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Quantum_Dom
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Oxidation of phenethylamine to (2-nitroethyl)benzene
Hi everyone !
I am interested in oxidizing phenethylamine to it's corresponding nitro compound (see scheme below). So far, I have found a few references [1-4] but
unfornutaly have not yet been able to read them as I can't have access to them. They basically involve the use of oxone or peroxyacids. But I think
the work in these references is done on primary amines attached to tertiary carbons or aromatic primary amines. My questions are:
1- Do anybody have expericence in the oxidation of primary aliphatic amines similar as the one illustrated in the scheme?
2- If so, what are the standard reaction parameters for such a procedure ?
Any heads up would be greatly appreciated. Thank you !
QD
[img] http://img120.imageshack.us/img120/7424/96247630eo4.png[/img]
[1] J. Am. Chem. Soc., 1957, 79, 5528
[2] J. Org. Chem., 1979, 44, 659
[3] Tetrahedron Lett., 1995, 36, 2377
[4]Tetrahedron Letters,Vol.27,No.21,pp 2335-2336,1986
[Edited on 7-7-2008 by Quantum_Dom]
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stoichiometric_steve
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the oxidation that you have in mind is impossible to achieve with primary aliphatic amines on primary carbons.
edit: you could have found that out by using the FORUM SEARCH
[Edited on 7-7-2008 by stoichiometric_steve]
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Quantum_Dom
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Thanks for the reply, I did use the search engine.
Could you please link me to the thread of interest in this case ?
BTW stoichiometric_steve : "All classes of primary amine (including primary, secondary and tertiary alkyl as well as aryl) are
oxidized to nitro compounds in high yields with dimethyl dioxirane [1]"- MArch's Advanced Organic Chemistry, 5 th edition, page 1540
[1] J. Org. Chem, 1989, 54, 5783
Tetrahedron Lett., 1988, 29, 4501
Also worth of looking:
http://books.google.ca/books?id=63jyyMt38-EC&pg=PA20&lpg=PA20&dq=Oxidation+of+Primary+Amines+by+Dimethyldioxirane'&source=web&ots=
skQknwtbyb&sig=rFuCt7Z84jlIO0XO2ps3d8X14tU&hl=en&sa=X&oi=book_result&resnum=2&ct=result#PPA20,M1
If I were you, I would be really careful in the future before claiming that something is impossible without proper verification.
[Edited on 7-7-2008 by Quantum_Dom]
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Ritter
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| Quote: | Originally posted by Quantum_Dom
Hi everyone !
I am interested in oxidizing phenethylamine to it's corresponding nitro compound (see scheme below). |
The compound you have drawn is (according to the hybrid Structure > Name nomenclature tool in ChemDraw) is (2-nitroethyl)benzene, not
phenylnitropropane.
Ritter
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Quantum_Dom
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Thank you, I will edit the post accordingly right away.
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MagicJigPipe
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Phenylnitroethane (or 1-phenyl-2-nitroethane) would also be technically correct. The latter would be the more accurate of the two since I suppose
there could be a nitro group on the 1 carbon.
In fact, I'm almost certain the IUPAC name would be the latter (1-phenyl-2-nitroethane).
I've found that learning how to do nomenclature without help of computers/programs tends to give better results.
[Edited on 7-7-2008 by MagicJigPipe]
"There must be no barriers to freedom of inquiry ... There is no place for dogma in science. The scientist is free, and must be free to ask any
question, to doubt any assertion, to seek for any evidence, to correct any errors. ... We know that the only way to avoid error is to detect it and
that the only way to detect it is to be free to inquire. And we know that as long as men are free to ask what they must, free to say what they think,
free to think what they will, freedom can never be lost, and science can never regress." -J. Robert Oppenheimer
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Ritter
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| Quote: | Originally posted by MagicJigPipe
Phenylnitroethane (or 1-phenyl-2-nitroethane) would also be technically correct. The latter would be the more accurate of the two since I suppose
there could be a nitro group on the 1 carbon.
