View Full Version : N-methylpyridine synthesis
Abigail
September 7th, 2006, 03:53 PM
I know some of megas recipes of explosives uses pyridine. I have chosen a detail of a side reaction of a reported method wich uses aluminium chloride as a substituent to yield N-methylpyridine.
Place 2 mol of methanol in a 1000 ml beaker and 1.4 mol of anhydrous aluminium chloride is stirred to the methanol. Prepare a second solution of 2 mol pyridine and 4 mol of methylene chloride in a 500 ml beaker.
The pyridine/methylene chloride solution is stirred to the methanol/aluminium chloride mixture and the flask is sealed with glass wool.
The flask is stirred for one day at 50 °C, cooled and 400 ml of 10 % hydrochloric acid is stirred to the solution and the crystals of N-methylpyridine should be precipate from the solution.
Does anyone know some about N-methylpyridine ?
nbk2000
September 8th, 2006, 10:13 AM
This wouldn't be, by any chance, intended for conversion into a fentanyl or other synthetic opiate now, would it?
meyer25
September 8th, 2006, 07:17 PM
What are you writing about when you mention N-methylpyridine? AFAIK, there are only N-methylpyridinium salts. Did you mean N-methylpiperidine?
nbk: I'm not avare of any reagent, able to oxidize N-substitued piperidine into N-R-piperidine-4-one. I rather doubt there are some such.
A good material to start with would be 4-hydroxypyridine.
Chris The Great
September 8th, 2006, 07:34 PM
It's pyridine, not piperidine/one needed for fentanyl. Pyridine is an aromatic system and is very different than the piperidines needed for fentanyls. I could be possible to reduce to piperidine with catalytic hydrogenation but why bother when piperidine is readily available from chemical suppliers? Pyridine isn't any easier to get and has a ton of hazmat etc on top of everything.
meyer25
September 8th, 2006, 08:07 PM
It's pyridine, not piperidine/one needed for fentanyl. Pyridine is an aromatic system and is very different than the piperidines needed for fentanyls. I could be possible to reduce to piperidine with catalytic hydrogenation but why bother when piperidine is readily available from chemical suppliers? Pyridine isn't any easier to get and has a ton of hazmat etc on top of everything.
Yes, but you need your piperidine to be 4-substitued to be a reasonable precursor for fentanyl synthesis. And you don't get anything like that (N-R-piperidine-4-one, N-R-4-hydroxypiperidine, let alone N-R-4-anilidopiperidine) readily from chemical supplier, because they are all listed as precursors for narcotics (for obvious reasons).
4-Hydroxypyridine instead, could be purchased. Or prepared e.g. by sulfonation or nitration of pyridine-N-oxide, subsequent alcalic hydrolysis (pyridine-N-oxide-4-sulfonic acid) and reduction, or reduction (4-nitropyridine-N-oxide to highly toxic 4-aminopyridine), diazotation and hydrolysis.
Next, quarterize the 4-hydroxypyridine with 2-phenylethylchloride, reduce with metalic sodium in anhydrous ethanol, oxidate with Jones reagent to N-ß-Phenylethylpiperidine-4-one. Further steps are well-known, I assume.
This is why to bother with pyridine if you wants to make fentanyl, unless you have access to scheduled precursors.
nbk2000
September 8th, 2006, 10:11 PM
http://opioids.com/fentanyl/synthesis.html
Well, while it's not directly used for making fentanyl, I'm fairly certain it's not being used for explosives or poisons, which greatly limits what it'd be used for, considering the nature of The Forum, eh? ;)
It just has that drug 'feel' about it.
Abigail
September 9th, 2006, 03:59 PM
Yes it is not usual for known explosives, but not to get. I would guess N-methylpyridine is a liquid and it dissociates in the solution.
C5H5N-CH3(+) Cl(-) ---> C5H5N-CH3
What N-methylpyridiniumsalt do you mean ? You can get pyridine-N-oxide from pyridine by oxidation possibly in a mixture of trichloroacetic acid/H2O2 but i`m not shure it is right to reduce from 4-methylpyridine-1-oxide.
Chris The Great
September 10th, 2006, 01:04 AM
\And you don't get anything like that (N-R-piperidine-4-one, N-R-4-hydroxypiperidine, let alone N-R-4-anilidopiperidine) readily from chemical supplier, because they are all listed as precursors for narcotics (for obvious reasons).
Suspicious, yes. Impossible, no. As of yet it is not illegal.
http://www.chemicalregister.com/N-Methyl-4-Piperidone/Suppliers/pid9584.htm
FUTI
September 10th, 2006, 03:00 PM
Pyridine-N-oxide could be of some use for E&W comunity, it can be easier nitrated then pyridine itself, as for N-methyl-pyridine salt I wouldn't be so sure.
As for 4-hydroxy-pyridine there is some procedure I have with mixed 2- and 4- substitution of pyridine-N-oxide with acetate IIRC. I have thought to give it to the students but now I have to change that decision due to bloody nannies who don't know a shit and call law enforcment forces when see a far-distant-cousin-of-a-precursor-of-missused-pharmaceutical.
meyer25
September 10th, 2006, 06:28 PM
Yes it is not usual for known explosives, but not to get. I would guess N-methylpyridine is a liquid and it dissociates in the solution.
C5H5N-CH3(+) Cl(-) ---> C5H5N-CH3
I'm sorry to say that, but you have to learn some theory of organic chemistry. N-methylpyridine exists only in form of its salts/catione, simply because of the configuration of the nitrogen atome in pyridine heterocycle. There is e.g. N-methyl-1,2-dihydropyridine, but that's not straight pyridine methylated on the N1 atom. Its empirical formula would be C5H6N-Me.
