Salicylic Acid (Fake plastic trees)

The urea entry ended up with a discussion in the comments I encourage you to read about early organic chemists, one of whom was Kolbe, who first prepared acetic acid (an indisputably organic and biologically relevant molecule) from inorganic compounds. He worked with Wohler (mentioned in the urea entry) as well as Robert Bunsen (of burner fame). From the ACS bulletin above:

In the course of work on chlorinated ethanes Kolbe effected the first complete synthesis of an organic compound, acetic acid, from inorganic precursors. His carbon source was carbon disulfide, chlorination of which gave carbon tetrachloride. This was pyrolyzed to yield tetrachloroethylene, aqueous chlorination of which gave trichloroacetic acid. This was reduced to acetic acid in an electrolytic cell.

This is like making diamonds by burning some gasoline, using the resulting CO2 to grow a plant, killing the plant and waiting around under suitable conditions for it to turn into coal, putting the coal under pressure and heat until you have something like graphite, and holding that under pressure and heat until you finally get a wee diamond. It's silly. But you can, in theory. That was the point for Kolbe - the route wasn't of any practical use, but it was a proof-of-concept.

Fortunately for the world, he didn't only work on such convoluted synthetic routes. He developed a way to turn phenol and carbon dioxide into salicylic acid (ortho-hydroxybenzoic acid, a precursor to aspirin). Before this, you had to get your salicylic acid from plants (You can find compounds of it in, among other places, willow trees, which are of the genus Salix, from which the compound gets its name.). It's a quick synthetic leap from salicylic acid to aspirin - acetylsalicylic acid (or, in German, acetylsalicylsäure, which is divertingly abbreviated ASS).

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While salicylic acid is laughably simple for a natural product now, it must have been positively intoxicating to discover a way to make tons of a product that previously had to be harvested from expensive plants via cheap phenol (you can find it in tar) and carbon dioxide (you're soaking in it). I was taught (although I'm not sure if it's true!) that the Kolbe process is still used today in the preparation of aspirin. How many of us can hope to invent something that has a useful life spanning three centuries and two millenia? Sometimes things like this make you feel like you're late to the game, but the comparatively frenetic pace of science today and five-digit page numbers in a year of JACS, for better or worse, reassure you that there's plenty left to do.

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Green chemistry! Young coal (ring alkyl groups) pulverized then slurried in water/KOH with a polyoxyethylene surfactant. Cook under 500+ psi of pure oxygen hot with violent stirring to get potassium benzenepolycarboxylates. Now, we Kolbe. Cook the powdered anhydrous salts under 400 psi CO2 real hot with cadmium iodide catalyst (not so Green) to selectively get potassium terephthalate, thence PET.

Uncle Al at Occidental Research/Petroleum discovered Cu(I) cyanide or iodide (kinda Green) massively outperformed cadmium iodide. It was declared a "trade secret" and deep-sixed. Oxy fabricated a white PET-from-coal handkerchief for Armand Hammer. A half ton of coal (plus a 5-gallon tub of Amoco polymer-grade terephthalic acid) became a ~30 gram PET handkerchief.

The best part of the bayer-ASS story is that in the early days of medchem they thought that acetylating shit just automagically made it better, so they acetylated cocaine and marketed it as a more effective, less addictive painkiller.

I think you are thinking of heroin, which is diacetylated morphine; there really isn't anything to acetylate on cocaine.

There is something to it, too, from what I understand, acetylating the hydroxyls on morphine gives it a lipophilicity boost (increasing its membrane permeability and ability to get to the brain).

Felix Hoffman did come up with it just days after he got the aspirin thing going, though. One can imagine thinking "hmm, if my trick worked on one natural product hydroxyl, why not get get the economy pack of acetic anhydride and have a little acetylation party."

Whoops, yes, I meant morphine. I'm hopped up on another stimulant today -- can't think strate

Chemistry and a Radiohead reference; be still, my beating heart!

Yes I was about to comment on the Radiohead angle as well, but looks like someone has beaten me to it!