No, the amine is not attacked first. I think you need to review SOCl2 chemistry: https://www.masterorganicchemistry.com/2011/12/03/reagent-friday-thionyl-chloride-socl2/
No, the amine is not attacked first. I think you need to review SOCl2 chemistry: https://www.masterorganicchemistry.com/2011/12/03/reagent-friday-thionyl-chloride-socl2/
I think the aniline is not really THAT reactive (I had some problems making amides without additional base). I mean there is highly deactivating group on the ring (not in conjugation though) and methyl grop ortho to amine proceting some steric hinderance. Also, methanol is in high excess.
Also, its possible that the reaction procees via formation of methylchloride from methanol and then alkylation of the carboxylic acid?
I think the aniline is not really THAT reactive (I had some problems making amides without additional base). I mean there is highly deactivating group on the ring (not in conjugation though) and methyl grop ortho to amine proceting some steric hinderance. Also, methanol is in high excess.
Also, its possible that the reaction procees via formation of methylchloride from methanol and then alkylation of the carboxylic acid?
No, the amine is not attacked first. I think you need to review SOCl2 chemistry: https://www.masterorganicchemistry.com/2011/12/03/reagent-friday-thionyl-chloride-socl2/
No, the amine is not attacked first. I think you need to review SOCl2 chemistry: https://www.masterorganicchemistry.com/2011/12/03/reagent-friday-thionyl-chloride-socl2/
I gotta say, it is a little weird to expect a acyl chloride and aniline to exist together. I guess the amine is protonated quite quickly but even so... I would have expected some amount of oligomer if you don't move fast.
I gotta say, it is a little weird to expect a acyl chloride and aniline to exist together. I guess the amine is protonated quite quickly but even so... I would have expected some amount of oligomer if you don't move fast.
I agree anilines aren't all that nucleophilic (certainly nowhere near as nucleophilic as alkyl amines). However, they are almost certainly more nucleophilic than carboxylic acids, which raises the question why does the SOCl2 react with the carboxylic acid not the aniline? Or does it react reversibly with the aniline? Maybe it's just early in the morning and I'm being dumb.
I agree anilines aren't all that nucleophilic (certainly nowhere near as nucleophilic as alkyl amines). However, they are almost certainly more nucleophilic than carboxylic acids, which raises the question why does the SOCl2 react with the carboxylic acid not the aniline? Or does it react reversibly with the aniline? Maybe it's just early in the morning and I'm being dumb.
Usually a huge excess of thionyl chloride is used in chlorination reactions. I typically use it as the solvent along with a catalytic drop of DMF.
So yeah, probably some gets consumed making the ammonium chloride salt, but there's plenty left to make acid chloride.
Kirggy, under acidic conditions that methyl chloride reaction doesn't sound very good. It's a very ordinary way to make esters to make the acid chloride, not really isolate it, then dump in a bunch of your desired alcohol.
Usually a huge excess of thionyl chloride is used in chlorination reactions. I typically use it as the solvent along with a catalytic drop of DMF.
So yeah, probably some gets consumed making the ammonium chloride salt, but there's plenty left to make acid chloride.
Kirggy, under acidic conditions that methyl chloride reaction doesn't sound very good. It's a very ordinary way to make esters to make the acid chloride, not really isolate it, then dump in a bunch of your desired alcohol.
Okay, thanks!
Okay, thanks!
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Also, its possible that the reaction procees via formation of methylchloride from methanol and then alkylation of the carboxylic acid?
Also, its possible that the reaction procees via formation of methylchloride from methanol and then alkylation of the carboxylic acid?
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I don't really understand the process after all. Is NH2 attacked?
I don't really understand the process after all. Is NH2 attacked?
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Aniline is too weak a base to fully deprotonate a carboxylic acid at 1eq.
Edit: here's the paper wiki is referring to https://royalsocietypublishing.org/doi/10.1098/rspa.1968.0003
DOI:10.1098/rspa.1968.0003
Aniline is too weak a base to fully deprotonate a carboxylic acid at 1eq.
Edit: here's the paper wiki is referring to https://royalsocietypublishing.org/doi/10.1098/rspa.1968.0003
DOI:10.1098/rspa.1968.0003
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So yeah, probably some gets consumed making the ammonium chloride salt, but there's plenty left to make acid chloride.
Kirggy, under acidic conditions that methyl chloride reaction doesn't sound very good. It's a very ordinary way to make esters to make the acid chloride, not really isolate it, then dump in a bunch of your desired alcohol.
So yeah, probably some gets consumed making the ammonium chloride salt, but there's plenty left to make acid chloride.
Kirggy, under acidic conditions that methyl chloride reaction doesn't sound very good. It's a very ordinary way to make esters to make the acid chloride, not really isolate it, then dump in a bunch of your desired alcohol.
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