Waffles SS
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Iminodiacetic acid
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Iminodiacetic acid, HN(CH2CO2H)2, often abbreviated to IDA, is a dicarboxylic acid amine (note that the nitrogen atom forms a secondary amino group,
not an imino group as the name suggests). The iminodiacetate anion can act as a tridentate ligand to form a metal complex with two, fused, five
membered chelate rings.The proton on the nitrogen atom can be replaced by a carbon atom of a polymer to create an ion-exchange resin, such as chelex
100.
IDA forms stronger complexes than the bidentate ligand glycine and weaker complexes than the tetradentate ligand nitrilotriacetic acid.
wikipedia
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There is some possible way for synthesis Iminodiacetic acid.like Oxidation of diethanol amine,hydrolysis iminodiacetonitrile and..
I want to know this is possible to make it by direct N-alkylation of ammonia by Chloroacetic acid?
Making Glycine by this method is possible by using 15 molar excess ammonia(Org syn. described this method in hippuric acid synthesis)
I know Secondary amine is more Nucleophile than Primary amine but i want to know this is possible to stop this N-alkylation in diacetic acid?
Using long chain or aromatic alcohol Chloroacetic acid esters may prevent Tri N-alkylation according to Steric effects?
http://www.orgsyn.org/demo.aspx?prep=cv2p0328
[Edited on 16-10-2014 by Waffles SS]
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Chemosynthesis
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1. Yes, see page 388 of the linked book for references. https://play.google.com/store/books/details?id=UWlZAAAAYAAJ&...
2. Stopping at diamine? Not sure. Probably just a stoichiometric proportion at a specific temperature and good separation.
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Waffles SS
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Thanks Chemosynthesis ,
"Iminodi acetic acid and nitrilotriacetic acid are formed upon boiling chloroacetic acid with concd aq ammonia"
I found this method on Merck index too but there is no detail.
I want to stop it at Dialkylated(diacetic acid) but as you know this reaction continue to Trialkylated.
What about Aromatic or Long Chain aliphatic Chloroacetic acid ester?or even protect glycine with acetyl or formyl group?(this make Amide that is
really less reactive than Amine)
[Edited on 17-10-2014 by Waffles SS]
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PHILOU Zrealone
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If you don't want to play with statistical workup induced by exces ammonia.
You may want to use a technique that favors secondary amine formation and blocks somehow one hydrogen atom from the amine:
1°) NH2-C#N (cyanamide)
H2N-C#N + 2 Cl-CH2-CO2H -base-> (HO2C-CH2-)2N-C#N + 2 base.HCl
H2N-C#N + 2 Cl-CH2-CO2R -base-> (RO2C-CH2-)2N-C#N + 2 base.HCl
then hydrolysis
(HO2C-CH2-)2N-C#N -H2O/base or acid-> HO2C-CH2-NH-CH2-CO2H
(RO2C-CH2-)2N-C#N -H2O/base or acid-> HO2C-CH2-NH-CH2-CO2H + 2 ROH
2°) glycine or glycine ester with glyoxilic acid or glyoxilic ester (in a 1/1 stoechiometric ratio)
HO2C-CH2-NH2 + O=CH-CO2H --> HO2C-CH2-N=CH-CO2H
RO2C-CH2-NH2 + O=CH-CO2R --> RO2C-CH2-N=CH-CO2R
then hydrogenation of the imine and eventual hydrolysis
HO2C-CH2-N=CH-CO2H -Hydrogenation-> HO2C-CH2-NH-CH2-CO2H
RO2C-CH2-N=CH-CO2R -Hydrogenation-> RO2C-CH2-NH-CH2-CO2R
and eventual hydrolysis
RO2C-CH2-NH-CH2-CO2R -H2O+base (or acid)-> HO2C-CH2-NH-CH2-CO2H + 2 ROH
[Edited on 17-10-2014 by PHILOU Zrealone]
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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Chemosynthesis
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No problem. Sorry I wasn't as beneficial as I thought. I can't check these right now, but I hope either of these are more helpful than my last:
1. Heintz, Ann. 149, 88 (1869).
2. J. Org. Chem. 15, 46 (1950).
Definitely interested in what you end up doing.
