atomicfire
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aniline derivatives
I am searching for a method to add a hydroxyl group in the ortho position on aniline. Does anyone know a productive method for this?
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ScienceSquirrel
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This is best done the other way.
Take phenol, nitrate and reduce it to form the aniline.
Most syntheses of phenolic compounds start from a phenol and add the other substituents as it is the easiest way.
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atomicfire
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Could one convert the hydroxyl to a carboxilic acid?
And also, wouldn't the nitrosation occur at the para position not the ortho?
[Edited on 7-6-2011 by atomicfire]
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ScienceSquirrel
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Converting a phenol to a carboxylic acid is fiendishly hard.
The phenol will direct nitration to the 2, 4 positions.
This is where organic chemists get cunning, often reaction conditions can be optimised to favour the one that you want eg
http://pubs.acs.org/doi/abs/10.1021/op0200120
or
http://www.oc-praktikum.de/en/instructions/pdf/5001_en.pdf
[Edited on 7-6-2011 by ScienceSquirrel]
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atomicfire
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My goal is to synthesize anthranilic acid.
So, if one were to start with benzoic acid could one add a nitro group then reduce it?
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DJF90
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Anthranilic acid is typically formed by the hofmann degradation of phthalimide.
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atomicfire
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Yeah, I don't think I can get bromine for that reaction.
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PHILOU Zrealone
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Maybe try via
toluene -nitration-> o-nitrotoluene isolation (via diluted HNO3)
o-nitrotoluene -acidic oxydation-> o-nitrobenzoic acid (via KMnO4/H(+))
o-nitrobenzoic acid -reduction-> antranilic acid (o-aminobenzoic acid) (via Zn/HCl or SnCl2/HCl)
PH Z (PHILOU Zrealone)
"Physic is all what never works; Chemistry is all what stinks and explodes!"-"Life that deadly disease, sexually transmitted."(W.Allen)
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ScienceSquirrel
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The easy mad chemist ways to anthranilic acid are from toluene as above or from phthalic acid from plasticisers.
If you wanted to start from aniline; you could make the nitroaniline, then do a Sandmeyer, hydrolyse to the nitrobenzoic acid and then reduce.
You cannot start from benzoic acid as the carboxyl group is 3 directing.
You need a starting material that is 2 directing or 1,2 substituted and then you want to do the chemistry that sets up your groups in the best way
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DJF90
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ScienceSquirrel - off topic but are you (or anyone else) aware of a high yielding, direct reaction to 3-chlorobenzoic acid? I know benzoic acid
*should* give the meta product upon chlorination, but all the literature I've seen so far describes a mixture of products.
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gsd
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Intra-Molecular Redox Reaction
o-Nitro Toluene ---------> o-Amino Benzoic acid (Anthranilic Acid)
Is this fantasy practically possible?
gsd
[Edited on 8-6-2011 by gsd]
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ScienceSquirrel
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Quote: Originally posted by DJF90  | | ScienceSquirrel - off topic but are you (or anyone else) aware of a high yielding, direct reaction to 3-chlorobenzoic acid? I know benzoic acid
*should* give the meta product upon chlorination, but all the literature I've seen so far describes a mixture of products. |
I suspect that electrophilic substitution of benzoic acid will always give a mixture of isomers.
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