[discodermolide]

Perhaps LiCl is not so bad after all?

[orgopete]

Isn't the next step caustic to make styrene oxide? If so, what happens if you just close tour eyes and treated it with caustic. If elimination, oops. If substitution, bingo.

[DrCMS]

Would a phase transfer catalyst or a surfactant help as I assume the water solubility of B is not that great.

Probably would help (also help my overall rates since A has horrid solubility in water too).

Have any chemicals that you'd reccomend trying? The 90°C / oxidising environment / low pH make the choice a tad confusing. 

I've used Cetyltrimethylammonium bromide in a warm (~40°C) acid hydrolysis reaction.

[curiouscat]

If so, what happens if you just close tour eyes and treated it with caustic. If elimination, oops. If substitution, bingo.

Will try! Thanks!

Perhaps LiCl is not so bad after all?

True. Zn / Fe / Cu salts might be cheaper / less toxic though. Not sure.

I'm happy if either option works! 

[opsomath]

Hello curiouscat,

I'm interested in adapting your peroxide/hydrochloric acid reagent to a green-chemical chlorination of an activated aromatic ring. If I understand your procedure correctly, you use more or less stoichiometric ratios of the oxidant to the styrene, run it at 90°C, and use 30% peroxide and acid? Or is the oxidant/acid stuff in excess?

[curiouscat]

Hello curiouscat,

I'm interested in adapting your peroxide/hydrochloric acid reagent to a green-chemical chlorination of an activated aromatic ring. If I understand your procedure correctly, you use more or less stoichiometric ratios of the oxidant to the styrene, run it at 90°C, and use 30% peroxide and acid? Or is the oxidant/acid stuff in excess?

Yep. ~10% excess of the oxidant (peroxide + acid) but that's only because we want to push the organic to complete conversion.

What seems to help though is adding everything to a bath with excess of water. It's weird though, just using correspondingly diluted HCl gives low rates.

My hunch is you need a certain min. conc. of acid and peroxide (probably around 30%) to get the active Cl-species but once reaction happens or during it you need the dilution with that large excess of water to keep byproduct reactions down.

Not sure that makes sense entirely, but that's my hunch. I'd be curious to know how your reaction goes.