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6) Reduction of Nitromethane

The lower nitroalkanes (sometimes refered to as nitroparaffins) are easily


reduced by a multitude of systems, but by far the easiest, and also the
highest yielding, is the Iron/Hydrochloric acid system. The reaction is:

4 RNO2 + 9 Fe + 4 H2O =HCl=> 4 RNH2 + 3 Fe3O4

First, your Nitromethane *may* require purification, especially if it was for


"fuel" use. In this case, it needs to be vacuum distilled at a vacuum of better
than 100mm Hg. At that pressure, it will come off at ~47C. Distillation at
atmospheric pressure is possible, but I do not recommend it due to the highly
flammable nature of the compound and because it's flash point is 42C. It's
your choice.

*CAUTION*
The lower nitroalkanes form shock and/or temperature sensitive EXPLOSIVE
compounds with amines and hydroxides. BE CAREFUL, DAMNIT! You have
been warned.

Assemble a 500mL RB flask with claisen adapter, thermometer down the


center to read the liquid temperature, and reflux condenser with a cork and
tube leading to a beaker of 1M Hydrochloric acid. Drop a stirrer magnet in,
then add 105g of 40 Mesh Iron filings, 225mL of water and 1g of Ferric
Chloride. Next, add 35mL of concentrated Hydrochloric Acid ("muriatic acid"
is ok). When the bubbling ceases, add 31g of Nitromethane.

Heat the reaction mixture to 100C and hold for 14 hours. A temperature
regulator is necessary if using a heating mantle, else use a large boiling
water bath (if you will be doing it overnight, so it doesn't run out).

At the end of this time, allow to cool then add enough 25% Sodium Hydroxide
solution to to get the pH above 11. Heat on a water bath or with gentle
electric heat to drive the Methylamine off as a gas into the same beaker of

Hydrochloric acid used as a trap during the reaction.

Evaporate the beaker contents to dryness on a glass plate in the oven to


collect the crystals of Methylamine HCl (hygroscopic!). The yield should be
approximately 15g (95%).

*NOTE*
Alternately, you may want to try using a Tin/HCl system which will give an
equivalent yield in a much shorter time with the disadvantage that Tin is a
much more expensive metal. The balanced equation for the reduction follows:

2 CH3NO2 + 6 Sn + 12H+ 2 CH3NH2 + 3 Sn(IV) + 4 H2O

Cognate procedure: Setup a flask with reflux condenser in which .25 mol of
nitromethane, .38 mol of granulated tin metal and a stirrer magnet have
been added. Carefully pour 115mL of 31.45% hydrochloric acid (muriatic
acid) down the reflux condenser in 10-15mL increments, waiting for the
reaction to settle down before pouring the next aliquot. If the reaction seems
to get out of hand (excessive frothing, vapor escaping the reflux condenser,
etc...) then quickly slide an ice bath in place until it slackens back down. Once
all the HCl has been added, heat the mixture to reflux with an electric mantle
for 1hr. At the end of this time, allow to cool, preferably in an ice bath, then
add, carefully, a chilled solution of 75g sodium hydroxide in 125mL of water.
If the flask contents start to bubble violently you will watch your yield go out
the window, so add slowly! Since methylamine readily dissolves in water, you
will need to distill the reaction contents carefully to first liberate the 40%
constant boiling solution (bp: 53C) and then the gas itself. The product is
best captured by bubbling the distillation vapor into a beaker of hydrochloric
acid (use a slight molar excess of HCl to insure no loss). Proceed as above by
evaporating the bubbler solution to yield the crystals (take care when
evaporating HCl solutions, as the excess acid will vaporize into the air,
corroding ovens, lungs, etc...). [Vogel's, pg 892]

Additional notes - Nitromethane is found in high performance RC model fuel,


usually as a mixture with methanol and various strange lubricants. One
particular brand, found at a local hobby shop, was 55% nitromethane.

Better method...

The soln is then saturated with 5g methylamine, obtained by dripping a


saturated soln of 15g MeNH2HCl onto 10g NaOH, dried thru NaOH.
The ratios used:

100g hexamine

- 500g HMTA

100g water

- 500g H20

310g HCl 30%

- 1550g HCl

100g ethylalcohol denat.

