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Author: Subject: Diethylamine Synthesis
DJF90
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[*] posted on 7-3-2009 at 21:21


Ideally water is present, but you are correct in saying that it is not needed. Heating an ester or amide with solid NaOH is pretty extreme though, when a solution of NaOH will do just fine. The water will aid the reflux, as you indirectly suggest.

Fusing an ester/amide with NaOH cannot really be done in a flask (i.e. on a preparative scale) because the molten caustic soda will eat away at the glass. This generally leads to using a corrosion resistant material (stainless steel? or nickel?) which is usually of the open topped variety (e.g. a crucible) for the hydrolysis (as in the thread you point to). At the temperatures required for fusion of the NaOH, the Et2NH is readily vaporised (bp ~ 50C) and I can imagine rigging up some kind of condenser to such a setup kind of challenging.

Using a solution of sodium hydroxide for the hydrolysis means a quickfit apparatus can be used, with minimal/no corrosion so long as the concentration is low enough. Most Et2NH will reflux back into the flask and when the hydrolysis is deemed complete, it can be distilled from the mixture.

My point is that fusing with NaOH is fine for isolating the m-toluic acid, but in the case of the volatile amine, an aqeuous solution is likely to prove more appropriate.

[Edited on 8-3-2009 by DJF90]
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haribo
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[*] posted on 8-3-2009 at 04:46


Hydrolysis of diethyl formamide with NaOH.
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panziandi
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[*] posted on 8-3-2009 at 15:38


Formamides are generally deemed toxic. I doubt you'd find any formamides OTC. Dimethylformamide is quite common solvent but is expensive, diethylformamide is uncommon and would be even more expensive! Dimethylformamide is a convenient source of dimethylamine which people often overlook. I think the best route to diethylamine for the home chemist is aqueous hydrolysis of DEET. This is quite an old thread I haven't been in this one for a while!



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nitric
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[*] posted on 15-4-2009 at 04:56


The DEET procedure seems the most fesiable procedure of all, using HCL may be the most efective, diethylamine HCl dosent melt 'till 227*C and doesnt boil untill 320*C, so the execce water and hydrochloric acid can be evaporated or distilled off leaving most likely pure diethylamine HCl and 3-methyl benzoic acid in the vessel which could have a NaOH solution added to it and the triethylamine distilled of( bp 55.5*C) and purified with 1-3 distillation more if no azotropes are formed of less if a fractionating column is used, sorry if this was posted before but i didnt read the second page.

[Edited on 15-4-2009 by nitric]
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Agent MadHatter
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[*] posted on 26-8-2009 at 18:28


I'm so lost. I've read all 10 pages and not one of you guys have successfully Distilled the DEA.

What I've got, is adding NaOH/H2O, with DEET (100% from target), and Ethanol/Methanol/Other solvent into a flask and refluxing for two days would produce a mixture of chemicals.

I'm just confused about what chemicals would be produced and getting DEA from it.
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[*] posted on 27-8-2009 at 00:13


In the DEET procedure you are hydrolysing the DEET in an alkaline enviroment (NAOH/H2O) to produce DEA and 3-methylbenzoic acid.
The DEA can then be distilled form the hydrolysis mix. That is a summary of the thread.
If you are so confused as to obtaining the DEA then maybe you should think twise about what you are planning to use it for! you are obviously new to org chem and it sounds like you are after the DEA for illegal purposes. Read the whole thread again, it contians plenty of information.

[Edited on 27-8-2009 by Saber]
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[*] posted on 28-8-2009 at 11:08


If you hydrolyze the benzamide in an alkaline environment, you'll be left with the conjugate base of the benzoic acid.
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panziandi
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[*] posted on 28-8-2009 at 11:48


This thread was lost ages ago! I gave up explaining the procedure to people.

DEET + alkali => DEA + salt of toluic acid

I personally would use 30% aq NaOH and have one very good reflux condenser, then distill out the diethylamine after the reaction is complete.

