Author Topic: For the vindication of Eleusis - Methylamine  (Read 56784 times)

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placebo

  • Guest
I concur abacus, yeilds of above were 50% of...
« Reply #140 on: August 12, 2004, 10:33:00 AM »
I concur abacus, yeilds of above were 50% of hex weight and also ended in that orange thick syrup that would not crystalise again even at freezer temp.
Second rxn running with...
700gm hex
2100gm HCl
100gm NH4Cl
I can tell you it has taken no longer or smellier then with EtOH.

Then it will be done without any NH4Cl


armageddon

  • Guest
I don't get it
« Reply #141 on: August 12, 2004, 11:00:00 AM »
Well yield of my unoptimized, experimental procedure was >100% w/w if you want to calculate yields from hexamine....

49g methylamine hydrochloride from 48g hexamine means 102.08% yield w/w to hexamine! Huh!?...
but 49g methylamine*HCl from 87g ammonium chloride means 45.11% molar yield calculated from NH4Cl...

(also note that my yield was calculated from the amount obtained after gassing...)

See why I calculate yields from molar amount of formaldehyde or ammoniumchloride, not weight of hexamine?

A


placebo

  • Guest
Mate you work it out any way you like, I just...
« Reply #142 on: August 12, 2004, 11:23:00 AM »
Mate you work it out any way you like, I just gave you figures.
But my 350gm MeNH2.HCl from 700gm of hex is a long way short of others alleged yeild.


armageddon

  • Guest
your personal molar yield calculator sez:
« Reply #143 on: August 12, 2004, 11:45:00 AM »
Your personal molar yield calculator Armageddon sez:

350g CH3NH3Cl from 700g hexamethylenetetramine corresponds to a molar yield of 25.95% calculated from the NH4Cl gotten from hex hdrolysis.


    700g hexamine = 4.9932 mol (140.19g/mol)
    350g methylammonium chloride = 5.1837 mol(67.52g/mol)
   
    4.9932 mol hexamine gives 19.9728 mol ammonium chloride upon hydrolysis
    (1 hexamine + 4 HCl -> 6 HCHO + 4 NH4Cl;  m(NH4Cl) = 53.49g/mol )


    5.1837 mol / 19.9728 mol = 0.259538
    ...meaning 25.95% molar yield.


And the molar yield calculator further sez: Of course you don't have to believe in my "alleged yields"!  :)

Greetz A


abacus

  • Guest
Placebo, another bee with REAL experience
« Reply #144 on: August 12, 2004, 12:35:00 PM »
Placebo, so correct.

I have done this hex/hcl reaction for years, from a 600g run of hexamine maximum yield i (I mean my professer) got, after said procedure, of removing NH4CL, and removing that orange syprup (that other bees keep locked up in solid mass) was 485g methylamine.hcl

Typically 600 grams hex makes 300-350g clean, dried methylamine.hcl.  Molar yields in the 30% range

Adding extra NH4CL does little IME, water did though so not to saturaate the solution and kicking the formaldehyde out of the reaction.

Other bees have previously stated that they are highly skeptical of anybody claiming a better result, I couldn't agree more.

Abacus

placebo

  • Guest
I concur again abacus, about the water added.
« Reply #145 on: August 13, 2004, 10:16:00 AM »
I concur again abacus, about the water added. I think the bad results with EtOH are probably due to no added water. I know it definately affects rxns without EtOH. I would have thought the added EtOH would do the same job as the water and stop saturation.
Results of second rxn are not forthcoming. Alas, due to unforeseen circumstances it was overheated and turned brown. But about 150gm was still isolated, the rest was fried. But it definately looked better then the first rxn (with EtOH), this opinion is based on the amount of NH4Cl recovered.

Further study required. Hexamine rxn of any kind still sucks. 500gm of Meam could be made in less then half the time, and cleaner and easier workup with formalin + NH4Cl. I think the extra time is better spent on looking for a source of formalin or para. Mind you the hex is a good source of NH4Cl.  :P

Nobody answered my question about how much NH4Cl should be recovered?

Next attempt with EtOH would be with water added.


cyrax

  • Guest
evaluation of reactions
« Reply #146 on: August 14, 2004, 04:53:00 AM »
empty

abacus

  • Guest
whats all this nonsense
« Reply #147 on: August 14, 2004, 02:20:00 PM »
Here we go, another analysis based on posts rather than first hand experiences.

Woops, I seem to have made an error in reporting my "yields" in experiments using ethanol, how silly of me. 

Please make adjustments in your evaluation

Did I say 300g, I meant 600g, and guess what, I made a perpetual motion machine as well so factor that in, and then come back and give us the results when done.

