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mbrown3391
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2 CH3CHO + NH4Cl --> CH3CH2NH3Cl + CH3CO2H
CH3CH2NH3Cl + CH3CO2H + 2 NaOH --> CH3CH2NH2 + NaCl + NaCH3CO2 + 2 H2O
Ethanal will react with ammonium chloride to form ethylamine and sodium acetate. Now if i can just find a source of Thionyl chloride...
[Edited on 1-9-2008 by mbrown3391]
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pantone159
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| Quote: | Originally posted by Vdara
Propose a Grignard synthesis |
What does that have to do with Et2NH? Nothing???
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ScienceSquirrel
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| Quote: | Originally posted by mbrown3391
2 CH3CHO + NH4Cl --> CH3CH2NH3Cl + CH3CO2H
CH3CH2NH3Cl + CH3CO2H + 2 NaOH --> CH3CH2NH2 + NaCl + NaCH3CO2 + 2 H2O
Ethanal will react with ammonium chloride to form ethylamine and sodium acetate. Now if i can just find a source of Thionyl chloride...
[Edited on 1-9-2008 by mbrown3391] |
Ethanal does not react in the same way as methanal which has certain unique properties. One of them being that it is a much stronger reducing agent
than any other aldehyde.
The reaction of ethanal (acetaldehyde ) and ammonia yields a trimer.
http://en.wikipedia.org/wiki/Acetaldehyde_ammonia_trimer
http://designer-drugs.com/pte/12.162.180.114/dcd/chemistry/a...
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mbrown3391
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i got my information from http://en.wikipedia.org/wiki/Ethylamine. Though now that i look at it, it does say "source needed" by that reaction. ill look into it some more
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mbrown3391
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Ok here's another possible route:
From Wikipedia:
| Quote: | | At various times in the past, ethyl chloride has also been produced from ethanol and hydrochloric acid |
So:
CH3CH2OH + HCl --> CH3CH2Cl + H2O
From the Chemical Thesaurus:
| Quote: | Bromoethane reacts with 2 moles of ammonia to give ethylamine and ammonium bromide.
... ethylamine can react further with bromoethane to give diethylamine... |
If Chlorethane could replace bromoethane in this reaction, then:
CH3CH2Cl + 2 NH3 --> CH3CH2NH2 + NH4Cl
CH3CH2NH2 + CH3CH2Cl --> CH3CH2NHCH2CH3 + HCl
CH3CH2NHCH2CH3 + HCl --> [CH3CH2NHCH2CH3]HCl
Possible?
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Klute
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Man, don't use Wikipedia as a reference source....
That reaction is the oh-how-famous Hofmann alkylation of amines. If you would ahev opened even the most basic organic chemistry book, you would have
learned about it, and knwo that what ever the condtiions, you get a mixture of priamry, secondary, tertiary and even quaternary amines.
I some industrial applications, it can be used to prepare amines, but it's often in gas phases, with catalyst, and a tough fractionnation/recycling of
unreaced substarte. In other words, they am for good selectivity, even if the yield is equal to a few percents. Not something that would suit you.
EDIT:
BTW, Vogel doesn't make acetaldehdye from paraformaldehdye and sulfuric acid, but from paraldehdye (the trimer of acetaldehdye) and H2SO4.... Just
think about it, where do you get that extra carbon? Even if there was some kind of condensation, how do you oxidize one alcohol, and get rid of
another? You should try answering these questions to yourself before considering anything see (or think tosee) written. It will save you a lot of time
and frustation, aswell as us.
If you had a look at the acetaldeyde thread, you would see how delicate it is to make without chromium salts. I very much doubt you isolated
acetaldehdye in more than trace amounts but recating H2O2 and EtOh, if you would have read on the subject, you would know that aldheydes are much more
easily oxidized that alcohols, so are oxidized as soon as they are formed, unless youuse a selective oxidant, or a way of removing the aldehdyes
before it get oxidized.
Please, please, take time to read what others are done before throwing out any idea that crosses your head. This is getting boring.
[Edited on 1-9-2008 by Klute]
\"You can battle with a demon, you can embrace a demon; what the hell can you do with a fucking spiritual computer?\"
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ScienceSquirrel
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1) You are going to need some fairly vigorous conditions to convert ethanol to chloroethane with hydrochloric acid, probably more vigorous than you
will achieve in a home laboratory.
2) It is a low boiling liquid / gas at room temperature bp 12 C, so storage and reactions with it are going to be difficult.
3) Alkyl bromides are preferred in the laboratory as they are a lot more reactive than alkyl chlorides.
