# Safe reduction of P2NP in small batches using NaBH4 and CuCl2



## Uncle Lee

For small batch reduction of P2NP, this method is faster and safer than using aluminum foil and mercury salts, and there are no toxic mercury salts in the reaction,and the yield of this reaction is relatively high

1-phenyl-2-nitropropene - 5 g (0.031 M, 1 eq), m.p. 65-66C
NaBH4 - 8.5 g (0.225 M, 7.2 eq)
THF - 120 ml
H2O - 60 ml
CuCl2 * 2 H2O - 0.53 g (0.0031 M, 0.1 eq), solution in 3 ml H2O

A 500 ml three-necked flask equipped with adequate RO, addition funnel and thermometer is charged with 80 ml of THF and 60 ml of water. NaBH4 was then added to the flask all at once, 7.2 equivalents, 8.5 g, stirring was turned on, and the flask was placed in an ice bath of snow and water. The nitroalkene, dissolved in 40-45 ml of THF, was carefully added via addition funnel, and after about half of the solution had been added, the flask was removed from the ice bath and the rate of addition of THF+RNO2 was increased. By the end of the addition, the temperature in the flask, the contents of which turned white, was about 45-50C - and, without thinking twice, a solution of 0.53 g CuCl2 / 3 ml H2O was added from a syringe through a reflux condenser. Copper chloride was added in one portion, very quickly, and Pm instantly turned black with a violent evolution of hydrogen. The temperature continued to be in the region of 50C - despite the obvious exotherm that took place inside. The released hydrogen thus cools Pm due to its "evaporation". The flask was then gently heated until the thermometer read 64-66C. At this moment, firstly, the active evolution of hydrogen stops and THF itself begins to boil. At the same time, secondly, Pm is clearly divided into 2 phases - an almost transparent upper layer and a lower layer black from copper. Swim thinks that a rise in temperature from 45-50C to 65C (Bp THF) is a very convenient indicator of the progress of a reaction.

Then Rm was cooled in an ice bath to 20C, and 15-20 ml of 37% hydrochloric acid was added through an addition funnel - no active reaction was observed, therefore, all the NaBH4 was consumed in the reduction process. After that, the flask was again cooled to 15–20°C, and 30–35 g of NaOH in ~150 ml of water were added through the same dropper. After a short stirring, Rm again divided into layers - and the lower, inorganic, became orange in color (as I understand it, the Cu-NH coordinate complex collapsed and copper was released in free form). And most importantly, there was a minimal amount in the organic phase of copper. This, of course, is by eye. Just in case, edible salt was added to Rm, and all the contents were poured into a separating funnel. The lower layer was extracted with a mixture of MTBE + THF (25+25 ml), the extract was combined with the main layer of THF and diluted with 40 ml of MTBE. After that, the organics were washed with 15% NaOH solution and saturated NaCl solution, dried with Na2SO4, and then neutralized with a weak solution of H2SO4 in CH3CN, diluted with ice-cold acetone, filtered and washed again thoroughly with acetone.

Yield: 4.3 g of 1-phenyl-2-aminopropane as sulfate salt.


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## Hip-Hop-Gruppe

Wow, how it's working? 
Can i use this reaction for DOH?


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## Uncle Lee

This reaction is applicable to the reduction of most non-halogenated nitroolefins


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## G.Patton

Uncle Lee said:


> This reaction is applicable to the reduction of most non-halogenated nitroolefins



Uncle LeeHi. Can you send an origin of this information, please?


