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Author: Subject: Diethylamine Hydrochloride Synthesis
MrHomeScientist
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[*] posted on 1-5-2013 at 07:42
Diethylamine Hydrochloride Synthesis


I'm very eager to try the experiment posted by smaerd in the Pretty Pictures thread - making the thermochromic salt bis(diethylammonium) tetrachlorocuprate(II). The only reagent that eludes me is diethylamine hydrochloride, so I am looking into ways of making it myself. Disclaimer: I know very little about organic chemistry!

There already exists a thread on making diethylamine, and I read this with the thought of making that compound then reacting with muriatic acid to precipitate the acid salt. However there was one method mentioned to directly make it using acid hydrolysis instead of base hydrolysis - here's an excerpt from page 4 of that thread:

Quote: Originally posted by Arrhenius  
Acid Hydrolysis (already suggested by Ritter):

I.) Reflux a solution of ~ 3:1 (v:v) DEET:HCl (30% muriatic acid is probably okay) for ~1-2hr.
II.) Cool the solution to room temperature.
III.) Extract the resulting solution with toluene (easy to get) to remove the (similar to toluene) m-methylbenzoic acid.
IV.) Boil off the water/acid in a fume hood or outdoors to yield Et2NH*HCl.
IIV.) For fun, let the toluene evaporate and hopefully you'll find your m-methylbenzoic acid left behind.

*Note: I don't believe there's anything particularly dangerous with this procedure. As always, a hot plate is preferred over a bunsen burner, toluene is flammable (DEET too), and if you get acid on yourself wash it with water immediately. HCl vapor is not particularly dangerous as it is too irritating to stay near for more than a couple seconds. Oh.. and don't eat any of your products.


My question is, does this sound feasible? Has anyone tried this? There was little talk about it in the rest of the thread. There were numerous mentions of needing a cosolvent like ethylene glycol for the base hydrolysis, but I'm not sure if it's necessary here. Again, I don't know much about organic. I was able to purchase 98.11% DEET, and I have a small amount of toluene (can anything else be used in its place? I'd prefer using something I have more of).

I'd have posted a reply in the existing thread, but I am more interested in the hydrochloride salt than diethylamine itself.
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[*] posted on 1-5-2013 at 09:35


This would be better suited to the organics section.



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MrHomeScientist
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[*] posted on 1-5-2013 at 11:50


I suppose; if a mod would like to move this please do so. I just had worried my lack of references would be offputting to some over there (plus organic is a big and scary place for someone as inexperienced in it as I!).
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[*] posted on 1-5-2013 at 15:17


I have also been looking into a route to make diethylamine hydrochloride so that I can synthesize the tetrachlorocuprate complex.
So far I have the following steps:

Cleave DEET to form diethylamine and the sodium salt of meta Toluic acid via the procedure suggested by Jon in the diethylamine thread

Quote: Originally posted by jon  
i got this from a chemist who made it from deet

OTC Hydrolysis of N,N-diethyl-meta-toluamide (DEET) to Diethylamine and M-toluic acid


To a 250ml autoclavable media bottle is added in order, 175ml N,N-diethyl-meta-toluamide (98.11% comerc grade, $15) followed by 40ml 70% EtOH. the media bottle is capped and vigorusly shaken for one minute. the EtOH and DEET should now be a homogenous mixture. to this solution is added 40g NaOH and once again capped. the media bottle containing the mix is now sealed and heated in a hot water bath (crock pot set on low) added to the bath at 55*C (125*F) ending at 70*C (160*F) periodicly agitating for the legnth of time it takes to compleatly desolve the NaOH plus 1.5hr. the solution should now be a deep yellow color the crock pot is turned off and allowed to cool to RT. it is removed from the bath and allowed to stand at RT for one day minimum. the bottle will then be carefuly opened after cooling in the refridgerator for 1hr. obsedved was the strong smell of diethylamine, no longer did it smell of DEET and EtOH. the solution is fractionaly distilled (dont forget boiling chips, this stuff likes to bump) collecting the fraction along a 9 degree tempeture arc centered on 55*C (51-59*C). the solution may solidify twords the end of the distilation and a small ammount of DH2O can be added to liquify the waxy mass of M-toluic acid and NaOH. total yeild form aprx 225ml of solution was 57ml of crystal clear diethylamine in freebase form. 25.3%

MeOH can be used in a pinch but i like EtOH, it mixes better with the DEET and has just enough water for the hydrolysis but not enough to cause separation.