- 500g EtOH

20g ammoniumchloride

- 100g NH4Cl

145g Methylamine.HCl in theory

The hexamine from fuel tablets (which are 100% pure here where I live) was
dissolved in 100ml water - not all hexamine went into solution. The HCl and
the alcohol where mixed and chilled and then slowly added to the hexamine,
at start some fumes evolved. This mixture was put in a 2l flask which was
equipped with a vigreux column (40cm) and a downright condensor, a
thermometer into the flask and a thermometer at top of the column. The
column was cooled by a fan (12V/8cm computerpart). Boilingstones (broken
flowerpot) were added and heat applied by means of a waterbath.
At 75C boiling started. The reaction was held at a steady reflux for about 2
hours then some liquid started coming over at 50C to 60C (measured on
top of the column). Probably the ethylformate - what else. This ceased after
about one hour and for the good of it the reaction was refluxed for one more
hour. Then the column was removed and the water distilled away under
aspirator vacuum. The temperatur in the flask never got higher than 90C. As
the water was mostly removed and a yellow slush remained in the flask, IPA
was added and the slush extracted. Three portions of IPA 200ml/100ml/100ml - brought to a boil and decanted. A snowwhite remainder

stayed in the flask - ammoniumchloride.


The extracts which of course contained some ammoniumchloride were joined
and set up for distillation. About one third of the liquid was boiled away
(azeotropic removal of remaining water) - some heavy bumping appeared at
the beginning also fresh boiling stones had been added. This was done to
remove remaining water by the azeotrope. The remainder was filtered hot
through a flutet filter for to remove the last ammoniumchloride.
The IPA was put on my balcony (a usual freezer might be substituted here)
and forgotten. After about 12 hours the jug was full of beautiful crystals, the
remaining IPA was poured out and - concentrated again and treated like
before.

The crystal were spread out and dried on a hot waterbath - careful methylamine is VERY hygroscopic!
A chloroform wash produced almost no dimethylamine - I actually guess there
was no dimethylamine at and the three grams produced by the chloroform
wash were by traces of water present in the chloroform.
Yield: 125g, 145g would be theory so thats ok for me.

Methylamine solution (shiff base)


An exothermic reaction occured with separation of water; start refluxing with
a Dean-Stark trap attached to the reflux condenser to collect the water that is
generated in the reaction. When no more water separates, distill off the
solvent(because Na2SO4 is used, it is probably not necessary to reflux with a
dean stark trap
According to the Merck Index, a saturated solution of methylamine in
benzene is 10.5 g MeNH2 in 100 ml benzene at room temp. Prepare the
benzene/methylamine solution by bubbling methylamine gas into benzene at
0C.
(use xylene or toluene)

Dreamer:

Yesterday i had a dream, i tried to reduce P2NP (phenyl-2-nitropropene)


to
amphetamine with amalganated Al. I amalganated 20gr of Al. To this 20gr
Al
i added 0.1 mol P2NP in 150ml Tetrahydrofuran (YES, tetrahydrofuran
with
his peroxides). The 150ml didn't cover the foil in the 1l Flask and i
added
another 150ml :). I putted the condensor on the flask and all was
immersed
in ice cold water!! (very important) Then i added slowly, in 10ml steps
100ml of a solution of (100ml 31% HCl and 50ml H2O), i didn't have 25%
HCl.

The reaction TE climbed to 50. To keep up the generation of bubbles i


added after 45 min the last 50 ml of HCl slowly in 10ml steps. The
whole
mixture colled down to 20 and i let stand everything over night. Next
day
i made all very basic through slowly addition of 50% NaOH (~100ml).
When i
saw that with the addition of NaOH generated other bubbles,so i let
everything stand again for 4h. Then i filtered the whole solution with
a
Buchner funnel, which was quite tedious because the grey shit is
plugging

(that should be "verstopfen" in english, http://www2.echo.lu/edic/ is a


really good page for someone, who didn't follow english lessons at
school)
the filter paper. Well, after 2h all was filtered. I extracted with
3*75ml
with a mixture of Chloroform and DCM (because once i recovered DCM i
poured
it to chloroform --> errors of a computerfreak, which is playing the
chemist), i washed with 500ml of 10% NaOH (maybe an error, if
amphetamine
dissolves in diluted NaOH, a lot of the product could be loosed, is
this
true ?) the solvents where recovered and a red oil was the result.

Now i made the sulfate salt instead of the HCl salt, because the
sulfate is
not so soluble in water (1part in 8.8parts of H2O). I added 2ml of the
oil
to 20ml of ether and a few drops of 96% H2SO4, i got amorphic crystals.

I tried with 20ml den. 90 ethanol, again only amorphic crystals,


maybe to
many impurities, so one should distill the amphetamine freebase at
102(13)
under vaccuum. I couldn't, because my vaccum setup exploded a week ago.

