brew
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Research in Organic Electrochemical synthesis
http://www.electrochem.org/dl/interface/spr/spr06/spr06_p59-...
This preperation of an electrode has given me some ideas. I thought i'd present it here. It is reasonably current-pardon the pun -. 2006. Perhaps old
for most, but interesting to say the least. I feel it is able to be done/perhaps/ for the home experimenter, I have sussed out carbon fibre/cloth -
not that expensive, and a cation compound and I am pretty sure the manganese oxide could be prepared. As far as the benzaldehyde preparation, one
could perhaps achieve that, and numerous other reactions with such a set up. Interesting I thought.
I just wanted to add, that I wasn't sure to post this in the beginners section, and if this is best their, I am not sure how to move it.
[Edited on 8-12-2008 by brew]
[Edited on 8-12-2008 by brew]
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brew
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well I thought it was fucking interesting, meme me eme, all about me
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hissingnoise
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Biomolecules are a turn-off for me; interest generated by electrolysis is negated by the B word.
| Quote: | Originally posted by brew
This preparation of an electrode has given me some ideas. |
Youse could tell us what those ideas might be. . .
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brew
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My ideas were the fact that this cloth is not that expensive, and I can access the polystyrene sulfanate, and some of these nanoparticles and their
preps, that I have found in the literature appears to be within the reach of someone doing this at home. I also have a few contacts that could help
me acquire some of this material. The notion of applying a cation and then adhering a negatively charged anion with catalytic properties such as the
manganese oxide appeals to me. I saw the student article and personaly found it interesting. Perhaps it is because I am a student and this is somewhat
new and therefore exciting. I seem to have this urge to want to experiment. I am slowly getting equipment, reagants and knowledge together. My
interest isn't just this one of oxidation of styrene, or the benzaldehyde prep, but to experiment with a range of perhaps selective oxidising
reactions. I am buying the cloth as it was only, I think it was about 70 bucks a square meter, but for experimentation, one wouldn't be wanting to use
a large electrode surface. Perhaps this is boring for most and quike frankly I dont really care, obviously I'd like to be posting things that
interests and is relevant for all, but we are all at different levels in our understanding of chemistry, so so be it. When I get the cloth and start
doing some chemistry with it, I will present my findings. Presently I have been working on the preparation of sodium nitrite, divided cell, and with a
degree of sucess, but very much exploring conc, time, electrodes, temp of cell. Perhaps if I end up with a reasonably consistent result, I will post
such findings. Personaly, I like experimenting myself, rather than just reading other peoples work and copying recipes, obviously there is a time and
place to do this, but I just like playing around with this shit.
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hissingnoise
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I'd say most here find electrochemistry fascinating.
Most threads, though, are on the inorganic preps side, but I easily forget that ethylenediamine, for example, is prepared by electrolysis of glycine
salts.
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brew
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That is very interesting. If it is reasonably simple, fuck. I just quikly looked it up, and found that it is the copper salt of these carboxylic acids
via electrolyses etc. This includes the use of aromatic ones such as 4-aminobenzoic acid, where this turns into benzidine via the copper
salts/electrolysis, I wonder how it would respond to the copper salt of say an AA and something such as the copper salt of acetic acid. Perhaps put
on my recreational attire. ? Perhaps a long way of and Ive misunderstood things. Perhaps not, but somewhat close. Interesting to say the least. Sort
of a coincidence as I have been very much enjoying making that particular copper salt. Not the prep, as it makes itself but the end result. NICE
color/.Time to get some AA and experiment perhaps. That nitrite prep is a real pain in the a$$. It reduces to ammonia very quickly, I am going to
splurge and get a decent power supply and upgrade my stirring capabilities. Perhaps sus out the use of a power supply via computer, etc.
[Edited on 21-12-2008 by brew] attroshus spelling.!
[Edited on 21-12-2008 by brew]
[Edited on 21-12-2008 by brew]
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brew
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Just thinking about this, I feel it may respond quite well. Obviously chirality would need to be considered. Ive never heard of this prep, so perhaps
I am jumping the gun, It does though somewhat seem feasible. Phe that is as a- copper salt and copper acetate, in the same set up as the glycine and
the 4 aminobenzoic acid prep. this removing both carboxy groups forming a carbon carbon bond and the resulting amine. Perhaps I have got it wrong,
which is fine. I haven't found a particular reaction condition for the glycine converted to ethylenediamine, so if you do have it, I would appreciate
a referance.
If the condensation or removal of CO2 is plausible for such conditions, it is a very useful bit of chemistry. I really want to find the mechanism and
conditions for this.
[Edited on 21-12-2008 by brew]
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Sedit
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http://www.electrochem.org/
They have a decent amount of publishings that can be viewed if one is a member plus a wealth of information on electrochemical methods
Hissingnoise would you be able to provide a source for the electrosynthesis of Ethylenediamine from glycine salts?
I have been looking for days for an electro method of synthesising Ethylenediamine and have come up with nothing. Plus a google search of glycine
and "ethylenediamine synthesis" produces one result that was worthless.
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not_important
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| Quote: | Originally posted by Sedit
Hissingnoise would you be able to provide a source for the electrosynthesis of Ethylenediamine from glycine salts?
