05-11-03 19:16
No 432643
Is there a less explosive way for alkylating phenyl-2-chloropropane with ammonia or methylamine than the one from JACS,68,1009(1946)? (pipe bomb, 160°C for 9 hours, alcohol, 50%)
Anyways, details on the JACS procedure would be very welcome as I have no access to JACS now.
thanks
ORG
(Hive Bee)
05-11-03 20:18
No 432649
Azide is the way
Do just an azide swap in DMSO like in ../rhodium /fenflur
BTW azide is OTC, prepare it with hydrazine and poppers in basic medium.
Or if you dont wanna synth/buy hydrazine, you can get NaN3 from airbags (~100g azide for a conductor airbag and ~300g for a passenger one).
...Yes I know it could bee an explosive way too, but certainly less than ammonia in EtOH at 160C°! Beware the heavy metals.
(Hive Addict)
05-11-03 20:27
No 432652
and higher yielding also thats nice.
Thanks Chimimani!
I will have to have a deeper look into the azide pathway now.
ORG
Addon:
You are referring to this yes?
To the chlorine (0.66 g; 3.0 mmol) in DMSO (4 ml) is added sodium azide (0.38 g; 2eq). One heats to 75°C for 8 h. One lets return to room temperature, adds 0.1N hydrochloric acid (10 ml) and extracts with ether (3 x 10 ml). The combined organic phases are washed with water (5 ml) and dried over magnesium sulfate.
......the azide(0.53 g; 78% yield; 95% GC...
Is the procedure using SnCl2 with methylamine in MeOH for to get the methylated form of the amine from the azide trustworthy? As the bromosafrole routes are not used any more it´s a long time since 
.
Psyloxy claims 98% yields for this in a old (04-28-2000) post (wow!)
200g safrole-azide is dissolved in 1000ml MeOH and 100g SnCl2 [or the dihydrate] are scraped in in small increments. Almost imediately heavy bubbling and heat will evolve. This is released N2, tells you that everything works. Then let stir for another 60mins. Remove the MeOH by vacuum distillation. To the remaining oil add 500ml ice cold dH2O. Bring the pH to 9-10 by addition of dilute NaOH soln. Saturate with NaCl. Extract with ether, wash ether extract with NaCl soln and dry thru Na2SO4. Remove solvent by distillation. Yield is 98%.
This would beat the borohydride route at:
../rhodium
/azide.r
searching further....