Sciencemadness Discussion Board - OTC diethylamine, the easy way

OTC diethylamine, the easy way

madscientist - 23-9-2003 at 09:48

Earlier, Madog stated that he thought diethylamine could be made from DEET (which he says can be found in non-pressurized 99% form in stores catering to outdoorsmen), so I took a look at the structure of the molecule. Turns out it's N,N-diethyl-3-methylbenzamide. Upon reacting that with strongly alkaline aqueous solution and subsequently distilling, diethylamine will be had!

Too easy. :cool:

[Edited on 23-9-2003 by madscientist]

Blind Angel - 23-9-2003 at 15:32

One word: Great!

Now for Dimethylamine?....

Madog - 24-9-2003 at 16:41

i realised theres a bottle of "maxi deet" in my basement, plastic, 2oz, bottle of 95% DEET, and guess what, the impurities are "other isomers"

you can get it at outdoors stores, even if you arn't planning to make diethylamine its good.

trinitrotoluene - 3-10-2003 at 13:17

In what synthesis is diethylamine useful in?

Mumbles - 3-10-2003 at 20:51

The first thing that pops into my mind when I hear Diethylamine is LSD(aka Lysergic Acid Diethylamine)

From http://www.osha-slc.gov/dts/sltc/methods/organic/org041/org041.html
"Diethylamine is used:

in preparation of textile finishing agents, surfactants, rubber processing chemicals, agricultural chemicals, and pharmaceuticals.

as a corrosion inhibitor in iron, steel, and metal industries.

as a polymerization inhibitor and catalyst in the polymer industry and as an intermediate in the dye industry.

as a depilatory of animal skins and in electroplating solutions."

diethylamine specifics

ra_sun423 - 20-10-2003 at 11:46

to mad scientist:

much appreciated knowledge..
could you be a little bit more specific?

Such as;
- as far as the reaction time time, and the distillation. How long to react, and do you mean reflux?
- as for the distillation... would all the distillate be pure diethylamine? or would it be wise to collect only the fraction that diethylamine boils at?

thanks for any additional help.. this knowledge will be put to good use.

madscientist - 20-10-2003 at 17:01

Reaction between NaOH and DEET in a solution of water and ethanol (say, 50/50 mixture) should proceed relatively easily at room temperature. I'd recommend magnetic stirring if possible, and having a heating option available in case the reaction decides to proceed slowly. A sign that the reaction is proceeding would be heat. I doubt the reaction would take more than an hour or so once started.

Distillation should be simple enough. Diethylamine boils at 56C, ethanol at 78C, water at 100C, and DEET at 111C. Separation of fractions shouldn't require any special distillation equipment unless your heating mantle unfortunately happens to be a brick of thermite. And yes, I would recommend collecting only the fraction that comes over at around 56C.

[Edited on 21-10-2003 by madscientist]

little off topic, but...

ghost711 - 21-10-2003 at 07:28

Method X is VERY secretly distributed..but takes a little (lot) of research to figure out the golden reference (somewhere) in royal society of (...??) describes a method to biosynthesize the great acid by "tricking" claviceps paspali in to producing it by modifiying the growth substrate to produce strictly the d- stereoisomer therefore bypassing synthesis or starting materials. Grow it on the "special, modified" subtrate...extract the goods...chromatograph for the purity freaks...and enjoy. This so called product is called "the natural" and boy oh boy. Wowee... Dont ya love how nature can synthesize stuff for ya! Amazing. Thats all I can say..Please dont email me regarding the refs/info. As I have none. Thats not my bag baby! Pays to know certain people I guess. Enjoy the search...takes a year or so to find the specifics. BTW- DEA hates this shit..amateurs need not apply. Leave this one to the pros. Enjoy!
:cool:

madscientist - 21-10-2003 at 12:53

That sounds a bit like "I know the future, but I'm not telling you it." How can you know about this, yet not have any useful details whatsoever to share?

