cmos6667
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New route to phenethylamines
Hi folks,
According to Taniguchi et al:
http://www.organic-chemistry.org/abstracts/lit3/109.shtm
Notice the second row? It can be isolated, I think. 
So: Styrene + Fe(NO3)3 + FeCl3 + MeCN reflux --> 1-chloro-1-phenyl-2-nitroethane (A)
A + Mg + Et2O --> 1-chloromagnesium-1-phenyl-2-nitroethane (B)
B + HCl --> 1-phenyl-2-nitroethane (C)
C + formaldehyde + base --> 1-phenyl-2-methyl-2-nitroethanol (D)
D + Zn + HCl --> 1-phenyl-2-methyl-2-aminoethanol (E)
Reducing that OH using HI/RP or KI/H3PO4 should be easy, no?
I haven't seen this discussed anywhere, so I thought I'd throw it out there and see what you guys think 
[Edited on 11-4-2015 by cmos6667]
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Crowfjord
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That's an interesting idea. I know that the nitro aldol with formaldehyde works; I will see if I can find the reference a little later. To get to
phenylalanine, the nitro would of course have to be reduced to an amine at some point. The oxidation might work, but I don't know how well. Careful
addition of dilute permanganate might oxidize the alcohol without harming the amine (assuming that is the proposed intermediate reactant), but I don't
know for sure.
[Edited on 10-4-2015 by Crowfjord]
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Nicodem
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Thread Moved
10-4-2015 at 10:39 |
cmos6667
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Ah yes, thanks, completely forgot the Zn/HCl step
Hypothetically, if you could make 1-phenyl-1-hydroxy-2-nitroethane using styrene monomer and little else, then you could... erm... open gates to hell,
no? (all otc, I can't find any thread where that synth is discussed, which is why I think it's a prohibited topic here)
Or is it just something nobody has heard about?
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Bert
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CuReUS
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Quote: Originally posted by Crowfjord  | The oxidation might work, but I don't know how well. Careful addition of dilute permanganate might oxidize the alcohol without harming the amine
(assuming that is the proposed intermediate reactant), but I don't know for sure.
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i dont think the amino group would survive the oxidation.besides,I thought that if you used KMnO4 on a benzene ring with any side
chain,the whole side chain would get removed and you would be left with benzoic acid.
Am I wrong ?
| Quote: Originally posted by cmos6667 |
Hypothetically, if you could make 1-phenyl-1-hydroxy-2-nitroethane using styrene monomer and little else, then you could... erm... open gates to hell,
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you could make 1-phenyl-1-hydroxy-2-nitroethane from styrene.Just nitrate styrene in presence of clay(there is an article on that,search for it)
and then addition of water should give you what you want.but what will you do with that Hydroxy ?
as for your first method,there are better ways to make amino acids
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cmos6667
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PPA 
[Edited on 11-4-2015 by cmos6667]
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unionised
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Re
"A + Mg + Et2O --> 1-chloromagnesium-1-phenyl-2-nitroethane (B)".
I doubt it.
I think the nitro compound would be acidic enough to decompose the grignard reagent.
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cmos6667
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So what you're saying is that the step after (using HCl) wouldn't even be necessary? Or are you saying that A on its own will eliminate to the
nitroalkene?
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cmos6667
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My bad, can't change the first post:
Ignore the metal-acid reductions, cause it will also reduce the nitro group... instead, I think doing the reflux with LiOH, then reducing using NaBH4
would be more useful.
After that, Zn/HCl, right?
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