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## Uncle Lee

Of course
This method has only become popular in the West in the last ten years. In recent years, it has quickly become the most popular method. The disadvantage is that it can only be produced in small batches. I have more experience with this reaction.


the hive archive


You can get the information you want from here, even pictures
Any questions can PM me


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## DEA:)

RnO2 is a gas right? what kind of device is used for releasing it into the reaction? It sounds good to not have to mess with mercury. Really RnO2? isnt radon radioactive? Or is it rNO2? whatever this is



> general procedure:
> add nabh4 (7.7 mol eq.) to ipa and water and stir until everything dissolved. then add the nitroalkene (1 mol eq.) in small portions (allow to react until the yellow colour has disappeared before adding the new portion). dissolve cucl2 (0.1 mol eq.) in water and add to the reaction mixture in one portion. reflux for one hour (one drop every two seconds). steam distill (if amine is steam volatile) or normal a/b workup.


here is nothing about gases, i think i am too uneducated for this


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## G.Patton

Uncle Lee said:


> the hive archive



Uncle Leethanks!


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## G.Patton

DEA:) said:


> RnO2 is a gas right? what kind of device is used for releasing it into the reaction? It sounds good to not have to mess with mercury. Really RnO2? isnt radon radioactive? Or is it rNO2? whatever this is
> 
> 
> here is nothing about gases, i think i am too uneducated for this



DEA:)It means NO2 in THF solution.


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## Uncle Lee

About radon gas is my mistake. For the production of amphetamine, in fact, only sodium borohydride, copper salt (copper chloride or copper sulfate) and P2NP are needed, and the equipment only needs equipment that can be heated and stirred and refluxed and a thermometer, and the solvent can be IPA instead of THF, only simple modification steps are needed


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## DEA:)

ah, thx for clearing this up, awesome, will read me into this


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## DEA:)

Uncle Lee said:


> About radon gas is my mistake. For the production of amphetamine, in fact, only sodium borohydride, copper salt (copper chloride or copper sulfate) and P2NP are needed, and the equipment only needs equipment that can be heated and stirred and refluxed and a thermometer, and the solvent can be IPA instead of THF, only simple modification steps are needed



Uncle Lee
hi uncle lee, 
could you please elaborate the simple modifications needed to use IPA rather than THF? that would be awesome  thx


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## Uncle Lee

Nitrostyrene 32 (2.77 g, 10 mmol) was added carefully in portions to a stirred suspension of NaBH4 (2.84 g, 75 mmol) in IPA (32 ml) and water (16 ml) causing an exothermic reaction increasing the temperature of the mixture to 50-60°C. Thereafter a 2M solution of CuCl2 (0.5 ml, 1 mmol) was added carefully dropwise causing further exothermicity. The reaction was then held at 80°C for 30 minutes using external heating. After reaching r.t, a 25% solution of NaOH (20 ml) was added under stirring and the phases were separated. The aqueous phase was thereafter extracted with IPA (3x30 ml). The extractions were combined, dried over MgSO4 and filtered. A stoichiometric amount of 4M HCl in dioxane was added to the filtrate under stirring. The mixture was evaporated yielding a greyish sludge that was suspended in dry acetone and stirred for 1 h. The suspension was thereafter filtered and washed with dry acetone to yield 33 as a colorless amorphous solid (2.02 g, 71%).

This is the original method, for more you can check the site I sent above, this site can be viewed with TOR browser and JS off


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## amines2Nend

Uncle Lee, this is a great reaction! Some more info here, all taken from the more recent information linked above:
a c++ script to auto calculate your ratios:


> #include <bits/stdc++.h>
> using namespace std;
> int main()
> {
> double grams;
> string name;
> map<string,double> m;
> m["dimethoxynitrostyrene"] = 209.20;
> m["trimethoxynitrostyrene"] = 239.22;
> m["p2np"] = 163.17;
> m["mdp2np"] = 207.18;
> double nabh4_mm = 37.83;
> double cu_salt_mm = 159.61;
> double nabh4_n_coefficient = 7.714;
> double cu_salt_n_coefficient = 0.015;
> cin >> grams >> name;
> double nitroalkene_n=grams/m[name];
> double nabh4_n = nabh4_n_coefficient * nitroalkene_n;
> double nabh4_m = nabh4_n * nabh4_mm;
> 
> double cu_salt_n = nabh4_n * cu_salt_n_coefficient;
> double cu_salt_m = cu_salt_n * cu_salt_mm;
> cout << grams << " g, " << nitroalkene_n << " mol " << name << endl;
> cout << nabh4_m << " g, " << nabh4_n << " mol NaBH4" << endl;
> cout << cu_salt_m << " g, " << cu_salt_n << " mol Cu salt" << endl;
> return 0;


