Well, well! :-[
I'll have you all know that I was just about to make a brand new thread, in this very forum about just this subject: the Hofmann-Martius Rearrangement, on N-phenyl methylamine (upon heating) to a mixture of ortho and para toluidine.
I decided at the last moment to UTFSE for this, and lo and behold, foxy2 beat me to it by several months. You bastard. :P
So I will be content to merely bump this back up for re-recognition of the possibility, and perhaps add a little extra info, if I may.
http://themerckindex.chemfinder.com/TheMerckIndex/NameReactions/ONR193.htm (http://themerckindex.chemfinder.com/TheMerckIndex/NameReactions/ONR193.htm)
and http://www.chemfinder (http://www.chemfinder)
states that:
p-Toluidine CASRN: 106-49-0
m.p.43C b.p.201C r.d.0.962 water solubility 0.664 g/100 mL
o-Toluidine CASRN: 95-53-4
m.p.-14.7C b.p.200.2C r.d.1.008 water solubility Slightly soluble. 1.66 g/100 mL
Notice the ~50C difference in melting points, allowing for a method of seperation.
One could easily prepare the N-phenyl methylamine by condensing aniline (easy to get chemical from a supplier) with trioxane (a formaldehyde trimer) in an aluminum amalgam to reduce the imine. Formation of a crude HCl salt and thermal transformation would yield your mix of p- and o- toluidines, ready for seperation. :)
PrimoPyro
Vivent Longtemps La Ruche!
Post 305141 (https://www.thevespiary.org/talk/index.php?topic=7141.msg30514100#msg30514100)
(halfapint: "Decarboxylating Benzoic", Chemistry Discourse) has my current grumbles about Decarboxylating Benzoic. Among the Organic Synthesis refs are mentions of aniline, glycerol and various other oxidants, but iodine is not among them. If you got a clue, shoot it to us.
For quinoline decarboxylation refs, I can only repeat Jerry March's list from Advanced Organic Chemistry. That's the only place I ever heard of it!
Cohen and Schambach, J. Am. Chem. Soc. 92, 3189 (1970)
Chowdowska-Palicka and Nilson, Acta Chem. Scand. 24, 3353 (1970)
Cairncross, Roland, Henderson and Sheppard, J. Am. Chem. Soc. 92, 3187 (1970)
Cohen, Berninger, and Wood, J. Org. Chem. 43, 837 (1978)
"In certain cases the carboxyl group can be replaced by groups other than hydrogen, e.g., NO"
Ibne-Rasa, J. Am. Chem. Soc. 84, 4962 (1962)
Tedder and Theaker, J. Chem. Soc. 257 (1959)
"or Br."
Grovenstein and Ropp, J. Am. Chem. Soc. 78, 2560 (1956)
JM has a few clues: "The reaction proceeds much faster if the acid is heated in quinoline with cuprous oxide instead of copper, provided that atmospheric oxygen is rigorously excluded... It has been shown that cuprous salts of aromatic acids are easily decarboxylated by heating in quinoline."
The real place to find information is interactively here at Hive. Last night I absorbed osmotically that I had prepared my benzoic batches wrong: I should have started with the salt, and then added another equivalent of lye, instead of starting with the free acid.
a half a pints a half a pound a half a world a half a round
Sidearm n. Flask neck tube.