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SpeechDiscussionTalk
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Pyridine synthesis/extraction
Hi!
Does anyone here know a good synthesis of pyridine from extremly OTC-chemicals like B6, nicotine or similar things? In "ancient" times it was made by
dry destillation of bones.
In my opinion (which isn't much influenced by very much knowledge of bones btw.) this dry destillation is a pyrolysis reaction of some proteins. Maybe
there is another source for these kind of proteins...
I would be grateful for any help!
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not_important
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Use the search engine before starting a thread
http://www.sciencemadness.org/talk/viewthread.php?tid=9650
http://www.sciencemadness.org/talk/viewthread.php?tid=286
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skullandfeather
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its partially responsible for the smell of coffee i hear.....
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Fleaker
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Ew, now that you mention it, I kind of can detect that odour! Thanks for ruining coffee for me :-/
In all fairness to SpeechDiscussionTalk, we do not have a good thread on the synthesis of pyridine or the acquisition from common OTC chemicals.
Don't look to me for information though, I'm no organic chemist, but I know there are people here who know how to synthesize it or extract it (that
should be easy).
I remember it being mentioned that pyridine is used as a denaturant in ethyl alcohol, but in what proportions, I do not know.
Pyridine is useful indeed, many wonderful complexes can be made from it (oxidizing agents, halogenating agents) and it also serves a catalytic
function in many reactions.
So why not discuss it some? I think it would be easy to buy, but why not try making it for the sake of making it?
Neither flask nor beaker.
"Kid, you don't even know just what you don't know. "
--The Dark Lord Sauron
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Sauron
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Pyridine is produced industrially by the reaction of acetaldehyde, formaldehyde and ammonia at elevated temperature and pressure over a catalyst. The
three isomeric picolines are formed simultaneously and the products fractionated.
There are other processes, but none of them OTC and all of them quite industrial.
[Edited on 29-12-2007 by Sauron]
Sic gorgeamus a los subjectatus nunc.
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SpeechDiscussionTalk
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The decarboxylation of niacin seems to be a good method to make pyridine. Is the decarboxylation of a compound like niacin anything else than making
the the Ca-salt and gentle heating until it slowly decomposes? Should i take some other things into account i forgot, or is it really that simple from
niacin?
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len1
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I dont believe this gives a measurable yield. Decarboxilating in the 3-position is much harder than in the benzene ring due to electron deficiency
there, is my understanding. Plus I have not seen such a reaction in any standard texts, rather the much more complicated condensation of
acetaldehyde, formaldehyde and ammonia. Len
[Edited on 29-12-2007 by len1]
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not_important
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Yields aren't great, you'll get some bipyridines/bipyridyls and other stuff, so you'll need to fractionate the product. The actual temperature needed
can be rather high, see the benzene from benzoic acid threads, including the on in Prepublication.
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leu
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1.5 g nicotinic acid and 2.5 g CaCO3, when heated to decarboxylation with a bunsen burner give 0.3 ml pyridine 
Chemistry is our Covalent Bond
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len1
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Well now youve got me interested, I shall ahve to try this out!
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Fleaker
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I'm more interested in having a shot at the high temperature route with the aldehydes and ammonia. Apologies in advance for being damn lazy, but what
pressure does it run at? If it's a few atm. I can go for it, anymore though and out of my league it will be.
Neither flask nor beaker.
"Kid, you don't even know just what you don't know. "
--The Dark Lord Sauron
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len1
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| Quote: | Originally posted by leu
1.5 g nicotinic acid and 2.5 g CaCO3, when heated to decarboxylation with a bunsen burner give 0.3 ml pyridine |
Surely you mean decarboxylation with Ca(OH)2 to give CaCO3. I cant see how CaCO3 will give you anuthing until it gets 'decarboxylated' itself at
700-900C! But there wont be much organics left at that temperature... Im afraid ive got my doubts again ...
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undead_alchemist
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Pyridine on eBay.
