RoundBottom
(Hive Addict)
06-20-02 02:34
No 323193
      Chromic’s Methylamine.HCl
(Rated as: excellent)
 Bookmark   

this is a repost from a somewhat obscure thread in the newbie forum... Post 322683 (RoundBottom: "Chromic’s Methylamine.HCl", Newbee Forum)  i don't think it was as visible as it would be in it's own thread, so here it is.

Written by RoundBottom (karma, money, sex belong to chromic)

Preface:
First, this is a first attempt at making any MeAm.HCl so what it is supposed to look and smell like is a complete unknown (but whooee bob stinky-twat smell is bang on).  Second, RB really knows nothing about chemistry other than what RB has learned since attending the Hive.  Also, RB has never written a lab report in his life, so if the format is really off, please make any needed edits.

Reagents:
· 179.7g Hexamine camping fuel tablets
· 500mL muriatic acid (31.45% HCl acid)
· 550mL MeOH
· 550mL Acetone

Apparatus:
· 1L distilling flask
· 500mL receiving flask
· standard distillation setup (with cooling)
· rubber hose
· 600mL beaker
· 1000mL beaker
· 1” egg stir bar
· stir plate
· mantle and controller
· filter flask
· Buchner funnel and stopper
· filter paper
· vacuum source

Notes:
· The white hexamine tablets were a very common, “green Canadian camping products” brand.  The tablets were put into a baggie and crushed to fit into a 1L flask. 
· Chromic’s write-up suggests mixing the muriatic acid with the Hexamine in the flask while it sits in an ice bath.  No temperature increase was noted, so this may be unnecessary.

Procedure:
Set up distillation apparatus as usual.  A rubber hose was run from the vacuum inlet on the vacuum adapter to a window to expel any fumes. 

Mix the muriatic and hexamine until dissolved.  Took about 15 minutes, but will vary depending on hexamine type.

A gentle reflux was maintained for about 7 hours at a temperature of about 80°C-85°C.  The heat was turned up to start the distillation.  Fluid started dripping into the receiving flask at about 102°C.  At about 11.5 hours, grains of AmCl were observed mixing in the distillation flask.

After about 12.5 hours the temperature had raised to 107°C and the drip rate had slowed down to about 1 drop per 4-5 seconds.  About 270mL of clear distillate was recovered.  It shouldn’t be required and can be disposed of later.

The heat was turned off and the reaction contents were allowed to cool down while still stirring.  The fluid in the distillation flask had a medium yellow colour to it, and was still clear.  There was also a large amount of spongy looking solids in the distillation flask that did not harden after cooling down, but remained sort of mushy.  Bubbles were still evolving even after the distillation flask was allowed to cool for about 45 minutes.

A note about smell: once the distillation flask was removed the smell was really evident.  It will stay in the room and on the skin for a few days.  If you can at all manage it, make a fume hood, do this outside, or at least with a fan blowing out the balcony door.  Smelly-twat, rotten anchovies, smegma dick… take your pick, it’s pretty nasty.  Don't expect to hold a dinner party there the next day.  The rubber hose is only useful while the distillation apparatus is connected.

Once cool, the contents of the distillation flask were vacuum filtered with saran wrap to squeeze out as much liquid as possible.  About 250mL of fluid was collected (murky and cloudy, dark urine coloured).  The crystals were put into the 600mL beaker and covered with 150mL room temp MeOH, manually mixed with a spatula for about a minute, poured into the filter.  The beaker was rinsed with about 50mL MeOH and poured into the filter funnel, and then vacuum filtered, again with saran wrap.  The AmCl crystals were put on a Pyrex dish to dry and kept for future use.  Once dry, the ammonium chloride weighed 104g.

The combined filtrate and MeOH washes were then put back in the distillation flask, and distillation was started again.  A temp of 40°C was reached in 25 minutes and fluid started coming over (BP of MeOH == ~64.6°C)

The temp climbed up to 108°C over 5.5h.  After about 300 minutes a white smoke started filling the distilling flask.  This is what we are waiting for, the sublimation of the MeAm.HCl.  "Distilling to dryness," means the flask doesn’t have any more water in it.  It does not mean, "Boil the hell out of it till everything's crunchy"

Once the smoke appeared, the heat was turned off and the contents were left to cool and solidify for 30 minutes.  Sorry, the appearance of the fluid at this point wasn't noted.  Once cool, 350mL MeOH was poured into the distillation flask and a reflux condenser was put on the flask (actually, the condenser from the distillation phase can be used, as it is already set up and this isn't a heavy reflux).  The heat was turned up again, and the solution was allowed to reflux for about 15 min.