4) Once again you are going to end up with a mixture of ethylamine, diethylamine and triethylamine.
Fine if you have your own chemical works with a 50ft column but a nightmare on a lab scale.
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mbrown3391
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| Quote: | Originally posted by Klute
I very much doubt you isolated acetaldehdye in more than trace amounts but recating H2O2 and EtOh |
I distillled approximately 40ml of liquid from the mixture which boiled at around 20 degrees C. it smelled characteristically fruity. I posted the
experiment on this forum, and was told it was ethanal, which boils at 20 degrees C.
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ScienceSquirrel
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| Quote: | Originally posted by mbrown3391
| Quote: | Originally posted by Klute
I very much doubt you isolated acetaldehdye in more than trace amounts but recating H2O2 and EtOh |
I distillled approximately 40ml of liquid from the mixture which boiled at around 20 degrees C. it smelled characteristically fruity. I posted the
experiment on this forum, and was told it was ethanal, which boils at 20 degrees C. |
Could you repost your results giving quantities of reagents used etc as I can't find your original post.
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Klute
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Yes, I have read this thread now, but I'm still septical. Have you tried forming the trimer? Acetaldehyde itself isn't very stable.
try making a Tollens test, or bisulfite, or ammonia adduct.
Please give use details, you said you mixed in the cold, then heated to distill? How much H2O2 did you use?
[Edited on 1-9-2008 by Klute]
\"You can battle with a demon, you can embrace a demon; what the hell can you do with a fucking spiritual computer?\"
-Alice Parr
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ScienceSquirrel
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| Quote: | Originally posted by Klute
Yes, I have read this thread now, but I'm still septic. |
Sceptical, dear heart, sceptical.
Septic is nasty 
[Edited on 1-9-2008 by ScienceSquirrel]
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Klute
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He he my bad, in french it's "sceptique" 
\"You can battle with a demon, you can embrace a demon; what the hell can you do with a fucking spiritual computer?\"
-Alice Parr
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ScienceSquirrel
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| Quote: | Originally posted by Klute
He he my bad, in french it's "sceptique" |
Your English is a lot better than my French, near non existent the last time I looked.
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mbrown3391
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| Quote: | | Just a quck question-- how does ethanol react with hydrogen peroxide with an acid catylist? i basicly followed the synthesis for acetone peroxide but
used ethanol instead of acetone. When I came back to my basement an hour after i added the sulfuric acid, the entire room smelled recognizably sweet.
I cant put my finger on the smell, but it smells almost like some sort of artificially flavored drink. But esters are formed with carboxylic acids, so
it couldn't be an artificial flavor. Any idea what was formed? |
that was my orriginal post. As you can see i did not list any specific quantities and i do not remember them now, other than to say that they were
similar to the ratios used in acetone peroxide synthesis, say 1 volume each of ethanol and 12%H2O2 and 1/10 of a volume of conc. h2so4. The ethanol
and hydrogen peroxide were cooled to 0 degree C and H2SO4 was added slowly. Then the mixture was placed in the freezer for a few hours.
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ScienceSquirrel
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You must have carried out the experiment on a substantial scale to distill out 40mL of product.
How many moles do you reckon 40mL of ethanal works out to be?
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mbrown3391
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I did not measure it, thats just an approximation. The reaction was carried out in a 500ml beaker, almost full. Since i was not trying to make
ethanal, i did not use the stoichiometrically correct amounts of reactants. and 40ml is about .7 mols
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ScienceSquirrel
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Interestingly alcohols can be oxidised with hydrogen peroxide to form aldehydes and ketones under some conditions.
http://www.ias.ac.in/currsci/jul252007/133.pdf
But it really does not matter anyway.
Ethanal will not react with ammonia to form ethylamine unless under some fancy industrial conditions that you will not be able to achieve.
[Edited on 1-9-2008 by ScienceSquirrel]
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S.C. Wack
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I like to point fingers too. Indignant finger-pointing...people don't think much about how much of their own house is made of glass. As for
spoonfeeding requests, many long time non-idiot members here make them. Note that very little of this site is people detailing syntheses that they
have done. About a quarter of it now is the posts of just a dozen people. It is often questions and conjecture that goes nowhere. And, not often
enough instead of too often, presentation of some relevant literature by a few members. The um, advice to read what is available is wise though. Maybe
the interest in drugs will be impetus to study, like explosives were for other generations of chemists.
