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Waffles SS
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Ethylenediamine diacetic acid
I think it should be possible to make it by reaction of 2 mol Mono chloro acetic acid and 1 mol Ethylene diamine but this would not be easy because
ethylene diamine tetra acetic acid will form also.
I want to make it and i am looking for any information about it procedure.Somebody has information?
[Edited on 7-8-2013 by Waffles SS]
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kch
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I don't think it is possible using just ethyldiamine and chloroacetic acid. Might be possible through reductive amination. At the least, you could do
the reaction carefully and just separate the products. That's probably your best bet.
[Edited on 8-7-2013 by kch]
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solo
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ethylenediamine and acetic anhydride, in thf might do the trick, i tried the ethylenediamine and acetic anhydride adding the latter to the first ,
very exothermic reaction and smokes a lot,....it needs the thf and cooling...it should work.....solo
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kch
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Found this... might be worth looking into
| Quote: | <a href="http://www.organic-chemistry.org/abstracts/literature/717.shtm" target="_blank"><img
src="http://www.organic-chemistry.org/abstracts/literature/717b.gif" /></a><img src="../scipics/_ext.png" />
In the reductive amination of some aldehydes with primary amines where dialkylation is a problem, a stepwise procedure involving imine formation in
MeOH followed by reduction with NaBH<sub>4</sub> was developed.
A. F. Abdel-Magid, K. G. Carson, B. D. Harris, C. A. Maryanoff, R. D. Shah, <em>J. Org. Chem.</em>, <strong>1996</strong>, 61,
3849-3862. |
<!-- bfesser_edit_tag -->[<a href="u2u.php?action=send&username=bfesser">bfesser</a>: replaced
naked (referenceless) image with everything in quote]
[Edited on 8.8.13 by bfesser]
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Waffles SS
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Some times ago i prepared Glycine by reaction of Imine(Formaldehyde + ammonia) + Chloroacetic acid and i think it is possible for Ethylene diamine
diacetic acid.there is no need for reduction by NaBH4 or anything else in this reaction.
I didnt see any reference for this reaction and this is just my experience
Quote: Originally posted by kch  | I don't think it is possible using just ethyldiamine and chloroacetic acid. Might be possible through reductive amination. At the least, you could do
the reaction carefully and just separate the products. That's probably your best bet.
[Edited on 8-7-2013 by kch] |
See Glycine synthesis(in orgsyn) by ammonolysis of chloroacetic acid
http://www.orgsyn.org/orgsyn/orgsyn
/prepContent.asp?prep=cv1p0298
[Edited on 9-8-2013 by Waffles SS]
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kch
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Wouldn't the imine hydrolyze in the second step reverting back to the diamine? Also your final product is inconsistent with the carbonyl location
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solo
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.....maybe reading this will help.....solo
http://www.erowid.org/archive/rhodium/chemistry/edda.html
It's better to die on your feet, than live on your knees....Emiliano Zapata.
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Waffles SS
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| Quote: Originally posted by kch | | Wouldn't the imine hydrolyze in the second step reverting back to the diamine? Also your final product is inconsistent with the carbonyl location
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Thanks @Kch.
I corrected the schema(i did mistake on drawing in chembio draw program)
I dont think imine hydrolyze again to diamine.i tried same reaction with ammonia(for making glycine)
Thanks Solo,bt it has different structure(it is ethylenediammonium salt)
[Edited on 8-8-2013 by Waffles SS]
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kch
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Also, your diagram shows acetylaldehyde, not formaldehyde
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Waffles SS
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Sorry.I corrected it again 
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kristofvagyok
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With chloroacetic acid you will get a mixed product, as mentioned previously, so I would not recommend it.
But if you react ethylenediamine with formaldehyde, to get the above mentioned imine, add some sodium, or potassium cyanide, to get
ethylenediamine-diacetonitrile (or how to call it) NC-CH2-NH-CH2-CH2-NH-CH2-CN, than hydrolyze it with an acid to get the above mentioned EDDA.
Recipe could be found in: U.S. Patent No. 2 558 923, U.S. Patent No. 2 387 735 or in Chem.Abstr., vol. 74, # 99423z
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Waffles SS
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Thanks @kristofvagyok,
I made Glycine by mentioned method several times(Imine + Chloroacetic acid) and i believe it should work for Ethylenediamine diacetic acid too.
I will try My method and your suggested method soon and i will share result.
Correct me if i am wrong in your suggested method for making EDDA.(according to US2387735 i double the material)
2Mol Na/KCN + 2 Mol CH2O + 1 Mol EthyleneDiamine +500 ml H2O + 10 gram NaOH(for PH 9)
[Edited on 9-8-2013 by Waffles SS]
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papaya
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I'm sorry for off topic, but does anyone know a doable way to ethylenediamine itself? Dichloethane + ammonia route requires autoclave conditions and
is only good for industry.
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kch
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| Quote: Originally posted by papaya | | I'm sorry for off topic, but does anyone know a doable way to ethylenediamine itself? Dichloethane + ammonia route requires autoclave conditions and
is only good for industry. |
Gabriel synthesis maybe?
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kristofvagyok
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That would be a bit expensive.