Or you can use 70% aq H2SO4 forming the DEA sulphate (hydrogensulphate), the toluic acid won't be very soluble. Can fractionally collect the DEA sulphate and then add excess base and distill to collect the DEA.

And to make a point, DEA is extremely volatile and extremely flammable, not to mention it is corrosive and smelly. So a very efficient condenser with pre-chilled water is essential (especially if you live in a warm country) and chill the receiver in ice-water. I would use an ether condenser.




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entropy51
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[*] posted on 28-8-2009 at 13:15


Quote: Originally posted by Agent MadHatter  
I'm so lost. I've read all 10 pages and not one of you guys have successfully Distilled the DEA.

The First Theorem of Science Madness: the longer the thread the less likely anybody saw any product

Quote: Originally posted by Saber  
If you are so confused as to obtaining the DEA then maybe you should think twise about what you are planning to use it for! you are obviously new to org chem and it sounds like you are after the DEA for illegal purposes.


New to org chem says the guy asking about using jelly jars instead of glassware just one year ago. And the same guy who was bragging about "legally" being able to possess red P and HI just yesterday. Give us a break. I don't see one word in Agent MadHatter's post that implies illegal intent. Neither do you. Read it slowly and sound out the words.
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[*] posted on 14-9-2009 at 15:55


Quote: Originally posted by entropy51  
Give us a break. I don't see one word in Agent MadHatter's post that implies illegal intent. Neither do you. Read it slowly and sound out the words.


Stop kidding yourself. I don't see one word that implies illelagl intent I see a whole fucking thread that practicaly states it outright.


Quote:

Do certain amides change forms from pH?

For example. Lysergic acid amide. If that amide was exposed in low pH (say 2) would the molecule turn into a salt?

And would it become freebase if it was exposed to a base (10-13 pH)?

Where would someone find information on similar amides? And solubilities of Salts/Freebase forms?


Hmmmm now do you think he's making dyes with that DEA and just wanted to know about freebasing lysergic acid amide?

Don't get me wrong I have nothing against people synthesizing LSD but people like MadHatter who have little to no chemistry experience are more likely to be injured or arrested than make any LSD.




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Picric-A
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[*] posted on 15-9-2009 at 07:13


Quote: Originally posted by crazyboy  
Quote: Originally posted by entropy51  
Give us a break. I don't see one word in Agent MadHatter's post that implies illegal intent. Neither do you. Read it slowly and sound out the words.


Stop kidding yourself. I don't see one word that implies illelagl intent I see a whole fucking thread that practicaly states it outright.


Quote:

Do certain amides change forms from pH?

For example. Lysergic acid amide. If that amide was exposed in low pH (say 2) would the molecule turn into a salt?

And would it become freebase if it was exposed to a base (10-13 pH)?

Where would someone find information on similar amides? And solubilities of Salts/Freebase forms?


Hmmmm now do you think he's making dyes with that DEA and just wanted to know about freebasing lysergic acid amide?

Don't get me wrong I have nothing against people synthesizing LSD but people like MadHatter who have little to no chemistry experience are more likely to be injured or arrested than make any LSD.




Try to rise above entropys stabbing... he seems to be doing it to everybody these days...

[Edited on 15-9-2009 by Picric-A]
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entropy51
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[*] posted on 15-9-2009 at 07:36


Quote: Originally posted by Picric-A  
Try to rise above entropys stabbing... he seems to be doing it to everybody these days...

Just to the three of you Picric, Saber, and Labxyz.:P

[Edited on 15-9-2009 by entropy51]
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[*] posted on 15-9-2009 at 23:09


Quote: Originally posted by crazyboy  

Hmmmm now do you think he's making dyes with that DEA and just wanted to know about freebasing lysergic acid amide?

Freebasing an amide...with diethylamine... :o
Edit: sorry - misread your post...

There seems to be two kinds of posters: Those that do chemistry (however amateurish it might be) and those who like to tell others what to do.

Does this board have a killfile feature? Since I have only little time at the moment it's quite annoying to wade through tons of (imho useless) posts produced by the latter kind. Or could we have a subforum where only people who really do chemistry are allowed to post or something like that?