Diethylamine C4H11N 73.14g/mol boiling point 55.5*C (131.9*F)

N,N-Diethyl-M-Toluamide C12H17NO 191.27g/mol boiling point 288-292*C (550.4-557.6*F)

M-toluic acid C8H8O2 136.15g/mol boiling point 263*C (505.4*F) (melt at 111-113*F)
-------------------------------------------------------------------------------------------------------------------------------------
Ethanol C2H6O 46.07g/mol boiling point 78.4*C (173.12*F)

Methanol CH4O 32.04g/mol boiling point 64.7*C (148.4*F)

water H2O 18.015g/mol boiling point 100*C (212*F)




Then reflux the Diethylamine with either aqueous or ethanoic hydrogen chloride to synthesize diethylamine hydrochloride

I am farly new to organic chemistry so I am not sure weather the conversion to diethylamine hydrochloride will work though.

DrSchnufflez
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[*] posted on 1-5-2013 at 20:06


Well if you ever get around to isolating the tetrachlorocuprate its a beautiful but hygroscopic compound.

The reaction conditions to make it need to be anhydrous as well.


Then when you have the best dry crystals you can achieve i would try to encapsulate the crystals between to microscope slides some how sealed.

This way you will have tiles that you can play with.

Also be careful with over heating them as you will quickly destroy them.


You will probably come to the realization that the best way to control them is a peltier device.

Then you will have tiles each controlled by a peltier device ... then of course you could form a large grid and control the color change with a computer program. Ether heating or cooling for the maximum wow factor...

Go further then i did my friend....


Cheers....






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[*] posted on 2-5-2013 at 05:45


Quote: Originally posted by DrSchnufflez  
I have also been looking into a route to make diethylamine hydrochloride so that I can synthesize the tetrachlorocuprate complex.
So far I have the following steps:

Cleave DEET to form diethylamine and the sodium salt of meta Toluic acid via the procedure suggested by Jon in the diethylamine thread

[snip]

Then reflux the Diethylamine with either aqueous or ethanoic hydrogen chloride to synthesize diethylamine hydrochloride

I am farly new to organic chemistry so I am not sure weather the conversion to diethylamine hydrochloride will work though.

DrSchnufflez


That was my initial thought as well (and I actually found that procedure where it was originally posted on Zoklet.net before I saw it on SM), but the mention of directly making it by refluxing with acid instead of base sounded simpler to me. Plus I don't have a fractionating column so isolating the product would be difficult, I think. I was hoping someone could comment on the validity of the acid hydrolysis method.

If no one has tried it, I suppose I should soldier on and experiment myself. I just don't know how to test the products I obtain, really.


Quote: Originally posted by aaparatuss  
Well if you ever get around to isolating the tetrachlorocuprate its a beautiful but hygroscopic compound.

The reaction conditions to make it need to be anhydrous as well.

Then when you have the best dry crystals you can achieve i would try to encapsulate the crystals between to microscope slides some how sealed.

This way you will have tiles that you can play with.

Also be careful with over heating them as you will quickly destroy them.

You will probably come to the realization that the best way to control them is a peltier device.

Then you will have tiles each controlled by a peltier device ... then of course you could form a large grid and control the color change with a computer program. Ether heating or cooling for the maximum wow factor...

Go further then i did my friend....

Cheers....


Neat ideas! I especially like the peltier element for more controllable temperatures. My idea for presentation was to sandwich the crystals between two watch glasses or petri dishes so I can hold it vertically, and heat it from behind with a heat gun. We'll see how that pans out.

Also you mention overheating can destroy them - are you sure? What temperature does this happen at? The papers that smaerd kindly provided me in the References section say that you can heat them until they melt with no decomposition. If they do melt, they have an interesting tendency to supercool in the yellow state, and only slowly switch back to green.
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[*] posted on 2-5-2013 at 11:38


Quote: Originally posted by DrSchnufflez  

Then reflux the Diethylamine with either aqueous or ethanoic hydrogen chloride to synthesize diethylamine hydrochloride

I am farly new to organic chemistry so I am not sure weather the conversion to diethylamine hydrochloride will work though.

