Alyx Woodward (obsolete) @Alyx@computerfairi.es

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

I don't remember all the details, but "Californian" was a few miles away and they saw the lights of a ship that was firing off skyrockets

and they did nothing

they convinced themselves it was just "company signals" or people having a party, and they did nothing

never even bothered to check. it wouldn't have taken long but it was just too much effort for them, for reasons unknown to us

"Titanic" was merely the biggest artifact of human society's positive _addiction_ to easily burnable carbon. white civilization, "Western civilization", just MAINLINED that shit, and it's almost killed us all

well

that's to one side. I wanna talk a little about a side-effect of "Titanic" going down, and that's the "Californian"

I bet a lot of "Titanic" nerds still talk endlessly about the design of the ship, as if this or that technical fix could have made the idea work

forgetting that the only reason "Titanic" floated at all was because of a huge number of human beings shackled to _coal_. digging coal out of the ground, turning coal into coke, shoveling the coke into a boiler, over and over and over

so of course it went to the bottom and because the society that built "Titanic" was awful and dysfunctional, the failure of the dream killed a thousand people or so

everything about "Titanic" was gross, in both senses of the word. both just BIG, and "gross" in the sense of disgusting. it was a vessel built to float not on water but on the stratification of humanity into a rarefied upper class and a solid dense mass of lower class humanity

I admit it, I've had an interest in disasters. I feel bad about it, but I feel also like I've learned something about how human beings break down under pressure

and I find myself thinking about "Titanic" right now, and the role played by a nearby ship, the "Californian"

"Titanic" should never have existed in the first place. it was a crime, that it even existed. human technology and society couldn't support it properly

TEMPO and its relatives are generally used catalytically, in small quantity. this catalytic quantity of the nitroxyl radical get oxidized _in situ_ to the active oxidizing agent, an N-oxammonium ion, by a co-oxidant present in excess. here? the auxiliary oxidant is simply air. copper(I) trifluoromethanesulfonate, 2,2'-bipyridyl, and N-methylimidazole in acetonitrile form some kind of system here that must bind molecular oxygen usefully so that it can oxidize the TEMPO

well, that's a fun one

the benzyl alcohol in question, 2-amino-5-bromobenzyl alcohol, is obtained from the corresponding benzoic acid via lithium aluminium hydride reduction in tetrahydrofuran. bleah! LAH isn't fun stuff. reacts explosively with water, and in fact the moisture from air is capable of setting the stuff on fire

but the TEMPO oxidation is straightforward. other oxidizing reagents might be expected to attack the aniline ring (aminobenzenes or anilines are notoriously sensitive to oxidation)