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ItaBier
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[*] posted on 17-11-2015 at 11:13
phosphoethanolamine


Hi anyone have any information on the simple synthesis of phosphoethanolamine, because here in Brazil is much talked about for its anticancer properties.
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Praxichys
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[*] posted on 17-11-2015 at 11:32


It should be pretty easy to make. It's just the phosphoric acid mono-ester of monoethanolamine.

I'd say reflux monoethanolamine with a large excess of phosphoric acid for a couple hours, basify with sodium carbonate, then see what can be distilled off under vacuum. Or, extract it with some inorganic solvent.

Not sure though. Sigma calls for -20C as a storage temp. Could be unstable.


[Edited on 17-11-2015 by Praxichys]




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[*] posted on 17-11-2015 at 12:38


Quote: Originally posted by Praxichys  
It should be pretty easy to make. It's just the phosphoric acid mono-ester of monoethanolamine.

Amazingly, under the tuition of the B&D Science School, i finally have a clue what all of those words mean.

It's a Revelation !




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[*] posted on 17-11-2015 at 18:08


Boiling with phosphoric acid will not give any product. You need a specialized phosphorylating agent such as, for example, dibenzyphopshoryl chloride. There is a huge literature on this subject (phosphorylation reactions and reagents) and it is relatively easy to find and learn from.

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[*] posted on 18-11-2015 at 00:57


Hi, i find the simple way, i see various syntheses with complex molecules, gold chloride, barium, etc. Already the largest university researchers have invented a process by the reaction of the two compounds(mea and phosphoric acid) in an alcoholic medium, washinhg with ethanol and heating at 190 degrees to transform phosphate in phospho and neutralization with calcium and magnesium carbonates with yeld of 90%. the problem is the details, here patents has no free access.
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Praxichys
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[*] posted on 18-11-2015 at 05:28


Well, phooey. For some reason I assumed phosphates were like borates. It does seem pretty straightforward with the right reagents though. All the preps in Brauer use POCl3 so they're kind of prohibitive for amateur use.

This paper has an interesting route:
http://www.sciencedirect.com/science/article/pii/S0040403908...
Facile synthesis of simple mono-alkyl phosphates.png - 8kB

The only difficult thing to get here is the pyridine.




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ItaBier
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[*] posted on 18-11-2015 at 09:30


Does there exist error in the following way: 1 mol ethanolamine + 1.1 mol of phosphoric acid + 1 mol of absolute ethanol at room temperature. wash the precipitate with absolute ethanol. Heat the precipitate by 190 C for one hour. neutralizing with calcium carbonate and dissolve in hot distilled water. wait for the crystallization and drying the precipitate (melting 240 C)
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[*] posted on 18-11-2015 at 12:05


I don't know about the difficulty in forming phosphate esters, but it's going to be a lot tougher to make an ester from ethanolamine than from ethanol. The amine group is basic, and a better nucleophile than the hydroxyl group of the alcohol.



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[*] posted on 18-11-2015 at 13:10


It's not impossible that method works, but you can't check it with taught chemistry. The first step would produce a salt which might dehydrate to produce the target on heating. The best way to check would be to look it up in proper literature.

There are a lot of desperate people wanting to believe in cures, something that can be cooked up from industrial chemicals sounds very risky to me.
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[*] posted on 1-1-2016 at 20:58


Quote: Originally posted by ItaBier  
Hi anyone have any information on the simple synthesis of phosphoethanolamine, because here in Brazil is much talked about for its anticancer properties.


Actually, here the phophoethanolamine made by Prof. Dr. Gilberto Orivaldo Chierice and his team was in the form of the mixed salts of Zn, Ca and Mg using a modified synthesis (Ca-EAP, Mg-EAP, sold OTC in USA and Europe as supplements).


Quote: Originally posted by Praxichys  
It should be pretty easy to make. It's just the phosphoric acid mono-ester of monoethanolamine.

I'd say reflux monoethanolamine with a large excess of phosphoric acid for a couple hours, basify with sodium carbonate, then see what can be distilled off under vacuum. Or, extract it with some inorganic solvent.

Not sure though. Sigma calls for -20C as a storage temp. Could be unstable.


