Author Topic: For the vindication of Eleusis - Methylamine  (Read 56886 times)

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armageddon

  • Guest
hehe
« Reply #160 on: August 20, 2004, 01:57:00 PM »
I WAS FASTER, I was faster.... ;D

(at least nobody believes that we are one person anymore, isn't it?  :) )

Also the quality of the hexamine and the denaturants in the ethylalcohol may be of importance

Propably right - I once used lab grade EtOH and got a greenish-tinted solution upon concentrating, but with standard den.EtOH, it is orange. I think the different denaturants cause side products. Anybody wanting to try it with expensive non-denat. alcohol maybe? Just to be sure?  ;)

And just for the record: BDB, Orgy and me weren't the only bees claiming the patent being of advantage:

  

Post 504433

(biffman: "Good results", Methods Discourse)
  
  

Post 507343

(Vaaguh: "finished", Methods Discourse)


(...)

A


abacus

  • Guest
ok
« Reply #161 on: August 20, 2004, 10:23:00 PM »
Org/Armageddon , whoever you are

I said 202g, from 1 mole HEX, I said nothing about adding extra ammonium chloride did I.

1 mole hex + 4 moles hex + 6 mole water = 4 moles NH4CL + 6 mole CH2O

So limiting factor is the formaldehyde in the reaction between the NH4CL and CH2O to make methylamine.hcl via hydrolysis of hexamine

You work it out anyway you like.

My reference to not stopping was based on your comments telling me to stop, obviously you didn't want anymore scrutiny.

But have it your way, I will stop now, go ahead and fool lots of bees with your claims, I have provided enough commentary for others to make up their own mind and hopefully, they will see through your fake claims like i have.

Abacus

armageddon

  • Guest
the patent is about adding extra NH4Cl, no?
« Reply #162 on: August 20, 2004, 11:19:00 PM »
The patent is about adding extra NH4Cl, isn't it?

Anyway: 140g hexamine gives 4 mol NH4Cl upon hydrolysis, this equals 213.96 grams.

Theoretically, this should result in 270g CH3NH3Cl, so your 202g are a molar 74% yield.

Who said that? Who claimed 75% yield?

So limiting factor is the formaldehyde in the reaction between the NH4CL and CH2O to make methylamine.hcl via hydrolysis of hexamine

Surely not. The limiting reactand is always present in smaller amounts than others, therefore he limits the amount of product that can form. And when you don't add any NH4Cl but use plain hexamine, the HCHO is clearly present in 50% excess (3:2 aldehyde/chloride)...

And about the fact that we (orgy and me) used additional NH4Cl whereas you didn't: well, who got higher yields in the end?

And the molar yield is well comparable, as it only tells about how much of the limiting reactand was converted - and in both cases, this means just how much of the NH4Cl became methylated, regardless whether it was added in addition to the hexamine or not.

The different yields just show that the amount of formed MeAm*HCl can be increased without using more formaldehyde, but by adding more NH4Cl. That's all about it. It is commonly called "proof" if something like this is elaborated.

Now what's your problem with both our calculations being made for reactions that involve the use of additional NH4Cl?? Your calculation is still wrong, and ours are both more ore less correct - so why do you try to start a new flamewar again?

I don't get it why you first doubt the results of other bees using additional NH4Cl, and try to prove them wrong by recalculating their yields, then others prove that you were wrong with your calculations, whereupon you start saying that those other bees calculated the yield for the wrong type of reaction!?!? You were trying to show that our yields were bogus by recalculating them, so why is it suddenly all wrong when we recalculate them??  :(  Your criticizm is absolutely not scientific but rather personal, I believe. (and I'm NOT Orgy BTW!!!)


>:(  >:(  >:(

A


Organikum

  • Guest
wuhahah...
« Reply #163 on: August 20, 2004, 11:28:00 PM »

I said 202g, from 1 mole HEX, I said nothing about adding extra ammonium chloride did I.


You critisized the 125g yields I claim and these were made by addition of NH4Cl. Thats the point and nothing else, cheap tricks now? - just funny.  ;D


So limiting factor is the formaldehyde


completely wrong, dumbass. Do the math. There is more than enough formaldehyde as 1 mol hexamine hydrolises to 4 mole ammoniumchloride and 6 mole formaldehyde. Good laugh - thanks baby.  ;)


go ahead and fool lots of bees with your claims


Now you tell I am a liar, yes? And some other bees obviously too?
You are dead meat asshole.  >:(




abacus

  • Guest
math this
« Reply #164 on: August 21, 2004, 06:28:00 AM »
Balanced equation is this

1 HEX  +  4 HCL  + 6 H2O >>>>>  4 NH4CL  +  6 CH2O

Correct???

The 6 moles formaldehyde reacts with ONLY 3 moles of the formed ammonium chloride as such, leaving an extra mole of NH4CL.

3 NH4CL  +  6 CH2O  >>>  3CH3NH3CL  +  3 HCOOH

Correct???

see posts

Post 513107

(Antoncho: "The mechanism", Methods Discourse)

Post 488683

(Organikum: "For the vindication of Eleusis - Methylamine", Methods Discourse)


So the combined equations give

1 HEX  +  4   HCL + 6 H2O  >>>>  3 CH3NH3CL  +  3 HCOOH + 1 NH4CL

Remove formic as formate if you wish by adding ethanol.