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Waffles SS
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Quote: Originally posted by Chemosynthesis  | No problem. Sorry I wasn't as beneficial as I thought. I can't check these right now, but I hope either of these are more helpful than my last:
1. Heintz, Ann. 149, 88 (1869).
2. J. Org. Chem. 15, 46 (1950).
Definitely interested in what you end up doing. |
Thanks chemosynthesis ,
I found J. Org. Chem. 15, 46 (1950) but i cant find Heintz, Ann. 149, 88 (1869). (i found nothing on google searching even nothing at archive.org)
| Quote: Originally posted by PHILOU Zrealone | If you don't want to play with statistical workup induced by exces ammonia.
You may want to use a technique that favors secondary amine formation and blocks somehow one hydrogen atom from the amine:
1°) NH2-C#N (cyanamide)
H2N-C#N + 2 Cl-CH2-CO2H -base-> (HO2C-CH2-)2N-C#N + 2 base.HCl
H2N-C#N + 2 Cl-CH2-CO2R -base-> (RO2C-CH2-)2N-C#N + 2 base.HCl
then hydrolysis
(HO2C-CH2-)2N-C#N -H2O/base or acid-> HO2C-CH2-NH-CH2-CO2H
(RO2C-CH2-)2N-C#N -H2O/base or acid-> HO2C-CH2-NH-CH2-CO2H + 2 ROH
2°) glycine or glycine ester with glyoxilic acid or glyoxilic ester (in a 1/1 stoechiometric ratio)
HO2C-CH2-NH2 + O=CH-CO2H --> HO2C-CH2-N=CH-CO2H
RO2C-CH2-NH2 + O=CH-CO2R --> RO2C-CH2-N=CH-CO2R
then hydrogenation of the imine and eventual hydrolysis
HO2C-CH2-N=CH-CO2H -Hydrogenation-> HO2C-CH2-NH-CH2-CO2H
RO2C-CH2-N=CH-CO2R -Hydrogenation-> RO2C-CH2-NH-CH2-CO2R
and eventual hydrolysis
RO2C-CH2-NH-CH2-CO2R -H2O+base (or acid)-> HO2C-CH2-NH-CH2-CO2H + 2 ROH
[Edited on 17-10-2014 by PHILOU Zrealone] |
Really you are helpful PHILOU Zrealone,
This is interesting method but i prefer not to using Cyanide components.also Glyoxylic acid is not available for me .
Whats your idea about reaction of N-acetyll Glycine with Chloroacetic acid?
Acetyl will make Amide and N-acetyl glycine is less reactive and Tri N-alkylation wont occur easily .am i wrong?
Also whats your idea about reaction of long chain aliphatic or even aromatic chloroacetic acid ester with glycine?maybe steric effect prevent Tri
N-alkylation
[Edited on 17-10-2014 by Waffles SS]
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Dr.Bob
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I would consider starting with benzylamine, then dialkylate with chloroacetic acid, then hydrogenate to get the desired product. It is very hard to
get a pure diamine by alkylation unless you block one position on the N. You might even get some quaternary amine if you go too hard, but that
generally won't happen if you don't use too much alkylating reagent and keep it dilute and cool.
You could also deprotonate Boc-Gly and alkylate, which would be pretty simple to do with only one equivilant of base, then de-Boc it. That should be
pretty selective.
[Edited on 17-10-2014 by Dr.Bob]
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kmno4
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http://www.docin.com/p-338557534.html
See (and read) cited literature.
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UnintentionalChaos
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What about the alkylation of the benzaldehyde aldimine formed with glycine ethyl ester? Would be similar to http://www.sciencemadness.org/talk/viewthread.php?tid=12542
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kmno4
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.... and this can be found - chloroacetic acid, Ca(OH)2 and NH3 aq :
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Waffles SS
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Thanks Dr.Bob,
also Special thanks for my friend Kmno4
[Edited on 19-10-2014 by Waffles SS]
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