1L
http://cgi.ebay.ca/ws/eBayISAPI.dll?ViewItem&item=120204...
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leu
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| Quote: | | Surely you mean decarboxylation with Ca(OH)2 to give CaCO3. I cant see how CaCO3 will give you anuthing until it gets 'decarboxylated' itself at
700-900C! But there wont be much organics left at that temperature... Im afraid ive got my doubts again ... |
Decarboxylation is a well known chemical reaction, the site where that information came from isn't on the internet anymore so you can either accept it
or reject it; it matters little in the grand scheme of things The person who
originally posted it is a well known member who can verify that he did if he wants to, but such spoon feeding seems unlikely  It's been discussed at another forum known to many of the members:
http://www.roguesci.org/theforum/showthread.php?t=3289&h...
http://www.roguesci.org/theforum/showthread.php?s=9684ba78f1...
There at least a dozen other little known methods such as:
Patent DE944251
Example 2
A solution of 200 parts 1,5-pentanedial in 800 parts 3% sulfuric acid is added, over the course of 2 h, to a boiling solution of 1100 parts
crystallized Fe2(SO4)3 and 200 parts (NH4)2SO4 in 1500 parts water. Workup as in example 1 yields 82% pure pyridine.
workup as in example 1: rxn-mixture is made alkaline and the aromatic base is distilled off.
and
While hydrogenations of pyridine forming piperidine have been the topic of many posts; the corresponding dehydrogenation of
piperidine forming pyridine seems to have escaped notice so far. This reaction can be carried out either by heating to 300° with concentrated
sulphuric acid, or with nitrobenzene at 200°; or with silver acetate in acetic acid  An old preparation of piperidine is by heating pentamethylenediamine hydrochloride (cadaverine); which is the result of putrefactive
enzymes on lysine. Cadaverine is quite toxic in addition to being very obnoxious, but the hydrochloride salt isn't so toxic. An alternative synthesis
can be found in Ber 56 625-30 (1926):
[Edited on 2-1-2008 by leu]
Attachment: pummerer.djvu (126kB)
This file has been downloaded 1130 times
Chemistry is our Covalent Bond
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not_important
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The ZIP file appears to be broken, near the end of it in the central directory the "version made by" offset is bad, looks like the zip creator
stuttered and had 0x1414 instead of 0x0014. What was used to create it?
As it is a DJVU file, zipping it saves little if any space. If the zip was needed to get the board software to take it, that's one thing and perhaps
the board could be configured to accept .djvu files, otherwise it might be better not to zip single .djvu files.
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Sauron
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We are having similar hassles in References. arkansas posted a zip file to me, no good. And a zip file to Rosco_Bodine also no good.
kmno4 was eventually able to recover the pdfs from Rosco's zip but, only after a lot of effort.
As for my requested files I am awaiting arkansas to kindly repost them without compression. As they are already pdf's, the only point of zipping is to
make one file out of two, but useless if it fucks them up, as something seems to be doing.
Sic gorgeamus a los subjectatus nunc.
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solo
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| Quote: | | Originally posted by leu An alternative synthesis can be found in Ber 56 625-30 (1926) |
------------------------------------------------------------------------------------------
Über eine verbesserte Methode zur Darstellung von Diaminen und Amino-alkoholen
N. Putochin:
Berichte der deutschen chemischen Gesellschaft (A and B Series Volume 59, Issue 4 (p 625-630), 1926
Attachment: Über eine verbesserte Methode zur Darstellung von Diaminen und Amino-alkoholen (p 625-630) .pdf (434kB)
This file has been downloaded 1135 times
It's better to die on your feet, than live on your knees....Emiliano Zapata.
