (200 mesh, EM Science, Cherry Hill, NJ
08034) was added to a 10% solution of alkene in octane.  ...


[13] Reagents for Organic Synthesis 1967, by Fieser, L. F., Vol. 1,
pp 723-731. (b)  Thomas, C. L., Catalytic Porcesses and Proven
Catalysts 1970, pp 126-133.  (c) Somorjai, G. A.; Chemistry in Two
Dimensions: Surfaces; 1981, pp 445-447 (d)  J. Phys. Chem. 1983, 87,
915. (e)  High Energy Process in Organicmetallic Chemistry,
 ... pp 223-245.




Read my Disclaimer:  http://cantsueme.homestead.com
 
 
 
 
    CHEM_GUY
(Hive Bee)
07-15-00 03:55
No 28935
      Re: Urushibara Style Amphetamine  Bookmark   

I have only one question about the procedure that you've stated:  You say "At this point Urishubara nickel catalyst is prepared and ready for reduction."  But in the above passage you never describe activating the Ni powder with a either a caustic or acidic wash.

Did you take the Ni preceptitated with the Al and wash it before the addition of the nitro- and the conc. HCl?

Also I assume you are using 36% (by weight or 12 M) HCl.

Read my Disclaimer:  http://cantsueme.homestead.com
 
 
 
 
    Antibody2
(Hive Bee)
07-18-00 22:50
No 30169
      Re: Urushibara Style Amphetamine  Bookmark   

Would neutralizing a Nickle Carbonate from a potters supply with HCl and then reducing, yield the Nickel chloride hexahydrate required for this catalyst?

I know you mentioned  regular reynolds wrap, but purely out of curiosity does the Al thickness have the same relationship to the RXN that it does with Al/Hg reductions? ei can the RXN be slowed or speeded up by varying foil thicknesses?

What are the pitfalls a novice chemist might anticipate in pursuing this route?

Thanxs again for blazing a new trail fer us bees

Life is a dream (until someonew wakes you up)
 
 
 
 
    Bwiti
(Hive Bee)
07-25-00 12:58
No 32821
      Re: Urushibara Style Amphetamine  Bookmark   

If that synth doesn't belong on Rhodium's site, then I don't know what does ! It's official folks, the war on drugs is a joke. Good job Chem_Guy !!
}>

If there really was a God, I would have been forwarded to Hell a long time ago.
 
 
 
 
    Ritter
(Stranger)
07-25-00 21:02
No 32946
      Re: Urushibara Style Amphetamine  Bookmark   

Chem_guy:
Oops, forgot to mention activation of catalyst!  Add this between first and second paragraph:

Precipitated Nickel powder was added to 100ml 20% NaOH soln and manually stirred at 60'C for 30 min.  Excess NaOH is decanted and nickel is washed with 5 x100ml aliquots of distilled water to remove excess base.

 
 
 
 
    psyloxy
(Hive Bee)
08-04-00 14:20
No 36552
      Re: Urushibara Style Amphetamine  Bookmark   


Precipitated Nickel powder was added to 100ml 20% NaOH soln and manually stirred at 60'C for 30 min.


The 1st paragraph ends with ppt Ni in EtOH soln. Does one have to filter off the Ni or could one also pour the 20% NaOH directly into the EtOH ? If it has to be filtered, what would be the best way to do so ?

--psyloxy--

 
 
 
 
    Antibody2
( )
01-22-01 18:04
No 168829
      Re: Urushibara Style Amphetamine  Bookmark   

This is a trully awesome reduction. Not touchy at all. A FOAF triied it on TMP2NP,  temps were up to 60-70C during catalyst prep. The catalyst was not isolated , just 3ml of HCl was added after catalyst prep, to activate. Not even certain that precipitation had finished, but hydrogen evolution had stopped. Temps were in the mid-high 60s throughout reduction which only took 3 hours.

Yield was 60+%. (closer to 50% after clean up) Way cool for the 1st kick at the can. I am impressed! Its all OTC!

Question though. could methanol be substituted for the ethanol? Be easier to control temperature that way.

BTW - FOAF found that temp increased with stirring as did hydrogen evolution (causing beaker to foam over). something to keep an eye on.

Also to avoid Ni at interface while separating layers toss a magnetic stir bar in and stir with the NaOH douse. All the Nickel will stick to it, then you simply transfer the stirbar w/ nickel to beaker of HCl and stir to regenerate your NiCl2(H20)6. (takes a couple days though) Probably a little Al goes over to, Oh well.

Curious though, there is a white precipitate in the HCl as well, is this Aluminum Chloride? Be sweet if Alumninum Chloride isn't H2O soluble cuz it'll make seaprating the Ni easier.

Antibody is wearing one big assed smile!


Just gone.
 
 
 
 
    uemura
(Hive Bee)
01-24-01 16:05
No 169112
      Re: Urushibara Style Amphetamine  Bookmark   

Bingo! This is very good stuff. Thank you Ritter!smile
 
 
 
 
    Lem
(Newbee)
01-25-01 20:53
No 169343
      Re: Urushibara Style Amphetamine  Bookmark   

LOL!
Chemicals!?!?!? WE DON'T NEED NO STINKING CHEMICALS!!!!!
laughlaughlaugh
Great work guys!!!!


The only right we have is to believe that we have rights.
 
 
 
 
    Vibrating_Lights
(Hive Addict)
06-07-02 07:17
No 318466
      solution  Bookmark   

"Dissolve 5g pure phenyl nitropropene in 50ml Ethanol and add to nickel soln."????
 If the 5%NaOh was decanted off the percipitated Ni then washed with water how is there a solution.  Is the Ni first placed into some EtOH?  Or is the nitropropene/EtOH added directly to the ni.powder?
 
 
 
 
    Lem2
(Hive Bee)
06-09-02 01:28
No 318966
      asdf  Bookmark   

as far as I can tell, it is a typo, perhaps what was meant was:
"Dissolve 5g pure phenyl nitropropene in 50ml Ethanol and add nickel TO soln."

He who makes a beast of himself gets rid of the pain of being a man.
 
 
 
 
    Antibody2
(Rehabilitated)
06-09-02 15:55
No 319114
      add it directly to the nickel after decanting the ...  Bookmark   

add it directly to the nickel after decanting the activation solution. Your rxn will get very viscous as it progresses, requiring the addition of more EtOH. It wouldn't hurt your rxn to bring your volume up to 125mls EtOH. You will still end up with a viscous slush at the end.  If you look on Rhodiums page you will see my variation of this same rxn for TMA-2. Check solvent volumes there.

happy redxnssmile