EDIT: 3 moles of ethanol is required and the reaction is this.

1 HEX  +  4 HCL + 6 H2O + 3 CH3CH2OH  >>>> 3 CH3NH3CL  +  3 HCOOHC2H5 + 1 NH4CL + 3 H2O

That’s the equation that my calculations are based on.

So 1 mole hex, 140g, would make 3 moles methylamine.hcl which is …202g

37% yield would be ..... 53g/100g hex like i said

All the formaldehyde is used, left over 1 mole unused ammonium chloride, thats why I said the formaldehyde from the hexamine hydrolysis is the limiting reagent.   

Knock yourself out with that.

Over AND OUT.

armageddon

  • Guest
So you made the astonishing discovery that no...
« Reply #165 on: August 21, 2004, 10:06:00 AM »
So you made the astonishing discovery that no matter if you add NH4Cl to hexamine/HCl or not, the NH4Cl will always be present in excess - or better said that numerous bees aren't able to calculate molarities whereas you show them after hundreds of posts about the subject that the AAAALL were WROOONG...(in case you didn't notice it: THIS WAS IRONY!)

Sure.

Go home and whine. But please don't start ranting about "only three out of four NH4Cl react, therefore formaldehyde is the limiting reactand".

It is NH4Cl, because everything else in present in excess.
(period)

A


Organikum

  • Guest
No, abacus
« Reply #166 on: August 21, 2004, 11:45:00 AM »
Thats wrong again. You mix things up because you dont know shit. Theoretical yields have been calculated by me plain by the molecules/atoms in the soup - as I told. The reaction mechanisms proposed by antoncho and the in the patent are guesses nothing else. A patent needs an explanaition how things happen to be accepted - nobody really would bet his ass that it proceeds this way in reality. So it is written "it is nelieved that....". And antoncho says also that "in his humble opinion" this is this way. Opinion. No prove.

The way things happen in chemistry is: Molecules in the box. Close box. Shake box. Open box, look at the results and make up a reaction mechanism which explains why one doesnt get theoretical yields of the desired compound or something complete different as thought.
The hen and the egg. Where you start your definition? Chemists love to start at the point where it makes yields look better. Simple.

Nevertheless: It is your problem if you are not able to run easy reactions in a way which provides you with the yields other bees get. I would like to say that you lack knowledge and more important you lack any patience and any insight. Search for failures at your own - but no, you prefer to look for somebody "guilty", somebody else to blame for your own mistakes. What do you believe is happening here? A multiple bee methylamine-conspiracy? Or do you believe I am posting with X usernames? You are mentally very ill boy. For sure you are.
Look I spent lots of time here because of your selfrightenousness. I look always if it was not I who made a mistake, so I redid all the calculations three times - this costs time, nerves and is overall not enjoyable. I almost believed that you are just fucking around with me.
The point is: You fucked it up again and you want to blame somebody else. You fuck quite a lots of things up yes? BzCl from BzOH, for example where you claimed "quantitative yields" and wondered about HCL in the second distillation. Hey, you are not the King of Chem - cant you see it. I am not the King of Chem either, but I know it and look at myself first when its on searching somebody to blame. And thats one difference between you and me. The other difference is that my mental illness makes me not as antisocial and annoying as yours makes you.

On topic: As long nobody shows me an article where intermediates have been isolated or radioactive isotopes were used (or equal methods applied) to determine the reaction mechanism I say that the mechanism is unknown - everthing told are barely educated guesses, nothing else. Like reading the future from the innards of a dead animal.

A remark to antonchos mechanism:

NH4Cl + 2HCHO __> CH3NH3Cl + HCOOH

Thus formed HCOOH reacts with ethanol:

HCOOH + C2H5OH __> HCOOC2H5 + H2O

forming ethyl formate, which is removed by dictillation.




The patent states that removal of the formate by distillation is NOT necessary. The formate dissoziates in aqueous solution to formic acid and ethylalcohol and the formic acid could then react again with ammoniumchloride, a Leuckard variation.
Just one possibility.
There are more thinkable ways and some unthinkable ones.  ;D

And now its over. You wont be ridden from sudden insight abacus (and at least two other names in this thread which are you - dont lie. btw.- any admin can prove that I and armageddon are NOT identical) - no chance to see this happen. Best you do as ever, get a bottle of booze and swap your frustration down, beat up your wife and your kids so available and hopefully go to jail for doing so. Or get some real help. You need it.


I spent to much time here trying to bring some good stuff - tried and true and reproduced by others - to the community.

Hereby I BEG some moderator to LOCK this thread now after this post. I dont ask for favors often as its known - now I do. I started the thread, grant me the last post and close it - PLEASE. There is nothing useful to come anymore - the work is done, there is more experimental data than anyone can ask for - close it.

Up to then I ask everybody with some decency left to refrain from posting here - as this should be the

END




armageddon

  • Guest
couldn't resist
« Reply #167 on: August 21, 2004, 09:54:00 PM »
As the thread is still open, I will take the opportunity to criticize something Organikum said - something else after all that flamewar, hm?  :)

The patent states that removal of the formate by distillation is NOT necessary. The formate dissoziates in aqueous solution to formic acid and ethylalcohol and the formic acid could then react again with ammoniumchloride, a Leuckard variation.

