guy
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Ideas for making ethylenediamine?
I noticed there is not thread about making and it looks like an interesting compound. Any ideas for making this? The most "obvious" way I thought of
is converting ethylene glycol into the dichloride and reacting that with ammonia, but that may have to use high pressures?
Any other ideas?
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solo
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Preparation of ethylenediamine
K. Segawa
Jpn. Kokai Tokkyo Koho 94,87,797, Mar. 29, 1994; Appl. Sept. 4,
1992
Abstract
H2NCH2CH2NH 2 (I) is prepared by gas phase treatment of adding ~>1 solvent; maintaining the mixture under conditions of H2NCH2CH2OH(11) with NH 3
at a molecular ratio of NH3/II > 20 and ~<200 using H ion exchange-type mordenite catalysts.
It's better to die on your feet, than live on your knees....Emiliano Zapata.
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john_do
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Whatever you do, don't get it in your mouth! 
Stuffing NaHCO3 into one's mouth is also unadvisable!
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tr41414
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I have a feeling that it will be hard to obtain ethylene dichloride from glycol... More likely chlorohydrin will be the result, unless you use some
pretty harsh conditions... The delephine reaction may be used to avoid pressure...
Could maybe reaction of acetylene and ammonia under anhydrous conditions do the trick? Or maybe even reacting acetylide with ammonia?
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DeAdFX
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I believe axt posted a synthesis of ethylene diamine in his ethylene dinitramine thread. I cannot seem to find it but I would assume it is buried
somewhere in the energetics forum.
If I remember correctly the synthesis involved the use of ethylene glycol and urea... Other than that I do not remember anything else.
Hot damn I am a beast....
here it is http://www.sciencemadness.org/talk/viewthread.php?tid=4282
[Edited on 31-5-2007 by DeAdFX]
[Edited on 31-5-2007 by DeAdFX]
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UnintentionalChaos
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What about the Kolbe Reaction with glycine?
It got mentioned very briefly in this (old and) quickly buried thread http://www.sciencemadness.org/talk/viewthread.php?tid=1050&a...
Department of Redundancy Department - Now with paperwork!
'In organic synthesis, we call decomposition products "crap", however this is not a IUPAC approved nomenclature.' -Nicodem
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not_important
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The Kolbe electrolysis doesn't give the normal results with alpha or beta amino acids, nor with aromatic acids such as benzoic and even
phenylacetic. In the case of alpha amino acids the primary products are the aldehyde formed by the oxidation and loss of the amino group after the
carboxylic group or by addition of OH then loss of NH3, or the nitrile RCH(NH2)CO2- => [ RHC(NH2) ] => RCHO , RCN, RCH2NH2, as well as the
desired dimers and other stuff.
Mentioned in US patent 5364851 among others. To get the more conventional dimer you need to protect the amino group, I don't know if a simple amide
would work.
Passing an alcohol with a large excess of ammonia over a hot (250 - 400 C) catalyst will generate a mixture of compounds, chiefly the RNh2, R2NH, and
R3N with the amounts controlled by the alcohol-ammonia ratio. Conversion is incomplete, it's messy with various byproducts, but for low cost
alcohols it's not too bad.
Catalysts used include copper, silver, copper chromite, nickel, cobalt, and mixtures of those. Some hydrogen may be added as well, it can reduce the
amount or number of side products.
So a possibility might be
HOCH2CH2OH + 2 NH3 (in 20 molar excess) ==(300 C, catalyst)==> H2NCH2CH2NH2 + 2 H2O
byproducts would include ethanolamine, acetaldehyde from simple dehydration of ethylene glycol, and amines where more than one glycol molecule reacted
with a given nitrogen.
The process is old, mentioned in org chem books from the 1920s, and has been refined over the decades - US patent 4760190 from the 1980s is an
example. At one time I believe it was used industrially to make the methyl amines, which were then separated using really good fractional
distillation.
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tr41414
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If working the glycol + urea seems a very good method... Any references on synthesis of other alkylamines from high-boiling alcohols?
What can EDA be used for (have heard rumors of birch but nothing solid)?
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hinz
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I once tried to make ethylene chlorohydrin. I put some NaCl together with ethylene glycol into a thee neck flask and heated it to 120°C and slowly
added 80% H2SO4 by the second neck. By this IO could make some 1,2-dichloroethane, but I don't know how pure it was. I originally wanted to make
ethylene chlorohydrin but when I destilled the product of the first step, I saw that there destilled something at 88-90°C, this could have been the
dichloroethane. Separating ethylene chlorohydrine from ethylene glycol and dichloroethane, together with HCl and water by destillation is difficult
because ethylene chlorohydrin forms an azeotroph with water and probably also with glycol. Here is a good article of the azeotrophes of ethylene
chlorohydrin.
http://www.pubmedcentral.nih.gov/articlerender.fcgi?artid=10...
