Alyx Woodward (obsolete) @Alyx@computerfairi.es

and finally water gets eliminated and you get the allene. or something like that. I'm trying to do that in my head instead of writing it down (it's good practice for me!)

well, fun! the _Organic Syntheses_ article then goes on to show a whole bunch of reactions that allenylcarbinol has been used in.

one to file away for who-knows-when.

synthesis involves refluxing propargyl alcohol, HC≡C-CH₂OH, with paraformaldehyde (that's the insoluble polymeric form of formaldehyde, much nicer to handle than formalin), diisopropylamine, copper(I) iodide as a catalyst, in tetrahydrofuran. well!

presumably the diisopropylamine is a sufficiently strong base to strip the acetylenic hydrogen on the propargyl alcohol, which then coordinates with the copper(I). then this acetylide attacks formaldehyde (formed in situ from the paraformaldehyde)

oh uh lemme do _Organic Syntheses_ roulette again

(among other things it's kinda calming)

and the number is 4263!

http://orgsyn.org/demo.aspx?prep=v94p0153

wow, ok...a curious reaction, synthesis of something that looks like a valuable synthetic intermediate even though it's only a few carbons long, allenylcarbinol. so H₂C=C=CH-CH₂OH. a more systematic name is 2,3-butadienol.

allenes are funny creatures!

well that's a fun one. looks like they're doing this all under nitrogen. probably just as well; some of the intermediates in this whole process must reek like nobody's business. plain unsubstituted thiophenol is famously stinky, being compared to the odor of burning tires, only...stronger. guessing that thiophenol is formed from vulcanized rubbers in combustion

(cont'd) and this ester, on prolonged heating with methanolic potassium hydroxide, rearranges and hydrolyzes to the thiophenol without, somewhat to my surprise, hydrolyzing the cyano group. this reaction has a name, the Newman-Kwart reaction: https://en.wikipedia.org/wiki/Newman%E2%80%93Kwart_rearrangement

then mild oxidation of the thiophenol with 30% hydrogen peroxide and anhydrous zirconium (??) chloride in acetonitrile yields the sulfonyl chloride. I believe there are other protocols for this

it's the phenol to thiophenol conversion that's the really fascinating step here, because that's not an ordinary sort of aromatic substitution. I think that it can be done with brute-force conditions on simple substrates: one obtains thiophenol from phenol by distilling with phosphorus(V) sulfide, I believe, and the yield is probably low (and the reaction smelly and dangerous)

but here, the phenol is converted to a dimethylthiocarbamate ester with dimethylthiocarbamoyl chloride (cont'd)

ok, let's do an _Organic Syntheses_ roulette

and the number is...818

I had to go to the third hit to find one that I don't remember doing some earlier time, haha

well it's a curious one. conversion of a phenol to a arylsulfonyl chloride

http://orgsyn.org/demo.aspx?prep=v94p0198

in this case the starting phenol is 4-cyanoguaiacol, the monomethyl ether of catechol only with a -CN group stuck para to the phenolic -OH

the -OH is first converted to -SH through a curious rearrangement, then oxidized to -SO₂Cl

what the hell has been going on

o-kay

what was _really_ going on? Lord never bothered to find out, never bothered to check

*spits*

I'm kinda tired of people who just watch from a distance, and do nothing. aren't you?

after "Titanic" went down and the full scale of the disaster became broadly known the captain of "Californian", Stanley Lord, tried hard to muddy the issue, spreading stories that maybe he'd really seen some *other* ship or whatever

none of the stories matter. what matters is what Lord did, which was 100% of nothing

I suppose that must have galled him, to the end of his days

the memory of the strange ship on the horizon, the skyrockets going up