The ethylformate will surely not dissociate into formic and ethanol as long as there is a large excess of water and ethanol present; which is the case in this reaction, until the last drop of EtCOOH has distilled. Reason is that every reaction is reversible, but this doesn't happen as long as the educts are present in excess - again leChatelier...

If the formic would react on ammoniumchloride, it would be fine; but I don't think this is possible. The "Gattermann" states that overalkylation is caused by formic acid acting as a methylating reducing agent, and the patent tells that alcohol circumvents the problem of overalkylation - and as we all know that it is alcohol reacting with the formic when using the patent, I draw again the conclusion that the removal of formic acid (gotten from oxidizing HCHO) through esterification with EtOH serves the purpose of avoiding overalkylation of already formed methylamine hydrochloride through leuckart-like reductive methylation.

So, the Leuckart similarity I mentioned earlier on is not the desired methylation of NH4Cl through HCHO but rather the undesirable methylation of CH3NH3Cl by reaction with HCOOH. But then again, there are also leuckart reactions using HCHO as reducing agent - maybe you're right? Anyway, I guess you were thinking about my "methylamine leuckart" post when you wrote this, so I wanted to clarify what I originally meant with "Leuckart-like"...

but the topic "Leuckart reductive methylation" sounds interesting - maybe it would be possible to directly methylate primary amphetamines (3,4MDA as well as plain benzedrine) via this route? (Of course only if a high-yielding method would be found/elaborated - with present yields being lower than 50%, I would of course rather methylate a precursor than to do same thing on primary amine - but things like MDA or MDMA are illegal to manufacture, so I probably will have to wait for my permission to synth controlled substances before trying anything like that  :) )

Last thing left to say: I strongly support Organikum's begging for the thread to be closed! Please, Rhodium - make an end to this, making methylamine with this patent is a topic being discussed enough IMO. And maybe others will beecome encouraged to start their own threads...

(dabei wurde es gerade soo lustig!)

A


placebo

  • Guest
Org, some of us are not putting down the ...
« Reply #168 on: August 22, 2004, 12:25:00 PM »
Org, some of us are not putting down the procedure, just trying to understand it. Care to respond to some of my questions above? I think the answer to the bad results is due to addition of water.


Organikum

  • Guest
?
« Reply #169 on: August 22, 2004, 03:28:00 PM »
Placebo, you wrote before that you believe the bad yields come due to not enough water

I think the bad results with EtOH are probably due to no added water


in

Post 525218

(placebo: "I concur again abacus, about the water added.", Methods Discourse)
Now you write


I think the answer to the bad results is due to addition of water


in

Post 526757

(placebo: "Org, some of us are not putting down the ...", Methods Discourse)
So you ask a question impossible to answer for me.

I can tell that I have got my best results by dissolvong the hexamine and the additional NH4Cl in water (not all NH4Cl dissolves, this doesnt matter), premixing HCl and EtOH and adding this - chilled - to the hexa/NH4Cl/water.
As described here:

Post 494587

(Organikum: "The alcohol used by me was simple denaturated...", Methods Discourse)


Points which maybe of importance:
- The denaturants in the alcohol
- Impurities in the HCl
- Impurities in the Hexamine
- The order in which compounds are added and the time given after every addition
- The temperature at which alcohol/HCl/hexa/ammoniumchloride are admixed - I recommend to do all this in the cold, mix well and heat up slowly then.
Eleusis rcommended to add HCl to the hexamine and to give lots of time for complete hydrolysis - might be a good idea.
Me myself learned that adding the HCl to alcohol and to let this chill down and then to add this in the cold to the hexa/NH4Cl/water (100g hexa, 20g NH4Cl partially dissolved in 100ml H2O, first dissolve the hexa then add NH4Cl) worked well for me.
The method as told by Eleusis - complete hydrolysis of the hexamine to formaldehyde and ammoniumchloride by giving mucho time is closer to the text of the patent. He didnt add more NH4Cl - I did and I recommend to do this.

There is more experimental data posted by BDB and armageddon - have a look there too.

By my best will I cannot tell what causes you problems, I only can tell what works for me and what not. Reactions with OTC reagents are often difficult to reproduce by others, this well known. You may see from the five points named by me only two are related to procedure.

After my OPINION more water doesnt hurt but is favorable, not enough water will. The french article states the importance of enough water, so I am not standing alone here. If the hexamine is hydrolysized first as Eleusis did it, I would say to thin the HCl (he uses 31%) down to 20%-25%.

The 125g methylamine.HCl from 100g hexa and 20g NH4Cl were not one-shot and for sure not first-shot. They were the result in three cinsecutive runs after three or four runs I fucked up for different reasons. Everybody to expect a foolprove receipt without own effort, fed on a silverspoon lives in fairyland and knows nothing about the mysteries of chemistry.

PS: A usual kitchenmixer is very helpful in the described procedures, a small paintmixer is preferred though (the kitchenmixer often tends to mix air into, paintmixers are designed not to do so) - hexamine dissolving etc. Also liquids dont mix perfectly just by addition in a second or two. Usually mixing IN THE COLD is the way to go when a reaction is to proceed with admixed compounds (liquid or solid makes no difference) in the heat. Say, you mix the cold stuff as intimately as any possible before applying heat. This is basic knowledge but rarely told not even in the better books. (or I overlooked it there... ;D )

Now you got:
- two possible procedures
- several points for failure analysis
- some always useful tips on howto do certain things in org-chem.
- and my opinion on the role of water in the reaction

hopefully you are satisfied.
ORG




java

  • Guest
Syntheses of Methyl amine as per Organic synthesis
« Reply #170 on: August 23, 2004, 03:33:00 AM »
Going through the recent made available Organic Synthesis ....

