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Storing Diethylamine?

Agent MadHatter - 14-9-2009 at 15:14

I recently distilled over 100grams of Diethylamine, but I can't find any information on storing it. I don't believe it reacts with light, but I don't want it to decompose either.

What is the best way to store decent sized amounts?

kclo4 - 14-9-2009 at 15:50

Are you sure it is diethylamine?
It might be good to keep it in a salt form.. such as its hydrogen chloride or sulfate.
I'd store it in a cool dark place in a glass container..

Agent MadHatter - 14-9-2009 at 16:01

Its in HCL form, and its in a flask with a stopper on it at the moment. Positive its Diethylamine.

zed - 14-9-2009 at 16:17

Exclude air. Brown glass bottle. Cool dark place.

entropy51 - 14-9-2009 at 16:25

Quote: Originally posted by Agent MadHatter

Positive its Diethylamine.

Anyone else find it odd that he's positive what he's got but hasn't a clue how to store it??

kclo4 - 14-9-2009 at 16:38

How did you get it? DEET hydrolysis?
You ought to report the success, not many people know if it works well or not.

Agent MadHatter - 14-9-2009 at 17:06

Hows it odd? I'm positive I have it, because I took off the acid and made it freebase and watched my product disappear into the air.

I did do hydrolysis though...I don't feel like I'm the right type of candidate to make a report about it.

kclo4 - 14-9-2009 at 17:11

Quote:

I did do hydrolysis though...I don't feel like I'm the right type of candidate to make a report about it.

I'd still report back the success you've had, how you did it, some simple observations, etc... That would at least be giving back to the community that has helped you out a lot with this little project..

entropy51 - 14-9-2009 at 17:30

Quote: Originally posted by Agent MadHatter

Hows it odd? I'm positive I have it, because I took off the acid and made it freebase and watched my product disappear into the air.

Well that proves it for sure!

No point in messing around with the Hinsberg test and other silliness, is there?

Agent MadHatter - 14-9-2009 at 17:44

Eh. I don't know how to do a Hinsberg test...

But I'll report back. Whats your name on TV?

kclo4 - 14-9-2009 at 18:10

Quote: Originally posted by entropy51

Quote: Originally posted by Agent MadHatter

Hows it odd? I'm positive I have it, because I took off the acid and made it freebase and watched my product disappear into the air.

Well that proves it for sure!

No point in messing around with the Hinsberg test and other silliness, is there?

Well, what other compound would form from H2SO4 or HCl and DEET? assuming that is how you made it..

Agent MadHatter - 14-9-2009 at 18:15

After hydrolysis I believe toluic acid would be left with Diethylamine. I distilled the DEA in a container with some HCL in it.

entropy51 - 15-9-2009 at 05:25

What else could it be? Who could even guess? He's not telling us how he thinks he made it. I guess he will divulge details after he gets a patent. I think the claim of 100 gms of DEA is suspect if we're talking about the hydrolysis of DEET.

DJF90 - 15-9-2009 at 08:58

I'm with entropy; to make 100g Et2NH2Cl you require a yield of 100% on the hydrolysis of 176.3g DEET. Thats in excess of £17 (retails at about £10/100mls). Now factor in that the yield will not be 100% (probably more likely to be between 60 and 90%, depending on conditions etc) and its looking expensive, especially for less than a mole of reagent.

Also with the acid hydrolysis of DEET you will not distil the diethylamine from the reaction mixture...

[Edited on 15-9-2009 by DJF90]

Picric-A - 15-9-2009 at 10:14

Just a quick note, 100% deet can be had for half the rrp off ebay UK
If this guy thinks hes distilling DEA.HCl from the mix he should really learn some basic chemistry

[Edited on 15-9-2009 by Picric-A]

entropy51 - 15-9-2009 at 10:56

I was giving him the benefit of a doubt that he either (a) hydrolyzed in base, in which case the DEA could be distilled out, or (b) hydrolyzed in acid, then added base.

