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conducter
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PEA and mek -> NPP?
i have seen a few people talking of Phenethylamine and mek could be used to make n-phenethyl-4 piperidone.
but cannot find a reference or writeup or anything..
also on the old synthetikal there was a mention of this...
"Double Mannich, using acetone, formaldehyde, & PEA" to get to NPP.
So i guess i need help if anyone has any info to hlep with.
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jon
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yeah i was looking for the same thing there's a J.A.C.S. article on it somewhere don't know where the mirrors for the hive don't exist anymore can't
find it. MEK would theroretically give 3-methylsubstituted piperidones which are even better.
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conducter
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would acetone give the desired piperidone, or another substitute? if you find any article please post cuz id love to find mor einfo on this
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transformer
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This makes me wonder if it is possible to make the normal 4-piperidone using acetone in theory it should bee possible however to selectively produce
the 4-piperidone one would have to bee very carefull with the rate and order of addition as there is a very big chance the main products will bee
2,2-dimethyl- and 2,2,6,6-tetramethyl-4-piperidone, then you also have the problem of the polymerization of 4-piperidone and the chances of
4-piperidone itself being reactive in the manich reaction, interesting nontheless if someone would get this working 
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chemrox
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I'd like to get some basic information on these compounds first such as solubilities in some of the more common solvents. I've not yet been able to
find such but am limited in my search efforts with not enough familiarity in the heterocyclic literature.
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stimo-roll
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yes i read same work (joc or jacs, cant find in cpu) - they took 1equ amine, 2equ aldehyde en 1ketone dissolved in GAA, boiled... isolated desired
piperidone. As ketones used mek, acetone, but aldehyde in all cases - benzaldehyde. All piperidones are 2,6-diphenyl :-( will this methode work on
formaldehyde.
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conducter
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i believe formaldehyde is the desired aldehyde.
If the amine was Phenethylamine, the ketone was Acetone, and the aldehyde is formaldehyde i believe that is when one will get N-phenethyl-4-piperidone
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jon
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how did they arrive at 2,6 substituted products? the non-enoliziable carbonyl should make the iminium ion and this add to the double bond system of
the enol, it does'nt make sense.
ohh I eat my words I see.
[Edited on 22-5-2007 by jon]
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stimo-roll
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Here this article. When i downloaded him from net (maybe synthetical) he was named "4-piperidones one-pot". This JACS 70,3853,1948 - "The Preparation
of Some Piperidine Derivatives by the Mannich Reaction"
Attachment: 4-piperidones-one-pot.rar (302kB)
This file has been downloaded 2497 times
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jon
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nice going I went the library no luck did'nt have beilsteins abstracts nothing.
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tr41414
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The disscussion on the hive seemed not to give any conclusive results. But as this reaction is not mentioned anywhere else in literature, I would say
that the reaction works with other aldehydes, but not the formaldehyde... So better stick with the acrylate procedure...
But regarding the use of acetone in mannich, i have heard rumors it could be used instead of acetone dicarboxylic acid in some other nice reaction
A bit off-topic: ammonia and acetone condense to tempidone - i think it is 2,2,6,6-tetramethyl-4-piperidone (?)
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tr41414
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just an idea - what about using glyoxylic acid or it's esters instead of formaldehyde? not as readily available and would add a few steps... but it
might work 
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jon
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why do you say formaldehyde won't work from a mechanistic point of view?
[Edited on 24-5-2007 by jon]
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tr41414
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sorry... have no references on that... but it would be the simplest of 4-piperidone synthesis and seems not to be in any literature i know...
hehe... but again, i might be wrong... will dig deeper and see if i can find anything interesting
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jon
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it does'nt jibe that formalin would'nt work it goes like this the aldehyde forms the aldimine this iminium carbocation adds to the electron rich
double bond system of the enol formed from the ketone and you have aminomethylated product, the adduct does'nt seem to be able to react further so i
don't see any complications from using an unsubstituted aldehyde like formaldehyde.