Post 526805

(java: "E-Books: Organic Syntheses Volumes", Chemistry Discourse)
I noticed the synthesis of methyl amine in volume 3 page 67, of Organic Synthesis , where the method discribed by Organikum is discussed. Ref and other methods are referenced there also . I thought I might interject this bit of info to this thread......java


armageddon

  • Guest
thanks
« Reply #171 on: August 23, 2004, 06:58:00 AM »
Exactly what was needed - and on the bottom of page 68, the following is stated about the yield (lo and behold!):

"The yield of recrystallized methylamine hydrochloride is 600-750g (45-51 per cent of the theoretical amount, based on the ammonium chloride used up in the process)."

...and that is for 2000g NH4Cl and 4000ml 35-40% aequ. HCHO solution. It is further said that 850-950g NH4Cl are isolated unchanged, meaning that ~1100g NH4Cl react to give ~675g CH3NH3Cl.

(Next time when I synth some MeAm I will weigh the isolated NH4Cl and then come back with some 70+ percent yields calculated from NH4Cl "used up in the process" instead of the standard % of theory, I promise!  :) )


And they don't use 1 mol alcohol per 2 mol aldehyde (only small amount of MeOH from stabilizing the formalin), so they have significant diMeAm inpurities and therefore do chloroform washes.


So the "Org.Syn" method is essentially the same, except that they don't use excess NH4Cl. And they don't add alcohol.



Left with the question: what has this procedure in common with the patented use of additional alcohol described by Organikum? Besides questioning higher yields than they got (common practice with methylamine manufacture  ;D ), the authors of this Or.Syn chapter don't do anything that hasn't been mentioned before, besides stating that EtOH isn't sufficient for purification purposes - I said it before, but nobody believed me - oh well...

In fact it is exactly the same procedure as posted by me  in this thread before (my translation of a part from "Die Praxis des organischen Chemikers",L.Gattermann, the one with the title "Leuckart reaction - methylamine through reductive methylation"), only difference that the Org.Syn authors did it big scale...

At least we have one more literature reference for this reaction - but, sorry to flame you Java, the patent DE468.895 isn't referenced to in Org.Syn. (only other old german patents), so your post is not really helpful, rather re-posting old news...

A


Organikum

  • Guest
You are wrong armageddon - the patent I ...
« Reply #172 on: August 23, 2004, 09:02:00 AM »
You are wrong armageddon - the patent I presented IS referenced in Organic Synthesis in the "discussion" part. I posted this already as an answer to Terbium here, but this thread got so fucking useless long that the snakes end seems not to be able to see its own head - already the danger arises that the snake will regard itself as prey and start eating itself.

Its Org. Synt. where I discovered it.

ORG

PS: Its ok that Java posted this here, it shows how shitty abacus´s yields are already on the original pathway and that his problems have to be based in his technique and not the method.

PS2: And now for the slower ones: The method using commercial formaldehyde is better yielding just because this contains alcohol for preservation - so the methods with formaldehyde are in part running after the pathway of the patent and in part after the Leuckard - thats very obvious. THATS why hydrolized hexamine SEEMS to give lower yields, it would give identical yields if the alcohol which is in commercial formaldehyde would be added to the reaction. In my opinion the alcohol suppresses formaldehyde destroying and CO2 evolving reactions - thats it.

PS3: Things come together. Times ago Terbium and Chromic did the dinosaur-fight here. Terbium said he had no CO2 evolved and the reaction just sat around. Chromic said - no CO2, no reaction. And both were right, as Chromic started with hexa and Terbium with formaldehyde stabilized by serious amounts of alcohol. Uh. Yes?

Addon: Learned is now that ethyl seems to work better as methylalcohol does. That more alcohol is better - about 1/2 molar of the formaldehyde present or a little bit more. That the addition of about 20% ammoniumchloride is favorable then. That the reactionpathway as outlined at Rhodiums page in the "Methylamine FAQ" doesnt fit to reactions with alcohol present, at least not as primary.
Still to learn: The optimal amounts of alcohol and NH4Cl for best yields and some details of the howto - distill away or siphon out the ethylformate at etc.

ORG


armageddon

  • Guest
didn't find it
« Reply #173 on: August 23, 2004, 02:25:00 PM »
Sorry if I did oversee it for the second time, but I wasn't able to relocate the patent number in the Org.Syn. text, neither in 2) Notes nor in 3) Other preparations or in the references they give.

Only thing referenced to in 2) notes is J.Chem.Soc. 11,850 (1917) (on bottom of page 69).

Now where exactly do they reference to the IG-Farben patent? Just for the sake of knowing I was really wrong... :)  (if this was the case; sorry then Java!)

