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           MDA from Bromosafrole using PTC and an azide intermediate
                                   by Ritter
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The following is adapted from  J. Org. Chem., 47, 4327

A mixture of 2-bromosafrole (24.1g, .1mol), hexadecyltributylphosphonium
bromide(5.1g, .01mol), sodium azide (16.2g, .25mol), and water (50ml) is
magnetically stirred at 80'C for 24 hours.  Flask is cooled and phases are
separated in sep funnel.  The dark reddish organic layer is diluted with toluene
(20ml) and poured back into flask and stirring is restarted.  A solution of
sodium borohydride (11.7g, .3mol) in water (30ml) is carefully added through an
addition funnel over 30 minutes as temp is raised to 80'C and held there for
16h.  Contents of flask are cooled and poured into a sep funnel. Aqueous layer
is sepped off and organics are washed w/ 50ml dH20.  Three 40ml portions of 4M
HCl (approx 10%) are used to extract MDA base from organic layer.
Combine all acid extracts and neutralize with 50% NaOH soln.  Golden beads of
MDA base will fall out of soln.  Use two portions of 50ml toluene to isolate
base.  At this point one of two things can be done.  If you are a greedy shoddy
chemist you will dry the toluene extracts with anhydrous MgSO4 then bubble with
HCl gas to isolate a relatively pure white MDA hydrochloride (8-12g) OR if you
have any pride in your chemistry skills and product, toluene will be evaporated
down to a orange oil and vacuum distilled using standard methods to yield
6.5-11.0g of water white pristine MDA base.  Distilled base is most easily
crystallized by adding about 6 times volume of dry IPA and neutralizing w/ conc.
HCl.  Place this in the freezer over night to find glorious white crystals of
the hydrochloride.  At this point not all of the salt has precipitated and it
won't  no matter how long you leave it in the freezer, so add the same volume of
dry acetone to ppt. entire yield (6-12g).

Notes:
1) 2-Bromosafrole was prepared using process developed by Fester.  HCl(g) is
   bubbled into a  soln of 48%(aq)HBr, HOAc and PURE DISTILLED safrole. The
   procedure is archived on rRhodiums site and runs exactly as Fester claims,
   believe it or not!

2) Yield of product is totally dependant on reaction time/temp of first step.
   If literature citing is examined yields above 85% are reported for all
   primary alkyl bromides.  Problem with lower yield here is the fact that we
   are dealing with a secondary bromide. This introduces the possibility of
   occurrence of two yield killing side reactions. Elimination of -Br resulting
   in isosafrole then elemination of azide may occur resulting in more isosafrole.
   Perhaps reducing the temp and extending rxn time will slow rate of
   elimination resulting in higher yield of alkylazide. Someone willing to try?

3) Hexadecyltributylphosphonium bromide is very expensive.
   Refs stating Aliquat 336 is a cheaper alternative PTC are on the Hive.

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