Sciencemadness Discussion Board - Ethylenediamine diacetic acid

Ethylenediamine diacetic acid

Waffles SS - 7-8-2013 at 12:22

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]

kch - 7-8-2013 at 15:30

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]

solo - 7-8-2013 at 16:31

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

kch - 7-8-2013 at 16:53

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 NaBH4 was developed.
A. F. Abdel-Magid, K. G. Carson, B. D. Harris, C. A. Maryanoff, R. D. Shah, J. Org. Chem., 1996, 61, 3849-3862.

[<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]

Waffles SS - 7-8-2013 at 22:17

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]

kch - 8-8-2013 at 07:38

Wouldn't the imine hydrolyze in the second step reverting back to the diamine? Also your final product is inconsistent with the carbonyl location

solo - 8-8-2013 at 08:53

.....maybe reading this will help.....solo

http://www.erowid.org/archive/rhodium/chemistry/edda.html

Waffles SS - 8-8-2013 at 09:00

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

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)

Quote: Originally posted by solo

.....maybe reading this will help.....solo

http://www.erowid.org/archive/rhodium/chemistry/edda.html

Thanks Solo,bt it has different structure(it is ethylenediammonium salt)

[Edited on 8-8-2013 by Waffles SS]

kch - 8-8-2013 at 12:27

Also, your diagram shows acetylaldehyde, not formaldehyde

Waffles SS - 8-8-2013 at 20:59

Sorry.I corrected it again

kristofvagyok - 9-8-2013 at 08:27

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

Waffles SS - 9-8-2013 at 10:37

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]

papaya - 9-8-2013 at 14:11

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.

kch - 9-8-2013 at 14:40

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?

kristofvagyok - 9-8-2013 at 15:47

Quote: Originally posted by kch

Gabriel synthesis maybe?

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

Waffles SS - 9-8-2013 at 21:03

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]

UnintentionalChaos - 9-8-2013 at 23:46

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.

Waffles SS - 10-8-2013 at 00:37

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]

Waffles SS - 21-8-2013 at 21:19

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]

kch - 22-8-2013 at 07:19

How did you dehydrate the reaction?

Waffles SS - 22-8-2013 at 09:43

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]

kch - 22-8-2013 at 10:08

Possibly imidazolidine as a condensation product

http://pubs.acs.org/doi/abs/10.1021/jo01148a003

PHILOU Zrealone - 17-9-2013 at 03:32

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.

Waffles SS - 17-9-2013 at 10:42

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?

PHILOU Zrealone - 18-9-2013 at 04:04

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

Waffles SS - 18-9-2013 at 21:09

Quote:

Another suitable method for the preparation of 2-imidazolidone,affording excellent yield on a laboratory scale,is based on the interaction of ethylenediamine with urea in the presence of water as a moderator.also, the interaction of ethylene glycol with urea leads to the formation of 20imidazolidone.
The reaction is best carried out in two steps.First, a mixture of ethylene glycol and an excess of urea is heated gradually from 150 to 240 during a period of several hours. Ammonia and carbon dioxide are evolved and a brittle resinous solid is obtained.Hydrolysis with water at 250c converts this material into 2-imidazolidone.

The Chemistry of Heterocyclic Compounds, Imidazole and Its Derivatives By Klaus Hofmann,p.227

Is there any easier way for preparing Imidazolidone?What is method for converting Imidazolidone to ethylenediamine or Ethylenediamine diacetic acid?