Surely there are methods out there to produce the secondary amine only. Some quite old, well-documented, and available perhaps and quite doable though
troublesome for various reasons. The aniline method comes to mind.
| Quote: | Originally posted by ScienceSquirrel
If you read my report you will see that I used potassium hydroxide in a mixture of ethylene glycol and water in an attempt to hydrolyse the amide.
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I don't feel that you approached it from a realistic preparative angle with the glycol, so it seems unfair to chemistry to say that it is so
difficult. Adding 10 ml. of solvent for 4 ml. of precursor, after doing whatever else first? That's not a lot of solvent and for all we know your
hydroxide was carbonate by then. As for the oil, how do you know that it wasn't toluic acid? Because the acid can and does oil out, even though it
also precipitates on addition of H2SO4 to the mixture. The oily acid crystallizes in the freezer. But boiling the acid/oil in 100 parts of water makes
it dissolve, giving a milky suspension on slight cooling, and with further cooling and time it is transformed to easily filtered light and thin
needles.
Your later suggested conditions sound rather more severe than necessary.
Using only 11 g. KOH, 4.25 g. DEET, 100 ml. ethylene glycol, 8 g. water, and 2 hours at 140C, there was obtained, with little care in the isolation, a
33% yield of snow white recrystallized toluic acid crystals. The purity is likely pretty good given the massive disparity in solubility in hot vs.
cold water. I suspect that the missing yield has little to do with unreacted material, even though the amine (as the hydrobromide, for hahas) was
isolated in even lower yield, 19%, from recrystallization in IPA/toluene.
I feel that this says more about the isolation methods used than anything else.
Amine was escaping during the reflux (out of a 19/22 Liebig, not the best choice), even though later, a large amount of (added) water was distilled
off (at 120C) before the distillate became neutral.
In methods that produce mixed ethylamines, separation methods other than fractionation of the base might be easier. Example:
[Edited on 2-9-2008 by S.C. Wack]
Attachment: jcs_113_899_1918.pdf (253kB)
This file has been downloaded 37447 times
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panziandi
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I'm finding this thread hard to keep up with! Whoever asked for literature references seems to have gotten more than they bargained for! The most
viable OTC preparations of DEA has got to be from DEET giving a pure clean product. Why are people looking at reductive aminations of aldehydes and
ammonolysis of alkyl halides? These methods a wholely unsatisfactory for DEA if you are after a lab prep for the pure compound OTC. If people want a
reference for DEET reaction all you have to do is look in any standard organic chem lab book to find experiements for the hydrolysis of amides which
can be adopted for DEET. I have no interest in the reaction as a source of DEA but I think we are loosing the point of the thread somewhat as whats
recently been posted seems to be about other routes to amines generally which wont yield DEA well IMHO.
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ScienceSquirrel
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I did suggest the reaction of calcium cyanamide with sodium hydroxide to form the dianion earlier in this thread.
The disodium cyanamide is then reacted with two equivalents of the alkyl bromide to form a dialkylcyanamide which is then hydrolysed to yield the
dialkylamine.
I have seen this preparation for dibutylamine somewhere in a book of organic preparations, I thought it was in Organic Syntheses but it isn't.
There is a good preparation of ethyl bromide on these boards so this should be a viable method.
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panziandi
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Yes that would prove a viable method especialy if sacling to larger batches too as calcium cyanamide can be had cheaply as a N fertilizer especially
in farming areas I'd imagine, although I have never come across it sold as such. I'd imagine OTC cyanamides are probably in huge lots kilos at a time,
could be unwanted if only making a small quantity of DEA?!
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ScienceSquirrel
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Calcium cyanamide is quite widely available in the European Union as Perlka.
http://www.garden-supply.co.uk/information.php?info_id=6
I found some US sites that mention using it as a lawn dressing and its toxicity to pets so I would guess that it may be available in smallish
quantities from a specialist supplier.
And it seems that it may be prepared quite readily from OTC materials anyway.
http://www.sciencemadness.org/talk/viewthread.php?tid=8594&a...
The warning about not consuming alcohol is because cyanamide has a similar effect to Antabuse
http://www.osha.gov/SLTC/healthguidelines/cyanamide/recognit...
And the reaction is referenced here by a large producer of cyanamide.
http://www.cyanamide.com/content/reactions_1.htm
[Edited on 2-9-2008 by ScienceSquirrel]
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mbrown3391
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Due to the post by panziani, I think I will have a go at DEET hydrolysis after all, using higher conentrations of hydroxide and longer reaction times.
I will, of course, take several safety preautions which I failed to observe in my previous incident.
