chemrox
International Hazard
Posts: 2961
Registered: 18-1-2007
Location: UTM
Member Is Offline
Mood: LaGrangian
|
|
2-amino-4,N-methylamino butane
A few years ago a chemical company sent me a sample of benzyl acetone. Nice smelling stuff. So, just for grins, I'm thinking of hitting it with
Hg/Al amalgam and adding ammonia. I don't have CH3NH2 but was planning to make the sec amine with CH3I.
All comments and ideas for the ketone welcome.
|
|
|
chemrox
International Hazard
Posts: 2961
Registered: 18-1-2007
Location: UTM
Member Is Offline
Mood: LaGrangian
|
|
one more thing
As most ot all of you know the TM has zero activity.
|
|
|
Sergei_Eisenstein
Hazard to Others
Posts: 290
Registered: 13-12-2004
Location: Waziristan
Member Is Offline
Mood: training
|
|
Controlled alkylation of amines with alkylhalogenides generally is difficult. I'd expect a mixture of mono-, di- and trimethylated amine. Better ideas
(regarding selectivity) are reductive amination or reduction of a corresponding amide (e.g. LAH reduction of N-formylamines to N-methylamines). Also,
I'm not sure the reductive amination of your ketone with amine can be achieved under normal reaction conditions. Most experiments I have seen involve
high pressure.
[Edited on 20-1-2007 by Sergei_Eisenstein]
damnant quod non intelligunt
|
|
|
chemrox
International Hazard
Posts: 2961
Registered: 18-1-2007
Location: UTM
Member Is Offline
Mood: LaGrangian
|
|
I believe you're right as to yield issues in going to the sec amine the way I indicated although there may be a way to control formation of tert ams
and quart am salts. I'm looking around for a possible solution to that. Option is to go straight there using the appropriate amine or amide. Might
have to.
You're wrong about the reduction requirements though. Shulgin uses Fe/HCl in at least on correspondng synthesis and there are boundless others in the
underground anals. I'll report results of that phase when I get to it. Also, before I do it, I'll look up some refs and report those so you have
more than, "Shulgin uses..." to critique.
Thanks for your thoughts and information.
|
|
|
Sergei_Eisenstein
Hazard to Others
Posts: 290
Registered: 13-12-2004
Location: Waziristan
Member Is Offline
Mood: training
|
|
I made a typo.
| Quote: | | Also, I'm not sure the reductive amination of your ketone with amine can be achieved under normal reaction conditions |
It should read: Also, I'm not sure the reductive amination of your ketone with ammonia can be achieved under normal reaction
conditions. I would be interested to see the reports where they use Fe/HCl for reductive aminations. I'm completely unaware of that. I suspect you're
confusing a few things with eachother.
damnant quod non intelligunt
|
|
|
Nicodem
Super Moderator
Posts: 4230
Registered: 28-12-2004
Member Is Offline
Mood: No Mood
|
|
The amination of phenylacetone with NH3 using aluminium amalgam is described in J. Chem. Educ., 51 (1974) 671 (see this). However the 30% yield achieved is understandably much lower as to the yield when using alkylamines which form the imine intermediate more
readily given their considerably greater nucleophilicity. I would expect the same reaction for benzylacetone would give similarly low yields. After
all, it is not without any reason that everybody uses oximes in such cases where a primary amine is to be formed from a ketone!
| Quote: | Originally posted by chemrox
As most ot all of you know the TM has zero activity. |
I have no idea what the hell "TM" is supposed to be, but I would not be so sure regarding the inactivity of the resulting 4-phenyl-2-aminobutane and
its N-methyl derivative.
| Quote: | Originally posted by chemrox
Shulgin uses Fe/HCl in at least on correspondng synthesis and there are boundless others in the underground anals. |
Strange. I never heard of a single such case where Fe/HCl is used in reductive aminations of ketones.
Edit:
Just curious, but what has the thread title "2-amino-4,N-methylamino butane" to do with the thread topic?
[Edited on 21-1-2007 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!
|
|
|
chemrox
International Hazard
Posts: 2961
Registered: 18-1-2007
Location: UTM
Member Is Offline
Mood: LaGrangian
|
|
TM=target molecule => title
|
|
|
chemrox
International Hazard
Posts: 2961
Registered: 18-1-2007
Location: UTM
Member Is Offline
Mood: LaGrangian
|
|
| Quote: | Originally posted by Nicodem
The amination of phenylacetone with NH3 using aluminium amalgam is described in J. Chem. Educ., 51 (1974) 671 (see this). However the 30% yield achieved is understandably much lower as to the yield when using alkylamines which form the imine intermediate more
readily given their considerably greater nucleophilicity. I would expect the same reaction for benzylacetone would give similarly low yields. After
all, it is not without any reason that everybody uses oximes in such cases where a primary amine is to be formed from a ketone!
| Quote: | Originally posted by chemrox
As most ot all of you know the TM has zero activity. |
I have no idea what the hell "TM" is supposed to be, but I would not be so sure regarding the inactivity of the resulting 4-phenyl-2-aminobutane and
its N-methyl derivative.
| Quote: | Originally posted by chemrox
Shulgin uses Fe/HCl in at least on correspondng synthesis and there are boundless others in the underground anals. |
Strange. I never heard of a single such case where Fe/HCl is used in reductive aminations of ketones.
Edit:
Just curious, but what has the thread title "2-amino-4,N-methylamino butane" to do with the thread topic?
[Edited on 21-1-2007 by Nicodem] |
|
|
|
chemrox
International Hazard
Posts: 2961
Registered: 18-1-2007
Location: UTM
Member Is Offline
Mood: LaGrangian
|
|
As far as reduction using ammonia, I think I was confusing a couple of things as has been sugested.
|
|
|
![[*]](images/xpblue/default_icon.gif){kind=icon}