Abacus

cyrax

  • Guest
Re:
« Reply #148 on: August 14, 2004, 03:08:00 PM »
Well then, no nonsense

armageddon

  • Guest
at the moment, the world is a disk...
« Reply #149 on: August 18, 2004, 10:15:00 AM »

Post 310000

(Rhodium: "Everybody at the Hive always wait for someone ...", Chemistry Discourse)
 ;D

Greetz, A


Organikum

  • Guest
A deep lack of understanding shows up again.
« Reply #150 on: August 18, 2004, 12:42:00 PM »
A deep lack of understanding shows up again.

Hexamine rxn of any kind still sucks. 500gm of Meam could be made in less then half the time, and cleaner and easier workup with formalin + NH4Cl



Oh my. Hexamine + HCl + water = ammoniumchloride and formaldehyde (hydrolysis).

Maybe your hexamine is shit?

And this thread is not a universal methylamine production thread. It is on a old-new method using alcohol for reasons of shorter reaction times with equal or better yields. Please discuss "traditional" hexamine to methylamine.HCl procedures in the related threads which are by the hundred on this board and refrain from posting here off-topic. Here are bees at work - not at talk, and repeating over and over old stuff which is only regarded worthy because it is old and was repeated over and over again is not very helpful at all.

regards
ORG




abacus

  • Guest
food for thought
« Reply #151 on: August 18, 2004, 01:40:00 PM »
ok

I’ll try to be as concise as possible

I tried the ethanol in reaction and it made no difference to me, ended up with slightly less amount of cleaned and dried methylamine.hcl and leftover syrup as usual.  No dimethyl or trimethyl was formed in the reaction, if your theory or the patent has any validity. 

Ethanol did provide benefits as previously posted.

But the difference was the workup, your write up does involve alcohol extractions whereas I followed the Vogel procedure (without vacuum).

Incidentally, previous experiments when reducing the liquid volume using vacuum still got the same result.

These differences in the post reaction workup are the only unexplored variables in my mind.

I get the same mass of solidified product by doing a post reaction Vogel type workup as Orgy’s does in his/hers posts by doing an IPA extraction and then boiling all the IPA away to leave the residue.

I then go on to crush up the solidified mass, vacuum filter, wash, and dry to be left with clean methylamine.hcl crystals as well as syrup that simply refuses to solidify no matter what (incidentally, soluble in water, ice cold ethanol, not soluble in acetone). 

The resulting dried methylamine.hcl is about half the mass of original solidified mass before crushing and washing, the difference being this liquid.

This result was the same when using ethanol in the reaction, ie made no difference.

Previously in this thread, Orgy mentioned very high yields after “recrystallising”.

Well, if that’s true I am left with a simple question.  

Maybe, the real benefit of the patent is the workup by way of alcohol extractions, keeping the temp down, avoiding side reactions etc, whereas the workup done by me is somehow causing this orange syrup thereby substantially lowering the observed yields.

And that to me is the only unanswered question.

At this point in time, I still doubt the idea that adding ethanol to the reaction itself stops this syrup, or increases yields, because I saw no evidence of this in my experiments and remain yet to be convinced by other posts.

I have no problem being wrong, and remain fully open to any suggestions.

If swapping to alcohol extractions does indeed solve my stated issues, fantastic.

Abacus

Organikum

  • Guest
As told before, my workup consists of hot-IPA...
« Reply #152 on: August 18, 2004, 03:02:00 PM »
As told before, my workup consists of hot-IPA extractions of the orange mass, removing the IPA from the joined extracts (collected for reuse for future extractions). I then add an excess of NaOH - not at once, over some time and in the cold - and collect the methylamine-gas in denat. EtOH. (94%) Some water will come over but this does by no way cause any problems in Al/Hg reactions.

But thats just mine.
I dont recommend it, I dont propose it, I dont tell it is "the best way" - no. I solely tell it as its comparable fast and gives me methylamine-base in EtOH/water and thats what I am after.


Do as you prefer, use what works best for YOU. If what works well with good yields for me doesnt work the same for you - cant help it, sorry.
When you have found YOUR preferred method, make a nice writeup and start a NEW thread. I will not jump into this thread then and post that other procedures are better, promised.

