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by Xicori
Here we go:
Step 1: N-piperidin-cyclohexene
Into a 250ml RBF with a Dean Stark water-trap, a Dimroth reflux condensor
and some boiling stones there were added 39,6ml of Piperidine, 34,5ml of
cyclohexanone, 500mg of p-Toluene-sulfonic-acid and 100ml Toluene as
solvent.
The mixture was heated with a heating mantle until all water had seperated
(~5,4ml). Heating was stopped, and after the contents had cooled down the
reaction mixture was washed with ~30ml of water to remove the catalyst
acid. The organic phase was seperated, dried over Na2SO4 and distilled
under aspirator vacuum to yield 45g of colourless, nearly smellless enamine.
(b.p. ~ 108C@good aspirator vacuum)
2) Reaction Mixture
Note:
Piperidine is corrossive, toxic, and has a very unpleasent amine smell avoid
spilling it -> use a syringe!
6) Apparatus
7) boiling mixture
Notes: At first 2 Layers are formed I think the top layer consists of Toluene,
and the bottom layer consists of melted P-Toluene-Sulfonic Acid Monohydrate.
-> Use a magnetic stirrer to mix the two phases well. During the seperation
of water the bottom layer dissappears -> anhydrous Acid dissolves into the
toluene.
All glassware for this step should be dried in an oven. Anhydrous solvents are
absolutely necessary! (use molecular sieves or Na to dry Et2O)
Into a 250ml 3-necked RBF were added 2,4g (01,1 mole) of Mg turnings, 1
small iodine xtal, and 30ml of ether. Now there were slowly added 0,1mole of
bromobenzene in 15ml of Et2O. The start of the reaction is noticed by
reaction just started let bromobenzene drip into the mix slowly
8) apparatus for grignard rnx note the drying tubes on condensor and
dropping funnel an effective reflux condensor is also necessary. A liebigcondensor will not work!!
9) Closeup
Notes:
The mixture turns a bit brown during grignard reagent formation. Thats no
reason to worry.
When the reaction goes to fast use a cold water bath to slow things down.
Step 4: Salting your enamine from step 1 with your anhydrous acid from step
2
Note: use a big stirrbar to allow stirring even if the flask contents get a bit
sticky
Step 4: PCP
Now add your Grignard-Solution to the slurry produced in Step 4. Cool with
ice, and add the solution dropwise! The temp should not go above 5C. Now
the slurry gets easy stirrable again. After everything is added remove the ice
bath and stir for additional 30-45min.
Now pour the reaction mixture onto 200ml of crushed ice, 20g of NH4Cl and
20ml of concentratet ammonia solution. Let the ice melt and stir well.
Everything should go into solution, and 2 layers form.
Transfer the Solution into a seperatory funnel and separate the organic (top)
phase.
Extract the water phase once more with 50ml of Ether, and add the extract to
the organic phase from above.
Now wash your combined organic phases once with 200ml of water, and dry
the organic phase with Na2SO4.
After 30min of drying (swirl the flask sometimes) the liquid was decanted and
the Na2SO4 was washed with a bit of fresh, dry Et2O. The wash was
combined with the etheral solution, and a HCl-Gas generator was set
together.
Now the freebase solution is diluted with additional 150ml of anhydrous Et2O,
and gassed for ~30sek. Move your gassing tube around to avoid clogging.
when the xtals have settled down gassing is continued until no more crystals
appear.
Now the solution was vacuum filtered to leave slight yellow, sticky crystals.
The crystals were washed with acetone to leave ~8g of finely white PCP
hydrochloride.
Notes: Maybe a acid/base extraction would avoid the stickiness of the xtals.
Bioassay (~5mg) was used to confirm identity of the substance. swim had a
very dissiociative night ;)
LG
xicori