Author Topic: Diethylamine? (Read 668 times)

Vesp · « **Reply #20 on:** August 28, 2009, 03:42:46 AM »

Diethylamine would form the sulfate and not distill as far as I know. You would need to neutralize the solution and then distill or separate the diethylamine which may or may not be significantly soluble in water.

Naf1 · « **Reply #21 on:** August 28, 2009, 04:04:56 AM »

"So when the boiling stops I'll know I've got my two products? "

Well, since DEET boils at about 300*C and sulfuric acid boils at 337*C. You aint gonna see boiling! unless you have the vacuum from hell. Hydrolysis will occur slowly with DEET with the reaction we discussed.
Vesp is right about the salt not distilling, you would need to free base before distilling. If you think about it, if the hydrolysis were to be preformed in NaOH you could attach distillation setup and just distill the diethylamine off as it formed! Otherwise the 2 phases that form from the sulfuric acid /DEET hydrolysis, the polar sulfuric acid phase would be saved and free based.

Vesp · « **Reply #22 on:** August 28, 2009, 04:11:35 AM »

Since the DEET doesn't dissolve you will want constantly mix, or form an emulsion of the DEET with the sulfuric acid while heating. So an overhead stirrer or a magnetic stirrer is going to be very important.

Since you will need to neutralize it later, or crystallize out the diethylamine sulfate via its solubility,if that is an option. You will want be conservative when it comes to the amount of H2SO4 you are using as it can take a lot of base to neutralize a large quantity of a diprotic acid.. Obviously use enough to form the diethylamine salt, plus some for time.

Agent Madhatter · « **Reply #23 on:** August 28, 2009, 04:21:31 AM »

So. Theoretically say I add 10ml of DEET. I'd add 2.5ml of Sulfuric acid solution in distilled water. Stir and heat at 76C for an extended period of time, assuming 24-48 hours? ( how will you know to stop?)

Then at that point, add NaOH, 5ml of H2O saturated with NaOH. At that point, remove the Diethylamine through distillation at 55C and collect in a cooled container with HCL solution?

Vesp · « **Reply #24 on:** August 28, 2009, 04:26:20 AM »

How did you get those figures?
The products from DEET hydrolysis are water soluble. So when the DEET is gone.

Agent Madhatter · « **Reply #25 on:** August 28, 2009, 04:30:18 AM »

Will the two chemicals be in a solid form? I know DEA evaporates at room temperature and I'm not so sure about the other acid produced.

I've only done one distillation before and it was quite simple so forgive my stupidity.

I came up with the figures from past threads on distillation of DEET and other information.

Once the DEET is gone, I will mix the residue with An NaOH solution and distill, correct?

poisoninthestain · « **Reply #26 on:** August 28, 2009, 09:56:04 AM »

I tried both acid and base hydrolysis back in the day several times under different reaction conditions and from what I remember all I got was distillate at ~75C and a black cherry color change from 100% tech. grade DEET after ~90 minutes reflux.

Eventually I gave up but gathered this.

1.)It takes over an hour of steady reflux if you want a few ml's. Don't crank up your plate too much.

2.) NaOH/KOH is much easier to work with than HX. I could be mistaken but I believe alkali hydrolysis favors equalibrium to the right here. Since it will distill over as the freebase without having to go through the sulfate salt and then having to liberate the amine again.

Agent Madhatter · « **Reply #27 on:** August 28, 2009, 02:46:39 PM »

I figured using a base would be better and also that KOH is better than NaOH. as for time yeah about a 12-48 hour reflux is needed. Which really makes my life hard since that means I need constant hear water and a cool bath for the DEA.

2bfrank · « **Reply #28 on:** August 28, 2009, 05:44:11 PM »

Excuse my Ignorance, but if one was succesful in obtaining this amine from DEET, I am assuming it is to be used for something to do with LSD.. if this is the case, what is the chemistry like for this endeavour.

Agent Madhatter · « **Reply #29 on:** August 28, 2009, 06:15:24 PM »

I'm not admitting that I'm trying to make LSD, because I'm
not. But from my research DEA can be used for any synth of LSD. Though I've read the easiest is using a peptide coupler.

2bfrank · « **Reply #30 on:** August 28, 2009, 06:22:47 PM »

Na I wasn't trying to find out if you were doing this or that, just thought for some reason it was associated, an if it was, I thought it was big time chem involved..Personaly my interest is the theory behind the chem. I am willing to discuss this on that level..

Enkidu · « **Reply #31 on:** August 28, 2009, 06:43:23 PM »

Quote from: Naf1 on August 28, 2009, 04:04:56 AM

Well, since DEET boils at about 300*C and sulfuric acid boils at 337*C. You aint gonna see boiling!

Close, but 98% H2SO4 boils at 337*C, whereas 25% boils at a much lower temperature. I've posted a paper about the microwave hydrolysis of benzamide in another thread. In my opinion, the acidic hydrolysis products are better, because the benzoic acid will be insoluble in cold water if there's already an excess of protons floating around.