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leu
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IZArc was used to zip the deja vu file, the forum software is corrupting zip files 
Pyridine is produced from the reaction of pyrrole and carbene; and Tschitschibabin published his laboratory studies of various syntheses of pyridines
made by passing ammonia and aldehyde vapors over granular alumina between 200 to 350 º C in JCS Abstr 1906, i, 451; 1915, i, 638; 1923, i,
1121-3 He obtained pyridine itself from the vapors of acetaldehyde and acrolein
with ammonia over alumina in these experiments
Chemistry is our Covalent Bond
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Nicodem
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I have yet to see a reaction where pyridine can not be substituted with another mild base (unless of course pyridine is used as reaction substrate).
Besides any method of its preparation is uninteresting as long as it is so cheap and so easily available (you can find it in just about any organic
lab).
But if it is just for the fun of preparing it, I guess nicotinic acid could be used. Though using CaCO3 (no need for Ca(OH)2 here, since nicotinic
acid is an acid, as the name implies anyway, and CaCO3 is a base) seems a bit counterintuitive since it is well known that the thermolysis of calcium
carboxylates gives mainly the products of decarboxylative ketonization and nearly no products of decarboxylation. For example, heating calcium acetate
gives mainly acetone and not methane as one would expect from the analogy of the reaction: NaOCOCH3 + NaOH => Na2CO3 + CH4; or the analogous:
NaOCOPh + NaOH => Na2CO3 + PhH. So, I would tend to believe the thermolysis of calcium nicotinate gives more bis(3-pyridyl) ketone than it would
give pyridine. Though perhaps no ketonization occurs with carboxylic acids lacking any alpha hydrogens. Still, rather give it rather a try with the
more classical thermolysis of sodium carboxylates in NaOH as it so well described for benzoic acid on this forum.
…there is a human touch of the cultist “believer” in every theorist that he must struggle against as being
unworthy of the scientist. Some of the greatest men of science have publicly repudiated a theory which earlier they hotly defended. In this lies their
scientific temper, not in the scientific defense of the theory. - Weston La Barre (Ghost Dance, 1972)
Read the The ScienceMadness Guidelines!
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len1
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Everything is an acid and everything is a base - its just a question of how strong.
Nicotinic acid is a weak acid, weaker than benzoic because the nitrogen withdraws electrons from the ring, and CaCO3 is a weak base, the weaker the
base the lower te yield in what is already a very low yield process. Try CaCO3 with benzoic acid.
[Edited on 2-1-2008 by len1]
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Nicodem
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I just remembered that decarboxylative ketonization proceeds also with acids lacking the alpha hydrogens (at least in the case of mixed calcium
formate/benzoate which gives benzaldehyde). So I would skip idea of using calcium carbonate and try with NaOH according to the method used for benzoic
acid.
| Quote: | Originally posted by len1
Nicotinic acid is a weak acid, weaker than benzoic because the nitrogen withdraws electrons from the ring, and CaCO3 is a weak base, the weaker the
base the lower te yield in what is already a very low yield process. Try CaCO3 with benzoic acid. |
Nicotinic acid is indeed somewhat less acidic than benzoic acid (pKa 4.9 vs. 4.2). But that is not because electron withdrawal since electron
withdrawing groups on benzoic acids increase their acidity (as long as there is no neighboring effect in o-substituted ones – like in salicylic
acid, for example). For example, you can compare: p-NO2-benzoic acid (pKa 3.44), m-NO2-benzoic acid (pKa 3.45), o-NO2-benzoic acid (pKa 2.17), benzoic
acid (pKa 4.20), p-MeO-benzoic acid (pKa 4.47).
Also, you confuse the proton transfer reactions in aqueous solution with what appears as an acid-base reaction among solids in melt (as is the case
here). If one of the products is a gas (CO2 in our case) then the reaction will proceed almost regardless how strong the acid and base are since the
reaction equilibrium will not be dependant on proton affinity, but on the removal of the volatile component (CO2). This is how glass is made from SiO2
and alkali carbonates even though silicates are more basic than carbonates - the reaction proceeds by the removal of CO2 and not as acid/base
equilibrium. Another inorganic example is the reaction of boric acid (a very weak acid) with carbonates at high temperatures.