While hot, the solution was decanted into a Pyrex dish (a 1000mL beaker is probably better).  Either way, the container was covered with saran wrap and left on the counter for 2 hours until cool.  It was then moved to the fridge and left overnight.  In the morning the beaker was moved to the freezer for another 2 hours.  The crystals were large crunchy flakes, and the remaining fluid had an amberish tint. 

It was once again vacuum filtered with saran wrap.  About 375mL of fluid was recovered.  At this point the crystals were large, white, translucent, and crunchy. 

The crystals were put into a 600mL beaker and washed with 200mL ice-cold acetone for 5 minutes, and again vacuum filtered with saran wrap.  The crystals were then spread out in a Pyrex dish to dry.  The crystals looked smaller, and had a slight grayish tint. 

The remaining fluid was crashed with 300mL ice-cold acetone and about 1.5g of crystals fell out.  It was decided that it wasn't worth boiling the liquid down to recover any more.

In total 98.2g of crystals were recovered. 

 


i learned a thing or two from charlie dontcha know.
 
 
 
 
    Rhodium
(Chief Bee)
06-20-02 02:51
No 323195
      Where is Chromic's original writeup  Bookmark   

Nice, Nice... Where is Chromic's original writeup, BTW? I can't find it on my page tongue
 
 
 
 
    RoundBottom
(Hive Addict)
06-20-02 02:58
No 323198
      dunno  Bookmark   

he passed me an early version, but said he wanted to tweak it a bit.  that was a few months ago, so i decided to post my report of his writeup.  i think he got busy and forgot... but i'm sure he'll be posting it here, soon.

i learned a thing or two from charlie dontcha know.
 
 
 
 
    Chromic
(Hive Addict)
06-20-02 10:01
No 323291
      Original writeup  Bookmark   

The original write up is on the Hive. The only real difference is the use of MeOH to recrystallize followed by washing with acetone.

The main advantage over the other MeAm.HCl writeups is the reduced solvent volume necessary to recrystallize. I found using IPA was a slow and tedious way to recrystallize. I hated using IPA or any other higher alcohol than MeOH (and hated washing with DCM), so I looked for solvents that would give a good purity of MeAm.HCl. MeOH was found and it worked wonderfully.

I also noted that the reaction does not take place with the solution at 104°C like other bees indicated. It takes place at a slightly higher temperature (the temp of the vapor, however, is 104° at the beginning). As I never repeated this synthesis more than 3 or 4 times I never released a final copy of my write up.

The yields are lower than other write ups (typically 50%, but sometimes lower), but it's so easy and the purity is so good, these two factors were never an issue. The key to getting a good purity is allowing the MeOH to cool very slowly and undisturbed. MDMA made with this MeAm is highly quality stuff too, I doubt there is much dimethylamine left in with the crystals. Btw, reducing the MeOH volume used might increase the yields... but I never experimented with it. (I just used amounts that I determined semi-quantitatively from my work recrystallizing MeAm.HCl... details found in other posts)

Good work RB! You finally brought this method to the public. smile
 
 
 
 
    pROcon
(Hive Bee)
06-21-02 01:25
No 323507
      Excuse me, sorry for invading this thread with my ...  Bookmark   

Excuse me, sorry for invading this thread with my minimal chem skills, but does this have any relevance to the smelly aldehyde E-quest murmering?

A myth was formed somewhere along the line - that Americas government is not the fault of Americans.
 
 
 
 
    GOD
(Hive Addict)
10-24-02 14:21
No 372131
      binders  Bookmark   

If the hexamine source (E....) is known to have binders in it, is it first nessisary to remove them before performing this rxn?

Loriel... because Im worth it!
 