DrSchnufflez


Once you've got the diethylamine, you won't have to reflux it with acid to get it to convert- just add the acid. Acid-base reactions are faster than most reactions.




Please remember: "Filtrate" is not a verb.
Write up your lab reports the way your instructor wants them, not the way your ex-instructor wants them.
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7-5-2013 at 06:24
MrHomeScientist
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[*] posted on 7-5-2013 at 06:29


My thread was moved here at my request (thanks woelen!), to see if anyone 'round these parts might have more input. I'm interested in the direct synthesis of the hydrochloride, so I don't have to go through the distillation step. I don't have a fractionating column, so I'm concerned about my ability to accurately collect a product over a narrow temperature range.
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MrHomeScientist
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[*] posted on 30-11-2015 at 13:47
Diethylamine Hydrochloride Disposal


I ended up purchasing some of the title compound to attempt the thermochromic crystal synthesis, and long story short I could never get it to work properly. So, I have a small amount (<25mL) of diethylamine hydrochloride in anhydrous ethanol to dispose of. Anyone know of any simple reactions to render this chemical into a less harmless, safe to dispose down the drain form? I have access to many standard inorganic laboratory chemicals (acids, bases, hydrogen peroxide, etc.), but not very many other organic reagents.

[Edited on 11-30-2015 by MrHomeScientist]
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[*] posted on 30-11-2015 at 14:02


I admire your persistence MrHomeScientist, truly.

How about we call in the Big Guns and try to work this out ?

Chances are that NaOH will wreck it up enough to render it 'disposable' although i am nowhere near an expert.

[Edited on 30-11-2015 by aga]




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[*] posted on 30-11-2015 at 14:09


As far as I am aware, diethylamine has a low order of toxicity, on par with ammonia. An ethanol solution of the hydrochloride salt is relatively innocuous, especially if it is a small quantity.
I would just dilute your diethylamine.HCl/ethanol solution with 10 x its volume of water and pour it down the drain or let it soak into the ground.
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[*] posted on 30-11-2015 at 14:16


If it is in usable condition someone might like to take that off your hands.
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[*] posted on 1-12-2015 at 13:21


Unfortunately it was purchased for my outreach program with Not My Money<sup>TM</sup>, so giving it away is unfortunately not an option.

My MSDS does list it with 1's across the board, so it certainly doesn't seem too dangerous. Just seeing if anyone knew of a way to destroy the compound in case drain disposal wasn't a good idea.
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[*] posted on 1-12-2015 at 15:29


NaOH will do nothing. Whatever you do, don't sell it: it's a List I chemical as an essential LSD precursor and you'll be riding the partyvan faster than you can say "phosphorus oxychloride".

Simple answer is to set fire to it, outside of course, as long as it contains no Cl or P you'll be fine.
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[*] posted on 1-12-2015 at 15:35


It's perfectly legal to possess phosphorus oxychloride, right?
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[*] posted on 1-12-2015 at 16:13


Yes. Also apparently it's monoethylamine that's listed, not diethylamine. Diethylamine is watched, but not listed. I guess ethylamine is a solvent for Birch reductions (shake n' bake meth). Still, I would not fuck with that.

[Edited on 2-12-2015 by clearly_not_atara]
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[*] posted on 1-12-2015 at 17:03


Hmmm. Perhaps, the list has changed.

Seems like I remember Diethylamine as being listed.

There are also , remember, other lists. Those pertaining to potential chemical weapons, and other WMD.

If you wish to purchase a trainload of PCl3, the rules are different. Some enthusiastic company will find a way to fill your order, regardless of regulations. Money talks.



[Edited on 2-12-2015 by zed]

[Edited on 2-12-2015 by zed]
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[*] posted on 1-12-2015 at 20:23


Diethylamine, and its salts are on the DEA "Special Surveillance List Published Pursuant to Title 21, United States Code, Section 842(a)(11)".