Greetz A


java

  • Guest
Organic Syntheses :Methylamine HCl....
« Reply #174 on: August 23, 2004, 03:23:00 PM »
All right here is the Organic Syntheses article and in bold red letters the patent Organikum  was referring to...... this is the internet version ....... java

http://www.orgsyn.org/orgsyn/default.asp?formgroup=basenpe_form_group&dataaction=db&dbname=orgsyn




Organic Syntheses, CV 1, 347
METHYLAMINE HYDROCHLORIDE
Submitted by C. S. Marvel and R. L. Jenkins.
Checked by J. B. Conant and F. C. Whidden.
1. Procedure
In a 5-l. round-buttoned flask, fitted with a stopper holding a condenser set for downward distillation and a thermometer which will extend well into the liquid, are placed 4 kg. (3711 cc., 47–53 moles) of technical formaldehyde (35–40 per cent; sp. gr. 1.078 at 20°) (see Note 1 on p. 378) and 2 kg. (37 moles) of technical ammonium chloride. The mixture is heated on the steam bath until no more distillate comes over and then over a flame until the temperature of the solution reaches 104°. The temperature is held at this point until no more distillate comes over (four to six hours). The distillate, which consists of methylal, methyl formate, and water, may be treated as described in (Note 1).
The contents of the reaction flask are cooled to room temperature (Note 2), and the ammonium chloride which separates is filtered off and centrifuged (Note 3). The mother liquor is concentrated on the steam bath under reduced pressure to 2500 cc., and again cooled to room temperature, whereupon a second crop of ammonium chloride is obtained. The total recovery of ammonium chloride up to this point amounts to 780–815 g.

The mother liquor is again concentrated under reduced pressure until crystals begin to form on the surface of the solution (1400–1500 cc.). It is then cooled to room temperature, and a first crop of methylamine hydrochloride, containing some ammonium chloride, is obtained by filtering the cold solution and centrifuging the crystals (Note 3). At this point 625–660 g. of crude product is obtained. The mother liquor is now concentrated under reduced pressure to about 1000 cc. and cooled; a second crop of methylamine hydrochloride (170–190 g.) is then filtered off and centrifuged.

 This crop of crystals is washed with 250 cc. of cold chloroform, filtered, and centrifuged, in order to remove most of the dimethylamine hydrochloride which is present; after the washing with chloroform the product weighs 140–150 g. The original mother liquor is then evaporated under reduced pressure, as far as possible, by heating on a steam bath, and the thick sirupy solution (about 350 cc.) which remains is poured into a beaker and allowed to cool, with occasional stirring, in order to prevent the formation of a solid cake (Note 2). The thick paste so obtained is centrifuged, and the crystals (170–190 g.) are washed with 250 cc. of cold chloroform; the solution is filtered and the crystals are centrifuged, thus yielding 55–65 g. of product. There is no advantage in further concentrating the mother liquor.

The total yield of crude centrifuged methylamine hydrochloride is 830–850 g. This product contains, as impurities, water, ammonium chloride, and some dimethylamine hydrochloride. In order to obtain a pure product, the crude methylamine hydrochloride is recrystallized from absolute alcohol (Note 4). The crude salt is placed in a 5-l. round-bottomed flask fitted with a reflux condenser protected at the top with a calcium chloride tube; 2 l. of absolute alcohol is added and the mixture heated to boiling. After about one-half hour the undissolved material is allowed to settle and the clear solution is poured off. When the alcoholic solution is cooled, methylamine hydrochloride crystallizes out. It is filtered off and centrifuged, and the alcohol used for another extraction.
 The process is repeated until the alcohol dissolves no more of the product (about five extractions are necessary). In the flask 100–150 g. of ammonium chloride remains, making the total recovery of ammonium chloride 850–950 g. The yield of recrystallized methylamine hydrochloride is 600–750 g. (45–51 per cent of the theoretical amount, based on the ammonium chloride used up in the process) (Note 5) and (Note 6).

2. Notes

1. Methylal and sodium formate may be obtained from the first distillate of the main reaction mixture. The crude distillate is placed in a flask fitted with a reflux condenser, and to it is added a solution of 200 g. of sodium hydroxide in 300 cc. of water. The methyl formate is hydrolyzed to sodium formate. The methylal layer is separated, dried over calcium chloride, and distilled. In this way 240–260 g. of methylal, boiling at 37–42°, is obtained. By evaporating the watery portion to dryness, a residue of about 280 g. of crude sodium formate is obtained.

2. The methylamine hydrochloride solutions should be cooled rapidly in order to bring the salt down in small crystals which may be easily purified.

3. Centrifuging the precipitates is the only satisfactory method of drying, as all the products tend to take up water when allowed to stand in the air.

4. Since ammonium chloride is not absolutely insoluble in 100 per cent ethyl alcohol (100 g. dissolve 0.6 g. at 15°), the methylamine hydrochloride purified in the manner described contains appreciable traces of it. A purer product can be prepared by recrystallizing from n-butyl alcohol, in which the solubility of ammonium chloride even at the boiling temperature is negligibly small. Methylamine hydrochloride is somewhat less soluble in this solvent than in ethyl alcohol, but as a rule three extractions carried out at 90–100° with 4–6 parts of fresh butyl alcohol for each extraction result in a substantially complete separation. Since the last traces of the solvent are not readily removed by exposure to air, a solution of the recrystallized material in a small quantity of water should be distilled until free of alcohol, and allowed to crystallize.
An entirely different method for preparing pure methylamine hydrochloride free of ammonium chloride has been described.1 It is based on the fact that when a mixture of methylamine and ammonia reacts with an insufficient quantity of hydrochloric acid the methylamine is preferentially neutralized and the ammonia left free.