What N-methylpyridiniumsalt do you mean ?
Whatever you wish. The most common are halogenides or methylsulfate (mesylate).
You can get pyridine-N-oxide from pyridine by oxidation possibly in a mixture of trichloroacetic acid/H2O2 but i`m not shure it is right to reduce from 4-methylpyridine-1-oxide.
You can get pyridine-N-oxide by oxidiation of pyridine with peracetic acid, which is used as a disinfectant. Virtually by any percarboxylic acid, in my opinion.
What I don't understand is how you got the 4-methylpyridine-1-oxide though. No one was mentioning it in previous posts. Anyway.
Suspicious, yes. Impossible, no. As of yet it is not illegal.
http://www.chemicalregister.com/N-Me...rs/pid9584.htm
The simple fact, that you find a supplier for a chemical doesn't mean that it's not scheduled/controlled. I won't mess up with precursors. Especially not in a country like USA, where 'Analogue Act' or something like that is in power.
For instance, you might find even N-benzyl-4-piperidone (the original Janssen precursor for fentanyl) suppliers:
http://www.buyersguidechem.de/AliefAus.php?pname=1-Benzyl-4-piperidinone&pnu=160575720355&cass=
But you may be sure that you can't purchase it unless you own a company authorised by state for making controlled substances, and any identified attempt to obtain this and similar substances would draw attention of law enforcement organs upon you.
cutefix
September 10th, 2006, 11:56 PM
Chemically speaking never heard from heterocyclic chemistry that N-methyl pyridine exist as a stable derivative from pyridine.
There is 2 and 4 methyl pyridine( picoline)
Now I am not sure what particular pyridine products was used in megas explosive files.... and is their a need to really synthesize this N methyl derivative and be useful?
Abigail could you point out what particular information is a pyridine derivative used in explosive synthesis?
Chris The Great
September 11th, 2006, 04:58 PM
Well, I never said it wasn't suspicious. In Canada it isn't even on a list, for the US I am unsure if it is listed as a precursor. But it isn't illegal, I know that for sure, and if you are willing to risk a bit of piggy attention it is possible to order it and have it shipped over here. If you happen to have a fake mailbox, then there isn't any danger at all, except it might be seized by customs.
Abigail
September 12th, 2006, 03:03 PM
You are right, a stable N-methylpyridine should exist as
N-methylpyridine hydrochloride and I think that is correct.
C5H5N(+)-CH3 Cl(-) It should be useful than pyridine hydrochloride as substituent, prepared from a cooled mixture of pyridine and HCl.
I guess the synthesis is useful to get N-methylpiperidine from methyl glycol/aluminium chloride and piperidine in methylene chloride. You can get ethylene glycol and N-methylpiperidine in one step by distillation of their boiling points.
I think it looks interested ! I don`t want post crap but the theory of `bring up a useful explosive from browsing a index` is not helpful.
I like megas recipes, a couple of good stuff to inspire anyone to bring useful ideas the forum.
I will thinking a while about pyridine and some good explosives.
Abigail
September 14th, 2006, 03:55 PM
cutefix: What do you mean ?
Now I am not sure what particular pyridine products was used in megas explosive files....
I have listet some explosive compounds within pyridine which you can make from megas recipes, i would think it is correct.
4,4´,6,6´-tetranitro-2,2´bipyridine
C10H4N6O8
336,175 g/mol
2,3,4,6-tetranitropyridine
C5HN5O8
259,09 g/mol
4-amino-2,6-dinitropyridine
C5H4N3O4
170,10 g/mol
2,3,4,5,6-pentanitropyridine
C5N6O10
304,08 g/mol
3,3'-diamino-2,2',4,4',6,6'- hexanitrobipyridine
C10H8N8O8
368,22 g/mol
cutefix
September 14th, 2006, 04:55 PM
Yes. casually looking ..pyridine is one of the component but are you sure its exactly N-Methyl pyridine as the precursor?
nbk2000
September 14th, 2006, 06:15 PM
You can make explosives from milk sugars, but that doesn't make it worth doing.
Are the pyridine based explosives worth the effort and risk of obtaining a meth precursor?
meyer25
September 14th, 2006, 08:32 PM
Are the pyridine based explosives worth the effort and risk of obtaining a meth precursor?
As for trinitropyridine (TNPy) and trinitropyridine-N-oxide (TNPyOX), they are "potent explosives" (Meyer, Köhler, Homburg: Explosives, ISBN 3-527-30267-0) with det. velocities of 7.470 m/s at 1,66g/cm³ for TNPy and 7.770 m/s at 1,72 g/cm³ for TNPyOX, but they are too expensive and complicated to synthetise (direct nitration to trinitroderivatives is not possible by any reasonable reagents), if you can much more easily synthetise PETN, RDX or just picric acid, there's no reason to deal with these pyridines.
Maybe it would be of interest to see how powerful TNPy-perchlorate is, but that's still nothing for wide use.
Abigail
September 19th, 2006, 02:49 PM
direct nitration to trinitroderivatives is not possible by any reasonable reagents
Why not possible ? I know you have many compounds to make an explosive. If they expensive and complicated to synthetise or not, The question is, a useful explosive or not and what will you do with it.
This seems interested, 3,5-diamino-2,4,6-trinitropyridine, DATNPy, C5H4N4O6
Tell me, why deal with pyridines ?
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