methylamine with etoh

8/9/2019 Methylamine With Etoh

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6) Reduction of Nitromethane

The lower nitroalkanes (sometimes refered to as nitroparans) are easilyreduced by a multitude of systems, but by far the easiest, and also the

highest yielding, is the Iron!ydrochloric acid system" The reaction is#

$ RN%& ' e ' $ !&% *!+l* $ RN!& ' - e-%$

irst, your Nitromethane .may. re/uire puri0cation, especially if it was for1fuel1 use" In this case, it needs to be 2acuum distilled at a 2acuum of betterthan 344mm !g" 5t that pressure, it will come o at 7$89+" :istillation at

atmospheric pressure is possible, but I do not recommend it due to the highly;ammable nature of the compound and because it?@A%BIC>compounds with amines and hydroDides" E> +5R>=A, :5FNITG Hou ha2ebeen warned"

5ssemble a 44mA RE ;ask with claisen adapter, thermometer down thecenter to read the li/uid temperature, and re;uD condenser with a cork andtube leading to a beaker of 3F !ydrochloric acid" :rop a stirrer magnet in,then add 34g of $4 Fesh Iron 0lings, &&mA of water and 3g of erric+hloride" NeDt, add -mA of concentrated !ydrochloric 5cid (1muriatic acid1is ok)" Jhen the bubbling ceases, add -3g of Nitromethane"

!eat the reaction miDture to 3449+ and hold for 3$ hours" 5 temperatureregulator is necessary if using a heating mantle, else use a large boilingwater bath (if you will be doing it o2ernight, so it doesn


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!ydrochloric acid used as a trap during the reaction"

>2aporate the beaker contents to dryness on a glass plate in the o2en tocollect the crystals of Fethylamine !+l (hygroscopicG)" The yield should be

approDimately 3g (K)"

.N%T>.

5lternately, you may want to try using a Tin!+l system which will gi2e ane/ui2alent yield in a much shorter time with the disad2antage that Tin is amuch more eDpensi2e metal" The balanced e/uation for the reduction follows#

& +!-N%& ' 6 Bn ' 3&!' & +!-N!& ' - Bn(IC) ' $ !&%

+ognate procedure# Betup a ;ask with re;uD condenser in which "& mol ofnitromethane, "-L mol of granulated tin metal and a stirrer magnet ha2ebeen added" +arefully pour 33mA of -3"$K hydrochloric acid (muriaticacid) down the re;uD condenser in 34M3mA increments, waiting for thereaction to settle down before pouring the neDt ali/uot" If the reaction seemsto get out of hand (eDcessi2e frothing, 2apor escaping the re;uD condenser,etc""") then /uickly slide an ice bath in place until it slackens back down" %nce

all the !+l has been added, heat the miDture to re;uD with an electric mantlefor 3hr" 5t the end of this time, allow to cool, preferably in an ice bath, thenadd, carefully, a chilled solution of 8g sodium hydroDide in 3&mA of water"If the ;ask contents start to bubble 2iolently you will watch your yield go outthe window, so add slowlyG Bince methylamine readily dissol2es in water, youwill need to distill the reaction contents carefully to 0rst liberate the $4Kconstant boiling solution (bp# -9+) and then the gas itself" The product isbest captured by bubbling the distillation 2apor into a beaker of hydrochloricacid (use a slight molar eDcess of !+l to insure no loss)" @roceed as abo2e bye2aporating the bubbler solution to yield the crystals (take care when

e2aporating !+l solutions, as the eDcess acid will 2aporie into the air,corroding o2ens, lungs, etc""")" OCogel


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Eetter method"""

The soln is then saturated with g methylamine, obtained by dripping asaturated soln of 3g FeN!&Q!+l onto 34g Na%!, dried thru Na%!"

The ratios used#

344g heDamine M 44g !FT5

344g water M 44g !&4

-34g !+l -4K M 34g !+l

344g ethylalcohol denat" M 44g >t%!

