Pickardjr
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Thermal decarboxylation
Hello and salutations. I want to try a thermal decarboxylation on lysine to produce diaminopentane. Yea I know Im a glutton for punishment. I'd like
to buy the lysine bulk(say a few ounces) and make the soda-lime myself. My intention is to form diaminopentane monohydrochloride and rapidly heat it
to cycilize it, a dry distillation set up would be used and the secondary amine distilled over as it forms. Questions are: Can this actually be
done using Na-lime
Do I need to use a flame to heat the flask
Any comments or suggestions are welcomed , I know its gonna stink and i have safety gear. So I am aware of that. Im only wanting to make about 100
mls of the 2nd-ary amine. thanks
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Marvin
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I'm not convinced either step will work. What makes you think a diamine will cyclise with heat?
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Nicodem
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Thread Moved
8-11-2013 at 07:17 |
Crowfjord
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Cadaverine (1,4-diaminopentane) can be cyclized to piperidine by pyrolysis. It's a free-radical reaction, I think. I can't find the reference at the
moment, I have a paper somewhere, I'll check a little later. It has been discussed on this forum before, also.
Edit: Here we go: Pyrolysis of Organic Molecules: Applications to Health ad Environmental Issues Link
[Edited on 8-11-2013 by Crowfjord]
[Edited on 8-11-2013 by Crowfjord]
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Pickardjr
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Its proven in literature that this reaction works to produce secondary cyclic amine, at what percentage , I dont know what yield it would have and I
know its gona stink like death. I've read tons of articles . those stating that ammonium chloride and a cyclic amine is produced upon dry distillation
of the monohydrochloride of 1,5- diaminopentane(cadaverine). I know it will work.
I have seen in different sources where the di-HCL is claimed to be used, and have seen in one report where just lysine was used with quite low yield.
Another report claims the mono-HCL is dry distilled.
At any rate I will attempt on a micro scale to assess feasibility.
[Edited on 9-11-2013 by Pickardjr]
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Marvin
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Piperidin aus Pentamethylendiamin by Ladenburg in Berichte der deutschen chemischen Gesellschaft (1885) is the only primary ref I can find and I can't
see the whole thing and I don't read German well.
The thesis that mentioned it talked about the dihydrochloride, same as the illustration in Crowfjord's reference.
Nothing I can see talks about yield, or anything other details. Without a detailed method, this turns from a nightmare preparation to a nightmare
investigation.
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Pickardjr
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deleted
[Edited on 9-11-2013 by Pickardjr]
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Pickardjr
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http://ir.library.oregonstate.edu/xmlui/bitstream/handle/195... as a side note
160 Celsius for 2 hrs in a sealed tube looks like a place to start, omitting the nitrite of course.
[Edited on 9-11-2013 by Pickardjr]
[Edited on 9-11-2013 by Pickardjr]
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Pickardjr
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Ok I have done some serious researching on this and it appears that lysine and glucose combine to form a shiffs base in a maillard reaction upon
addition of heat, aka the browning reaction in culinary cooking. Resulting in decarboxylation and cyclization. Cold this actually work? Im gonna try
this one for sure but cant say when I'll get the time.
http://commons.wikimedia.org/wiki/File:Maillard_reaction_asp...
In a recent isotope labeling experiments using lysine/glucose model systems, Nikolov and Yaylayan (2010) reported that lysine can generate piperidine,
a reactive amine capable of undergoing Maillard-type interactions. These investigators identified two possible mechanisms for the formation of
piperidine: one arising through decarboxylation of lysine alone to generate cadaverine (1,5-diaminopentane) followed by deamination to form
pent-4-en-1-amine which in turn can cyclize into piperidine. On the other hand, in the presence of sugars, lysine, similarly to asparagine and
phenylalanine, can undergo a carbonyl-assisted decarboxylative deamination reaction to generate pent-4-en-1 -amine, the counterpart of acrylamide. The
pent-4-en-1 -amine thus formed can then cyclize to form piperidine. Given the current approved uses of piperidine as a flavoring agent (21 CFR
172.515); it is unlikely to cause adverse effects.
[Edited on 11-11-2013 by Pickardjr]
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