Simple OrganicDiamines

Quote: Originally posted by Sedit

Its a good possibility. I have the same suspicions as you do about the formation of hexamine as being a product also. Thing is why would this compound want to eliminate ammonia where as EDA does not? I have seen abstracts while one the prowl for information that stated CH2(NH2)*2HCl being used as a slow NH3 source for the formation of secondary amines so it does release NH3 but im unsure as to the conditions of it. Also would this not be a basic material to begin with?

I have been doing a bit of hunting with the time I'v had and still even though information of this compound seems sparce outside of its dihydrogen chloride salt I did manage to find this patant that seems to explain why there is not much talk of it.

Methylene diamine ester and method of making same -



Link: http://www.freepatentsonline.com/2290412.pdf

That states exactly what myself and everyone else seemed to suspect in that it is a very unstable creature in the freebase form but gives nothing conclusive that I could see at first glance as to what it destabilized to. Since I have seen mention of the salt being used to deliver a slow steady amount of NH3 to a reaction I'v concluded that the free form of it will more then likely lose the NH3 rather quickly but after that I don't know.

I will keep searching as much as time allows.



[Edited on 30-6-2009 by Sedit]

Quote: Originally posted by Sauron

Wow. A whopping 13% tield amounting to < 500 mg.

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?

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.

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