I have been looking for days for an electro method of synthesising Ethylenediamine and have come up with nothing. Plus a google search of glycine
and "ethylenediamine synthesis" produces one result that was worthless. |
---------------------------------------
Electrolysis of Glycine. Otto Kuhling (Ber., 1905, 38, 1638—1646).—Aqueous glycine solutions are at first very bad conductors, but as the
electrolysis proceeds the conductivity of the solutions increases owing to the formation of better conducting products.
After electrolysis, the solutions are found to contain ammonia and small quantities of ethylenediamine, whilst if the conductivity of the original
solution is increased by the addition of an indifferent substance, no ethylenediamine is obtained. The gaseous products consist almost entirely of
carbon dioxide, whilst carbon monoxide, nitrogen, and formic acid are formed in small quantities.
---------------------------------------
On electrolysis, the acid or the copper salt yields ethylenediamine (Lilienfeld, D. R. P. 147943; : Chem. Zentr. 1904, i. 133; Kuhling, Ber. 1905,
1638 ; 1907, 757).
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CONDENSATION BY ELECTROLYSIS.
Many years ago, Brown and Walker 3 found that by electrolysis of mono-esters of dibasic acids, carbon dioxide was removed, and the residues condensed
to form a dibasic ester of higher molecular weight.
For example, ethyl potassium malonate reacts in the following manner, giving diethylsuccinic ester :
/COOK CH 2 'COOC 2 H 5
2CH 2 <^ = | + 2C0 2 + 2K.
COOC 2 Eu, CH 2 ' COOC 2 H 5
The method has been expanded by Mulliken and Weems, 4 and also by von Miller and Hofer. 5
The principle has been applied to the preparation of aromatic compounds from the carboxylic acid copper salts. 6 The disappearance of the blue colour
of the copper salt indicates the completion of the reaction. Ethylene diamine is produced from the copper salt of glycine :
(CH 2 NH 2 COO) 2 Cu = C 2 H 4 (NH 2 ) 2 + 2C0 2 + Cu.
1 D.B.P. 64405 (1891). * Ibid. 108838 (1899).
3 Annalen, 1891, 261, 107 ; 1893, 274, 41.
4 Amer. Chem. Journ., 1893, 15, 323 ; 1894, 16, 569.
5 Ber., 1895, 28, 2427, 3438. 6 D.B.P. 147943 (1904).
the last from
http://www.archive.org/details/manufactureofche00halerich
Note that a lot of Victorian and even Edwardian era chemistry, especially organic chemistry, has "synthesis" that are low in yield with a mixture of
products.
[Edited on 20-1-2009 by not_important]
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brew
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Thankyou Sedit and Not_important. JUst wondering if anyone has tried this ethylene diamine, prep. . For the record. I am in no way interested in
forming the copper salts of Phe with acetic acid. I just jumped on that bandwagon for abit of fun for the hype involved with that small mountain.
Wouldn't do it, but think the potential for the removal of carboxylic groups are of interest. I purchased some glycine, and have been playing around
with making copper salts and will post results when finished. Thanks again for the links
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Sedit
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The prep I have seen for producing the copper salt involved mixing the glycin with copper acetate to produce the copper salt of glycin. Sorry I cant
provide more information on it but I dont have the refrence handy. I am going to try this when I find some glycin but have yet to find any pure.
Knowledge is useless to useless people...
"I see a lot of patterns in our behavior as a nation that parallel a lot of other historical processes. The fall of Rome, the fall of Germany — the
fall of the ruling country, the people who think they can do whatever they want without anybody else's consent. I've seen this story
before."~Maynard James Keenan
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brew
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I haven't bought aa from this lot, but I have seen it advertised. http://purebulk.com/glycine-c-31.html
and there is definately pure aa here. http://www.aminoguy.com/Default.asp?c=204153.
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Sedit
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The first dont sound to bad price wise but the second is just horrible.
40$ for 200 grams to roughly condense half that to ethylene Diamine, Not worth it from a practical aspect.
The first on the other hand when they are not sold out 1 Kg for the same price as the second dont sond to bad for experimenting at all but I have
looked more local then online so I cant compare prices properly.
.
Thank you brew.
Peace
~Sedit
Knowledge is useless to useless people...
"I see a lot of patterns in our behavior as a nation that parallel a lot of other historical processes. The fall of Rome, the fall of Germany — the
fall of the ruling country, the people who think they can do whatever they want without anybody else's consent. I've seen this story
before."~Maynard James Keenan
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not_important
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| Quote: | Originally posted by Sedit
40$ for 200 grams to roughly condense half that to ethylene Diamine, Not worth it from a practical aspect.
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Maybe worse than that, remember
| Quote: | | After electrolysis, the solutions are found to contain ammonia and small quantities of ethylenediamine, |
As I stated before, 19th century ochem contains a lot of "preparations" with the named product having yields of less than 10%.
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brew
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It appears that there are multi products and not high yields. I am buying this carbon fibre, so I can cut out strips and attatch to electrodes - Ill
probably use iron rods, as I have lots of them, I was thinking some resin/hardener, there must be ones that dont get easily attacked by acids/bases.
You guys had any experience attatching fibre like I am describing?
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brew
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One thing I have thought of, is the possible use of dicarboxylic acids, and using these in conjunction with another carboxylic acid, in a Kolbe
set-up. No doubt one would get a range of products, but it could be an interesting way to obtain carboxylic acids that aren't easily prepared or
obtained.
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