…there is a human touch of the cultist “believer” in every theorist that he must struggle against as being
unworthy of the scientist. Some of the greatest men of science have publicly repudiated a theory which earlier they hotly defended. In this lies their
scientific temper, not in the scientific defense of the theory. - Weston La Barre (Ghost Dance, 1972)
Read the The ScienceMadness Guidelines!
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len1
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1) In your previous post you stated CaCO3 is a good reagent to decarboxylate niacin because its a base, now you are stating its got nothing to do
with it - it actually just CO2 formation that drives equilibrium.
2) Sorry - electron withdrawl from the ring does make the COOH group more acidic, however you are out of luck with niacin - COOH is in the meta
position and nitrogen lone pair mops up the protons.
3) Acidity isnt just of relevance in aquesous solutions
4) Things are actually a lot more complicated. Both drive the reaction. If it was just gas formation then CaCO3 is not needed, but the
decarboxylation will occur at way too high T to save the pyridine - thats why a base is added in the reaction, it lowers delH and the reaction
proceeds at a lower temp The stronger the base - the better - (thats actually part of the the reason for your observation that Ca(OH)2 doesnt
decarboxylate as well as NaOH).
5) Take a close look at what you are proposing:
niacin + CaCO3 -> Pyridine + CO2 + CaCO3
CaCO3 contributes nothing to the delH of the reaction - you are suggesting it as a catalyst. Good luck with the reaction.
[Edited on 4-1-2008 by len1]
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Nicodem
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1.) Obviously, you misunderstood my post since I was saying just the opposite. I was commenting Leu's citation about nicotinic acid decarboxylation
over CaCO3, expressing my opinion that the use of CaCO3 is a bad choice if pyridine is the target product since it is well known that the main path in
calcium carboxylates thermolysis is not the decaboxylation but decarboxylative ketonization instead (see the attached review if you are unfamiliar
with this reaction). Hence the main product would not be pyridine but bis(pyridin-3-yl) ketone (aka dipyridin-3-ylmethanone). In such ketonizations
the base can indeed be used as catalyst since it is unaffected by the reaction (see the example using ThO2 in Vogel's). When such catalytic methods
are not used, the carboxylates of Ca, Ba, Pb, Fe and other multivalent metals are preprepared from the corresponding carbonates or hydroxides and then
subjected to the thermolysis yielding the corresponding ketones.
But if decarboxylation is the desired path, one better stick to the original conditions using NaOH in excess (like I already said). There is a
mechanistic explanation on why excess hydroxide is required (you can also use thermodynamic arguments like you did, but I prefer mechanistics). And
according to this reaction mechanism, the reaction can not proceed equally with CaCO3.
2.) Pyridine is not a substituted phenyl ring. Your comparison makes no sense. The electronic characteristics of pyridinyl group are different from
the phenyl group. Hence the pKa of nicotinic acids are not the same as for benzoic acid, neither are they comparable from the substitution point of
view (also, substituents on the meta position of benzoic acid do influence the acidity through inductive effect; see the examples in my previous
post). I was not explaining the origin of their difference, but merely correcting your erroneous statement: "Nicotinic acid is a weak acid, weaker
than benzoic because the nitrogen withdraws electrons from the ring". What I also found strange in your comparison with benzoic acid is in that you
seem to claim that benzoic acid would form the carboxylate with CaCO3 while nicotinic acid wouldn't, even though the benzoic acid is only 5 times more
acidic than nicotinic acid.
3.) Never said it is of relevance only in aq. solutions. Proton transfers occur in all kind of solvents, just the proton affinity changes with the
solvent properties. I just said that you should not only count the acid/base equilibrium where there are present also other equilibriums that drive
the reaction to competition.