 
 
 
    Rhodium
(Chief Bee)
10-24-02 15:04
No 372142
      That's a good thing, as you don't know what the ...  Bookmark   

That's a good thing, as you don't know what the binders are. They are usually not water soluble.
 
 
 
 
    RoundBottom
(Hive Addict)
10-24-02 19:11
No 372201
      example  Bookmark   

the hexamine tablets used in my example were well formed pucks about the size of a quarter and about 1/2" thick.  when struck with a hammer, they easily crumbled to powder. 

Now with 12% more Bottom!
Nymphomania is not a disease, its a goal! (Methadist)
 
 
 
 
    ChambeRed
(Hive Bee)
10-25-02 19:18
No 372589
      I've tried two different brands of hexamine ...  Bookmark   

I've tried two different brands of hexamine tablets and bolth seem to work just fine,they bolth come just like chromic described.Pm me if you doubt yours for a sure thing.Peace,Chambered.

Bee's don't die,we just multiply.
 
 
 
 
    Diggity
(Drama Queen)
10-25-02 20:04
No 372604
      ?>  Bookmark   

What is the brand name of some good working Hexamine tabs? I have yet to try this method, and am feeling a bit bored this afternoon. Thnx,

& I'm, somethin of a phenom, no need for da cron, I'm un-stopable.   
 
 
 
 
 
 
    Chromic
(Synaptic Self-Mutilator)
10-25-02 20:49
No 372623
      Any of them  Bookmark   

Any of them will work. Make sure they're white, hexamine and crumble apart. Chromic had good luck with the yellow and black packages, but the blue and whites ones work too. Go out & look.
 
 
 
 
    GOD
(Hive Addict)
10-30-02 20:53
No 374603
      clarification  Bookmark   

Set up distillation apparatus as usual. A rubber hose was run from the vacuum inlet on the vacuum adapter to a window to expel any fumes.
...
A gentle reflux was maintained for about 7 hours at a temperature of about 80°C-85°C. The heat was turned up to start the distillation. Fluid started dripping into the receiving flask at about 102°C. At about 11.5 hours, grains of AmCl were observed mixing in the distillation flask.


This means to set up for simple distillation, or is a fractionating column used?  Swim ASSuMEs this to mean simple distillation, but since a reflux is mentioned...

BTW, those E**** brand cubes (come in a red box) definatly come with a binder in them, recrystalisation of 2 boxes (12 X 14 grams/box) yielded 329.7G hex. and ~6G hard, semi-waxy binder.

Loriel... because Im worth it!
 
 
 
 
    RoundBottom
(Hive Addict)
10-30-02 21:14
No 374621
      simple  Bookmark   

you are correct, simple distillation.

i've only used one brand, and there isn't much in the way of binder.

Now with 12% more Bottom!
Nymphomania is not a disease, its a goal! (Methadist)
 
 
 
 
    Chromic
(Synaptic Self-Mutilator)
10-30-02 22:03
No 374654
      Red box hexamine  Bookmark   

Yes. The german brand has got a wax binder in them and this has been discussed before. Do not recrystallize your hexamine. The content of binder is very low (I think someone even had a web page up with pictures on this topic), so just throw them into the flask (they even fit, unlike the black & yellow box which you have to smash up).

The methanol recrystallization will not take any of that binder into your purified methylamine.

Is anyone else paying out the ass for these things? They cost me ~$15US for ~250g. Oh well, it turns into 100-125g of methylamine, so I guess it's all good.
 
 
 
 
    GOD
(Hive Addict)
10-31-02 00:08
No 374704
      $4.99 US for 168G/box  Bookmark   

$4.99 US for 168G/box

Loriel... because Im worth it!
 
 
 
 
    ChambeRed
(Hive Bee)
10-31-02 04:44
No 374793
      2.99 a box and 144g. a box and with no noticeable ...  Bookmark   

2.99 a box and 144g. a box and with no noticeable binder,Sta*sp*r* brand.Found it a the "action figure/cartoon hero)" sporting goods store.

Bee's don't die,we just multiply.
 
 
 
 
    majic22
(Newbee)
10-31-02 07:42
No 374857
      vacuum filtraion with saran wrap?????????  Bookmark   

this may sound like a dumb question but ive always been told the only dumb question is one not asked so here goes...where does the saran wrap come in?  I have a basic understanding of vacuum filtration but i dont understand how you "vacuum filter with saran wrap"  thanks

"My girlfriend said I had to choose between her and chemistry....Im gonna miss her."
 
