and I'll do an _Organic Syntheses_ random-word roulette
random word of the day is..."tire"
http://orgsyn.org/demo.aspx?prep=v95p0060
ooh, this one's rather curious. an unusual reaction: oxidation of a primary amide to a _nitrile_, so... R-CH2NH2 to R-C≡N. I can see that being handy, a way to get at nitriles without having to deal with cyanide (the usual method for nitrile synthesis is nucleophilic substitution of alkyl halides etc. with cyanide. tasty stuff, it's not)
they're making lauronitrile, the 12-carbon straight-chain nitrile derivative of lauric acid (dodecanoic acid), from laurylamine
the oxidant is "Oxone", a trade name for potassium peroxymonosulfate. (it's a pool chemical, I happen to know, a non-chlorine pool disinfectant). catalysts, "acetamido-TEMPO" with pyridinium bromide in pyridine and methylene chloride, carried out under nitrogen
so, what's this "TEMPO" stuff?
"TEMPO" is a common abbreviation for 2,2,6,6-tetramethylpiperidinyl-N-oxyl, a rare example of a _stable free radical_. put a pic of it down below
most chemical compounds have all their electrons in pairs. each atomic or molecular orbital can hold two, of opposing spin. molecules with only _one_ electron in an orbital are *generally* unstable under usual conditions, highly reactive and short-lived species that like to grab or give up an electron from anything they bash into
but "nitroxyl" radicals with the >N-O˙ group can be remarkably stable, especially here where there's bulky groups immediately adjacent. TEMPO and substituted derivatives like 4-acetamido-TEMPO (used in this _Organic Synthesis_ procedure) have been found to be versatile reagents for organic oxidations
in use, the nitroxyl group is oxidized by some auxiliary oxidant (the Oxone, here) to an N-oxammonium group, >N⁺=O, which is the active oxidizing species
anyway, that's one to file away for later consideration I think!