Mumbles - 21-10-2003 at 14:07

We spoke of this in American History actually. They didn't come out and say it, but I knew. The Puritans and other colonials did this accidentally. It extended as far south as the Carribean(sp?). It was theoretically the cause of the Salem witch hunts, besides the economical benefit of having the village of Salem rejoin the town of salem, but that has nothing to do with the topic. We didn't learn any specifics, but I think it has something to do with the methods of refridgeration. IE bury, pack with snow, and cover in saw dust. The humidity had something to do with it also, I believe in the case of the West Indes. The marshes possibly too. Maybe there was something special in the water. Perhaps the "seasoning" of the waters did something special.

I know this might not be a lot of help, but it may provide a good place to start for any individuals interested. I don't specifically know if the breed of plant mentioned in the last post is the same, all I know is that the plant in the colonial times was used to make bread and other grain based goodies.

yea..that was a bit cryptic I guess

ghost711 - 21-10-2003 at 14:20

Im not trying to be a cryptic know-it-all here. But- ever wonder why no one talks about making the stuff...and every internet "recipe" out there is so detailed and outdated that anyone who even attempts it would be taking on a huge investment, requiring elaborate lab equipment, and more importantly- starting materials that the DeEeAy has long since flagged for decades. If a person is smart- they wouldnt even touch it with a 10-foot pole. It is distributed online strictly as a novelty. Did the hippies in the 60's and 70's do it this way?- When they came to parties with gallon jugs of the stuff?? I think not. Using a reference database these days like scifinder scholar turns up hundreds of different juicy tidbits on circumventing these "perceived" hurdles- one bypassing another to get an end result. People who actually do, do it..are really, truly on a quest for the correct (current) information for a viable method of clandestine production- not Hoffman's original synth of step by step, tedious labwork from materials that were handed down to him. And, when they do actually find it--they are not so quick to just give the info away. I did have one journal reference that I found after a long search of everything that was out there in college libraries, chem journals, alt. knowledge books, etc. And when I did finally find this- and read it- a big bright light flicked on in me..and a huge grin took over my face. I did not even want to attempt what was in the text. Having the knowledge was sufficient enough. And that is why the info isn't just "given out"--its the journey, not the destination. All I can say is- start with claviceps paspali when you begin the search...

GHOST

madscientist - 21-10-2003 at 14:31

I can't imagine any advantages over the well-known ergot process that would make it worth spending so much time searching.

I find the idea of hoarding knowledge to be disgusting. Science, including the clandestine branch, wouldn't have gotten anywhere if it weren't for people sharing the destination with others, rather than watching them embark on the journey.

http://www.rhodium.ws/chemistry/lsd.synthesis.txt

[Edited on 21-10-2003 by madscientist]

nice

ghost711 - 21-10-2003 at 19:06

Ok, thats fine i'll bow out of this one. Anyone interested in this is free to explore all the VAST info on this subject at the hive. Just be very careful will gallons and gallons of claviceps purpurea, phosphorus oxychloride, hydrazine, etc. Im not hiding, or withholding anything- I mentioned everything I know about the subject already. Case closed.

Blind Angel - 14-11-2003 at 06:18

Would like to know, is there a way to "cut" diethylamine in two yielding Ethylamine and something else? I was thinking of an acidic environnement con. H<sub>2</sub>SO<sub>4</sub> maybe? (would yield an ethyl sulfate as side product so i'm not sure of this...)

Mumbles - 14-11-2003 at 09:48

I'm not sure about "cutting" the diethylamine molecule. If you are after Ethylamine, it is often produced in DEA proceedures starting from Ethanol. It is then reacted further to produce the diethylamine. A few proceedures from the Hive.

Both of those produce produce ethylamine.

unionised - 16-11-2003 at 03:57

I have a nasty feeling that the deet alcohol water diethylamine system would form a nasty set of azeotropes.

