Author Topic: Phenylacetaldehyde + MeNH2 (g) in methanol  (Read 2213 times)

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tropine

  • Guest
Phenylacetaldehyde + MeNH2 (g) in methanol
« on: November 11, 2003, 06:03:00 PM »
a 250 gram bottle of phenylacetaldehyde (50% in isopropol alcohol) is mixed with the equivalent amount of MeNH2 dissolved in methanol @ 0 C.  The solvent is then removed in rotovap to dryness.  This is then immediately  dissolved in ether and and the equivalent amount of MeMgBr is added.  Any comments?

Aurelius

  • Guest
Grignard and Imine?
« Reply #1 on: November 11, 2003, 09:07:00 PM »
Is this what your are proposing to yield amphetamine?


tropine

  • Guest
yes, I am also wondering if instead of MeMgBr,
« Reply #2 on: November 12, 2003, 08:01:00 AM »
actually I think it would yield methampethamine, I am also wondering if instead of MeMgBr, one could use MeLi

Aurelius

  • Guest
addition
« Reply #3 on: November 12, 2003, 10:19:00 PM »
The second equivalent might add to the nitrogen, but if it does actually do so, I see no reason that it won't dimethylate.  It would probably be best to use one eq. to yield amphetamine and then mono-methylate using procedures found here and at Rhodium's.


josef_k

  • Guest
The methyl gringard does not add to the ...
« Reply #4 on: November 13, 2003, 07:37:00 AM »
The methyl gringard does not add to the nitrogen, but to the carbon in the imine doublebond. This is what he's going to do:

https://www.thevespiary.org/rhodium/Rhodium/chemistry/meth.phenylacetaldehyde.html


tropine

  • Guest
exactly, but..
« Reply #5 on: November 13, 2003, 07:41:00 AM »
yes that is what I am refering to, but I am wondering if MeLi can be substituted for the grignard, and what kind of conditions are used for MeLi, as in room temp or -78?

Aurelius

  • Guest
Temp and Lithium
« Reply #6 on: November 13, 2003, 08:42:00 PM »
Yes, the Li comp will also work, and -78*C probably isn't necessary, but it should probably be kept well below 0*C.

(embarrassing, josef_k is absolutely right about the addition- I understood the addition to the imine, but didn't realize the rest- it should have been obvious )


josef_k

  • Guest
While you're at it you should try to use ...
« Reply #7 on: November 15, 2003, 07:52:00 AM »
While you're at it you should try to use EtMgBr too, to get 1-phenyl-2-methylaminobutane. I don't think anyone here has made it yet?

Vitus_Verdegast

  • Guest
1-phenyl-2-(methyl)aminobutane
« Reply #8 on: November 15, 2003, 08:28:00 AM »
SWIM is busy at the moment  ;)

Reports to follow soon...


Aurelius

  • Guest
Methyl analog
« Reply #9 on: November 15, 2003, 12:36:00 PM »
Yes, somebody has already made it.  Although it was not me, I have tried it.  Decent stimulant, though weak.  good for a little bit of a mood lift and energy boost- much like caffiene, but stronger.


I've tried on several occassions to contact the person who had made it, but He/She has been gone without notice for the longest time.


moo

  • Guest
Maybe it should be called aephetamine, as in a
« Reply #10 on: November 15, 2003, 12:54:00 PM »
Maybe it should be called aephetamine, as in alpha-ethylphenethylamine. :)

If one was looking for a practical stimulant lacking the side-effects of caffeine while being milder and shorter lasting than plain amphetamine, could this be it?


Aurelius

  • Guest
Tastings
« Reply #11 on: November 16, 2003, 11:06:00 PM »
Depends on which side effects you are talking about.  Caffience doesn't have a lot of side effects (at least not many serious, commonly encountered side effects).  From experience, it leaves a good taste in the nose.


Vitus_Verdegast

  • Guest
aephetamine
« Reply #12 on: November 17, 2003, 05:59:00 AM »
Hehe, nice name, but the compound is already named butanamine in post

Post 461403

(Chimimanie: "Ariadne and the Butanamines", Serious Chemistry)


We could use both names of course..


roger2003

  • Guest
1-phenyl-2-pyrrolidylbutane
« Reply #13 on: November 17, 2003, 06:54:00 AM »
I think, this would be the best

;)


Kinetic

  • Guest
2-methylamino-1-phenylbutane
« Reply #14 on: November 19, 2003, 01:24:00 PM »
Aurelius, to the best of my knowledge, nobody knows exactly what's happened to the bee you mention. Fingers crossed he's safe...

2-methylamino-1-phenylbutane is a pet project of mine, mainly because of it's legal status, but also because it's a cheap way to test new methods before wasting more valuable precursors.

I made it from the corresponding ephedrine analogue (which was made from benzene -> butyrophenone -> methcathinone analogue), but after a crappy workup put me in a really bad mood, I threw away the 6g impure salt which refused to precipitate after titration of the freebase... Hence I'm yet to bioassay it.

tropine: I'd be cautious if you're planning on using methyllithium instead of the weaker methylmagnesium halide, as it may well work as an efficient base, deprotonating the benzylic carbon of the phenylacetaldehyde methylimine. I've tried a Grignard with ethylmagnesium iodide on the similar benzyl cyanide, only to be left with a strange smelling orange goo, which I suspect is formed by deprotonation of the benzylic carbon of benzyl cyanide, and subsequent attack by this on another molecule of benzyl cyanide. The end result is a trimer: 6-benzyl-3,5-diphenyl-pyridine-2,4-diyldiamine (courtesy of Beilstein). I'm not sure how much of a problem this will be with the N-methyl imine instead of the nitrile; deprotonation would still be favourable, going on the stability of primary vs. benzylic carbanions. This may not be a problem of course: Rhodium has a very respectable yield of amphetamine in his

One Pot Amphetamine synth from BzCN, MeI and NaBH4

(https://www.thevespiary.org/rhodium/Rhodium/chemistry/amphetamine.html); low temperature and high dilution (hence slow addition) favour the desired reaction.

I'm intrigued about 1-phenyl-2-pyrrolidinylbutane; very similar in structure to Prolintane. ;)  Do you have any more details, roger? Specifically on effects, as the synthesis would be really easy, either from phenyl-2-butanone, or via reduction of the cathinone analogue 1-phenyl-2-(1-pyrrolidinyl)-1-butanone...

Vitus, I'm not sure if you'll beat me to 2-methylamino-1-phenylbutane or not; I'll post details too, whenever I get there. From one method, I have some 1,2-epoxide which I'll hopefully be able to rearrange to phenyl-2-butanone (LiI was unsuccessful); whether that works or not, triethylaluminium on benzyl cyanide should do the job, as per a slight modification of

P2P by Trimethylaluminium alkylation of Benzyl cyanide

(https://www.thevespiary.org/rhodium/Rhodium/chemistry/phenylacetone.html#me3al), a method which seems to initially come from Aust. J. Chem, 23, (1970), 1921-1937, in which trimethylaluminium is reacted with 4-fluorobenzyl cyanide to give 4-fluorophenylacetone.

I'll post any relevant details once I retrieve the article.