&4g ammoniumchloride M 344g N!$+l

3$g Fethylamine"!+l in theory

The heDamine from fuel tablets (which are 344K pure here where I li2e) wasdissol2ed in 344ml water M not all heDamine went into solution" The !+l andthe alcohol where miDed and chilled and then slowly added to the heDamine,at start some fumes e2ol2ed" This miDture was put in a &l ;ask which wase/uipped with a 2igreuD column ($4cm) and a downright condensor, athermometer into the ;ask and a thermometer at top of the column" Thecolumn was cooled by a fan (3&CLcm computerpart)" Eoilingstones (broken;owerpot) were added and heat applied by means of a waterbath"

5t 89+ boiling started" The reaction was held at a steady re;uD for about &

hours then some li/uid started coming o2er at 49+ to 649+ (measured ontop of the column)" @robably the ethylformate M what else" This ceased afterabout one hour and for the good of it the reaction was re;uDed for one morehour" Then the column was remo2ed and the water distilled away underaspirator 2acuum" The temperatur in the ;ask ne2er got higher than 49+" 5sthe water was mostly remo2ed and a yellow slush remained in the ;ask, I@5was added and the slush eDtracted" Three portions of I@5 M&44ml344ml344ml M brought to a boil and decanted" 5 snowwhite remainder


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stayed in the ;ask M ammoniumchloride"

The eDtracts which of course contained some ammoniumchloride were oinedand set up for distillation" 5bout one third of the li/uid was boiled away(aeotropic remo2al of remaining water) M some hea2y bumping appeared at

the beginning also fresh boiling stones had been added" This was done toremo2e remaining water by the aeotrope" The remainder was 0ltered hotthrough a ;utet 0lter for to remo2e the last ammoniumchloride"

The I@5 was put on my balcony (a usual freeer might be substituted here)and forgotten" 5fter about 3& hours the ug was full of beautiful crystals, theremaining I@5 was poured out and M concentrated again and treated likebefore"

The crystal were spread out and dried on a hot waterbath M careful M

methylamine is C>RH hygroscopicG

5 chloroform wash produced almost no dimethylamine M I actually guess therewas no dimethylamine at and the three grams produced by the chloroformwash were by traces of water present in the chloroform"

Hield# 3&g, 3$g would be theory so thats ok for me"

Fethylamine solution (shi base)

5n eDothermic reaction occured with separation of waterS start re;uDing witha :eanMBtark trap attached to the re;uD condenser to collect the water that isgenerated in the reaction" Jhen no more water separates, distill o thesol2ent(because Na&B%$ is used, it is probably not necessary to re;uD with adean stark trap

5ccording to the Ferck IndeD, a saturated solution of methylamine inbenene is 34" g FeN!& in 344 ml benene at room temp" @repare thebenenemethylamine solution by bubbling methylamine gas into benene at49+"

(use Dylene or toluene)

:reamer#


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Hesterday i had a dream, i tried to reduce @&N@ (phenylM&Mnitropropene)

to

amphetamine with amalganated 5l" I amalganated &4gr of 5l" To this &4gr

5l

i added 4"3 mol @&N@ in 34ml Tetrahydrofuran (H>B, tetrahydrofuran

with

his peroDides)" The 34ml didn climbed to 49" To keep up the generation of bubbles i

added after $ min the last 4 ml of !+l slowly in 34ml steps" The

whole

miDture colled down to &49 and i let stand e2erything o2er night" NeDt

day

i made all 2ery basic through slowly addition of 4K Na%! (7344ml)"

Jhen i

saw that with the addition of Na%! generated other bubbles,so i let

e2erything stand again for $h" Then i 0ltered the whole solution with

a

Euchner funnel, which was /uite tedious because the grey shit is

plugging


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(that should be 12erstopfen1 in english, http#www&"echo"luedicis a

really good page for someone, who didn


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(while heating a miDture under 2acuum i didn2erything seemed ok, but when i tried

to

add more acetone i miDed up the K !&B%$ with the acetone (same color

of

the ;ask #(() and i poured ml of 6K !&B%$ in the 5cetone, den"

>thanol

and 5mphtamine Bulfate" There was a lot of 0ing and the crystals

disappear GGGG

J!H J!H J!H

:oes acetone react with conc" sulfuric acid or ethanol and did one of

these


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reaction byproducts destroy my amphetamine sulfate

Reco2ering the other crystals from ether ga2e 3 gr of brownMwhite with

acteone washed crystals" I don


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If the T> of such a reduction is kept low, will this reduction work for

F:M@&N@ and is it possible to make a sulfate salt of F:5 with a low

solubity in water too

Owww"rhodium"wsP OP O+hemistry 5rchi2eP

Reduction of Nitroalkenes with 5luminium 5malgam

Translation and +ompilation by 5ntoncho

!TFA by Rhodium

I" Introduction

This procedure describes an ecient, highMyielding and completely %T+ wayof reducing 2irtually any nitrostyrene %R phenylM&Mnitropropene using

aluminium amalgam"