You can cleave amines by acid hydrolysis but the reaction is slow. The other product is alcohol.

acx01b - 6-5-2004 at 13:27

sorry my english is not good:

i didnt understand: what is the product free sold contaning the n,n-diethyl amide ?
(what does otc mean? lol)

separation of products

blazter - 16-5-2004 at 17:31

Even if distillation was to fail, I have a feeling one could take advantage of soluabilities of DEET and diethylamine to have a clean separation. According to the merck index, DEET is insol. in H2O, sol. in alcohol, ether, and benzene. Also, diethylamine HCl is sol. in water, alcohol, and chloroform and insol. in ether. Not sure exactly about the properties of the freebase, though I would suspect it to similar to methylamine. So its possible to also use diethylamine's property of forming salts with acids, and somehow partition between organic/water layers.

Hope this helps, someone should try this and see if its feasible.

If_6_was_9 - 25-5-2004 at 15:44

Quote:

Originally posted by ghost711
Method X is VERY secretly distributed..but takes a little (lot) of research to figure out the golden reference (somewhere) in royal society of (...??) describes a method to biosynthesize the great acid by "tricking" claviceps paspali in to producing it by modifiying the growth substrate to produce strictly the d- stereoisomer therefore bypassing synthesis or starting materials. Grow it on the "special, modified" subtrate...extract the goods...chromatograph for the purity freaks...and enjoy. This so called product is called "the natural" and boy oh boy. Wowee... Dont ya love how nature can synthesize stuff for ya! Amazing. Thats all I can say..Please dont email me regarding the refs/info. As I have none. Thats not my bag baby! Pays to know certain people I guess. Enjoy the search...takes a year or so to find the specifics. BTW- DEA hates this shit..amateurs need not apply. Leave this one to the pros. Enjoy!
:cool:

I found something about the Proceedings of the Royal Society of London in US patent 3224945. Also see US3219545

If_6_was_9 - 25-5-2004 at 15:59

See this too:

https://www.the-hive.ws/forum/showflat.pl?Cat=&Number=44...

(post 446606)

[Edited on 26-5-2004 by If_6_was_9]

Unsymmetrical secondary aliphatic amines

Sandmeyer - 23-3-2005 at 07:36

The route is IMO pretty nice as it avoids the use of reducing agents and chemicals are readily obtainable...

First the benzaldehyde is condensed with an alkylamine, the condensation product is then treated with the alkylhalide of choice and finally hydrolysed with water/NaOH to give the unsymmetrical amine as a freebase.

Examples:

http://www.orgsyn.org/orgsyn/prep.asp?prep=CV5P0758 (N-methylethylamine, employing alkylhalide)

"This preparation illustrates a general method for the synthesis of N-methylalkylamines. The submitters have used it to prepare N-methylbutylamine (Note 4) and N-methylallylamine, and the checkers have used it to prepare N-methylisopropylamine (80%), N-methylisobutylamine (67%), N-methyl-tert-butylamine (52%), and N-methyl-2-methoxyethylamine (55%)."

http://www.orgsyn.org/orgsyn/prep.asp?prep=CV5P0736 (N-methylbutylamine, employing dimethylsulfate)

"The procedure is a general one for the preparation of unsymmetrical aliphatic amines, for the submitters have used it to obtain good yields of N-methylpentylamine, N-methylhexylamine, N-methylheptylamine, N-ethylbutylamine, N-ethylpentylamine, and N-ethylheptylamine."

They use benzene for the azeotropic removal of water, but toluene of course works too..

An easier route to diethylamine?

Reverend Necroticus Rex - 25-3-2005 at 03:48

I found a possibly far easier way to prepare secondary alkylamines.

Phospham, PN2H, prepared by passing gaseous NH3 over heated phosphorus, yields secondary alkylamines directly from the primary alcohol.

I unfortunately lost the article I had on phosphorus chemistry, that detailed the preperation and use of phosphazines when I formatted my hard drive recently to purge it of window$ XP, but I distinctly remember it being succesfully used for preparing dialkylamines.

