The Vespiary

The Hive => Novel Discourse => Topic started by: Rhodium on November 27, 2001, 12:19:00 PM

Title: Phenylacetonitriles from toluenes
Post by: Rhodium on November 27, 2001, 12:19:00 PM

In US Pat 3,002,836 they react o-nitrotoluene with diethyl oxalate to form ethyl-o-nitrophenylpyruvate, which is reacted with hydroxylamine followed by H2SO4 to form o-nitrophenylacetonitrile.

This sounds like a great way to phenylacetonitriles, but they do not give any details on how to do it, and I do not know if the nitro group has anything to do with the reaction. Is there anyone who knows more about this reaction, and possibly have any useful references?

Title: Re: Phenylacetonitriles from toluenes
Post by: Greensnake on November 27, 2001, 04:48:00 PM

Nitro group (or another strong electron withdrawing group) is required, it makes Me protons acidic enough to allow condensation proceed. Approximate procedure for this condensation

http://orgsyn.org/orgsyn/prep.asp?prep=cv5p0567 (http://orgsyn.org/orgsyn/prep.asp?prep=cv5p0567)

of course there is nothing about further reaction with hydroxylamine and dehydration to nitrile. Anyway this will not work, if there will not be electon withdrawing group on benzene ring.

Title: Re: Phenylacetonitriles from toluenes
Post by: Aurelius on November 28, 2001, 02:00:00 AM

would multiple methoxy's work?

Title: Re: Phenylacetonitriles from toluenes
Post by: Rhodium on November 28, 2001, 02:34:00 AM

They are electron donating, so I guess that would make the reaction even more unlikely than without the nitro.

Title: Re: Phenylacetonitriles from toluenes
Post by: Aurelius on November 28, 2001, 03:16:00 AM

oops, got electron affinity mixed up in that question