[Edited on 17-11-2015 by Praxichys]



The attached patent say that equimolar amounts could be used with good yields.


http://pubchem.ncbi.nlm.nih.gov/compound/2-Aminoethyl_dihydr...

melting point: 241-243 °C, about the same of patent attached ( 240-242°C).

EDIT: I found this synthesis: https://orgprepdaily.wordpress.com/?s=ethanolamine where author report about 50% yield from this reaction and says mp of product is 230-234°C.




Attachment: US3644603-aminoethyl phosphate.pdf (119kB)
This file has been downloaded 185 times

[Edited on 2-1-2016 by Aqua_Fortis_100%]




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[*] posted on 2-1-2016 at 02:21


MDMa is supposed to be anticancer drug. Go make some MDMA then.
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[*] posted on 2-1-2016 at 14:20


Quote: Originally posted by byko3y  
MDMa is supposed to be anticancer drug. Go make some MDMA then.


No thanks.

Actually phosphorylethanolamine is an important endogenous substance used to form cell membranes and also as a signaling agent in the body.




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[*] posted on 3-1-2016 at 10:08


The problem is how to cristalize a viscous liquid like honey.
Brazilian patent:

Attachment: PI0800460.pdf (497kB)
This file has been downloaded 461 times

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[*] posted on 4-1-2016 at 07:55


I think it should be pretty straightfoward, just add ethanol and cool it down. You could omit the inert atmosphere too, just bubble some air in to drive water out.

90% is just too good to believe though...




Bromine, definitely bromine.
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[*] posted on 4-1-2016 at 08:34


Quote: Originally posted by ItaBier  
The problem is how to cristalize a viscous liquid like honey.
Brazilian patent:


Like the NexusDNA said, the real problem is not this, cause this liquid is just molten and crude phosphorylethanolamine. I would simply put the molten thing in a big glass plate to cool down and then break it finely to dissolve it and recrystallise.

Note that phosphorylethanolamine is just the precursor to make the mixed salts that are composed the USP pills -> "1 mol phosphoethanolamine neutralized by 0,42 mol CaCO3 + 0,11 mol MgCO3 + 0,06 mol ZnCO3" referenced in the USP team patent.

The method they use to neutralize the phosphoethanolamine (mixing the carbonates and the phosphoethanolamine moisting it with water and letting it react for 5 days at 70°C) maybe can alter the crystal structure of final product and explain the higher biodisponibility of phosphoethanolamine salts.





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[*] posted on 4-1-2016 at 08:52


I haven't had time to try it myself, but wikipedia states that a high temperature reaction between phosphorus pentoxide and sodium chloride produces phosphoryl chloride vapor, which could be collected and used to produce the phosphate ester.



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[*] posted on 4-1-2016 at 14:06


Quote: Originally posted by Amos  
I haven't had time to try it myself, but wikipedia states that a high temperature reaction between phosphorus pentoxide and sodium chloride produces phosphoryl chloride vapor, which could be collected and used to produce the phosphate ester.


I wouldnt waste precious P2O5 neither phosphoryl chloride in the synthesis of phosphorylethanolamine since it can be made from phosphoric acid, maybe you can use for another phosphoric esther that would be hard to make from plain phosphoric acid.





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[*] posted on 6-1-2016 at 10:14


The attached doc GB1092185 is the Hans Nieper / Franz Kohler patent regarding Ca-EAP and a mix of K and Mg aspartates. It is stated that treating with Ca-EAP alone can develop Mg and K deficiency, so the aspartates of this salts are administred along with Ca-EAP. In the end of the patent in procedure I and II they say the simplest way how to get Ca-EAP from phosphoethanolamine.


Another attached patent US5068228 is a much more general and interesting document, as it focuses on alkylamino esters of phosphoric acid not just phosphoethanolamine but its salts and related substances and some possible pharmaceutical uses. They make EAP salts somewhat different, as they dissolve phosphorylethanolamine in alkaline media, add calcium hydroxide and bubble CO2 and filter calcium phosphate and carbonate. They state a high yield (88%) although I think this way seems to hydrolise the phosphoric ester to some extent.



Attachment: fosfo-GB1092185A.pdf (241kB)
This file has been downloaded 446 times

Attachment: US5068228-usos de eap e correlatos.pdf (332kB)
This file has been downloaded 205 times





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[*] posted on 4-7-2016 at 03:19


Oi Ita. Eu consegui resolver este problema. Tens face? nos falamos in box
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