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tr41414
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There seem to be only 3 threads on the hive regarding this way of 4-piperidone synthesis:
ning: OTC piperidone -- fentanyl
hehe... ning 's the man... he is really revolutionary about his various OTC synthesis
albert_grieves: methyl acrylate synthesis
here some thing interesting is done hmm... divinyl ketone via mannich (acetone
& formaldehyde) + elimination ... Maybe some antipolimerization agent would do the trick in our mannich synth?
Megatherium: Discussing the Mannich reaction
hmm... about a year after his otc fentanyl post he is still convinced the reaction works, but yet again he has no references to this specific rxn... I
wonder if he has done the reaction....
So, maybe someone should try the reaction and report... That is the biggest drawback of the hive... usually no or very few reports of success (or
attempted reactions) were posted  sadly it's now only the archive and we can't
contact the original posters...
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stimo-roll
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| Quote: | | divinyl ketone via mannich (acetone & formaldehyde) |
May you got some refs for preparation, low temp needed, may be hydroquinone as stabilizer.
divinyl ketone also known as 3-pentadienone also may used in reaction with mmm MeAm. intresting how make 3-pentadienone from cyclopentanone, any
ideas.
may be anybody got access to springer, it this article is intresting?
| Quote: | 1. A method was found for the preparation of 2,4-dimethyl-3-pentadienone from 2,4-dimethyl-3-pentanone.
2. 1,3,5-Trimethyl-4-piperidone was synthesized from 2,4-dimethyl-3-pentadienone. |
http://www.springerlink.com/content/n11x184817l13kl2/
[Edited on 25-5-2007 by stimo-roll]
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jon
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I still don't have an explanation as to why acetone formalin and pea would'nt work?
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Comedy
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I found a reference to this reaction in my merck index:
http://www.chempensoftware.com/reactions/RXN295.htm
Which is about a substituted piperidone: unfortunately I don't know how to look up the references.
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tr41414
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Actually the reaction between acetone, methylamine and formaldehyde has been documented, and it does not produce the wanted compound But it is interesting that diethyl ketone does react to the piperidone... Maybe MEK
would then be better choice for a reactant, also acetone dicarboxylic acid derivates will probably work better... Hmm... And who knows what a pinch of
hydroquinone would do  (but this again is just a speculation)
Anyway it sure can be done as a two step rxn...
Ref: Organic Reactions (1942), Vol. 1, p. 305
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jon
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is that the ref. for the reaction between methylamine formalin and acetone?
acetone dicarboxylic acid derivatives could it seems be used and then decarboxylated, keto acids will decarboxylate pretty easily.
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mono
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| Quote: | Originally posted by stimo-roll
| Quote: | | divinyl ketone via mannich (acetone & formaldehyde) |
May you got some refs for preparation, low temp needed, may be hydroquinone as stabilizer.
divinyl ketone also known as 3-pentadienone also may used in reaction with mmm MeAm. intresting how make 3-pentadienone from cyclopentanone, any
ideas.
may be anybody got access to springer, it this article is intresting?
| Quote: | 1. A method was found for the preparation of 2,4-dimethyl-3-pentadienone from 2,4-dimethyl-3-pentanone.
2. 1,3,5-Trimethyl-4-piperidone was synthesized from 2,4-dimethyl-3-pentadienone. |
http://www.springerlink.com/content/n11x184817l13kl2/
[Edited on 25-5-2007 by stimo-roll] |
edit:
link dead.
[Edited on 9-9-2007 by mono]
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stimo-roll
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thanks mono
diethylketone is cheap, react him with 2Br2 and after dehydrobromination with di(m)ethylaniline and you got divinylketone. Another theoretical route
to piperidones.
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john_do
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NPP
Once upon a time, Ning gave me a detailed writeup of the double mannich in question, along with several good relevant references. For what it's worth,
he was confident that it would produce the goods as such. That is so long as a dash of HCl was added for flavour. His words not mine!
Anyhow, the archives have been sanitized since those days...
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jon
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Hcl according to one of the papers does'nt work so well because it interferes with iminium ion formation if the ph goes to low, they use acetic acid
with better results.
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