Alkali metal alkoxides: finally, OTC!

[blondie]

the first article states that the method can be used on alcohols with up to 6 carbons. anybee want to speculate if this would would with tert- butyl alcohol to give potassium tert-butoxide or does the alcohol need to be a straight chain?

[Antoncho]

anybee want to speculate if this would would with tert- butyl alcohol to give potassium tert-butoxide or does the alcohol need to be a straight chain?

I dunno. But check out this. They say the method works on any alcohol w/chain length 2-6 which forms a lower-boiling azeotrope w/benzene and water. Specific examples aren't given, but tert-BuOH is listed among them in the patent:

From

Patent US1712830

:

https://www.thevespiary.org/rhodium/Rhodium/hive/hiveboard/picproxie_docs/000257912-file_weiu.gif" title="View this image"> 

IMHO, also quite cool.

That would bee the procedure #5

Antoncho

[blondie]

Another nice find Antoncho!! - and thanks posting the image extract. i noted that t-butyl alcohol is specifically mentioned in the patent. k-t-butoxide is useful in a couple of codeine conversions, o-demethylation to morphine with n-propanethiol and also an Oppenauer oxidation + reduction to hydrocodone - so i was wondering about the otc possibilities of preparing this chem from t-butyl alcohol. thanks again.

[Antoncho]

Our outstanding SWI-Vitsh of HyperLab forum did some xperimentation and the results are:

1) Route via Na2S is not practically feasible as purification from residual sulphides isn't possible in kitchen.

2) Stirring ~30.5g  K2CO3 in 200mls at RT for 7 hrs yielded 7,7 gr of KOMe, after evaporation the soln to 11 mls volume. all went excactly as described in the patent.

,

Antoncho

[foxy2]

Post 236749 (missing)

(foxy2: "This is even better.", Chemistry Discourse)

[catastrophe]

Yes, SWIM remembers that post foxy. That last paragraph looks great too...

"Removal of hydroxide ion from alkoxide ion solutions

Abstract
The concentration of alkali metal hydroxide contaminants in solutions of alkali metal alkoxides in alcohols is reduced to below about 0.1 percent by adding an alkyl alkanoate ester. For example, a solution of sodium methoxide in methanol containing about 0.04 percent sodium hydroxide was obtained by adding a small amount of methyl acetate. The alkali metal alkanoate salt formed as a by-product does not deleteriously affect most uses of such solutions. "

Thanks for reminding us