 
 
 
    raffike
(Hive Addict)
10-31-02 12:43
No 374934
      I paid something like that: 12$ for 35 kg bag of .  Bookmark   

I paid something like that:
12$ for 35 kg bag of AmCl and
6$ for 33 liter canister of Formalin.
and i don't feel like being ripped off.
I once tried that Hexamine to methylamine synth but it was very time consuming and low yielding for me.I'm completely satisfied with AmCl/Formalin synth.

A friend with speed is a friend indeed
 
 
 
 
    Chromic
(Synaptic Self-Mutilator)
10-31-02 15:55
No 374982
      Saran wrap  Bookmark   

The saran wrap pushes down on the crystals to get more solvent out. Just put a piece over the buchner funnel when you're done pouring the slurry thru the filter. It gets sucked to push on the crystals by the vacuum.
 
 
 
 
    uncle_buck
(Stranger)
11-07-02 19:10
No 377345
      A suggestion or three...  Bookmark   

Great write-up!

Some quick suggestions/observations:

1.  purchased hexamine powder gives better results, this is based purely on personal observation

2.  ammonium chloride can be rextallised from boiling water and feed into more methylamine production thru the route with (para)formaldehyde, thus upping yield

3.  rextallising methylamine.hcl from isopropyl alcohol instead of methanol gives cleaner results, again based on personal observation only

cheers!

ub
 
 
 
 
    Chromic
(Synaptic Self-Mutilator)
11-07-02 20:16
No 377360
      IPA  Bookmark   

>recrystallizing methylamine.hcl from isopropyl alcohol gives cleaner results

Sure does, but it takes a lot of IPA to dissolve, say, 250g of MeAm.HCl--even at reflux.
 
 
 
 
    Rhodium
(Chief Bee)
11-07-02 21:27
No 377373
      Methylamine Hydrochloride Recrystallization  Bookmark   

When recrystallizing methylamine hydrochloride from methanol, I have found it to be very effective to dissolve the crystals in a minimum amount of boiling methanol, then allowing the solution to slowly cool to room temp, then to 5-10°C in the fridge, and finally to -15-20°C in the freezer before vacuum filtering and then washing the crystals with a very small amount of freezer-cold isopropanol results in very pure, spectacular thin plates (usually up to 1x1 cm) of methylamine hydrochloride. Drying the crystals in a dessiccator over KOH completes the process.

The filtrate gotten after the filtration can be diluted with an equal amount of isopropanol and again cooled in the freezer to give another crop of slightly less pure crystals, maximizing the yield without having to concentrate the alcoholic solution by evaporation or distillation, and without having to introduce any acetone anywhere in the process, which potentially can react with the MeAm.HCl, forming acetone methylimine...
 
 
 
 
    Chromic
(Synaptic Self-Mutilator)
11-08-02 04:20
No 377530
      Smart idea  Bookmark   

I like your idea of crashing out the methylamine hydrochloride with another solvent after getting the first crop of crystals.

Don't worry about an acetone imine forming, it doesn't happen (or if it does, it's highly reversible). I've found the best way to dry the crystals is to turn the hot plate to low and put the acetone-wet crystals on it until the smell of acetone is gone... then placing in a tightly sealed jar and waiting until you're ready to use them. Don't attempt the clean up on a hot and humid day though... the methylamine will pick up water pretty fast.

Why did you skip the acetone (or DCM or chloroform) wash after recrystallizing? The last run I made, the crystals were beautiful white shards, but I always like washing just to make sure.

P.S. even running this reaction slowly still produces a gas unlike what Terbium has said a number of times. Perhaps this is a difference between the hexamine route and the formaldehyde route he used... or he just didn't notice it?
 
 
 
 
    Rhodium
(Chief Bee)
11-08-02 05:35
No 377551
      Chloroform  Bookmark   

The chloroform wash is performed on the crude product before the recrystallization in my scheme (to remove dimethylamine and whatnot). After the methanol recrystallization the crystals are so large that I hardly could believe any contaminants being present. The ice-cold IPA wash of the crystals is just to wash off possibly contaminated methanol from the crystal surface.
 
