06-02-03 17:26
No 437357
High Bees!
swim trid to make some MeAm-HCl this evening...
50 Paraformaldehyde, 45g Ammon Chloride and 130ml of Water were added to a 250ml RB flask, and it was set up for simple distillation...
The oil bath was slowly heatet to 104°C (the solution turned clear), and some bubbling/cooking was noticed, but nothing destilled over (?!)... The temperature was held at ~104°C for 4 hours, and then the the oilbath-temp was increased to 150°C... water started to distill over, and 1/2 of the volume was distilled off.
The flask was cooled, and Ammoniumchloride was filtered off...the filtrate was distilled again to half of its volume, and vakuum was applied... Crystals started to appear again - they looked exacty like the Ammonium Chloride fraction from before... the crystals were filtered off again, and the the filtrate was again vakuum destilled... after no more water came over there was a yellowish oil left in the flask.... the flask was cooled, and the oil crystallised into a yellowish/white solid...
is this methylamine.hcl, or whent something wrong, because nothing distilled over @ 104°C?
can Chloroform (used to seperate Methylamine/Dimethylamine) be substituted for DCM?
many thanks ;)
xicori
(Stranger)
06-02-03 19:46
No 437375
yellow/white is meam.hcl it's probably a bit wet and kind of "slimey" just leave alone it's fine for the next step
(Hive Addict)
06-02-03 23:33
No 437423
but nothing destilled over (?!)
That's exactly how it should be,when a bee uses paraform,there isn't any methanol that could react with formic acid(byproduct of this reaction) to produce methyl formate that would distill over.How large was yield?With these quantities it should be 20-30 grams.
For those about to synth,we salute you
(Hive Addict)
06-03-03 03:23
No 437477
(Rated as: good idea!)
A perhaps helpful modification of the synthesis is to use zincdust as catalyst. Lower reaction temperatures and significantly higher yields as all formaldehyde is available for forming the methylamine and gets not used up as reducing agent forming formic acic (which is partly decomposed whereby CO2 evolves).
An 50% to 100% overfold (of theory) of ammmoniumchloride suppresses here the formation of dimethylamine virtually completely. A polymerisation of methyleneimine to the trimer was never encountered. If thus had taken place then only in amounts not important for the reaction.
The reaction runs best at ambient or lower temperatures
With Hexamine and ammoniumchloride:
100 gram HMTA are dissolved in 1 liter H2O at about 10°C. The flask is placed in a waterbath. Over about 5 hours under strong stirring slowly is added 30% HCl, 25 gram ammoniumchloride (salmiac) dissolved in 0,5 liters H2O and zincdust. During this time cold water runs through the waterbath cooling the flask. It should not get to hot now thats all. Done. The reaction is forgotten overnight (stirrer runs medium) and next day it is regretted to have used an open vessel. No harm but stink. This reaction forms methylamine and not methylamine HCl if done right. The amine freebase gets steamdistilled (basify if necessary, not worth to mention) and is collected in dil.HCl if the hydrochloride is whats wanted or in H2O if a aquesous solution is what one heart desires. It is advised to form the hydrochloride and wash with chloroform to remove possible dimethylamine residues at least the first times this is done. If the chloroform washes show that no or near to zero dimethylamine is present this may be skipped in future if the procedure stays otherwise unchanged.
Yields are up to 80% of theory counted on the used hexamine, the overfold on ammoniumchloride may be extracted from the residue and reused I guess.
A closed vessel and ventilation are recommended, also to setup the complete rig incl. steamdistillation from start on. It can be done without having to open the vessel once and no smell at all (ok, not absolute but no problems causing). Very brave ones may do this in a open beaker with a handmixer - they will have no friends for weeks.
The LEUCKART-WALLACH reaction is often better catalyzed by zinc/HCl than formic acid. Itīs worth a look for all interested in this "good old style" reactions.
Zinc: For those who donīt have the possibility or donīt want to buy zincdust at a chemsupplyhouse there are two ways to aquire it as I know: Recovering the zincdust from spray or paint or milling metallic pure zinc. The metal is easy available as ingoy and not watched. (Only the dust for itīs impacts on health and the possible use in explosives maybe restricted - check your tribal rules for this). As zinc gets brittle at about 220°C it is astonishing easy to get the dust, the metal if pure nearly mills itself at this temperatures. (to use steelballs for milling is plain stupid - lead or ceramic/glass, nonsparking, the dust IS explosive).
Oh, I forgot the amounts of HCl an zinc?
No, I didnīt.