5. The literature2 claims a yield of methylamine hydrochloride amounting to 79 per cent of the weight of ammonium chloride used up in the reaction. This figure is probably based on the weight of crude methylamine hydrochloride and not of the recrystallized material.
6. Methylamine can be purified through its benzal derivative, which is distilled and then hydrolyzed by concentrated hydrochloric acid.3 This method has been checked and found satisfactory by one of the editors.
3. Discussion
Methylamine can be prepared by the action of ammonia on methyl iodide,4 methyl chloride,5 dimethyl sulfate,6 methyl p-toluenesulfonate7 and methyl alcohol with a catalyst and at elevated temperatures;8 by the action of bromine and alkali9 and of bleaching powder10 on acetamide; by the action of sodamide on methyl iodide;11 by the reduction of chloropicrin,12 hydrocyanic or ferrocyanic acid,13 hexamethylenetetramine,14 nitromethane,15 methyl nitrite,16 or formaldoxime;17 from acetyl chloride and sodium azide;18 and by the action of formaldehyde on ammonium chloride.19

References and Notes

   1. Sharp and Solomon, J. Chem. Soc. 1477 (1931).
   2. Werner, J. Chem. Soc. 111, 850 (1917).
   3. Sommelet, Compt. rend. 178, 217 (1924).
   4. Hofmann, Ann. 79, 16 (1851).
   5. Vincent and Chappuis, Bull. soc. chim. 45, 499 (1886).
   6. Ephrian and Gurewitsch, Ber. 43, 139 (1910); Denham and Knapp, J. Chem. Soc. 117, 236 (1920).
   7. Rodionov, Bull. soc. chim. (4) 45, 109 (1929).
   8. Davis and Elderfield, J. Am. Chem. Soc. 50, 1786 (1928); E. I. du Pont de Nemours and Co., U. S. pat. 2,017,051 [C. A. 29, 8001 (1935)].
   9. Hofmann, Ber. 15, 765 (1882); François, Compt. rend. 147, 430, 680, 983 (1908).
  10. Bader and Nightingale, U. S. pat. 1,489,380 [C. A. 18, 1836 (1924)].
  11. Chablay, Compt. rend. 156, 328 (1913).
  12. Geisse, Ann. 109, 282 (1859); Wallach and Boehringer, Ann. 184, 51 (1877); Frankland, Challenger, and Nicholls, J. Chem. Soc. 115, 159 (1919).
  13. Mendius, Ann. 121, 139 (1862); Debus, Ann. 128, 201 (1863); Denham, Z. physik. Chem. 72, 674 (1910); Riedel, Ger. pat. 264,528 [Frdl. 11, 110 (1912–14)]; Dreyfus, U. S. pat. 2,072,247 [C. A. 31, 2619 (1937)].
  14. Meister, Lucius, and Brüning, Ger. pat. 73,812 [Frdl. 3, 15 (1890–4)]; Trillat and Fayollat, Bull. soc. chim. (3) 11, 23 (1894); Kundsen, Ger. pat. 143,197 [Frdl. 7, 24 (1902–4)]; Meister, Lucius, and Brüning, Ger. pat. 148,054 [Frdl. 7, 26 (1902–4)]; Isono, J. Pharm. Soc. Japan No. 397, 209 (1915) [C. A. 9, 2232 (1915)].
  15. Pierron, Bull. soc. chim. (3) 21, 783 (1899); Mailhe and Murat, ibid. (4) 7, 954 (1910); Zerewitinov and Ostromisslensky, Ber. 44, 2403 (1911).
  16. Gaudion, Bull. soc. chim. (4) 7, 824 (1910); Ann. chim. phys. (8) 25, 136 (1912).
  17. Takaki and Ueda, J. Pharm. Soc. Japan 58, 276 (1938) [C. A. 32, 5376 (1938)].
  18. Naegeli, Grüntuch and Lendorff, Helv. Chim. Acta 12, 227 (1929).
  19. Brochet and Cambier, Bull. soc. chim. (3) 13, 534 (1895); François, Compt. rend. 147, 429 (1908); Werner, J. Chem. Soc. 111, 848 (1917); Jones and Wheatley, J. Am. Chem. Soc. 40, 1411 (1918); Wietzel and Köhler, Ger. pat. 468,895 [C. A. 23, 846 (1929)].