In fact, I'm almost certain the IUPAC name would be the latter (1-phenyl-2-nitroethane).
I've found that learning how to do nomenclature without help of computers/programs tends to give better results.
[Edited on 7-7-2008 by MagicJigPipe] |
And I've found that using a computer program to generate names helps avoid this sort of 'just how many ways can I name that compound?'-type
discussion. We all know that there are a number of (correct) ways to name the same compound. The point is to be unequivocal so that everyone knows
what we're talking about.
[Edited on 7-7-2008 by Ritter]
Ritter
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\"The production of too many useful things results in too many useless people.\"
Karl Marx
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ScienceSquirrel
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Let me think;
1) Decarboxylate phenylalanine to phenylethylamine
2) Oxidise it to phenylnitroethane
3) React it with two moles of n-BuLi to make the dianion
4) Alkylate with MeI
5) Reduce to amphetamine
6) Beam me up Scotty! 
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Quantum_Dom
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| Quote: | Originally posted by ScienceSquirrel
Let me think;
1) Decarboxylate phenylalanine to phenylethylamine
2) Oxidise it to phenylnitroethane
3) React it with two moles of n-BuLi to make the dianion
4) Alkylate with MeI
5) Reduce to amphetamine
6) Beam me up Scotty! |
FYI, phenethylamine is widely availlable commercialy. You should also know that nitro compound reatcs with carbonyl compound to yield nitrolalkenes
through a nitro-aldol condensation. (See link provided below).
1) Oxidize phenethylamine to phenylnitroethane
2) Condense phenylnitroethane with formaldehyde to 3-phenyl-2-nitroprop-1-ene.
3) Hydrogenation to amphetamine.
4) Yawwwnnn....Scotty you still trying to make methyl iodide OTC ?
5)....
6)Cheers
http://img297.imageshack.us/img297/975/proposalag1.png
[Edited on 7-7-2008 by Quantum_Dom]
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ScienceSquirrel
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| Quote: | Originally posted by Quantum_Dom
| Quote: | Originally posted by ScienceSquirrel
Let me think;
1) Decarboxylate phenylalanine to phenylethylamine
2) Oxidise it to phenylnitroethane
3) React it with two moles of n-BuLi to make the dianion
4) Alkylate with MeI
5) Reduce to amphetamine
6) Beam me up Scotty! |
FYI, phenethylamine is widely availlable commercialy. You should also know that nitro compound reatcs with cabonyl compound to yield nitrolalkenes
through a nitro-aldol condensation. (See link provided below).
1) Oxidize phenethylamine to phenylnitroethane
2) Condense phenylnitroethane with formaldehyde to 3-phenyl-2-nitroprop-1-ene.
3) Hydrogenation to amphetamine.
4) Yawwwnnn....Scotty you still trying to make methyl iodide OTC ?
5)....
6)Cheers
http://img297.imageshack.us/img297/975/proposalag1.png
[Edited on 7-7-2008 by Quantum_Dom]
[Edited on 7-7-2008 by Quantum_Dom] |
You really have to work on your spelling!
Let me see now, carbonyl starts with curly C not kicking K.
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Quantum_Dom
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| Quote: | Originally posted by ScienceSquirrel
You really have to work on your spelling!
Let me see now, carbonyl starts with curly C not kicking K. |
Thanks for you advice! .
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ScienceSquirrel
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Touche!
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ScienceSquirrel
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By the way, do you spell 'the' as T H E or have you adopted the modern American spelling T E H?
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Quantum_Dom
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1- I am not an american nor do I intend to adopt the spelling.
2-If you are trying to hurt my feelings by correcting my grammar or spelling, you are wasting your time. You should invest it in learning basic
organic chemistry of the nitro functional group. You are not in the right forum if your only arguments are linguistics-related.