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zed
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With a high pressure reaction vessel, Diethylamine is easy to produce. Clean, cheap, and OTC.
Such a reactor, can be bought, begged, borrowed, or built. Alternately, the reaction mix can be forced through a long, small diameter reaction
tube, heated by a salt bath, but how such wizardry is achieved, I do not understand.
Check local regulations before proceeding.
Take Glacial Acetic Acid, Ammonia, Ethanol, and a Catalyst ( Cupric Chloride works well) Put 'em in your reaction vessel, seal it up, and flush it
with N2 (or use a vacuum) to evacuate the air.
Heat to 200 to 300 degrees C, with stirring or shaking, for a few hours....And Shazzam! A reasonable yield of DiethylaminoAcetamide.
Works best if you start with Acetamide, and Anhydrous Ethanol. It's a reversable reaction,(The reaction is driven forward by the removal of water
from the reaction mixture) and excess water slows the rate of reaction.
Since the Ammonia substituent of Acetamide only has two free hydrogen atoms to react with ethanol, the reaction tends to go no further than
Di-substitution.
The reaction is widely applicable, and there really isn't much waste, as between runs, the water formed during the reaction can be distilled off,
and any unreacted organic material , augmented, and re-reacted.
Check out the Patent.
US Patent 3,674,851 July 4th, 1972
Oh yeah. If you're kind of inexperienced, or your not sure about the service-ability of your reaction vessel, don't even think about trying this.
High pressure reactors can develop pressures of thousands of pounds per square inch. They are sometimes referred to as "bombs". If something goes
wrong and the vessel ruptures while it is pressurized, if you're near by, there's a good chance you will be heading off for a new incarnation.
[Edited on 7-9-2008 by zed]
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Klute
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That's actually a very good idea Zed!
Basicly, you are forming acetamide in-situ, and alkylating it. But you can use alkyl halide instead of alcohols with much less harsh reaction
conditions....
This reminded me of a serie of article I bumpe dinto when I was looking to methylate a N-substitued formamide... And its seems di-ethylation of
phenylacetamide is acheiveable under smooth condtions (reflux, PTC):
| Quote: |
In our study of the alkylation reaction of 2-phenylacetamides under basic conditions,
different systems were used as reaction models. At the beginning, N-ethyl-2-phenylacetamide
was alkylated under phase-transfer conditions using ethyl bromide,4 n-butyl bromide,
5 allyl bromide6 and benzyl bromide.7 When ethyl bromide was used, the N-alkylation
product was the only product at 60 ºCafter 2.5 h.
(ref given: D. @. Mijin, N. D. Stojanovi, S. D. Petrovi, Ind. J. Chem. 35B (1996) 1201 )
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Alkylation of N-substitued 2-phenylacetamides: Benzylation of N-(4-chlorophenyl)-2-phenylacetamide
Acetamide would be even less hindered, so I think di-ethylation could evry well be possible with 2.2eq of EtX and PTC in the solvent of choice.
Here is a revelant article on the n-monoalkylation of acetamides using KOH on alumina:The Selective N-Monoalkylation of Amides With Alkyl Halides In The Presence Of Alumina and KOH
One could start off the alkylation with KOH:Al2O3 and 1eq of RX, then add some PTC and another eq. of RX. Or just add both equivalents and heat to
relfux with a PTC. Then hydrolyze the di-alkylated amide by refluxing in HCL, and you have your diethylamine hydrochloride.
This could also be a good preparation of ethylamine: prepare aectamide (AcOEt + NH3), mono-ethylate, and hydrolyze.
Other interesting read:
Alkylation of N-substitued 2-phenylacetamides
Now, this could be a better approach for th ethread starter: get yourhands dirty with some simple synthesis: ethyl bromide from ethanol and KBr/H2SO4,
acetamide form ethyl acetate and conc. NH3, preparation of tetraethylammonium bromide (PTC) from NH3 and excess ethyl bromide, and then ethylation of
acetamide and subsequent hydrolysis. Now that's a nifty project to get started with intermediate organic chemistry. By the time to get through this,
you will haev developped some knowledge and experience in handling reagents and performing organic reactions. But that does means handling pretty
dangerous reagents (H2SO4, NH3, KOH), so don't go doing stupid mistakes like before....
If, and I mean if, you ever wanted to get that diethylamine to cook some acid, hopefully by the time to obtain it you will realize this is a dead end
But of course this is pur speculation on my part, feel free to shut me up and
prove otherwise
\"You can battle with a demon, you can embrace a demon; what the hell can you do with a fucking spiritual computer?\"
-Alice Parr
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