Initially this approach to reducing nitroalkenes was pursued by BunAight3based on an old Uerman reference&" !owe2er, due to the suboptimal workMupstrategy, his results were far from ideal, which lead to this direction ofresearch being almost completely buried in 2ain"

Auckily, some four years later an ad2enturous !yperAab Eee (who modestly

wished to remain anonymous) decided to once again take a look at thisprocedure" !is eDperiments ended in a complete and un/uestionablesuccessG

This news was pri2ately communicated to certain reputable !i2e and!yperAab members (who also wished to keep their names pri2ate) in order to
http://var/www/apps/conversion/tmp/scratch_2/www.rhodium.wshttp://var/www/apps/conversion/tmp/scratch_2/www.rhodium.ws


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2erify the author


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the ar


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M >arendel for being of an in2aluable help

M Fescalito for pointing the author (& D $4 mA)" The organiclayer had a red colour, while the a/ueous phase had a yellow appearance"

The latter was made alkaline with F Na%! solution and eDtracted with 344mA chloroform" The organic phase was dried o2er anhydrous sodium sulfateand the sol2ent remo2ed under reduced pressure and recuperated" Thisyielded " g of an amber oil"

Hield# 6"K


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Notes

I ha2e had the impression that impure nitropropene does ha2e a negati2ein;uence on the yields, as was stated by !yperAab Eee V3 as well" I ha2etried TF5 yesterday, and yields were awful" The starting nitropropene,howe2er, was far from pure" Today, I tried a new $MF5 batch with impurestarting productS &4"4 g $MmethoDyphenylM&Mnitropropene yielded "4 gfreebase after the workup I pre2iously described" !owe2er, my end productsha2e always been 2ery pure"

I made a small modi0cation, howe2er" %f the $4 g 5l that I added, there was

only g made a2ailable for the reaction start" %nce the reaction started (in a2iolent way), the reaction was maintained by gradually adding all 5l, eachaddition being accompanied by another small portion of !g salt" This way,there was no sol2ent loss 2ia the re;uD condenser" 5lso, when no more fumesescaped from the top of the condenser, additional U55 was added" This didnot restart the reaction, e2en though some 5l was clearly left unreacted"

V-" Reduction of -,$MmethylenedioDyM@&N@ by !i2e Eee V&"

g recrystallied -,$ methylenedioDyphenylM&Mnitropropene was dissol2ed ina warm solution of 644 mls !%5c and 3444 mls I@5 in a Aiter ;ask withmagnetic stirring and heating mantle" 3 g !g+l& dissol2ed in -44 mls !&%was added and miDture was brought up to 64 9+" 5 total of 4 grams ofregular thickness kitchen aluminum foil was shredded by folding a sheet inhalf(doubling it o2er) and running it through a crossMcut paper shredder" Thiswas added in &4 gram portions at a rate which kept the temperature atapproD 84 9+ for the entire rDn" Fag stirring was not impeded by using foil ofthis type and the rDn was o2er in about $ hours" 3444 mls 4K Na%! solnwas added at a rate which pre2ented boiling o2er, phases separated and theli/ui0ed 5lNa%5c phase was tapped o lea2ing a light orange I@5 solnorganic layer in the funnel" I@5 was stripped o at the roto2ap lea2ing behinda thick deep red oil which smelled of amine" 5cidbase cleanup resulted in adark red oil which was not suitable for crystalliation" %il was distilled (34M34L9+, 3" mm!g) to yield -& grams (approD" 6K yield) of waterMwhite F:5


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base"

Notes#

>Dperiments were performed on 4 g substrate

3) !%5c reduced to 44 ml, 5l was reduced to 64 g" Hield * &$ g F:5 base

&) !%5c reduced to 44 ml and 344 g aluminum was di2ided into threeportions of -- g which were added as the pre2ious increment was consumed"

Hield * - g F:5 base"

V$" Reduction of unsubstituted @&N@ by !yperAab Eee V&"

Into a -MA E there was placed 344 mls water, &4mls U55 and a solution of3g mercury in &M- mls conc" !N%-"

& g (& packs 34 meters each) of 5l foil were folded into 8ML layers, cut inpieces -D- cm and loaded into the ;ask"

