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Formatik
National Hazard
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Quote: Originally posted by Sedit  | So it does form Methylamine then Formatik?
I thought alot about it being a novel MeNH2 synthesis after UnintentionalChaos mentioned the possible formation of Methyleneimine but could not figure
an efficiant way other then neutralizing with HCl and fractional crystalizing to seperate the Ammonia Chloride and Methylamine. Since I did not want
to waste HCl not knowing if it formed or not I did not attempt it.
Its good to know thank you Formatik. Do you have a link to the given reference? |
Beilstein's Handbuch can be found in big uni libraries. Volume 1 of the last printed edition (4. Auflage) is on google books or archive.org, or in a
link in my profile. I don't have the supplements. There might also be the option of accessing Beilstein Crossfire at an uni. The references for those
reactions are given by Beilstein. I still haven't considered if the older editions might not have some info.
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Sauron
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Almost the complete Hauptwerk (4th Auflage) that is, Bands 1-16 which is everything but the ten or so volumes on heterocyclic systems, were digitized
by titan and posted on the Russian forum, with links given ub References - I know because I downloaded them. I have them on a CDR. Maybe a DVD I don't
recall.
This is the Beilstein Main Work covering the lit. through 1910.
The five supplement sets are organized in same fashion and extend coverage till IIRC c 1970 but alas no one has seen fit to scan them - a daunting
undertaking that would be!
Sic gorgeamus a los subjectatus nunc.
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Sedit
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Ok I just want to make sure I have all my ducks in a row hear before I attempt this again hopefully later tonight. Even though I am not getting what I
was expecting I have gained an interest in this reaction due to the fact of it being a 'novel' Methylamine and Formic acid synthesis.
When the DCM reacts with (aq)NH3 the products are HCl, Formic acid, and Methylamine. The Methylamine will most surely react with the HCl and go into
solution as the hydrogen chloride salt but I can't help but wounder about what Sauron said about the formation of formamide or ammonia formate at the
very lest. It seems like there are many factors at work here and since I know next to nothing about figureing up the way the equilibrium should work I
will have to assume that the majority of product will be MeNH2*HCl and Formic acid.
I am in a toss up of if I should generate the (aq)NH3 directly prior to reacting it with the DCM or generate it when DCM+H2O are already together.
More then likely will not make much difference but my main concern is how to reflux this without loss of NH3. What is the azeotrop of NH3+H2O so that
the NH3 stays in solution even though its being refluxed if at all possible. I am also annoyed by the fact that excess NH3OH will raise the PH and
free any MeNH2 from its salt and generate additional chloride.
Work up:
I would think the best way would be to heat until the PH drops to a steady place near neutral from the consumption of NH3 into the salts.
Distill the fluids and titrate distillate to try and figure out the formic acid concentration.
Weight remaining salts and test melting point ect..ect..
If all seems well I would think that freeing the formed MeNH2 and feeding it into water(MeOH?) and titrate should give me a round about value of the
MeNH2 made also in the reaction.
Any thoughts, or other ways I could go about trying this and determining what is formed?
[Edited on 1-7-2009 by Sedit]
Knowledge is useless to useless people...
"I see a lot of patterns in our behavior as a nation that parallel a lot of other historical processes. The fall of Rome, the fall of Germany — the
fall of the ruling country, the people who think they can do whatever they want without anybody else's consent. I've seen this story
before."~Maynard James Keenan
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Nicodem
Super Moderator
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| Quote: Originally posted by Sedit |
I am in a toss up of if I should generate the (aq)NH3 directly prior to reacting it with the DCM or generate it when DCM+H2O are already together.
More then likely will not make much difference but my main concern is how to reflux this without loss of NH3. What is the azeotrop of NH3+H2O so that
the NH3 stays in solution even though its being refluxed if at all possible. I am also annoyed by the fact that excess NH3OH will raise the PH and
free any MeNH2 from its salt and generate additional chloride. |
What are you talking about? What methylamine? What reflux? To get a redox reaction going you need to heat the mixture way beyond the CH2Cl2 boiling
point! Do you use an autoclave or not?
…there is a human touch of the cultist “believer” in every theorist that he must struggle against as being
unworthy of the scientist. Some of the greatest men of science have publicly repudiated a theory which earlier they hotly defended. In this lies their
scientific temper, not in the scientific defense of the theory. - Weston La Barre (Ghost Dance, 1972)
Read the The ScienceMadness Guidelines!
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Sedit
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The Methylamine was one of the products of the high temperature reaction but you have made your point about the autoclave I ignorently overlooked it
because of the appeared reaction at lower temperature. Since I do not have an autoclave and be damned if im going to stopper up anything and just heat
that can not be tested.
However there appears that some reaction takes place even at room temperatures with stirring so im left to wounder what the products formed are. Some
equilibrium that can not make it all the way to the right without the high temperatures or what?
Here is what I have observed so far by just mixing and shaking and evaporating. It did not go as planed hence the reason I started this threed because
the information on what I thought would form is just not there.
When the Dichloromethane and (aq) ammonia are mixed together the DCM appears to be consumed and the solution goes cloudy. Initial thoughts where that
there where sufficants in the Ammonia because I would expect a formed salt solution to be clear. I evaporated some of the original Ammonia solution
but it evaporated cleanly with no residue like I would expect with sufficants. Then there was the issue of DCM's solubility in H2O so the same bulk of
non ammonia H2O was added to some DCM and shaken just the same yet it quickly droped to the bottom leaving a clear solution completely different then
when shaken with (aq)Ammonia.
The cloudy solution was then evaporated on a low heat at first to see if DCM left the solution boiled out but there was no sign of it and the solution
retained its cloudy consistency all the way to the end of its evaporation leaving behind a small amount of light tan powder that did not appear to be
enough for the amount of DCM used to begin with. Excess NH3 could be smelled when the solution was first heated making me wounder how any salt could
be formed due to the high PH enviroment yet there was something left behind that acted like an amine by liquifying when added to sodium carbonate/NaOH
(trace NaOH because the sodium carbonate came from waste NaOH that was left out to react to the elements. Used for throw away experiments to not waste
the cleaner reagents I have) and the slight smell of fish could be detected simular to the alkylamine smell of epoxy hardener.
I understand that this is not all scientific but thats why I wanted to repeat this again under better controled conditions.
Improvments to rule out as much contamination and variables as possible will include refluxing the DCM in activated carbon and redistilled to make
sure that there is no contamination in the DCM getting in the way. It appears to have cleared it up a bit but since it was clean looking to begin with
its hard to tell.
Also I want to generate a higher concentration of (aq)NH3 to rule out DCM just going into solution normaly and im looking for the solubility of DCM in
a high PH enviroment.
Higher heat to push any equilibrium that may setup further to the right. Since I do not have an autoclave I plan on packing the condenser with glass
wool within reason to build slight pressure and reach a little higher temperature.
I hope all this clears up what my intentions and reasoning behind them is. Keep my sig in mind because if I knew what the hell I was doing I wouldn't
have half as much fun doing it
~Sedit
Knowledge is useless to useless people...
"I see a lot of patterns in our behavior as a nation that parallel a lot of other historical processes. The fall of Rome, the fall of Germany — the
fall of the ruling country, the people who think they can do whatever they want without anybody else's consent. I've seen this story
before."~Maynard James Keenan
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