I'm thinking he meant he distilled it INTO HCl. But that wouldn't form the crystals of the amine HCl that he seems to think he has, would it? No mention of using HCl in Et2O, which would form crystals.

I love chemical mysteries!

We'll be able to figure it all out when his patent is issued.

[Edited on 15-9-2009 by entropy51]

Picric-A - 15-9-2009 at 11:16

I think he distilled the amine out into HCl(aq) then boiled down forming the salt!
but indeed this is a mystery, no wonder he doesnt want to document it

[Edited on 15-9-2009 by Picric-A]

DJF90 - 15-9-2009 at 12:29

Quote: Originally posted by Picric-A

If this guy thinks hes distilling DEA.HCl from the mix he should really learn some basic chemistry

[Edited on 15-9-2009 by Picric-A]

I seem to recall you making the same mistake (not basifying) here: http://www.sciencemadness.org/talk/viewthread.php?tid=12366#...

And as to the mystery, we're still waiting on pictures of that contact process plant. I wander why you dont want to document it...

panziandi - 15-9-2009 at 12:33

I suspect it was base hydrolysis with vapours leading over to hydrochloric acid,which was evaporated down and crystalised and stored? I suspect this was the route chosen, however, DEA.HCl will be very hygroscopic and deliquescent, probably difficult to crystalise nicely. I would personally store it, assuming it is the chloride, as the solid in an amber glass jar with a tight fitting wadded lid preferably in a dessicator over solid sodium hydroxide, as one should store methylammonium and ethylammonium chlorides. Alternatively if it is the free amine, a brown glass bottle with a polycone style lid would be suitable.

Oh dear, caught out? I expect Picric-A learnt from his mistake? I mean he is going to try the infamous Skraup reaction, notorious for run aways, remember the quinoline is an amine so don't try and distil any quinoline.H2SO4

[Edited on 15-9-2009 by panziandi]

DJF90 - 15-9-2009 at 12:37

It is possible base hydrolysis was used, although the thread author says he expects (m-)toluic acid to remain in the flask. So he could have done it either way. But in any case there seems to be a fundamental misunderstanding of acid-base chemistry (and he isnt the only one

); you cant have toluic acid after a basic hydrolysis, and you cant distill diethylamine after an acid hydrolysis, unless of course he basified and forgot to mention it...

Picric-A - 15-9-2009 at 12:49

Quote: Originally posted by DJF90

Quote: Originally posted by Picric-A

If this guy thinks hes distilling DEA.HCl from the mix he should really learn some basic chemistry

[Edited on 15-9-2009 by Picric-A]

Yes so i then went out and learnt the basic chemistry- im not being a hypocrite!

I cant no be bothered to repeat what i have said so many times before

panziandi - 15-9-2009 at 12:57

So I would quite like to know how the thread's author actually went about this. Because the DEA thread has kind of been a drag to keep up with over the months, in fact I gave up on it until recently something caught me eye again but I quickly gave up. Would be nice to see someones detailed attempt at this, method, yield pictures perhaps?

sonogashira - 15-9-2009 at 13:04

Here is some information on purification from Armarego:

Diethylamine [109-89-71 M 73.1, b 55S0, d 0.707, n 1.38637, pK15 11.38. Dried with LiAlH4
or KOH pellets. Refluxed with, and distd from, BaO or KOH. Converted to the p-toluenesulfonamide and
crystd to constant melting point from dry pet ether (b 90-120°), then hydrolysed with HCl, excess NaOH was
added, and the amine passed through a tower of activated alumina, redistd and dried with activated alumina before
use [Swift JAm Chem Suc 64 115 19421.
8 A polystyrene diethylaminomethyl supported version is commercially available.

Diethylamine hydrochloride [660-68-41 M 109.6, m 223.5O. Crystd from absolute EtOH. Also
crystd from dichloroethane/MeOH. Hygroscopic.

kclo4 - 15-9-2009 at 18:36

Be interesting to see at least a write up, etc.

sonogashira - 15-9-2009 at 23:57

Quote: Originally posted by kclo4

Be interesting to see at least a write up, etc.

