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Author: Subject: Ethylamine Synthesis
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[*] posted on 5-7-2012 at 14:51


Making a primary amine

The reaction happens in two stages. In the first stage, a salt is formed - in this case, ethylammonium bromide. This is just like ammonium bromide, except that one of the hydrogens in the ammonium ion is replaced by an ethyl group.


There is then the possibility of a reversible reaction between this salt and excess ammonia in the mixture.

What do you actually get if you react bromoethane with ammonia?

Whatever you do, you get a mixture of all of the products (including the various amines and their salts) shown on this page.

To get mainly the quaternary ammonium salt, you can use a large excess of bromoethane. If you look at the reactions going on, each one needs additional bromoethane. If you provide enough, then the chances are that the reaction will go to completion, given enough time.

On the other hand, if you use a very large excess of ammonia, the chances are always greatest that a bromoethane molecule will hit an ammonia molecule rather than one of the amines being formed. That will help to prevent the formation of secondary (etc) amines - although it won't stop it entirely.


Basically use as much ammonia as possible or a very large excess of ammonia and react with bromoethane. I don't know much of the details or conditions of the reaction

The ammonia removes a hydrogen ion from the ethylammonium ion to leave a primary amine - ethylamine.

The more ammonia there is in the mixture, the more the forward reaction is favoured.



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Note: You will find considerable disagreement in textbooks and other sources about the exact nature of the products in this reaction. Some of the information you'll come across is simply wrong!

You can read the arguments about the products of this reaction by following this link.

Warning! That page is in the mechanism section of the site. Return to the current page using the BACK button on your browser. If you use the links at the bottom of that page, you could get seriously lost!



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Making a secondary amine

The reaction doesn't stop at a primary amine. The ethylamine also reacts with bromoethane - in the same two stages as before.

In the first stage, you get a salt formed - this time, diethylammonium bromide. Think of this as ammonium bromide with two hydrogens replaced by ethyl groups.

There is again the possibility of a reversible reaction between this salt and excess ammonia in the mixture.

The ammonia removes a hydrogen ion from the diethylammonium ion to leave a secondary amine - diethylamine. A secondary amine is one which has two alkyl groups attached to the nitrogen.



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[*] posted on 5-7-2012 at 14:58


Wait! There's more!
What do you actually get if you react bromoethane with ammonia?

Whatever you do, you get a mixture of all of the products (including the various amines and their salts) shown on this page.

To get mainly the quaternary ammonium salt, you can use a large excess of bromoethane. If you look at the reactions going on, each one needs additional bromoethane. If you provide enough, then the chances are that the reaction will go to completion, given enough time.

On the other hand, if you use a very large excess of ammonia, the chances are always greatest that a bromoethane molecule will hit an ammonia molecule rather than one of the amines being formed. That will help to prevent the formation of secondary (etc) amines - although it won't stop it entirely.



Basically, use a large excess of ammonia and react it to bromoethane. I don't know much of the details of the reaction.
http://www.chemguide.co.uk/organicprops/amines/preparation.h...
:cool:


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[*] posted on 5-7-2012 at 15:01


Hooray for ethylamine!:D

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[*] posted on 18-7-2012 at 02:21


Methyl Ethyl Ketone ----haloform---> sodium (calcium) propionate -----> propionic acid ---urea----> propanamide ----Hofmann rearrangement---> ethylamine
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[*] posted on 7-9-2012 at 10:00


Can ethylamine be obtained from reacting hydroxylamine with ethyllithium?



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[*] posted on 7-9-2012 at 10:55


Acetaldehyde reacts with Hydroxylamine to produce ethylidenehydroxylamine.
CH3CHO + NH2OH ==> CH3CH=NOH
It might have nothing to do with ethylamine though. :D




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[*] posted on 8-9-2012 at 12:00


Jeeze, buy some Platinum, produce some catalyst, and hydrogenate Acetonitrile.

Some of the guys get gallons of Acetonitrile for free. Under some conditions, Diethylamine may be produced, when the imine intermediate condenses with already formed Ethylamine.