Appendix
Compounds Referenced (Chemical Abstracts Registry Number)

benzal derivative

chloropicrin

hydrocyanic or ferrocyanic acid

ethyl alcohol, alcohol (64-17-5)

calcium chloride (10043-52-4)

hydrochloric acid (7647-01-0)

Acetamide (60-35-5)

ammonia (7664-41-7)

methyl alcohol (67-56-1)

ammonium chloride (12125-02-9)

sodium hydroxide (1310-73-2)

formaldehyde (630-08-0)

acetyl chloride (75-36-5)

chloroform (67-66-3)

bromine (7726-95-6)

dimethyl sulfate (77-78-1)

methyl chloride (74-87-3)

butyl alcohol, n-butyl alcohol (71-36-3)

Methyl iodide (74-88-4)

Methylamine hydrochloride (593-51-1)

methylal (109-87-5)

methyl formate (107-31-3)

dimethylamine hydrochloride (506-59-2)

sodium formate

methylamine (74-89-5)

hexamethylenetetramine (100-97-0)

Nitromethane (75-52-5)

methyl nitrite (624-91-9)

sodium azide (26628-22-8)

sodamide (7782-92-5)

Methyl p-toluenesulfonate (80-48-8)


armageddon

  • Guest
that's quite puzzling
« Reply #175 on: August 24, 2004, 10:39:00 AM »
Strange - I apologize for doubting what you said, java; but for justifying my doubts I want to mention that the references you cite are not the same as the references in Org.Syn. Vol. 3 (1923) page 70 (downloadable "offline"  version;

http://rzv073.rz.tu-bs.de/bib/dir1/Books/Chembooks/Polytom/orgsyn/OrgSyn-03-1923.djvu

).

Here is what it says on page 70 (references of the methylamine hydrochloride chapter; the first ref is on bottom of page 69, it is J.Chem.Soc. 111, 850 (1917)):

  2. Ber. 18, 1922 (1885)
 3. Jahresb. 1873, 686; Ann. chim. phys. (5) 1, 444 (1874)
 4. Ann. chim. phys. (5), 23; 316 (1881)
 5. Ann. 71, 332 (1849)
 6. Ann. 79, 16 (1851)
 7. Bull. soc. chim. 45, 499 (1886)
 8. Compt. Rend. 48, 344 (1959); Ann. 110, 255 (1859); Jahresb. 1862, 327; Ann.chim.phys. (5), 23, 321 (1881)
 9. Ber. 43, 139 (1910); J. Chem. Soc. 117, 236 (1920)
10. Ber. 8, 458 (1875)
11. Ber. 17, 639 (1884)
12. D.R.P. 64.346, Frdl. 3, 13 (1890-94)
(...)
20. Bull. soc. chim. (3) 13, 534 (1895); Compt. Rend. 147, 429 (1908); J. Chem. Soc. 111, 848 (1917); J. Am. Chem. Soc. 40, 1411 (1918)


Don't want to retype the whole reference list; but in the offline version you linked to, there is no patent DE468.895! As you can see, the list differs completely from the one you provided us with.

The Brochet&Cambier article is referenced to (red letters), but not the IG-Farben patent Orgy posted about...

Now that's strange, isn't it?! (but you see why I doubt what you just said, I guess  :) ) And as the offline version is a scan of a printed one, I suspect that the error is due to the online version being updated, which is impossible with printed texts... ::)

Greetz, A


lugh

  • Guest
Issues With Chronology
« Reply #176 on: August 24, 2004, 11:25:00 AM »

Now that's strange, isn't it?! (but you see why I doubt what you just said, I guess) And as the offline version is a scan of a printed one, I suspect that the error is due to the online version being updated, which is impossible with printed texts...




All that typing when a simple inpection of the dates of publication solves your puzzle, the IG Farben patent was granted a few years after the publication of the volume of Organic Synthesis that was uploaded  ;D  The Collective Volume of Organic Syntheses was published after the IG Farben Patent, thus it was incorporated into the text  ;)




abacus

  • Guest
interesting
« Reply #177 on: August 24, 2004, 01:26:00 PM »
Orgy I think it would be better for you to keep your comments about me within the scope of science.

Lets see, Javas  post from Organic Synthesis.

We have already established that ammonium chloride and formaldehyde can be made by the reaction between hexamine and HCL and water, and that the end result is the well published reaction between the resulting ammonium chloride and formaldehyde.

That is, 1 mole hex + 4 HCL + 6 H2O >>>  4 NH4CL + 6 CH2O

The reaction is then as per Javas post, this involves.

37 moles NH4CL, this can be made from 37/4 = 9.25 moles hexamine, ie 1295g

47-53 moles formaldehyde, this can be made from 47/6 = 7.83 moles hexamine, ie 1096g hexamine (minimum)

So to get to the minimum level of reactants in the synthesis in Organic Synthesis via the hydrolysis of hexamine, we would need at least 1096g hexamine.

Much more if anyone thinks NH4CL is the limiting reactant (I don’t, as already indicated).

The result as published is 600-750g pure methylamine.hcl. 

Exactly the range that I have already stated what my yields were and not surprising as this is basically the procedure that I followed, and I get the same results, except I used hexamine and HCL as my starting ingredients.

You can claim I have shitty yields if you like, but at least I know it’s no worse than the authors of the published synthesis.

Abacus

java

  • Guest
Old stuff ...same topic methylamine syntheses....
« Reply #178 on: August 25, 2004, 12:37:00 AM »
Going through the archives looking for gems I ran into this thread that may be of some historical or enlighting information.......java

Post 108244

(smokemouth: "Methylamine - better yields - Rhodium", Novel Discourse)



armageddon

  • Guest
ever did read a chemistry textbook? *lol*
« Reply #179 on: August 25, 2004, 03:14:00 AM »
Abacus, you wrote:

37 moles NH4CL, this can be made from 37/4 = 9.25 moles hexamine, ie 1295g

47-53 moles formaldehyde, this can be made from 47/6 = 7.83 moles hexamine, ie 1096g hexamine (minimum)

So to get to the minimum level of reactants in the synthesis in Organic Synthesis via the hydrolysis of hexamine, we would need at least 1096g hexamine.