What is to write up?! It is a hydrolysis!

Picric-A - 16-9-2009 at 02:09

quantities used, reaction time, problems encountered, colour changes ect!

panziandi - 16-9-2009 at 02:18

I agree, molar quantities used, method chosen, yield obtained ought to be enough, just to provide some experimental clarity to the extensively waffley and hard to follow crap thats come out of the DEA thread to date.

entropy51 - 16-9-2009 at 05:11

Quote: Originally posted by sonogashira

Quote: Originally posted by kclo4

Be interesting to see at least a write up, etc.

What is to write up?! It is a hydrolysis!

Please check out the thread on hydrolysis of DEET and you will see that the devil is in the details.

That's the reason that papers in chemical journals normally include a section entitled "experimental" in which the details are explicitly described.

"It is a hydrolysis!" is analagous to "He was a man!" in reply to the policeman who asked you who shot you in the arm. Such a reply doesn't convey much information that is helpful.

sonogashira - 16-9-2009 at 06:35

Thank you for you nice analogy and (ironic?) response - you begin to remind me of someone who left not so long ago (perhaps before your time?)

Please tell me what the devil in the details is. Heating for extended periods with excess 20% NaOH/ethylene glycol - as described in nearly every organic chemistry book - does not work? I would be surprised.

I can see no devil in the details - just poor experiments and impatient experimenters.

entropy51 - 16-9-2009 at 07:21

Well, exactly. Now someone hints at having done a GOOD experiment so some of us would like to know how it was done. That's sort of why we're here on the forum.

It would just be nice to have a happy ending to a long and confused thread.

You say NaOH/ethylene glycol and that sounds reasonable. But AgentMadHatter may have found a better way. Perhaps a better solvent? Sometimes KOH is better than NaOH. How long is "extended periods"? How did he purify the product? What was the yield? Who can say?

Agent MadHatter - 16-9-2009 at 15:06

Ok. After thinking the thread was done by confirming all I needed was an amber bottle with a proper seal...I didn't look back until today. If you guys honestly don't believe this was my procedure.

I got a lot of bottles of 30ml of 98% DEET and 2% other (Suspected Alcohol since it allowed water and the DEET to mix)

I threw in 500mls of the DEET with Dilute Sulfuric acid at a 28% concentration. Once the PH was at 3, I refluxed for 8 hours at 70C, using water to prevent any evaporation.

After adding distilled water and seeing that it did not form two layers, I knew the hydrolysis was complete. At which Point I added KOH until the mixture was at 7 pH.

Distilled off the DEA through my condenser into a cooled container of HXl in EtOH. Forming DEA.HCl.

I have the liquid sitting in an amber glass. Trying to figure out if letting it evaporate under a vacuum will cause any DEA vapors or anything.

That was my procedure.

entropy51 - 16-9-2009 at 16:02

Fantastic! So it was an acid hydrolysis rather than base. Good to know. So by distilling into HCl/EtOH you didn't get any crystals of the HCl salt?

I'm still not sure what you meant by this:

Quote: Originally posted by Agent MadHatter

I'm positive I have it, because I took off the acid and made it freebase and watched my product disappear into the air.

Because the BP of Et2NH is 55.5 C, I don't know what you mean by "disappear into the air".

Did you recover the m-toluic acid product? Did you calculate a percent yield? BP during distillation?

Good job.

[Edited on 17-9-2009 by entropy51]

Agent MadHatter - 17-9-2009 at 12:51

Like I said...I'm not chemistry major. If I get product, thats good enough for me. I don't know how to calculate percent yield compared to theoretical yield, I do know the BP was around 60 C but not over it. 55-60C.

But whats the best way to get the DEA HCl crystals out of the ethanol now? Just evaporation? Or will the DEA evaporate?