[Edited on 16-9-2009 by turd]
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JohnWW
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[*] posted on 16-9-2009 at 01:10


"DEA" also stands for the corrupt U$ "Drug Enforcement Agency". I wonder what would happen if you mixed the two DEAs together.
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[*] posted on 22-9-2009 at 01:41


you would end up with sea bacon pigs that swim in the sea :)



e3500 console login: root
bash-2.05#

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[*] posted on 5-3-2010 at 16:10


To approximately 50 grams of deet in 50-60 grams of ethanol was added 50 grams of conc. H2SO4 in 100 mls of water, this formed a yellow solution. Upon cooling following a 5 hour reflux a viscous clear oil separated which stuck to the walls of the flask when swirled in a gel like fashion. The smell of the solution had changed to an appealing mint like aroma.

The solution was cooled in the freezer overnight a large amount of white wax and gel like substance separated, this would surely be impure m-toluic acid (?), suspect EtOH is solubilizing the toluic acid when at room temp. When some of this semi-solid was scraped from the flask and added to cold water it was insoluble, a sticky white solid with the minty aroma.

To the workup of this mixture to obtain the free amine.. current thinking goes along these lines.. remove EtOH by distillation >> filter solids >> basify to 10 >> gently distill amine (use column?) to ice/salt bath receiver. Need i remove the alcohol and filter at all?

[Edited on 6-3-2010 by The_Natural]
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DJF90
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[*] posted on 6-3-2010 at 09:37


Hate to say it, but that faint mint smelling aroma... sounds to me like diethyl sulfate... and the conditions suggest it could have been made too.
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[*] posted on 6-3-2010 at 17:03


ok so the ethanol should have been removed prior.. glad i didnt decide to boil away whats left of the ethanol and this brown oil in an open beaker or anything like that..

anyhow.. more water was added to the mix and separated were lots of white solid on the flasks walls and a brown minty oil (my bad) which was discarded. The white solid was insoluble in acid but easily soluble in NaOH.

Now left with a cloudy aqeous solution that does release a strong ammonical odor upon addition of base and heating of small samples.

I unsure, however, if i want to proceed any further with this mix knowing that diethyl sulfate may still be present..

that and the fact that i just discovered a cooling spray containg only Diethylamine Salicylate 10%w/w; Camphor 0.5% w/w; Menthol 0.75% w/w; Hydroxybenzoates 0.3% w/w

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[*] posted on 11-7-2011 at 13:46


experimental:

to 127 ml of 95% ethanol in a 500 ml flat bottom boiling flask on a stirplate was added 124 grams of ethyl bromide. the flask was fitted with a two hole stopper, through one of which was led a length of 8mm glass tubing. the other hole was vented outside using a length of hose.

the glass tubing was used to feed dried (by passing through a washing bottle filled with calcium chloride) NH3 gas into the reaction mixture. over the course of two days, several additions (with good stirring to maximize contact) of ammonia were made by using one mole of NH4NO3 to one mole of NaOH producing one mole each of NH3 + H2O + NaNO3. some of the ammonia gas is lost to the water formed in the reaction and will be recovered by evaporation of the dissolved ammonia into distilled water for later use as will the NaNO3 be recrystallized and used to produce HNO3 and whatever else my twisted heart desires.

after 12 additions had been completed and after standing, a very fine, almost imperceptible, suspension of micro-crystalline NH4Br was observed. after this point, five more additions were made, for a total of 17 moles of NH3 (minus the NH3 absorbed into the water so closer to 10-11 moles). the process was stopped at this point and the reaction mixture allowed to react in a refrigerator overnight. upon standing the next day, while allowing residual ammonia to evaporate, NH4Br began to crystallize out of the solution. after filtering, an addition of NaOH solution (40 grams to 40 ml H2O) was used to decompose the mixed amine hydrobromides to release the amine freebases.

the remaining mixture is now being fractionally distilled through a 300 mm vigreaux. i will report back with results and yields later today (or tonight).

fractionation is not yet complete but i have so far obtained approx. 20 ml of a clear, colorless liquid with a strong ammonical odor that came over at a range between 50 - 70 degrees celsius. will perform a boiling point test shortly.