(while heating a mixture under vacuum i didn't realize, that the water
trap
of my vacuum hose was damaged, so the pressure in the glass of my
vacuum
distillation setup, which was not fixed, growed, pushed the glassware
out
of the ground joints, ...,) So i poured the last ~10-12ml of red oil to
the
amorphic crystals in a 30ml 90% den. ethanol. I added a little bit of
96%
H2SO4. I waited 1min and i got a dense red-white mass. Remembering
eleusis's acetone wash of mdma, i poured 100ml of acetone into the
mass, a
lot of crystals separated out. Everything seemed ok, but when i tried
to
add more acetone i mixed up the 95% H2SO4 with the acetone (same color
of
the flask :(() and i poured 5ml of 96% H2SO4 in the Acetone, den.
Ethanol
and Amphtamine Sulfate. There was a lot of fizzing and the crystals
disappear !???!!!

WHY ?WHY ?WHY ?

Does acetone react with conc. sulfuric acid or ethanol and did one of
these

reaction byproducts destroy my amphetamine sulfate?

Recovering the other crystals from ether gave 1 gr of brown-white with


acteone washed crystals. I don't know how high the yield is, maybe
around
50%.I am sure that i can improve this reduction, because i was really
imprecise.

When i used tetrahydrofuran there where two layers. Is it ok if there


are
two layers with the P2NP in the organic layer, without an alcohol, that
dissolves P2NP even in the water layer? Would it raise the yield if i
add
some Alcohol? Could it be that in such a reduction with amalganated Al
the
solvent is reduced too (acetone, methyl ethyl ketone -->in denaturated
ethanol) and reduces the reduktion power of the reaktion?
It is impossible for me to get methanol and pure isopropylalcohol
without
acetone (i can get tetrahydrofurane or ethyl ether like distilled
water,
but so funny it sounds no mathanol and 1l pure isopropyl alcohol costs
like
95% ethanol). Is there a possibility to eliminate all chemicals beside
methanol and ethanol, and what does denaturated 1category mean?

If the TE of such a reduction is kept low, will this reduction work for
MD-P2NP and is it possible to make a sulfate salt of MDA with a low
solubity in water too?

[www.rhodium.ws] [] [Chemistry Archive]

Reduction of Nitroalkenes with Aluminium Amalgam


Translation and Compilation by Antoncho

HTML by Rhodium
I. Introduction

This procedure describes an efficient, high-yielding and completely OTC way


of reducing virtually any nitrostyrene OR phenyl-2-nitropropene using
aluminium amalgam.

Initially this approach to reducing nitroalkenes was pursued by SunLight1


based on an old German reference2. However, due to the suboptimal work-up
strategy, his results were far from ideal, which lead to this direction of
research being almost completely buried in vain.

Luckily, some four years later an adventurous HyperLab Bee (who modestly
wished to remain anonymous) decided to once again take a look at this
procedure. His experiments ended in a complete and unquestionable
success!

This news was privately communicated to certain reputable Hive and


HyperLab members (who also wished to keep their names private) in order to

verify the author's results. Very soon they also reported a pronounced
success with this reaction.
II. Experimental

#1: The original procedure by Hyperlab Bee #1.

Into a 3 liter kitchen jar.....yes, exactly :-).

So... into a 3 liter kitchen jar theres placed:

- 75 mmoles of any nitrostyrene or phenylnitropropene (that should bee ~20


g) [Note 1]
- 200 mls GAA
- 300 mls IPA
- 100 mls water
- 0.75-1.3 g Hg(NO3)2 [Note 2]

Lastly, 40 g of kitchen Al foil is dumped into the soup.

The suspension is incubated for 30-40 mins after which it assumes black color
and starts heating up.

At this moment SWIM simply takes the whole shebang and shakes it violently
until the full dissolution of the nitro. At this point the mixture is usually
vigorously boiling and is so hot that it can't bee held with bare hands.

From that moment the reaction proceeds for 5-10 mins, leaving a grey
aluminous sludge as the result. The sludge is immediately dissolved in 300 g
KOH in 800 mls water (which makes the mixture again boil so violently that

the jar's bottom once fell off - after that we switched to using plastic
canisters). Surprisingly, this treatment seems to not harm the product at all

The result is a two-phase mixture, the upper layer being the desired amine in
IPA.

The procedure has been tested multiple times on the nitroalkenes


corresponding to TMA-2, TMA-6 and 2C-H. It always gave yields not less than
70%. [Note 3]

[Note 1]: the nitroalkene must bee purified (rextallization from IPA) as much
as possible. Using dirty nitroalkenes results in a sharp drop in yield.

[Note 2]: the actual quantity of mercuric salt was never accurately measured
- SWIM just added it at the tip of the knife.

