Author Topic: ROmoval of halogens from Rings  (Read 2102 times)

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Vibrating_Lights

  • Guest
ROmoval of halogens from Rings
« on: June 18, 2003, 04:37:00 PM »
Is It possible to remove a p-halogen from a phenylacetone Bisulfite adduct.  By reacting the comound in anhydrous THF With ButLi.  The add H2O to leave an unsubstituted ring. Recoverng the desired ketone by liberation with a base?
VL


Rhodium

  • Guest
Bisulfite adducts doesn't like n-BuLi
« Reply #1 on: June 19, 2003, 01:55:00 AM »
Bisulfite adducts are not compatible with n-BuLi, the Li will add sequentially to the three oxygens on the SO3 group, wasting the precious reagent.

A better suggestion might be to dehalogenate using Superhydride (LiEt3BH) or maybe BER - see

Post 241350

(foxy2: "Aromatic Dehalogenation [ BER - Ni(OAc)2 ]", Chemistry Discourse)
?

Lilienthal

  • Guest
Wouldn't that also hydrogenate the keto group?
« Reply #2 on: June 19, 2003, 12:26:00 PM »
Wouldn't that also hydrogenate the keto group? The ketone could be protected as an acetal...

Rhodium

  • Guest
protecting group
« Reply #3 on: June 19, 2003, 04:05:00 PM »
If the bisulfite stayed on the entire time, the ketone could survive - but I do not know if that is possible though. Using an acetal as protection group is of course infinitely better, if making that is an option.

Aurelius

  • Guest
Option?
« Reply #4 on: June 19, 2003, 08:33:00 PM »
Why wouldn't that be an option?  Acid sensitivity?  Polymerization?


Rhodium

  • Guest
Why I was unsure the advice would help
« Reply #5 on: June 19, 2003, 08:51:00 PM »
The original poster wanted to dehalogenate the bisulfite adduct of a p-Halophenylacetone, and I have cotten used to that many people here just say "aw, fuck it" when my advice involves adding another step to their original route... I cannot help becoming a little cynical. The problem is definitely not with the actual acetal protection, but if the poster would bother to do it or not...

In this case the acetalization of the ketone would be effected by refluxing the phenylacetone in toluene with excess ethyleneglycol and 1% of a suitable acid catalyst (tosic acid) while separating the formed water using a dean-stark apparatus (the water removal drives the rxn forward). Workup involves washing twice with 5% bicarbonate, once with brine, dry the solution over MgSO4 (or even better Na2SO4, as it is less acidic) and evaporating the toluene in vacuo. Ideally this Phenyl-2-propanone ethylidene acetal should now be vacuum distilled before the next step.

Deprotection is a breeze - heating the acetal in 5% H2SO4, or by any other well-known method, UTFSE.

Aurelius

  • Guest
Rhodium
« Reply #6 on: June 19, 2003, 08:57:00 PM »
I know the pro/depro techniques, I just thought maybe there was an exception for this compound that you knew about.  Thanks for the information though.  And it's nice to know at least somebody's willing to do some work.  (no offense to bees like Barium, et. al.)