I'll try to produce a reference.
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[*] posted on 13-9-2012 at 14:08


Quote: Originally posted by zed  
Jeeze, buy some Platinum, produce some catalyst, and hydrogenate Acetonitrile.

Some of the guys get gallons of Acetonitrile for free. Under some conditions, Diethylamine may be produced, when the imine intermediate condenses with already formed Ethylamine.

I'll try to produce a reference.

I think that may involve having the reactants in the gas phase.




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[*] posted on 13-9-2012 at 14:10


What about ethylamine dissolved in acetonitrile and using an amalgamation type reaction with Al/Mg (Aluminum and Mercury). :cool:



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[*] posted on 24-9-2012 at 10:28


LXXXII.—The preparation of ethylamine and of diethylamine
Emil Alphonse Werner
J. Chem. Soc., Trans., 1918, 113, 899-902.
DOI: 10.1039/CT9181300899

Attachment: The preparation of ethylamine and of diethylamine.pdf (136kB)
This file has been downloaded 789 times





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[*] posted on 29-9-2012 at 17:16


I don't have access to the full article, but I was thinking of something more along these lines.

http://www.deepdyve.com/lp/elsevier/liquid-phase-hydrogenati...


www.springerlink.com/content/t2004w4m2418n779/

https://docs.google.com/viewer?a=v&q=cache:CYh-nxTSnJEJ:...

[Edited on 30-9-2012 by zed]

[Edited on 30-9-2012 by zed]
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[*] posted on 4-10-2012 at 13:22


Maybe ethylamine can be obtained via ethanol and a tosyl chloride intermediate. Then reacting the intermediate with ammonia. Maybe there will be ethylamine without diethylamine or triethylamine. :cool:
Here's the reference.
http://www.erowid.org/archive/rhodium/chemistry/mdma.tosylat...


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[*] posted on 6-10-2012 at 07:47


Try the decarboxilation of alanine in high boiling solvent with ketone catalyst.
In this article, the authors made it with tryptophan obtaining tryptamine:

S. Takano, T. Nishimura, K. Ogasawara "Heterocycles 6(8), 1167-71 (1977) ".
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[*] posted on 14-10-2012 at 12:36



Decarboxylation of amino acids


Quote:

Methylamine from glycine
10 g glycine and 15 g urethane (molar excess) were dissolved in 50 ml 0.25M Ba(OH)2 and heated for 2 hours. After precipitating the baryta as the carbonate by passing CO2 through the solution, the filtrate was acidified with a couple of drops of HCl and the solution was evaporated. The hydantoin was not isolated, yet 50 ml conc HCl was added and this was refluxed for 10 hours, after which the major part of the solution was evaporated.
This caused the hydantoin to completely transform into methylamine, so that by addition of ethanol no hydantoin was precipitated, and the characteristic reaction (2) of amines with sodium nitroprusside and acetone was obtained.
The solution was decolorised with animal charcoal and picric acid was added. After evaporation the picrate was obtained as brightly yellow plates with mp 215°C. Yield: 29 g picrate (84%)

M. Wada - Biochem. Z. 260, 47, 1933
http://www.sciencemadness.org/talk/viewthread.php?tid=9915&a...

I think replacing alanine with glycine should lead to Ethylamine





[Edited on 15-10-2012 by Waffles SS]
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[*] posted on 20-10-2012 at 14:18


OK, I'd probably try hydrogenating acetonitrile over CoB on Carbon, in Isopropyl alcohol saturated with NH3.

Worked extremely well for reducing Propionitrile to Propylamine. As in example 7.29

http://www.scribd.com/doc/73915503/Handbook-of-Heterogeneous...


The whole of "The Handbook for Heterogeneous Hydrogenation for Organic Synthesis" , now seems to be available online, for free perusal. Courtesy of Wiley.

[Edited on 20-10-2012 by zed]
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[*] posted on 26-10-2012 at 14:59


Ammonium chloride condenses with formaldehyde to form methyleneimine. Can a grignard reaction be done with the grignard reagent of methyl chloride to form ethylamine?