[Note 3]: The lowest yield thus far was 12 mls of 2C-H freebase from 20 g of
2,5-diMeO-nitrostyrene.

Credits:

The author wants to thank:

Jess The Rabbit - the Muse, without whom nothing of the above would ever
happen!

SunLight for his original work that has been the source for everything that
happened.

Bees of HyperLab:

- Earendel for being of an invaluable help


- Mescalito for pointing the author's attention into this direction.
- Antoncho for his assistance in translation and being a friend :-)
Experimental

#2: The experimental trials by Hive Bee #1.

A 3-necked 2L RB was equiped with a reflux condenser and a magnetic


stirbar. The setup was charged with 100 mL GAA, 50 mL H2O and 150 mL IPA.
The mixture was stirred and 1.0 g Hg(II) chloride was added. When all salt
was dissolved, 10.0 g 4-methoxyphenyl-2-nitropropene was added.

21 g Al foil was ripped in small pieces (ca 1 x 3 cm) which were pressed (not
firmly) into bals. When the nitropropene went into solution, the Al foil was
added one ball after the other. The initially yellow solution colours greenish
with a hint of black, and as the reaction proceeds, changes to a unattractive
grey. All Al is added over a 30 min period. This prevents the reaction mixture
from overheating. Alot of heat is produced during the reaction... When I
noticed that gas evolution and bubbling of the slurry had stopped, I decided
to add another 100 mL GAA (2 x 50 mL). This restarted the reaction.

About 90 minutes after addition of the Al, the reaction mixture was treated
with aqueous NaOH: first with 150 g NaOH in 400 mL water, followed by 75 g
NaOH in 200 mL water and by 50 g NaOH in 150 mL water. This reaction is
very exothermic, so beware... When all aqueous NaOH was added, there were
two phases, viz a clear orange upper layer with IPA smell and the Al sludge.
The orange layer was isolated and diluted with aqueous HCl (20 mL conc HCl
+ 80 mL H2O). The mixture was extracted with DCE (2 x 40 mL). The organic
layer had a red colour, while the aqueous phase had a yellow appearance.
The latter was made alkaline with 5 M NaOH solution and extracted with 100
mL chloroform. The organic phase was dried over anhydrous sodium sulfate
and the solvent removed under reduced pressure and recuperated. This
yielded 5.9 g of an amber oil.

Yield: 69.9%

Notes

I have had the impression that impure nitropropene does have a negative
influence on the yields, as was stated by HyperLab Bee #1 as well. I have
tried TMA yesterday, and yields were awful. The starting nitropropene,
however, was far from pure. Today, I tried a new 4-MA batch with impure
starting product; 20.0 g 4-methoxyphenyl-2-nitropropene yielded 5.0 g
freebase after the workup I previously described. However, my end products
have always been very pure.

I made a small modification, however. Of the 40 g Al that I added, there was


only 5 g made available for the reaction start. Once the reaction started (in a
violent way), the reaction was maintained by gradually adding all Al, each
addition being accompanied by another small portion of Hg salt. This way,
there was no solvent loss via the reflux condenser. Also, when no more fumes
escaped from the top of the condenser, additional GAA was added. This did
not restart the reaction, even though some Al was clearly left unreacted.

#3. Reduction of 3,4-methylenedioxy-P2NP by Hive Bee #2.

55 g recrystallized 3,4 methylenedioxyphenyl-2-nitropropene was dissolved in


a warm solution of 600 mls HOAc and 1000 mls IPA in a 5Liter flask with
magnetic stirring and heating mantle. 1 g HgCl2 dissolved in 300 mls H2O
was added and mixture was brought up to 60 C. A total of 90 grams of
regular thickness kitchen aluminum foil was shredded by folding a sheet in
half(doubling it over) and running it through a cross-cut paper shredder. This
was added in 20 gram portions at a rate which kept the temperature at
approx 70 C for the entire rxn. Mag stirring was not impeded by using foil of
this type and the rxn was over in about 4 hours. 1000 mls 50% NaOH soln
was added at a rate which prevented boiling over, phases separated and the
liquified Al/NaOAc phase was tapped off leaving a light orange IPA soln
organic layer in the funnel. IPA was stripped off at the rotovap leaving behind
a thick deep red oil which smelled of amine. Acid/base cleanup resulted in a
dark red oil which was not suitable for crystallization. Oil was distilled (105108C, 1.5 mmHg) to yield 32 grams (approx. 65% yield) of water-white MDA

base.

Notes:

Experiments were performed on 50 g substrate


1) HOAc reduced to 500 ml, Al was reduced to 60 g. Yield = 24 g MDA base

2) HOAc reduced to 500 ml and 100 g aluminum was divided into three
portions of 33 g which were added as the previous increment was consumed.
Yield = 35 g MDA base.