Much more if anyone thinks NH4CL is the limiting reactant (I don’t, as already indicated).


Wrong (of course). To get the minimum amount of reactands used by the Org.Syn. method, one would need 1295g - as with 1096g one would only get 31.3 mol NH4Cl instead of 37 mol, which is the smallest amount "allowed". And you said "level of reactands", so I assume you don't want to change ratios!? So the only solution to achieve same ratio with minimum HCHO but still same ratio of reactands when you use hexamine ís: add some NH4Cl to the hex/HCl/EtOH!

And as you have noticed that the amount of HCHO is variable; why do you think it is the limiting reactand? Usually non-limiting reactands can be added in excess without any difference, whereas the limiting reactand becomes non-limiting reagent when a certain amount is reached...

And the factor "limiting reactand" wasn't invented by me or Organikum, dumbass: its a commonly known definition for the reactand limiting the reaction, and this is always the reagent of which you have the smallest amount present - and because its lack of availability, it limits the overall reaction, whereas all other reagents are present in excess (compared to the limiting reactand) and therefore they don't limit the yield. And that's it. No considering or believing, just learn by heart and know it.

Your yields may be fine for the Vogel's procedure; they are nevertheless shitty when seen in comparison with the yields other bees were able to obtain with the IG-Farben patent. Come on, open a new thread about how cool your yields are when using standard methods - then you have no need to distract this thread (which is NOT about the Vogel's method, nor about comparing it with other methods... :) )

One last note: I wonder why you start thinking about it only when Java posts it; I really translated exactly the same procedure/method from the "Gattermann", and nobody seems to have noticed it in retrospect!? (

Post 514413

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


Oh and about yield differences: ever thought about the fact that Org.Syn. states the yield as molar percent of the NH4Cl being used up, whereas other bees here at the hive stick to the standard non-fake yield calculation method and state their yields as molar percent of the NH4Cl that they put into the reaction. Of course this means that the Org.Syn. yield is in fact even lower, calculated from the NH4Cl used by the chemist (and not "used up" by any mechanism!). for example: 100g NH4Cl present, 30g are isolated unchanged. The chemist gets 35g of the remainder to react, giving some ??g CH3NH3Cl, and claims 50% yield, calculated from the 70g that were "used up in the process". In fact, he gets to react only 35g out of 100g starting material he used, so his yield is in fact just 35%. See what I mean?

But of course it sounds better if he first checks how much starting material remains unchanged and then calculates how much of the remaining compound forms the desired product and how much of it gives rise to side products, and calculates his yield on that basis. Especially when he is about to publish in a chemistry journal! Oh, other common cheat when publishing: claiming high yields in the first line of the abstract, but telling on the last page that you calculated the yield from the amount of dang expensive specialty catalyst you used - and that the ratio reactand/catalyst is something like 50000:1, so to say that 90% of the few mmol of your catalyst reacted successfully on several mol of starting compound, giving 0.9 times a few mmol of product. Usually nobody realizes the fraud.  :P




Java: Nice thread, they had the same problems (not knowing about how the reaction works in detail, just experimenting with adding EtOH or changing ratios of NH4Cl/HCHO) - but someone in that old thread said EtOH would lower yield...
This is true; but only if the yield is calculated from HCHO, which is not the limiting reactand  :P  - as the alcohol should ideally be added in a 1:2 ratio to the aldehyde - but wait! It happens that I have the patent lying in front of me; and the first lines are:

"It is known that the corresponding salts of mono- and dimethylamine can be obtained by treating ammonium salts with formaldehyde or paraformaldehyde. Usually only a small part of the formaldehyde is involved in forming the amine; whereas a great part of the aldehyde is transformed into carboxylic acid. It has now been found that during the production of mono- or dimethylamine (or their salts) through action of formaldehyde (or formaldehyde releasing compounds) on ammonium salts, the formation of carboxylic acid can be mostly if not completely avoided if alcohol is added to the reaction/reactands, preferably in a ratio of 1 (or more) mol alcohol per 2 mol aldehyde ".

- Now that sounds exactly the other way round?!? Like alcohol would cause ~50% of the formaldehyde to react, in contrast to a smaller part reacting when no alc is used? Reason: two partial reactions happen in this rxn; and through adjusting the rate of the one, the other gains benefit - no idea about how this could look like though.

But I think this is meant, because the somewhat spontaneous thermal decomposition of HCOOH (sonds dangerous, eh?  :) ) to CO2 (less dangerous then..) is made controllable through adjusting the rate of esterification, which replaces the (uncontrolled) plain oxidation to CO2 with subsequent diMeAm formation, in case some additonal EtOH is used.
Some kind of alcohol buffered reaction between HCHO and NH4Cl if you want to call it that way - just like when acids aren't "agressive" anymore when buffered, because there is always some buffer ion for the H+ to stick to.
And exactly this is what the alcohol brings about too - preventing an unwanted reducing agent from doing bad things, by intercepting its harmful dissociated ions. And this means a more controlled reaction, and this in turn means the molecules are forced to find their counterparts in this dance, therefore less HCHO remains unchanged. (?) Same principle behind it, isn't it?

Just my thoughts. (think I need some sleep  :P )

A