Agent Madhatter · « **Reply #32 on:** August 28, 2009, 10:05:16 PM »

I've read that a simple microwave hydroylsis can be one and will yield great results but I don't know how to do that, nor have microwave I can risk being exposed to DEET, or equipment that can be microwaved.

Though the acidic hydroylsis is easier in the end it takes many more hours of reflux to get the diethylamine to appear for some reason about basic solutions and amines. It's on another thread o read on the topic.

I have no problem taking the diethylamine salt and converting it back into the required form then converting to the HCL DEA I need.

Though I think buying would be easier.

Naf1 · « **Reply #33 on:** August 28, 2009, 11:37:52 PM »

"whereas 25% boils at a much lower temperature"

Oops, but still should not see any boiling at the beginning.

"because the benzoic acid will be insoluble in cold water"

In the case of DEET instead of benzamide it will not be benzoic acid but will be m-toluic acid, and it will precipitate as white flakes upon cooling below 20*C.

Agent Madhatter · « **Reply #34 on:** August 29, 2009, 12:24:48 AM »

So after refluxing for an extended period of time, (using a solution of Sulfuric acid and DEET)(When do you start refluxing? For example, you mix the DEET and sulfuric acid together, stir for awhile, but how long will you stir for? When will the hydrolysis be complete?) Then reflux for awhile, collecting everything in a cool container.

What I'm confused about is twofold.

1. What will be left over after I distill out the Diethylamine? m-Toluric acid?

2. What form will the DEA be in, once condensed back into a liquid?

Naf1 · « **Reply #35 on:** August 29, 2009, 12:56:38 AM »

DUDE! This is it! No more!!

When do you start refluxing?

1, You start flowing water through your reflux condenser from the start, as soon as you start applying heat start the condenser (and it will run for the entire hydrolysis, it will run until the solution cools).

but how long will you stir for?

2. From the start to the finish!!! Vesp already told you this!

When will the hydrolysis be complete?

3. The DEET is non-polar so once the non-polar phase has gone. Vesp already told you this!!

Then reflux for awhile, collecting everything in a cool container.

4. NO that would be distillation, and that is not required yet.

What will be left over after I distill out the Diethylamine? m-Toluric acid?

5. You start with; Water/Sulfuric Acid/DEET
As the hydrolysis proceeds, the DEET is cleaved into Diethylamine and m-Toluic acid. So you are left after hydrolysis with; Water/Sulfuric acid*/m-Toluic acid and Diethylamine.

Sulfuric acid*= Sulfate ions, but was left out for clarity.

After basing the above solution, you now distill it, at about 55-60*C the diethylamine will start rolling over. Once the temperature climbs above 60*C and keeps going remove the heat and then remove your receiving flask as you have got all the diethylamine.

"What form will the DEA be in, once condensed back into a liquid?"

6. Open wide here comes the aeroplane..... I am not answering that!

"once condensed back into a liquid?"

Agent Madhatter · « **Reply #36 on:** August 29, 2009, 01:12:07 AM »

Hahaha thank you sir. You add some humor into a serious topic. But I should have picked a better term... I meant what will the diethylamine be? Diethylamine sulfide? Diethylamine toluric acid?

Vesp · « **Reply #37 on:** August 29, 2009, 01:17:15 AM »

Read this entire thread over again, think about it, sleep on it, etc.
It'll help.

Agent Madhatter · « **Reply #38 on:** August 29, 2009, 01:42:14 AM »

I'll re-read it when I get home from work. But I'll tell you this. I'm not really that understanding of how the mixing of chemicals react. I remember a sheet from college that listed all the elements and their levels of reactivity. Like if you have copper sulfide, and magnesium chloride, I believe the magnesium is more reactive than copper so it will change into magnesium sulfide, leaving copper chloride. But I could be wrong.. And I don't have that list so I don't know sulfurs placement compared to, whatever diethylamine would be. Though I believe the simple act of exposing the two would make diethylamine sulfuric acid. While adding the base would neutralize it, meaning back into the freebase of diethylamine.

Right?

Enkidu · « **Reply #39 on:** August 29, 2009, 01:50:51 AM »

Quote from: Naf1 on August 28, 2009, 11:37:52 PM

"because the benzoic acid will be insoluble in cold water"

In the case of DEET instead of benzamide it will not be benzoic acid but will be m-toluic acid, and it will precipitate as white flakes upon cooling below 20*C.

Sry, should have been "ring substituted benzoic acid." I meant to use benzoic acid generally

Author Topic: Diethylamine? (Read 668 times)

Vesp

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Naf1

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Vesp

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Agent Madhatter

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Vesp

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Agent Madhatter

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poisoninthestain

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2bfrank

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Agent Madhatter

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Enkidu

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Naf1

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Vesp

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Enkidu

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