Maybe you can increase the amount of dichloroethane by refluxing the glycol for a long time with HCl followed by a destillation. Then you could salt
out the dichloroethne and put the rest of the ethylene chlorohyrine and glycol back into the refluxing flask.
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john_do
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EDA
EDA can be used as a substitute for NH3 in metal/solvent solutions. Li & Na dissolve fine at room temp. Not sure about K.
Electrons behave the same way as in traditional birch.
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12AX7
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Hmm, can probably seperate them by Kf -- those long amines form good complexes with e.g. iron, nickel, copper, etc.
Tim
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Ozone
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@Solo,
Are you interested in the reaction, or is EDA suddenly very hard to acquire (which means I need to pay much greater attention)?
Just curiousity, as EDA is pretty cheap at high purity (usually as the HCl salt).
Cheers,
O3
-Anyone who never made a mistake never tried anything new.
--Albert Einstein
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garage chemist
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I want to mention the obvious method of reacting ethylene with chlorine, which gives pure ethylene dichloride.
Ethylene from ethanol + excess of conc H2SO4 plus some alumina as additional dehydration catalyst. Store in a gasometer (over water in inverted
bucket) or balloon until chlorine generator is ready. No catalyst and no heating is required for the reaction of the two gases.
Reacting ethylene dichloride with less than a giant excess of ammonia will give rise to all sorts of secondary, tertiary and even quaternary amine
oligomers.
A much preferred method of replacing -Cl with -NH2 is the
reaction with potassium phthalimide (obtained by neutralisation of ethanolic phthalimide solution with ethanolic KOH, avoiding heating). With ethylene
dichloride, the resulting species would be called 1,2-bis(phthalimido)ethane.
Hydrolysing the four amide bonds by long reflux with conc HCl, or better heating under pressure (enclosure tube) with conc HCl, results in phthalic
acid and ethylenediamine- phthalic acid crystallizes out, giving a solution of EDA dihydrochloride.
This is called the Gabriel synthesis of primary amines.
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LSD25
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Could you go via the glutamine route with TCCA - should give the 4-carbon should give the 4 carbon amido-nitrile with TCCA or the 2 carbon
amino-aldehyde with OCl shouldn't it (Strecker degradation on one end - where the amino acid-type group - and a Hoffman at the other - on the amide)?
At least the TCCA should only affect the amino acid end, in accordance with the article posted by Solo & the other by Fleaker, here - so maybe
hydrolysis of that to the 4-carbon diamide? Do diamides undergo normal Hoffman type reactions? If so, it would be a short route to the 2-carbon
diamine wouldn't it?
Whhhoooppps, that sure didn't work
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sonogashira
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How about a route from succinic acid:
Succinic acid ---> succinic acid diester ---(Curtius)---> ethylenediamine (see Org. Syn. Vol. 4 p819 for NH2NH2 and NaNO2 in place of NaN3 to
give the diamine)
or perhaps a Schmidt reaction (with HN3) directly on succinic acid will give ethylenediamine. (see Org. Rxs. Vol. 3, p307 for Review)
Perhaps it is also possible to form the diamide of succinic acid (avoiding dehydration to succinimide) and performing a Hofmann reaction on that
(NaOCl or NaOBr)?
Or maybe a Lossen reaction (NH2OH, P2O5) would work?
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497
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Any ideas on how one would optimize the reaction of ethylene glycol with urea to produce ethylenediamine rather than ethyleneurea? Would you want an
excess of glycol or not? Maybe you could just collect the distillate rather than refluxing? Would the temperature need to be as high since the goal is
not to make ethyleneurea?
Attachment: ethylenediamine-from-ethyleneglycol-urea.pdf (440kB)
This file has been downloaded 1193 times
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Nicodem
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You can not obtain ethylenediamine using that reaction in a useful way. Apparently you get N,N'-ethyleneurea and crap as major products.
Ethylenediamine is just a putative intermediate, since itself readily reacts with urea or carbamates to form N,N'-ethyleneurea. You can
hydrolyse N,N'-ethyleneurea to get ethylenediamine if that is what you want. Lowering the excess of urea would probably only cause the
formation of ethylenecarbonate instead, especially at lower temperatures. Also keep in mind that the pyrolysis of the intermediate resin is not
something you wish to do in a glass flask since it will probably be a pain to clean and might break on cooling.
Wasn't there a thread about this reaction? I think BromicAcid did some experiments, or maybe I just imagined it.
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