Ethylamine QM.jpg - 7kB

[Edited on 26-10-2012 by ChemistryGhost]




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[*] posted on 26-10-2012 at 23:05


Quote: Originally posted by ChemistryGhost  
Ammonium chloride condenses with formaldehyde to form methyleneimine.

Seriously? Please give us a reference for a preparative reaction of methyleneimine.
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[*] posted on 28-10-2012 at 15:09


to chemistryghost:
the reaction between formaline and ammonium chloride goes on and lead to methyl, dimethyl, trimethylamine hydrochloride.
The Grignard reaction to methyleneimine should works, but it's very difficult to obtain it.
Impossible by the reaction you proposed.
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[*] posted on 1-11-2012 at 14:24


Well, I don't like your chances. Polymerization is more likely, and of course the H20 formed via the condensation of formaldehyde and ammonia, is probably more reactive than the imine.

In fact, the DOJ has reported regrets that such reactions usually do not work.

During several raids on novice labs trying to produce Methamphetamine, they found zero product.

The reaction sequence of condensation of Acetaldehyde with Methylamine, followed by Sodium Sulfate drying, and reaction with Benzyl-Magnesium Chloride....Does not work well.

More stable imines can reportedly be used in such reactions,
Methyleneimine is probably not a good prospect.


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[*] posted on 1-11-2012 at 16:14


Quote: Originally posted by Waffles SS  

Decarboxylation of amino acids


Quote:

Methylamine from glycine
10 g glycine and 15 g urethane (molar excess) were dissolved in 50 ml 0.25M Ba(OH)2 and heated for 2 hours. After precipitating the baryta as the carbonate by passing CO2 through the solution, the filtrate was acidified with a couple of drops of HCl and the solution was evaporated. The hydantoin was not isolated, yet 50 ml conc HCl was added and this was refluxed for 10 hours, after which the major part of the solution was evaporated.
This caused the hydantoin to completely transform into methylamine, so that by addition of ethanol no hydantoin was precipitated, and the characteristic reaction (2) of amines with sodium nitroprusside and acetone was obtained.
The solution was decolorised with animal charcoal and picric acid was added. After evaporation the picrate was obtained as brightly yellow plates with mp 215°C. Yield: 29 g picrate (84%)

M. Wada - Biochem. Z. 260, 47, 1933
http://www.sciencemadness.org/talk/viewthread.php?tid=9915&a...

I think replacing alanine with glycine should lead to Ethylamine
[Edited on 15-10-2012 by Waffles SS]


I think not. Had you used the search engine, you would have found that the Wada article is complete bullshit, and that hydrolysis of the hydrantoin will just give back the original amino acid.

link to the pdf: An Investigation of Wada’s method of Converting alpha-Amino acids into 2-Substituted Ethylamines

Quote:
The reaction (Wada, Biochem. Z., 1933, 260, 4T), whereby an a-amino-acid is converted into a 2-substituted ethylamine by hydrolytic decarboxylation of the corresponding hydantoin, could not be repeated: the amino-acid was regenerated in each case. Some observations on the Rimini reaction for primary amines are recorded.




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[*] posted on 3-11-2012 at 02:25


@Sydenhams chorea ,
You are right,it seems this is bullshit article

But what about :
Amino Acid DecarboxylationCatalyzed by 2-Cyclohexen-1-One

http://www.erowid.org/archive/rhodium/chemistry/trp.decarbox...

This is bullshit too?
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[*] posted on 1-1-2021 at 09:01


I think propionitrile hydration with hydrochloric acid to propionamide, then sodium hypochlorite Hoffman rearrangement to ethylamine could work.



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[*] posted on 1-1-2021 at 12:45


Feasible but your source of propionitrile is..?
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[*] posted on 2-1-2021 at 09:41


Quote: Originally posted by ChemistryGhost  
I think propionitrile hydration with hydrochloric acid to propionamide, then sodium hypochlorite Hoffman rearrangement to ethylamine could work.

You again with the proposing of noneconomical routes, Blue Dex?
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