 
 
 
    terbium
(Old P2P Cook)
11-08-02 06:06
No 377560
      Snowflakes not shards.  Bookmark   

The last run I made, the crystals were beautiful white shards, but I always like washing just to make sure.
Methylamine.HCl crystals should be large plates, as Rhodium mentioned, not shards!


Baseline Does Not Exist.
 
 
 
 
    RoundBottom
(Hive Addict)
11-08-02 10:50
No 377629
      term  Bookmark   

is "plates" a technical term?  i would describe them as flat translucent flakes.  kind of shiny, sparkly looking, and "silky" feeling.

SWIM's last MeAm run was a disaster.  vac pump siezed during first suction filtering.  *sigh*  stuff had to sit for 2 weeks while waiting for repair.  final product was very discoloured... not a good enough MeAm during the recrystalization.  SWIM will repeat the recrystalization and hope to rescue it.

SWIM also found that the final acetone wash produced smaller, greyer, less translucent flakes... a la the write up.

Now with 12% more Bottom!
Nymphomania is not a disease, its a goal! (Methadist)
 
 
 
 
    Chromic
(Synaptic Self-Mutilator)
11-08-02 16:25
No 377665
      Ooops!  Bookmark   

Terb, you and Rhod are right. I looked in the dictionary, for the definition of shards it says pieces of broken pottery (not quite the right word) What I got was very thin plates. After recrystallization they look like pieces of very thin mica, 0.5-1cm in length, <0.5mm in thickness. Kind of like the way snow appears when it's freshly fallen and is very fluffy and has not been packed. I should have just posted a picture.
 
 
 
 
    Boris_Silicunt
(Stranger)
08-22-03 02:25
No 454924
      This particular synthesis looks simple enough...  Bookmark   

This particular synthesis looks simple enough but I have two small questions.

Could someome answer them please?

If i understand roundbottoms Hexamine& Hcl and some of the other Synthesis i have read it goes like this

-mix X mols of Hexamine and Hcl together
-Reflux for no less than 8 and no more than 24 hours
-distill off the portion up to 107 C(slowly)
-filter out and wash precipitated ammonium chloride
-return combined filtrate and methanol washes to the distillation setup
-distill off all other liquids up to 108 C(slowly)
-filter precipitated methylamine hydrochloride
-wash and recrystallise methylamine chloride

the two points that are not clear in roundbottoms writeup are-

does the thermometer reach into the solution or is the thermometer readings from a standard distillation.(thermometer in the three way adaptor)?

is stirring required? (i have read that stirring is always required when distilling, but roundbottom does not mention it so i figure he left it out as it might interfere with crystal precipitation)
thanks
 
 
 
 
    Rhodium
(Chief Bee)
08-22-03 03:34
No 454933
      Methylamine help  Bookmark   

does the thermometer reach into the solution?

Yes, in this case, the 104°C max distillation temp is measured with a thermometer immersed into the liquid in the distillation flask.

is stirring required? (i have read that stirring is always required when distilling, but roundbottom does not mention it

Yes, stirring should always be used even if it isn't mentioned in a writeup - it's rather so that if stirring is not to be used, then that is mentioned explicitly.
 
 
 
 
    Boris_Silicunt
(Stranger)
08-22-03 04:17
No 454936
      thanks rhodium  Bookmark   

>the 104°C max distillation temp

so roundbottom should not have exceeded 104 celcius when he/she distilled? (roundbottom mentions temps of 107 and 108 celcius)

could this lead to higher yield?

in your opinion, would a higher reflux temperature of 80-85 C and a longer reflux time be more benificial.

thanks
 
 
 
 
    Rhodium
(Chief Bee)
08-22-03 11:07
No 454998
      104°C tops  Bookmark   

could this lead to higher yield?

Yes, as the formation of the byproduct dimethylamine is minimized, see these documents:

Organic Syntheses, CV 1, 347 (http://www.orgsyn.org/orgsyn/orgsyn/prepContent.asp?prep=CV1P0347)
Methylamine Synthesis FAQ (../rhodium/chemistry /methylamine.html)