cmos6667
Hazard to Self
Posts: 50
Registered: 10-4-2015
Member Is Offline
Mood: No Mood
|
|
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]
|
|
|
Crowfjord
Hazard to Others
Posts: 390
Registered: 20-1-2013
Location: Pacific Northwest
Member Is Offline
Mood: Ever so slowly crystallizing...
|
|
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]
|
|
|
Nicodem
|
Thread Moved
10-4-2015 at 10:39 |
cmos6667
Hazard to Self
Posts: 50
Registered: 10-4-2015
Member Is Offline
Mood: No Mood
|
|
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?
|
|
|
Bert
Super Administrator
Posts: 2821
Registered: 12-3-2004
Member Is Offline
Mood: " I think we are all going to die. I think that love is an illusion. We are flawed, my darling".
|
|
If you're not sure of what is permitted here (or why this was moved to "beginnings"), please read this part of the FAQ:
http://www.sciencemadness.org/madscifaq.html#2.1_Board_topic...
| Quote: |
It is okay to be ignorant when first arriving and posting. However, you must be willing to make an effort to learn. If you are unable to cite
references in support of an idea or as background to your question, the post belongs in Beginnings. Questions that provide background information and
show effort are more likely to receive good responses.
If an existing thread covers the topic you're about to post about, post in that thread instead of a new one. It makes it easier for members to keep up
with topics of interest. You may need to search before posting if you're unsure whether or not a thread already exists. The search engine is not very
powerful and may miss relevant threads, but please make at least a cursory effort.
Do not request spoonfeeding of information for clandestine drug manufacture. However, every sort of chemistry is a permissible topic of discussion if
you discuss it like a scientist. If someone is asking about obtaining chemicals used in drug manufacture and using the vocabulary of a SWIM—"someone
who isn't me"—-mer more than a chemist, report it and the thread will be dealt with after a moderator has confirmed your findings. Similarly, if
someone is asking for help with a synthetic "recipe" for a known street drug, report that too. Don't bother to berate the cooks in the thread itself
instead; that doesn't bring the mods any faster. In truth the mods and most members dislike any thread where someone is seeking or using a "recipe"
and doesn't show any deeper interest in chemistry, but this has been mostly a problem with drug synthesis because of the many people who want to
quickly get rich or high.
Certain topics are unwelcome no matter what section they are posted in. The discussion of criminal enterprises or weapons production is inappropriate.
|
Rapopart’s Rules for critical commentary:
1. Attempt to re-express your target’s position so clearly, vividly and fairly that your target says: “Thanks, I wish I’d thought of putting it
that way.”
2. List any points of agreement (especially if they are not matters of general or widespread agreement).
3. Mention anything you have learned from your target.
4. Only then are you permitted to say so much as a word of rebuttal or criticism.
Anatol Rapoport was a Russian-born American mathematical psychologist (1911-2007).
|
|
|
CuReUS
National Hazard
Posts: 928
Registered: 9-9-2014
Member Is Offline
Mood: No Mood
|
|
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.
|
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,
|
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
|
|
|
cmos6667
Hazard to Self
Posts: 50
Registered: 10-4-2015
Member Is Offline
Mood: No Mood
|
|
PPA 
[Edited on 11-4-2015 by cmos6667]
|
|
|
unionised
International Hazard
Posts: 5126
Registered: 1-11-2003
Location: UK
Member Is Offline
Mood: No Mood
|
|
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.
|
|
|
cmos6667
Hazard to Self
Posts: 50
Registered: 10-4-2015
Member Is Offline
Mood: No Mood
|
|
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?
|
|
|
cmos6667
Hazard to Self
Posts: 50
Registered: 10-4-2015
Member Is Offline
Mood: No Mood
|
|
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?
|
|
|
![[*]](images/xpblue/default_icon.gif){kind=icon}