#4. Reduction of unsubstituted P2NP by HyperLab Bee #2.

Into a 3-L FBF there was placed 100 mls water, 250mls GAA and a solution of
1g mercury in 2-3 mls conc. HNO3.
52 g (2 packs 10 meters each) of Al foil were folded into 7-8 layers, cut in
pieces 3x3 cm and loaded into the flask.
The flask was heated to 40 C. When the start of amalgamation was clearly
visible in several minutes, heating was discontinued and into the reaction
there was added a suspension of 30 g non-recrystallized phenyl-2nitropropene in a mixture of 50 mls GAA and 100mls IPA (nitropropene was
obtained a la Bariums MeAm condensation - an important notion since this
method gives the product of superior purity).

The next 5-7 minutes the reaction proceeded rather smoothly... I only turned
away from it for some half a minute... and when I turned around once again I
saw that the mixture inside the flask tries to surpass the last inches of the
flasks neck! Grabbing the flask I rushed to the sink..... and then..... it was like
as if I was standing on Baikonurs starting table trying to hold back the
rocket-launcher Soyuz during its blastoff.... The reactive stream of "exhaust
gasses" hydrogen and IPA vapours - was quite something.

Thanks goodness, cooling helped and the foam only slightly escaped the
flask. The fireworks lasted for a minute or two, after which the flask was
placed into a cold water bath for 15 mins and its contents were periodically
shaken by hand. Cooling was removed and the reaction was allowed to stand
for another 40-50 minutes. At first the temperature held itself at 85
spontaneously, then a little heating had to bee applied.

The obtained grey porridge in which there still was some unreacted
aluminium was cooled and cautiously basified with 500 g KOH in 500mls
water. Two layers formed: the lower, aqueous, with some unreacted
hydroxides and the upper, consisting of IPA and the product. The mixture was
extracted with 2x150 mls ether, the pooled extracts dryed and the solvent
stripped off at rotovap. 25 g of crude amphetamine base was obtained as a
muddy (inorganics) liquid of skin color.

It was vacuum distilled with a short column. 1st fraction 0.8g, b.p. 67-72 C/6
mmHg, 2nd fraction the product, 20.8 g, b.p.72 C. And this is despite
heating with a gas flame, instead of a bath!

So, the yield was 20.8g (83.5%) of a crystally clean product. And if we are to
count the 1st fraction, from which a goodly amount of a colorless sulfate was
later made, we get a yet higher figure. Moreover, a certain quantity of
amphetamine was lost in rotovap the baths temperature was 80 and
vacuum around 20 C. In the morning it formed white granules of carbonate
on the rotors walls.

In addition I want to note that the quantity of foil used can bee evidently less
as it doesnt react fully anyway. I think 30-35 g should bee enough.

Another note I researched a little the reaction of Al foil with various


proportions of water:IPA:GAA and it appears that the originally used mixture
gives the fastest reaction rate.

Well, that's it. I'm throwing all my LAH into the trashcan tomorrow morning :-)
References

Sunlight, Reduction of 2,5-Dimethoxynitrostyrene (1999)


Monatsh. Chem. 79, 72-77 (1948)

Direkte Reduktion des Nitrokorpers zum Amin:


1g 2,3-Dimethoxy--nitrostyrol wurde in einer Mischung von je 1ccm.
Essigsaure, Alkohol und Wasser in der Warme gelost und 2g feine Al-Spane
eingetragen. Die Reduktion kam nach Zusatz von wenig HgCl2 in Gang und
wurde nach etwa 2-stundigem Stehen bei 20C auf dem warmen Wasserbade
vervollstandigt. Die Aufarbeitung erfolgte in analoger Weise wie bei der
Reduktion des Oxims. Bei der Destialltion erhielten wir im ganzen 0.58g
Destillat (bei 1 Torr und 80 bis 110C Luftbadtemperatur), das 0.67 g Pikrat
lieferte.

Translation by Osmium (1998):

Direct reduction of the nitro compound to the amine:


1g 2,3-dimethoxy--nitrostyrene was dissolved by warming in a mixture of
1ml AcOH, 1ml EtOH and 1ml H2O and 2g fine Al turnings were added. The
reduction started after the addition of some HgCl2 and was completed by
heating on a warm water bath after standing for two hours at RT. Workup was
done in an analogous manner to the oxime (apparently filtration, solvent
remolval, acid-base extraction). 0.58g was obtained after distillation at
1mmHg, 80-110C, air bath temperature. From that 0.67g of the picrate salt
was obtained.

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