[Edited on 11-7-2011 by Rogeryermaw]

checking the boiling point was done with a carefully monitored warm water bath held at 50 degrees and slowly raised until mild effervescence was noted in a test tube suspended in the bath. the crude product showed signs of boiling at about 53 degrees indicating a small amount of impurity, likely ethylamine or ethyl bromide. i am leaning toward ethyl bromide since any ethylamine produced would have been gaseous at 16 degrees and up. will re-distill from KOH to remove any water.

the triethylamine has not yet been accounted for since i have not had the distillation bath above 80 degrees. the boiling point of TEA is 88.5 degrees. that report comes later.

[Edited on 11-7-2011 by Rogeryermaw]

[Edited on 11-7-2011 by Rogeryermaw]




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Rogeryermaw
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[*] posted on 13-7-2011 at 12:06


after distilling the triethylamine i stopped after about 30 ml (it's more than i will likely ever use). after re-distilling the diethylamine from KOH i have 18 ml of a clear ammonia smelling liquid that boils at a steady 55 degrees. it is highly flammable and leaves no soot or smoke.

i would like to repeat this experiment while adjusting the ammonia content to see how it affects the division of the products.




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[*] posted on 14-7-2011 at 07:00


Does anyone know the difference between diethylamine and diethylamide?
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[*] posted on 14-7-2011 at 09:07


Quote: Originally posted by overload  
Does anyone know the difference between diethylamine and diethylamide?


One is an amine, the other is an amide (or part of one anyway)...

Nitrogen forms three bonds. In diethylamine, two of those bonds are to methyl groups and the third is to a hydrogen. In diethylamide, two of those bonds are to methyl groups, and the third is to a carbon double-bonded to an oxygen.

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Rogeryermaw
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[*] posted on 15-7-2011 at 19:34


i'm sorry if forgot to mention that the liquid boiling at 55 degrees (that i suspect is diethylamine) gives a pH reading of 14 or higher (i do not yet have the means to measure pH above 14 or below 0) and the liquid boiling in the 87-89 degree range (that i suspect is triethylamine) gives a pH of around 13.

does this sound consistent with these products? are there any tests (within the range of home chemistry) that i can perform to verify these products? i may wait till the school season begins and ask if it can be tested by the university chemistry department with their available apparatus (if they have such capabilities).




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[*] posted on 16-7-2011 at 18:26


Glad to see you're working away roger.

If you have some accurate volumetric glass, like a pipette or flask, and one of those 0.01g pocket balances, you could check it's density. Should be 7.074g for 10 mls. Class A volumetric flask have a 0.02 / 0.03ml error on the volume I think (0.2 / 0.3%). You could determine the mass with about 0.5% error using a 0.01g pocket balance, from my experience with them. The cheap .01g pocket balances are excellent value for money (remarkably accurate and resistant for £5)! Get one with a bigger than microscopic pan on it though, because those tiny ones are barely usable with larger masses, unless they're weighing lead. One that plugs into a wall adaptor would be good, so it's not chewing through the batteries.

You could also try freezing it with some dry ice, using a low temperature thermometer to check when it melts. And can produce a nice graph by recording the temperature every 30 seconds or minute or so. There'll be a horizontal line at the melting point.

[Edited on 17-7-2011 by peach]




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[*] posted on 16-7-2011 at 18:50


those are some excellent suggestions. i do happen to have a recently purchased .001 g scale for about 40 dollars on ebay with calibration weights and a lid to prevent inaccuracies from drafts. unfortunately it does have a dismally small dish but i can weigh accurately enough on it. i have several 3 ml syringes that i can use for accurate volume. i will weigh 1 then 2 then 3 ml and report back with the results. the melting point analysis will have to wait until i can afford to get the dry ice.

thank you peach for the suggestions...i feel a bit daft for not checking the density as soon as it was distilled:(




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