Looks to me, for those who can aqquire or refine phosphorus, to be a practical synthesis for secondary alkylamines.

garage chemist - 25-3-2005 at 07:27

Dimethylformamide, a common solvent used in laboratories, could perhaps be split into dimethylamine and sodium formate by boiling with NaOH.
Would this work?

Also, I think carboxylic acid amides can be split into the acid and the amine group with mineral acid, too. When acetamide is heated with dilute H2SO4, it soon smells like acetic acid, and the solution contains ammonium ions.

frogfot - 25-3-2005 at 13:21

Have a feeling that DEET is hard to hydrolyse due to shielding of carbonyl group. But anyway, easiest would be to boil the DEET with plain aqueous NaOH, as mentioned in beginning.. (maby DEET is more soluble in water at high temps..) ..hydrolysis will go faster in plain aqueous soln..

The formed diethylamine could be distilled of, through the whole reaction, with a short fractionating column.

I've never seen this stuff yet.. so I'm not able to test this reaction..

Phel - 26-3-2005 at 04:09

frogfot, you should be able to buy a mosquito repellant at your local pharmacy, containing up to 20% DEET, under the name MyggA. But it is very expensive.

Norway seems to be free of DEET restrictions, since I've managed to find an insect repellant containing up to 50%.

guaguanco - 28-3-2005 at 14:16

Quote:

Originally posted by garage chemist
Dimethylformamide, a common solvent used in laboratories, could perhaps be split into dimethylamine and sodium formate by boiling with NaOH. Would this work?

Yes.

garage chemist - 11-4-2005 at 14:17

I mixed a dash of dilute NaOH with a squirt of DMF, the DMF dissolved completely. On heating the solution, a nasty ammoniacal stench was produced.
Of course, DMF is not so easy to get.

What is dimethylamine used for anyways? Why is it listed as a chemical weapon precursor?

enima - 12-4-2005 at 08:09

DMT synthesis? maybe? not sure exactly. You can also make it by reacting ammonium chloride and paraformaldehyde at high temperatures. It is a byproduct in the production of methylamine.

The_Davster - 25-9-2005 at 19:45

I have done a few experiments with DEET chemistry today. I added 24% DEET to water, it formed 2 layers, then added IPA till everything went into solution. It ended up a light yellow solution for some strange reason. To this KOH was added(a lot was added) while magnetic stirring until the reaction mixture separated into two layers(both around the same colours, but the top layer a bit darker orange/yellow). The layers were separated with a separatory funnel and to each part (both tested as basic) I added lots of HCl until it was rather acidic. The lower portion upon addition of acid emitted fumes, like the way HCl and ammonia react, and became clear. The upper level upon addition of acid fumed to the same degree as the lower solution, it also became a darker colour, and a white precipitate occured, likely 3-methylbenzoic acid.

I could still smell DEET in both parts, so perhaps refluxing with KOH next time would be benefecial.

Anyone have any ideas on separating the diethyamine from either layer(other than distillation), as a pure liquid or as a diethylammonium salt?

[Edited on 26-9-2005 by rogue chemist]

The_Davster - 27-9-2005 at 20:40

Sorry about the double post....

I mixed the two solutions together today bacuse I needed one of the flasks for something else, and I was rewarded with a single phase, and a large ammount of precipitate, and the DEET smell was nearly gone. The reaction between DEET and KOH just must require time, but I do not know what chems would be in each initial layer formed, so I do not even know whether the KOH and DEET would have been in the same flask. Although I imagine the KOH and water would have formed one layer, and DEET and alcohols the other layer, which would mean the KOH and DEET could not react as they were in different flasks...Wait I added HCl after...so perhaps just not enough was added to one flask to cause precipitation of 3-methylbenzoic acid.

Oh well, I now have 2 new compounds to lay around my lab in vials, the methylbenzoic acid and after I work up the diethylamine I should get diethylammonium nitrate.