And Abacus: Let it go now. Its enough, I cant see what you are after except more annoyance. But I have seen in earlier threads of yours that you plain dont know when to stop. STOP IT NOW!

btw. I have posted in this thread solely as Organikum and as nobody else. Thats obviously more than others can claim. The strange ways of doublethink......


tryin

  • Guest
methylhydroxylamine hydrochloride
« Reply #153 on: August 18, 2004, 04:36:00 PM »
Could one use this method to make methylamine then convert to methylhydroxylamine? If so what would be the best way?

armageddon

  • Guest
yes
« Reply #154 on: August 19, 2004, 02:46:00 PM »
Yes - you can use this method quite well for making methylamine. But for hydroxylation questions, this is again the wrong thread... :)

Maybe halogenation, followed by hydroxylation with NaOH? Dunno... (UTFSE)




Abacus: Maybe re-read 

Post 514413

(armageddon: "NH4Cl removal / leuckart methylamine", Methods Discourse)
, especially those lines:

"250g ammonium chloride (4.7 mol) are slowly heated with 570g 35% formaldehyde solution in a distilling flask fitted with downward condenser. The temperature (thermometer reaching below surface of rxn) is slowly raised to 104°C and held there until no more distillate comes over (4.5h from beginning). The distillate will consist of 100-120g water and methanol (from the 35% formalin solution). After cooling down the dist.flask content, the precipitated ammonium chloride is filtered with suction and the filtrate is reduced to half of its volume on a steam bath. After cooling, the NH4Cl is again separated with suction filtering and the remaining liquor is concentrated until it forms a surface skin. After cooling, the MeAm*HCl is filtered out (suction) and the mother liquor further concentrated (residual water being removed with a vacuum exxicator/NaOH(s) or H2SO4). The residue is freed from di- and trimethylammoniumchloride by washing w/chloroform and dried with suction. Together with the first crystallization, 110-125g of crude MeAm'HCl are collected.
To free the crude salt from residual NH4Cl, it is extracted by boiling with 250ml abs. alcohol for 0.5 hours.
The alcohol is cooled, precipitated MeAm*HCl is filtered and the mother liquor is used for another exctraction.
After five extractions, one gets approx. 100g (37% of theory)."



Perhaps this helps in understanding.

As you can see, even with the common methods, it is advised to purify the crude MeAm*HCl by extracting repeatedly with hot alcohol and recrystallizing.

So this cannot be the main benefit of the IG-Farben patent.



But:

- In case you believe what I posted earlier on, you know that the patent results in no di- or trimethylamine WITHOUT chloroform washes - I tested it.

- In case you believe in Organikums and my (and others) high yields of pure methylammonium chloride, you know they are higher than yours and even Placebo's with the Vogel's method, although Placebo seems to bee quite xperienced and knowledgable..

Now combine those two benefits with the minor advantages (nicer rxn) you already know, and you might understand why some bees start getting angry when you doubt the usefulness of this patent and criticize them... ;)

Greetz, A


bbeeasheets

  • Guest
strange distillate?
« Reply #155 on: August 20, 2004, 03:00:00 AM »
after 4 tries, following as close to posted trials as i can

100g hexamine
100ml dH20
330g Muratic acid
120g denatured alcohol

slow heat until 60 (reaction temp) reflux for 4 hours
no distillate at thiis temp
raised temp slowly
distillate started to come over at (81deg reaction temp)
vapor temp 67 degrees!

4 tries exactly the same  (i only went thru alcohol removal, reflux 4 hours and water removal once)

is there any way to definatively check for methylamine without a GC or mass spec?

also what could the strange distillate be? could impurities from denaturant or from the hexamine raise the bp of ethyl formate by that much?

armageddon

  • Guest
vapor separation
« Reply #156 on: August 20, 2004, 03:47:00 AM »
Try adjusting the heat more carefully - every time I did the reaction, applying too much heat resulted in steam temp. climbing to above 60°C - which is not what is wanted (EtCOOH bp 53°C)...

Did you choose an appropriately sized flask, at least 2x rxn volume? With a half-filled flask and standard dist. setup (without claisen), the difference between reaction temp. and steam temp. is usually around 30°, so your reaction temp. should allow for a good separation of the vapors (EtOH and EtCOOH).
But if your flask is more than half-filled, it could well be that the space between surface of the rxn liquid and still head isn't big enough, and the missing extra headroom doesn't allow for a proper separation before the vapor mixture gets cooled - with properly sized flasks, the space between liquid and still head works like an easy column.

Maybe you should try using some sort of column, or maybe just some big glass tubing - the vapors separate quite well if you give 'em enough time and space, and it is possible to collect pure EtCOOH, believe me...

(and I started to distill from the beginning, no reflux was done before. I just heated very slow to 80°C during the first hours... remember this is in fact a leuckart reaction!  :) )

Greetz A


abacus

  • Guest
I agree
« Reply #157 on: August 20, 2004, 11:42:00 AM »
Alright, I'm sick of this bullshit, and I'll get straight to the point.

First off, Orgy, I have only one user name and this is it.   If you cant handle a peer review too bad. 