Picric-A - 17-9-2009 at 12:54

Quote: Originally posted by Agent MadHatter

But whats the best way to get the DEA HCl crystals out of the ethanol now? Just evaporation? Or will the DEA evaporate?

Is it DEA or DEA.HCl????
If it is the latter then no it will not evaporate, you can gently remove the ethanol by heating on a steam bath.
If it is the former i would convert it to its HCl salt then do as above.

entropy51 - 17-9-2009 at 15:17

Quote: Originally posted by Agent MadHatter

Like I said...I'm not chemistry major. If I get product, thats good enough for me. I don't know how to calculate percent yield compared to theoretical yield, I do know the BP was around 60 C but not over it. 55-60C.

But whats the best way to get the DEA HCl crystals out of the ethanol now? Just evaporation? Or will the DEA evaporate?

Chem major or not you should keep a notebook recording what you did and what you observed. Then when you need to ask a question you could give us some background information.

Do you have crystals? The amine HCl is soluble in both EtOH and H2O.

But the amine HCl is not volatile, so you may be able to evaporate off the solvents and get crystals. The way this is usually done is to add the amine to Et2O saturated with HCl gas, forming nice crystals that can be filtered off.

And you still haven't clarified your statement that you watched the product evaporate into the air when you "removed the acid". I'm starting to wonder if you have any product at all.

panziandi - 20-9-2009 at 17:18

Personally, Agent MadHatter, I would have made the reaction mixture far more basic than pH7! I would have added KOH until I got pH10 or something, using saturated aqueous KOH. Then Distilled the liquid collecting anything coming over below 60, collected using ice-cold water in the condenser and submerging the flask in salt/ice bath. then I would have dried the liquid of solid KOH (atleast a few hours! Perferably a day) and then redistilled it. I wouldn't bother with the HCl salt as it is too hygroscopic! If you REALLY want the salt, I would distill the dried amine into ether saturated with HCl (or ether solution of amine treate dwith HCl). Alcohol contains too much water to get nice crystals.

UnintentionalChaos - 20-9-2009 at 20:18

Quote: Originally posted by Agent MadHatter

Ok. After thinking the thread was done by confirming all I needed was an amber bottle with a proper seal...I didn't look back until today. If you guys honestly don't believe this was my procedure.

I got a lot of bottles of 30ml of 98% DEET and 2% other (Suspected Alcohol since it allowed water and the DEET to mix)

I threw in 500mls of the DEET with Dilute Sulfuric acid at a 28% concentration. Once the PH was at 3, I refluxed for 8 hours at 70C, using water to prevent any evaporation.

After adding distilled water and seeing that it did not form two layers, I knew the hydrolysis was complete. At which Point I added KOH until the mixture was at 7 pH.

Distilled off the DEA through my condenser into a cooled container of HXl in EtOH. Forming DEA.HCl.

I have the liquid sitting in an amber glass. Trying to figure out if letting it evaporate under a vacuum will cause any DEA vapors or anything.

That was my procedure.

The 2% are other isomers of DEET (Probably with ortho and para methyl groups instead, or with only one ethyl group present)

The reason for this is simply that it's not worth industry's time or money to refine their starting materials to ultra-high purity unless the contamination is a hazard instead of just being inert. If N,N-diethyl-o-methylbenzamide is harmless, boils within a half degree of the desired DEET, and the average consumer won't know or care if the product is 98% or "100%"(nothing is ever 100%) DEET, then why throw away 2% of profit, plus spend money fractionating the two compounds better? Perhaps people would care if it was around 95% but I tend to think that the average shopper rounds 98% up to 100% in their head.

It's simple economics.

[Edited on 9-21-09 by UnintentionalChaos]

Ephoton - 22-9-2009 at 01:28

who cares how he made it or even if he did. it was a simple question how too store it.

simple amines dont react with them selves and dont oxidise over time. they do absorbe water though. dark bottle simple

nearly getting laid as a post whore.