4 and 5.) I was proposing:
A.) 2 {pyridin–3-yl}–COOH + CaCO<sub>3</sub> => Ca(OOC–{pyridin-3-yl})<sub>2</sub> + CO<sub>2</sub>
B.) Ca(OOC-{pyridin-3-yl})2 => CaCO3 + {pyridin-3-yl}–CO–{pyridin-3-yl}
… and side products among which there might be pyridine as indicated from Leu's post.
Obviously the reaction A proceeds without problems at the temperature where the nicotinic acid melts (238°C; though it is probably over by that T
since the partial pressure of nicotinic acid is not zero at temperatures lower than that). The reaction B also requires temperatures higher than
200°C, generally 300-400°C.
Attachment: Ketonization of Carboxylic Acids by Decarboxylation_Mechanism and Scope.pdf (154kB)
This file has been downloaded 2075 times
…there is a human touch of the cultist “believer” in every theorist that he must struggle against as being
unworthy of the scientist. Some of the greatest men of science have publicly repudiated a theory which earlier they hotly defended. In this lies their
scientific temper, not in the scientific defense of the theory. - Weston La Barre (Ghost Dance, 1972)
Read the The ScienceMadness Guidelines!
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len1
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I think weve reached the point of diminishing returns - youve stated your position Ive stated mine. Fortunately this isnt abstract psychology, the
reaction is simple enough to be tested, putting the misunderstandings aside, there are real differences between what you and I say.
PS I mentioned CaCO3 + benzoic acid in jest, sure I dont expect it to work. Plus the fact that niacin resists decarboxilation, is in the literature,
precisely because its in the meta position.
PSS I dont expect substituted benzene and pyridine rings to be identical, where do I say that? But the principle of resonance structures applies
equally to both!
Now if there is an actual testable disagreement it is this:
You expect
benzoic acid + Na2CO3 -> benzene + CO2 + Na2CO3
to yield well, just as
benzoic acid + 2NaOH -> benzene + CO2 + Na2CO3 + H2O
I expect much better results in the later, for the reasons I have outlined (but you havent understood).
we shall see..
[Edited on 4-1-2008 by len1]
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Nicodem
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| Quote: | Originally posted by len1
Now if there is an actual testable disagreement it is this:
You expect
benzoic acid + Na2CO3 -> benzene + CO2 + Na2CO3
to yield well, just as
benzoic acid + 2NaOH -> benzene + CO2 + Na2CO3 + H2O
I expect much better results in the later, for the reasons I have outlined (but you havent understood).
we shall see.. |
Read my previous post again. I said exactly the opposite, that:
benzoic acid + Na2CO3 -> benzene + CO2 + Na2CO3"
does not go because benzophenone is the main product! <-wrong, see bellow
Edit:
Sorry, this time it was me who misread your post. I thought the above was about "benzoic acid + CaCO3". I don't know why you brought out Na2CO3
when the issue was about CaCO3, but in the case of "benzoic acid + Na2CO3" the main products should be benzene, sodium phthalate and other
byproducts, depending also on the temperature, closed/open system, O2 and H2O presence, etc.. Benzophenone forms only when the calcium salt is used
where ketonization is the main pathway. In the themolysis of sodium benzoate less than 3% of conversion is accounted to the ketonization, while the
themolysis of the potassium salt is even cleaner, yielding only benzene and potassium phthalate in 4.75 : 1 ratio. On the contrary, calcium benzoate
yields benzene and benzophenone in a 2 : 1 ratio in a closed deareated system at 400-500°C (the formation of benzene is attributed to the presence of
moisture in the starting material – obviously there is no explanation for its formation unless a proton donor is present). See: Energy &
Fuels, 19 (2005) 365–373 and references therein for a better understanding.
[Edited on 4/1/2008 by Nicodem]
…there is a human touch of the cultist “believer” in every theorist that he must struggle against as being
unworthy of the scientist. Some of the greatest men of science have publicly repudiated a theory which earlier they hotly defended. In this lies their
scientific temper, not in the scientific defense of the theory. - Weston La Barre (Ghost Dance, 1972)
Read the The ScienceMadness Guidelines!
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