Aziridine + ammonia + little acid in hot water? That usually works. But ethylenediamine is a commercial reagent, if you have to make this, than you
will have hard times with the other stuffs.
| Quote: Originally posted by Waffles SS | Correct me if i am wrong in your suggested method for making EDDA.(according to US2387735 i double the material)
2Mol Na/KCN + 2 Mol CH2O + 1 Mol EthyleneDiamine +500 ml H2O + 10 gram NaOH(for PH 9) |
That should be okay... If it won't polymerise just as you add the formaldehyde 
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Waffles SS
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| Quote: Originally posted by papaya | | I'm sorry for off topic, but does anyone know a doable way to ethylenediamine itself? Dichloethane + ammonia route requires autoclave conditions and
is only good for industry. |
I usually make Ethylenediamine by Delpine reaction.(Dichloroethane + Hexamine + ethanol and HCl)
http://en.wikipedia.org/wiki/Del%C3%A9pine_reaction
http://www.organic-chemistry.org/namedreactions/delepine-rea...
Use below instruction but double materials and time(hexamine + EtOH +HCl):
http://www.orgsyn.org/orgsyn/orgsyn/prepContent.asp?prep=cv5...
[Edited on 10-8-2013 by Waffles SS]
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UnintentionalChaos
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I would consider replacing the formaldehyde in the above sequence with benzaldehyde to avoid polymerization. I believe that another one of our members
has a writeup for monomethylation of a primary amine by this approach. reflux with iodomethane gives the iminium salt which yields the secondary amine
on hydrolysis.
Department of Redundancy Department - Now with paperwork!
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Waffles SS
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| Quote: Originally posted by UnintentionalChaos | | I would consider replacing the formaldehyde in the above sequence with benzaldehyde to avoid polymerization. I believe that another one of our members
has a writeup for monomethylation of a primary amine by this approach. reflux with iodomethane gives the iminium salt which yields the secondary amine
on hydrolysis. |
Edgar F. Kiefer, J. Med. Chem. 15(2), 214 (1972)
[Edited on 10-8-2013 by Waffles SS]
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Waffles SS
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I tried reaction of Formaldehyde(37%)solution with Ethylenediamine yesterday and got amazing result.
Beaker A: 0.1mol Ethylenediamine + 0.2mol Formaldehyde(37%)solution and 10ml methanol.
Beaker B: 0.1mol Ethylenediamine + 0.2mol Formaldehyde(37%)solution and 10ml methanol+ 1gram BHT.
(Adding Methanol to Ethylenediamine produce lot of Heat)
After 1 hour Color of Beaker A turned dark but Color of Beaker B turned yellow and white precipitate produced.
I want to know does BHT prevent polymerization in this case or not.?what is white precipitate in Beaker B?
Somebody knows?
[Edited on 22-8-2013 by Waffles SS]
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kch
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How did you dehydrate the reaction?
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Waffles SS
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I didnt dehydrate the rection.I just add reactant at room temperature without heating.
For making Imine water should be removed but really I am confuse about white precipitate in Beaker B !
[Edited on 22-8-2013 by Waffles SS]
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kch
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Possibly imidazolidine as a condensation product
http://pubs.acs.org/doi/abs/10.1021/jo01148a003
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bfesser
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Thread Moved
23-8-2013 at 05:40 |
PHILOU Zrealone
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Maybe ethylenurea would prevent polyaddition of haloacetic acids or of cyanomethanol (formaldehyde-cyanide adduct).
Ethylenurea (imidazolidone) has 1 active hydrogen atom on each of its two nitrogen atoms.
Those can condense with two formaldehyde molecule into dimethylol-ethylene-urea.
So action of CH2=O and CN(-) will most likely lead to dicyanomethyl-ethylene-urea...which upon basic or acidic hydrolysis would lead to the desired
ethylenediaminediacetic acid or salt.
Ethyleneurea should fix two equivalent of haloacetic acid or ester with a basic catalyst...after acid or basic hydrolysis, one would get the desired
ethylenediaminediacetic acid or salt.
PH Z (PHILOU Zrealone)
"Physic is all what never works; Chemistry is all what stinks and explodes!"-"Life that deadly disease, sexually transmitted."(W.Allen)
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Waffles SS
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| Quote: Originally posted by PHILOU Zrealone |
Those can condense with two formaldehyde molecule into dimethylol-ethylene-urea.
So action of CH2=O and CN(-) will most likely lead to dicyanomethyl-ethylene-urea...which upon basic or acidic hydrolysis would lead to the desired
ethylenediaminediacetic acid or salt.
Ethyleneurea should fix two equivalent of haloacetic acid or ester with a basic catalyst...after acid or basic hydrolysis, one would get the desired
ethylenediaminediacetic acid or salt. |
Thanks my friend @PHILOU Zrealone,
Do you have any reference or detail about it?
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PHILOU Zrealone
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I did not search for specific references, sorry.
It is based on generaly admitted and known organic chemistry (as you should
have guessed it is my speciality  ):
-dimethylol ethylenurea synthesis
-the dialkylurea and urea chemistry
-the synthesis of parent EDTA (ethylendiamine tetra-acetic acid) via ethylendiamine, formaldehyde and cyanhydric acid, followed by hydrolysis
PH Z (PHILOU Zrealone)
"Physic is all what never works; Chemistry is all what stinks and explodes!"-"Life that deadly disease, sexually transmitted."(W.Allen)
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