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ScienceSquirrel
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Righto, I am sure that everyone is going to pile in with lots of advice on making amphetamine
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Quantum_Dom
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| Quote: | Originally posted by ScienceSquirrel
Righto, I am sure that everyone is going to pile in with lots of advice on making amphetamine |
This thread was never intented to brought the subject of amphetamine. Read the title of the thread.
You brought the subject, trying to make a cynical attempt at "revealing" my intentions, by providing an overlong and tedious reactional scheme. It
failed and it came right back at you. I am sorry about it but don't take it personal, it happens sometimes.
[Edited on 7-7-2008 by Quantum_Dom]
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Nicodem
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Contrary to what March’s lead you to believe on the subject of R-NH2 => R-NO2, the oxidation works nice only for amines where R is aryl or a
tertiary alkyl (like t-butyl and such). There are few references where R was a primary alkyl (like in your example), but the yields were either
mediocre or only exceptional substrates worked.
PS: I don’t want to see anymore off topic replies. If anyone wants to discuss the synthesis of amphetamine or grammar please do so in appropriate
forums other than SM.
…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!
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Quantum_Dom
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Hmmm I see nicodem, any references I should have a look to ?
Many thanks for your comment. Shame that such an authority like March can mislead people like that.
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ScienceSquirrel
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Your best option would be a full search using Chemical Abstracts.
You do face the disadvantage that you are going 'against the grain'.
Generally aliphatic amines are the target molecule as they are useful either as end products in themselves or as intermediates while nitro compounds
tend to be starting materials so chemists tend to focus on that reaction.
Developing reactions that will be used in other peoples work is good as your paper will be be cited again and again, developing a reaction that is
never used will doom you to an academic career teaching at Doo Hickey State College.
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Quantum_Dom
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Fair enough, will have a look at the abstracts, will post any information that I find (if there is any) worth of mentionning.
I have always liked working in some scientific direction that nobody else is working in.
--Linus Pauling (a great teacher and chemistry Nobel prize winner)
[Edited on 8-7-2008 by Quantum_Dom]
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Panache
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Recently i was reading that TCCA review article posted by sauron and theres a fascinating cohalogenation/oxidation of of a hydroxyl amine in there
using DCCA and either a further Cl or Br source. It oxidises your hydroxyl amine as well as halogenating on the like carbon. its on page 392-393 of
the article.
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Quantum_Dom
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Will search for the paper, posted by Sauron, Panache. Thanks !
Halogenation, followed by nucleophilic substitution with NaNO2, is a topic much more known, that is for sure.
[Edited on 9-7-2008 by Quantum_Dom]
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Methyl.Magic
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All amines can be oxidised with trifluoroperacetic acid. I have recently seen another method using 3,3-dimethyl-dioxacyclopropane as osidising agent.
In theory amines can be oxidisez with KMnO4 but it seems dubious.
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Klute
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| Quote: | | The reaction of 3-chloroperoxybenzoic acid with aliphatic primary amines (2-butylamine, 1-hexylamine, 1-propylamine, 2-phenylethylamine, and
cy-clohexylamine) in dichloromethane at room temperature has been shown to give excellent yields of the dimeric nitroso compounds.185
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reference cited: Gilbert KE, Borden WT. J Org Chem. 1979;44:659.
Source
\"You can battle with a demon, you can embrace a demon; what the hell can you do with a fucking spiritual computer?\"
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sonogashira
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| Quote: | Originally posted by Klute
| Quote: | | The reaction of 3-chloroperoxybenzoic acid with aliphatic primary amines (2-butylamine, 1-hexylamine, 1-propylamine, 2-phenylethylamine, and
cy-clohexylamine) in dichloromethane at room temperature has been shown to give excellent yields of the dimeric nitroso compounds.185
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reference cited: Gilbert KE, Borden WT. J Org Chem. 1979;44:659.
Source |
...and mCPBA in 1,2-dichloroethane gives 73% of 1-nitro-2-phenylethane:
Attachment: Peracid Oxidation of Amines to Nitroalkanes.pdf (390kB)
This file has been downloaded 1513 times
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