Medium-scale methylamine a la raffike...

[raffike]

Many bees are making methylamine out of hexamine and HCl acid.Raf thinks it's very time consuming and HCl is pretty nasty.Raf has found that one can easily make lots of good quality methylamine from ammonium chloride and formalin.Only drawback with this method is that one must have good quality formalin.It may have paraform sediment in the bottom,it doesn't hurt,not even a bit but formalin has to be strong and not some diluted shit.35-40% is fine.
Now to the more-less foolproof method.If you do like said below,you get around 400-450 grams of pretty pure dimethylamine free methylamine hydrochloride which is perfect for Al amalgamations.

Methylamine from Ammonium chloride and formalin a la raffike

Chemicals needed:
 1100 grams of ammonium chloride
 2 liters of 35-40% formalin
 about half a litre of chloroform

The process:

Pour your formalin into a big round bottom(use at least 5 liter RB) flask along with ammonium chloride and stir a bit.Raf used 12 liter round bottom flask:

Start heating slowly and every once in a while stir a little.
Soon it looked something like that,at 40 C or so:

At 80 C:

At 90 or so it exothermic reaction kicks in(it needs to be cooled in a water bath once in a while at the beginning in order to keep temperature below 104-106C):

Soon reaction slows down and cooling isn't needed anymore,reaction flask must be heated carefully to keep temperature at 104-106 or so.It looks something like that:

Keep that temperature 3-4 hours or so,then turn heat up and boil water away till you see ammonium chloride coming out of solution.Cool to 20 C and vacuum filter ammonium chloride out with large Buchner funnel(raf has 25 cm one).You should get a clear yellowish filtrate like that:

Transfer it to a smaller flask like raf did and boil water away till you see internal temperature rising over 160C,then turn on vacuum and continue,first temperature falls some tens of degrees C and if when rises back to 160 C or so,methylamine is pretty water-free.Turn heating and vacuum off.Raf had something like that:

Pour your methylamine in a beaker.First it's liquid(in this picture it has started to solidiy,you can still see some orange liquid in the bottom of the beaker):

Cool your methylamine down and you have a big chunk of hard and dry methylamine.Wash few time with chloroform and you have totally white mush looking like that:

Vacuum filter to get pure and dry methylamine.HCl that reeks chloroform smell which could be removed using a vacuum desiccator.DO NOT try to use oven to get rid of these traces of chloroform,it picks water from air like nothing.Only vacuum for sucessful drying but these CHCl3 traces don't hurt methylamine at all and may be left in,but you just may be a perfectionist...
Final yield of snow white non-sticky powder,which consists mostly of methylamine and maybe few % of ammonioum chloride and almost no dimethylamine.HCl,is,if everything done correctly,over 400 grams like nothing,even 500 grams if your formalin was 40%.

[El_Zorro]

So how do you know how pure this MeAm*HCl is, if it's just a powder?  I mean, it hasn't been recrystallized, and there's no way to estimate purity by the crystal shape, since it's just a powder.

But I guess you've been getting some pretty good MeAm*HCl, since I haven't seen you say anything about poor yeilds in your Al/Hg.

Oh, and another thing, what kind of stirring are you using?  Do you even use any stirring during the main reaction?

[ragnaroekk]

Have you had a look how much dimethylamine is in the chloroform ?
If not, could you be so kind and look for?

Yes?


bombastic!
I am impressed - no joke!

[raffike]

Main byproduct in this reaction is dimethylamine.HCl.Raf thinks recrystal is nice but not necessary and definetely not easy.Once he rextaled 500 grams of methylamine with denat and got back less than 100 cuz methylamine was pretty soluble in ethanol which may and usually does contain water.The other main impurity is ammonium chloride.Maybe few percent of that in final product but since methylamine reacts more readily with carbonyl group than plain ammonium,almost no MDA is formed(methinks less than 1% with this methylamine).Ammonium chloride is very sparingly soluble in concentrated water/methylamine solution and will be almost completely pushed in that cooling-filtering part,methinks.60 grams of once-distilled ketone,25 grams of aluminium,0.1 mm thick and 90 grams of methylamine.HCl you see in that jar above gave 46 grams of snow-white amine.HCl which is the best amine raf has ever had.This is first time he washed his methylamine with chloroform and result is impressive,raf suspects very little dimethylated amine content in final product(MDMA that is).Raf did 4 rx's with this methylamine and every time yield was 44-46 grams making final yield close to 180 grams.He started with 240 grams of once-but-carefully distilled ketone.Too bad raf didn't have his camera with him when his friend was dreaming Al/Hg,it was nice.Maybe some other time...
Ketone in receiving flask(not too dirty IMO):

[raffike]

to ragnaroekk:
Next time he will evapp chloroform,after washing it was yellowish though.

[raffike]

Oh, and another thing, what kind of stirring are you using?  Do you even use any stirring during the main reaction?

Raf shook flask with hands,it's not that heavy.When temp reached 90 and rx kicked in,he didn't bother anymore cuz it was foaming heavy and ammonium chloride was dissolved already.He didn't use condenser but drove these nasty fumes outside(he did NOT dream in city but in rural area with closest houses being at few hundred meter away and there aren't lot of fumes,but they smell very nasty(formaldehyde and formic acid plus some volatile rx byproducts,methyl formate maybe.)

[raffike]

It would be cool if Rhodium could copy these pics to his server and change thread so they could be linked from his site.I'm not sure i can keep these pics on my web hosting space very long.

[Rhodium]

I have saved the images, I'll make a doc at my page of those and your post soon. Good work posting those pictures - pics are always welcome!

[raffike]

Raf likes pics also,these are made with Olympus 510-D which is pretty cheap yet good cam.Raf has same pics with higher resolution too but these take too much bandwidth when posted.If needed,PM.I'll post more few interesting pics i'm sure you can stick em somewhere.I don't they are too incriminating,you can see very few things on a background and amounts are small

Distilled isosafrole,made from 975 grams of quite pure safrole(sg 1.095-6).3 hours and 230 C.Gave horribly low yield of 55%
Will try vacuum isomerizing methods,maybe they give better yield,55% is unacceptable for Raf.It was of a good quality though
Here it is:

400 grams of ISO went into 7 liter rx flask along with 1 liter HPLC grade DCM and some soda.Performic acid being added:

Rx mix,just started adding performic acid:

Peformic acid added:

After 12 hours of stirring:

Glycol and DCM:

DCM stripped off glycol:

Hydrolysis mix after 3 hour 80C:

Crude,washed ketone:

Distilled ketone(total yield from 400 grams of isosafrole was 245 grams,little low yield due bad pump,good quality ketone though):

[technology]

It is good to see this kind of detail on the hive, it helps all newbees like my self of the colours of numourous rxns.. and for some even how to setup.."

all the best i appreciate the info you have posted..thanks

[hellman]

You R the One Raffike,
You are the one that we have all been waiting for,
Such passion inside you,

We have been waiting for someone like you for a long, long time.

I don't think you will ever understand just how important you are, to this site,.


from an ol' retired bee,.


hellmantus