The ;ask was heated to $4 9+" Jhen the start of amalgamation was clearly2isible in se2eral minutes, heating was discontinued and into the reactionthere was added a suspension of -4 g nonMrecrystallied phenylM&Mnitropropene in a miDture of 4 mls U55 and 344mls I@5 (nitropropene wasobtained a la EariumWs Fe5m condensation M an important notion since thismethod gi2es the product of superior purity)"

The neDt M8 minutes the reaction proceeded rather smoothly""" I only turned

away from it for some half a minute""" and when I turned around once again Isaw that the miDture inside the ;ask tries to surpass the last inches of the;askWs neckG Urabbing the ;ask I rushed to the sink""""" and then""""" it was likeas if I was standing on EaikonurWs starting table trying to hold back therocketMlauncher [Boyu\ during its blasto"""" The reacti2e stream of 1eDhaustgasses1 Z hydrogen and I@5 2apours M was /uite something"


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Thanks goodness, cooling helped and the foam only slightly escaped the;ask" The 0reworks lasted for a minute or two, after which the ;ask wasplaced into a cold water bath for 3 mins and its contents were periodicallyshaken by hand" +ooling was remo2ed and the reaction was allowed to standfor another $4M4 minutes" 5t 0rst the temperature held itself at L ]

spontaneously, then a little heating had to bee applied"

The obtained grey porridge in which there still was some unreactedaluminium was cooled and cautiously basi0ed with 44 g X%! in 44mlswater" Two layers formed# the lower, a/ueous, with some unreactedhydroDides and the upper, consisting of I@5 and the product" The miDture waseDtracted with &D34 mls ether, the pooled eDtracts dryed and the sol2entstripped o at roto2ap" & g of crude amphetamine base was obtained as amuddy (inorganics) li/uid of skin color"

It was 2acuum distilled with a short column" 3st fraction Z 4"Lg, b"p" 68M8& +6mm!g, &nd fraction Z the product, &4"L g, b"p"8& +" 5nd this is despiteheating with a gas ;ame, instead of a bathG

Bo, the yield was &4"Lg (L-"K) of a crystally clean product" 5nd if we are tocount the 3st fraction, from which a goodly amount of a colorless sulfate waslater made, we get a yet higher 0gure" Foreo2er, a certain /uantity of

amphetamine was lost in roto2ap Z the bathWs temperature was L4 9] and2acuum Z around &4 9+" In the morning it formed white granules of carbonateon the rotorWs walls"

In addition I want to note that the /uantity of foil used can bee e2idently lessas it doesnWt react fully anyway" I think -4M- g should bee enough"

5nother note Z I researched a little the reaction of 5l foil with 2ariousproportions of water#I@5#U55 and it appears that the originally used miDturegi2es the fastest reaction rate"

Jell, that


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Bunlight, Reduction of &,M:imethoDynitrostyrene (3)

Fonatsh" +hem" 8, 8&M88 (3$L)

:irekte Reduktion des Nitrokorpers um 5min#

3g &,-M:imethoDyM^Mnitrostyrol wurde in einer Fischung 2on e 3ccm">ssigsaure, 5lkohol und Jasser in der Jarme gelost und &g feine 5lMBpaneeingetragen" :ie Reduktion kam nach _usat 2on wenig !g+l& in Uang undwurde nach etwa &Mstundigem Btehen bei &49+ auf dem warmen Jasserbade2er2ollstandigt" :ie 5ufarbeitung erfolgte in analoger Jeise wie bei derReduktion des %Dims" Eei der :estialltion erhielten wir im ganen 4"Lg:estillat (bei 3 Torr und L4 bis 3349+ Auftbadtemperatur), das 4"68 g @ikrat

lieferte"

Translation by %smium (3L)#

:irect reduction of the nitro compound to the amine#

3g &,-MdimethoDyM^Mnitrostyrene was dissol2ed by warming in a miDture of3ml 5c%!, 3ml >t%! and 3ml !&% and &g 0ne 5l turnings were added" The

reduction started after the addition of some !g+l& and was completed byheating on a warm water bath after standing for two hours at RT" Jorkup wasdone in an analogous manner to the oDime (apparently 0ltration, sol2entremol2al, acidMbase eDtraction)" 4"Lg was obtained after distillation at3mm!g, L4M3349+, air bath temperature" rom that 4"68g of the picrate saltwas obtained"

methylamine with etoh

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