Edit by LT/ : see Post 414873 (Rhodium: "Cyclic Methyleneamines. Part I.", Tryptamine Chemistry)
Edit by Organikum/ : see also Post 378615 (Organikum: "hexamine to methylamine a old new way?", Methods Discourse)
In the post of Rhodium the reaction is to hot (reflux) and to much HCl ("excess HCl") is added at a time. If done right virtually only monomethylamine is the product and this is mostly in the form of the freebase - only small amounts of NaOH are needed to free all for steamdistillation. (so far I can judge this of course. Yields in first, not optimized runs seem to back it up).
But a highly interesting read this post of Rhodium hidden in the Tryptamines forum, for sure.
(Hive Bee)
06-03-03 05:01
No 437512
High bees!
thanks for the replies.... Swim spent a good time getting the rocklike solids out of the RB-Flask :) Heating with a hairdryer helped a lot....
Swims final yeild is 27,5g but the product may be still a bit wet or contamined with some NH4Cl...
Whats the beste way to get the Ammonium Chloride out? Recrystallise from MeOH?
Greetings,
x
(Hive Addict)
06-03-03 05:46
No 437518
yep rxtal from MeOH or IPA is ok.This rx is easily scale-uppable to 1 kg of ammoniumchloride and 2 liters of formalin(or 1,1 kg paraform),raf can confirm it.
For those about to synth,we salute you
(Stranger)
06-03-03 20:05
No 437691
raf what was the size of the reaction vessel and how was stirring maintained?
(Hive Addict)
06-03-03 23:58
No 437718
Flask was 12 liter RB and heating was 2 kwt with variac.Temperature was a bit hard to keep stable but finally managed to stabilize at 102-105.There was no stirring during the reaction,when ammonium chloride was added raf periodically shook rx vessel with hands but when ammonium chloride was already dissolved in formalin,no further stirring was employed.
For those about to synth,we salute you
(Stranger)
08-06-03 10:25
No 452119
regarding Organikum's zinc catalysed procedure above. I don't see the amounts given, nor do I see how the amounts are calculated from the info., for zinc or HCL. Any help is appreciated.
(Hive Bee)
11-22-03 15:16
No 472578
A writeup on several possible improvements of the hexamine to methylamine process is in preparation - some personal difficulties hindered me up to know to post something final on this - also I hoped someone would jump on the experimention train - its boring to work out all shit alone.
(A Different Title)
12-01-03 03:37
No 474051
Hexamine is cheap & available to me, so that was my preferred route.
But I never seemed to get yields higher than 25%, sometimes as low as 10%, using the methods on Rhodium's site. Perhaps there is a variable I'm simply not aware of. But I don't complain, it's OTC and cheap.
Anyone need a small mountain of ammonium chloride?
They call them fingers, but I never see them fing... oh, there they go.
(Fat Ass)
12-01-03 13:00
No 474129
wow, that's a really low yield. are you using commercial hexamine or camping tablets? SWIM has only used camping tablets, and has never had below 50% yield.
as to the mountain of AmCl, SWIM knows what you mean. you can always get some formaldehyde and try that synth with it.
Now with 12% more Bottom!
Nymphomania is not a disease, its a goal! (Methadist)
(A Different Title)
12-01-03 18:15
No 474198
Camping tablets. It's a bit of a mystery, but like I said probably a variable I'm not aware of. My *guess* is that I'm somehow losing formaldehyde before it has a chance to do its thing, except that the smell of formaldehyde is never that strong, but the smell of formic acid sure is after a while...
They call them fingers, but I never see them fing... oh, there they go.
(Synaptic Self-Mutilator)
12-03-03 10:04
No 474508
The important variable is to slowly heat the mixture. Last run that advice wasn't followed (heating was over in about 4 hours), and 5g MeAm came from 35g hexamine. Whoops.
(Horrible Personality)
12-04-03 13:58
No 474694
to add much more water (2liters per 100gram hexamine) and less HCl (start with 1/10th or less and add more so need is obvious - what shouldnt be the cause).
Why?
Look, the HCl hydrolizes the hexa and if there is too much it forms heaps of ammoniumchloride which shits out - if there is more water and less HCl then this runs sweet: hydrolize to methylamine - hydrolize to methylamine as we want it.
If you add some Zn powder over about 4 hours this runs at roomtemperature or lower - 12 to 24 hours stirring and VERY good yields.
But even without Zn only more water and less HCL boosts yields.
And this was definitivly the last time I tell it on this board.
ORG
out