Hello
Last day I used a route which was from my concurrent imagination. Aim was to understand the basics of aromatic acylation and oxidationn of benzylic
carbon
Starting with o-Toluidine the route was as follows:
Acetylation (N-acetyl ortho Toluidine)
2mls of o-Toluidine was put in a 250ml rbf equipped w/an efficient reflux condenser, cacl2 moisture protection tube, a pressure equalized addition funnel and an egg shaped stirbar which was heated by means a silicone oil bath. Stirring started and 5mls of acetyl chloride was slowly added in portions being careful to keep the violent, exhothermic reaction under control. After the adiition was complete the reaction was stirred for a further 2 minutes with heating and when no further HCl formed there was added150mls of H2O slowly, to decompose the excess acetyl chloride and the diacetyl ester of o-Toluidine. The paste like reaction mixture slowly crystallyzed inside the H2O which was brought to a gentle boil then left to cool overnigt. Next day the the crystals were iltered to obtain a theoritical amount of odorless, needle like crystals of unknown purity (Didnt bother w gc/ms)
Oxidation (N-Acetylanthranilic Acid)
The crystals were put inside 20mls of H2O2 . No reaction occured. I instantly got some naoh(1N ) from the shelf and added some into the rxn (I dont know why I did this, its just an instict) the reaction started violently which was cooled w/ an icebath and died off pretty quickly (45min). It was let to cool, the ph was adlusted to 7.3 with HCl and crystals were preticipated by addition of acetic acid. It was left overnigt. Next day crystals were filtered w suction dried in a dessicator to yield an unspecified amount to powder like meterial. It smelled very aromatic and sweet.
Questions
-Can o-Toluidine HCl form in the acetylation phase? (the rxn was anhydrous but can HCl react w the amine to form the o-Toluidine HCl?)
-Can H2O2 accomplish the N-acetyl,o-toluidine to N-Acetylanthranilic Acid?
-What is the efftect of the base?(It does accelerate the decomposition of H2O2 but is this important? And why?)
-Does N-Acetylanthranilic Acid or Anthranilic Acid smell sweet and aromatic as above? Or is it tbe the decomposition product - benzoic acid?
-What is the oxidation mechanism of (IV) oxidizers (permanganates, dichromates) and what do they do that H2O2 cant? -Please show some references for this
Thank you very much for reading!