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## amines2Nend

Also from the referenced sources: a Detailed write up for synthetic mescaline! Same exact method


> Quote from: Orange on February 14, 2021, 07:25:49 PM
> hxxps://en.wikipedia.org/wiki/Nickel_boride_catalyst so with copper its not forming?!
> No with copper its predominantly nanoparticles.
> They made a paper about it and its linked in here.
> Title: Re: P2NP to amine with NaBH4-Copper. One pot, no messing with metals or
> acids.
> Post by: Orange on February 14, 2021, 07:31:19 PM
> interesting.. so my first thought and claim back then was actually right xD
> Title: Re: P2NP to amine with NaBH4-Copper. One pot, no messing with metals or
> acids.
> Post by: blade_runner on February 14, 2021, 09:48:56 PM
> Sometimes you can physically see little streaks of copper in the reaction flask...
> Title: Re: P2NP to amine with NaBH4-Copper. One pot, no messing with metals or
> acids.
> Post by: Orange on February 14, 2021, 10:59:18 PM
> for me its all black, when i add base and heat it turns into copper colored shards
> Title: Re: P2NP to amine with NaBH4-Copper. One pot, no messing with metals or
> acids.
> Post by: sparklebags on February 15, 2021, 02:36:15 PM
> I also reduced the MeOH volume from the numerous recrystallizations - there was a fair
> amount of yellow shiny crystals left in the solution. Essentially not as big and pretty as
> the main volume, not sure if this is worth recovering or of high enough quality to use. It
> appears to just be smaller shards of the larger crystals.
> Title: Re: P2NP to amine with NaBH4-Copper. One pot, no messing with metals or
> acids.
> Post by: aes256 on February 16, 2021, 02:23:25 PM
> Orange's method for the reaction; H2SO4/Acetone workup; carried out in 3-neck 250 mL
> FBF with good stirring, temp at ~22-24 C.
> 2.80 g NaBH was added to a chilled FBF of 20 g IPA + 20 g H2O. Fizzing immediately
> occurred, the reducing agent dissolved readily upon initiation of stirring.
> 2.75 g 3,4,5-TMNS was added in small portions (about a green pea in volume), letting
> the yellow of the nitrostyrene disappear and convert to white before adding the next
> portion, being careful to not let the temp get too close to 25 C.
> 0.2 g CuSO4 in 2 mL of water was added in one go. Solution immediately turned black
> with black precipitate forming at the interface between the solution and the flask wall.
> The flask was manually agitated in order to get the solution to swirl the precip back into
> itself, then left to reflux for 1 hour at about a drip rate of 1 drip/ 2 seconds.
> The reaction mixture was cooled and 2 g NaOH pellets added. The now alkaline solution
> 
> gave off flickers of elemental Cu. pH strips indicated it was about 10-11 so another 1 g of
> NaOH was added for good measure.
> The aqueous layer settled to the bottom after about 10 minutes. The next day it was
> removed by pipette, leaving the alkaline IPA mixture behind. This slightly sludgy mixture
> was easily and quickly filtered through a cotton ball in a funnel.
> The "dark Cognac" filtrate was slowly neutralized with drops of H2SO4 from a eye-
> dropper, giving off "explosive" vaporous puffs with each addition, and almost congealing
> the solution with its thickness. The solution was swirled to distribute the acid and then 2x
> the volume of dry acetone was added to draw up impurities, precip any remaining
> product, and make the whole thing easier to work with.
> The product was filtered on the pump, washed 2x with cold, dry acetone at the pump,
> and air dried.
> Yield: 1.9g mescaline sulfate; 53.4% molar yield.


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## MadHatter

Can copper chloride be replaced with copper sulphate?


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## Uncle Lee

Yes, you can


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