So are sodium metal, magnesium metal turnings, sodium and potassium dichromate, formic acid, Freon-11 and Freon-113.
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[*] posted on 2-12-2015 at 07:14


Let's not all panic here. This chemical was bought from Alfa with government money for a government outreach program. I'll be fine.
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[*] posted on 2-12-2015 at 07:55


I have been curious about this DEA listing thing for some time, and pay close to attention to what is on their lists, but for their regular list II (not "special surveillance") includes things like: acetone, potassium and sodium permanganate, MEK, toluene, hydrochloric acid, sulfuric acid, and MIBK -- all of which can be purchased OTC for various uses (mostly from standard hardware stores).

Knowing that these common chemicals appear on a "DEA list" is what motivates me to try to understand what is really a likely cause of harassment by law enforcement.

If you look at the reporting quantities of the things I listed above the amounts are very large: 50 gallons (*per month*) of toluene and acetone for example.

Clearly they aren't tracking these List II chemicals like they are some List I chemicals like white phosphorus or pseudoephedrine.

For the "special surveillance list", which diethylamine appears on, the corresponding regulation appears to be simply the admonition (in its entirety):

"The Comprehensive Methamphetamine Control Act of 1996 (MCA) makes it unlawful for any person to distribute a laboratory supply to a person who uses, or attempts to use, that laboratory supply to manufacture a controlled substance or a listed chemical, with reckless disregard for the illegal uses to which such laboratory supply will be put. Individuals who violate this provision are subject to a civil penalty
of not more than $25,000; businesses which violate this provision are subject to a civil penalty of not more than $250,000. The term "laboratory supply" is defined as "a listed chemical or any chemical, substance, or item on a special surveillance list published by the Attorney General, which contains chemicals, products, materials, or equipment used in the manufacture of controlled substances and scheduled listed
chemicals."

This is in a 76 page handling manual, providing guidance to people actually selling this stuff on what to do.

It appears then that the "special surveillance list", which includes diethylamine, has no reporting requirements, and is not actually being tracked at all in an active sense. I would come into play (I gather) when an operation gets busted, and criminal charges are being prepared (i.e. seller beware).

So far I have not seen any clear account on this site about someone being visited by the law for a small purchase of a List II or "special surveillance" chemical.

http://www.deadiversion.usdoj.gov/pubs/manuals/chem/chem_man...
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[*] posted on 2-12-2015 at 08:10


Quote: Originally posted by MrHomeScientist  
I ended up purchasing some of the title compound to attempt the thermochromic crystal synthesis, and long story short I could never get it to work properly. So, I have a small amount (<25mL) of diethylamine hydrochloride in anhydrous ethanol to dispose of. Anyone know of any simple reactions to render this chemical into a less harmless, safe to dispose down the drain form? I have access to many standard inorganic laboratory chemicals (acids, bases, hydrogen peroxide, etc.), but not very many other organic reagents.

[Edited on 11-30-2015 by MrHomeScientist]

I'd be interested in your long story long ;)
Seriously, what exactly did you try?

Offtopic: A while ago I tried to synthesize Ni(en)2(PbI3)2, but without any success. This left me puzzling, as the publication simply calls for a strong solution of Pb(OAc)2 in KI solution (1:4 ratio - top of my head) and dripping into this Ni(OAc)2 with (en) (1:1 ratio) dissolved in 50ml of H2O.
Nothing happened, just the green nickel solution on top of the PbI2 that had remained largely undissolved.
I'm trying to dry this in a desiccator, but to no avail, as a thin layer of PbI2 forms on the surface, preventing further evaporation of the solvent.
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[*] posted on 2-12-2015 at 08:46


Apparently I've already posted my experimental details: http://www.sciencemadness.org/talk/viewthread.php?tid=30117

I came across that while looking up the paper I based the experiment on, so lucky for me I didn't have to type it all again :P
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[*] posted on 4-12-2015 at 08:40


Thanks, going to read through it right away :cool:
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[*] posted on 4-12-2015 at 16:01


Right stupid to buy some diethylamine hcl and toss it out, fuckin dumb. I swear some people have no buisenss tinkering with chemicals.
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[*] posted on 2-1-2016 at 15:56


Eh....No big deal. Easy to make. Lots of ways to make it.

Some of the guys seem to have no problem, just buying it by the liter.
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