Secondly, Armageddon, I know this, I also agree with 37% yields.

So with that in mind.

1 mole hex, 140g, makes in theory 202g methylamine.hcl

37% of that is 75g.

100g hex in theory makes 144g methylamine.hcl, 37% yield gives 53g

So has it ever crossed anybody's mind how anybody can claim 125g methylamine.hcl from 100g hex, which is more than TWICE the result that would be expected based on the literature.

Abacus

armageddon

  • Guest
wrong calculation?
« Reply #158 on: August 20, 2004, 01:42:00 PM »
Hi!

You say:

"1 mole hex, 140g, makes in theory 202g methylamine.hcl

37% of that is 75g.

100g hex in theory makes 144g methylamine.hcl, 37% yield gives 53g."



Actually, I'm not completely satisfied with your calculation!  ;)


I think you refer to the post linked below when you wrote this:

Post 500578

(Bond_DoubleBond: "Nothin special, but here ya go . . .", Methods Discourse)


So let's recalculate the molar proportions bouble bond used:


100g hexamine + 104.03g HCl + 77.12g H2O  ->  152.62g NH4Cl + 128.53g HCHO

(The remaining water from the HCl amounts to 226.22g - 77.12g (used for hexamine hydrolysis) = 149.1g (or ml))


152.62g NH4Cl + additional 30g  ->  182.62g NH4Cl


(if the concentration of the acid BDB used was w/w, he used in fact 103.76g HCl instead of 104.03g - but that's neglectible, let's simply say he had used the correct amount  :) )

So the ratio of reactands are:


    3.41 mol NH4Cl
    4.28 mol HCHO
    2.11 mol EtOH (again not exactly 2x the molar amount of HCHO, but close enough)


The limiting reactand is obviously the NH4Cl.


Now I don't see how you came to your statement that 100g hexamine results in 144g MeAm*HCl theoretically - because the max. theoretical yield would be 3.41 mol * 67.52g/mol = 230.24g methylamine hydrochloride

He claimed having got 120g pure product (anhydr. IPA recrystallization). Therefore:


    230.24 / 120 = 0.5212  ==>  52.12 percent of theory


There's nothing wrong with getting twice as much as with standard, well-known procedures if you use some new/unknown improvement. And the claimed yields seem achievable, at least seen from the mathematical point of view...

I got 45.11 percent of theory BTW, and that was after gassing - I think "BubbleBond"s (nice nick  ;D ) 52.12 percent correspond pretty well with that...

Greetz, A


Organikum

  • Guest
Lets see: 100g hexamine (0,71 mol) hydrolyses...
« Reply #159 on: August 20, 2004, 01:51:00 PM »
Lets see:

100g hexamine (0,71 mol) hydrolyses to
- 152g NH4Cl (2,84 mol)
- 128g CH2O (4,26 mol)

You see there is excess formaldehyde present.

I add 20g NH4Cl, thus we have 172g and we have a theoretical yield of 218,6g methylamine.HCl. Yes?(*)

I get 125g methylamine.HCl yield which represents about 57% of theory and is not so far from the 40-45% yield by the Vogel´s method (your 37% is low - why? Its not on the method its on you I guess) - if it is done right.
Therefor I always told that this method gives slightly better yields and its main advantage is that it doesnt take so long.

Based on the literature for this variation - this literature is the patent from the first post and nothing else - the yields I claim are absolutely correct. The patent actually tells near to 145g yield to expect - based on the reactionpathway presented and the claims - and hey! Patents ARE scientific literature per definition.

In short:
Theoretical yields: 218g (by molecules present, not by reactionpathway presented in the patent)
Yields claimed by patent: near 145g (by the reactionpathway)
My yields: 125g

Remark: Reactionpathways are merely ideas and the patent clearly states that it is THOUGHT that the reaction proceeds this way. It may, or it may not - nobody REALLY knows. Claiming that a certain reaction DEFINITIVLY goes by a certain pathway is nothing but a mishabit. The old chemists knew this well, modern chemists often forget about this.

And now dear abacus you will perhaps understand why you are not regarded as a peer to me. And not by anyone else with knowledge on chemistry.

(*) Please anybody be aware that the added alcohol by no way reacts to 100% - how much reacts strongly depends on how this reaction is done. Therefor the amount of alcohol to add depends on how one plans to run the reaction. Also the quality of the hexamine and the denaturants in the ethylalcohol may be of importance - distilling the alcohol from salts and recrystallazing the hexa may help here.

abacus, I asked you to stop this shit. You PM´d me you will NEVER stop it. Ok. Go on showing off what idiot you are not able to do simple calculations and such. I will have lots of fun with you I guess.  :P