eugenol --> (iso)safrole

malatesta · Thu Apr 21, 2005 1:49 am

CherrieBaby I seem to remember an xfile (a wizardx file iow) detailing the use of HI (in the cold first to form the iodopropyl side chain) and then reflux to cleave the ether and, if I remember it correctly to transform the iodopropyl to a propenyl side chain, tar formation being impeded by use of hydroquinone. Result eugenol to isosafrole.

comments?

nubee · Master Archiver

US Patent 2396580: contains: eugenol, etc. + 60% HBr --> alkyl bromide which is aminated with NH3 in ETOH (example 2)

could someone have a look at this and get back to us as to whether they're's anything of use in here...?

http://rapidshare.de/files/1361679/US-Patent-2396580.pdf.html

i found this at http://www.geocities.com/dritte123/phenpat.html

Ephoton · Sun Jul 03, 2005 10:30 am

way to rehash the hive guys not much in the way of new resurch
what about thatboric acid table salt method of making BCl3 flotting around
then all we would need would be the right solvent and bubble the gas into the
phenylether solvated if this doesnt work what about if the phenylether was
an amphetamine as described above.
there tring to take this one away from us fellow bee's lets get serious about
this pracs, pracs and more pracs if the stuff on the hive was the way no one
would be asking for sassi and getting pissed if it didont arive.
peace and its great to see everyone here

Quantum Smile

Ephoton · Sun Jul 03, 2005 10:34 am

dont forget otc and if anyone knows of a few tests that can be done to
see if the alkene has been saturated with a halogen or if the ether cleaved
properly this would help I think in the production of a real rightup.
ill go back to my library on this and let you know what I find.
its great to be back on the web what the fuck happened to the hive ?

Ephoton · Mon Jul 04, 2005 3:32 am

this is not good I could read my post without a login great not the jaks can
use webspiders to find out whats happening it was so much nicer when they
had to go through each page at a time now keyword bang got ya Sad

anyway on to the searching.
any chlorinated or halogenated solvent will do the trick if one was to take
the opiod demethylation into mind. the more halide and less carbon the higher the yeild would me be my guess as DCM gives lower yeilds than Chloroform (could be way off the mark on this one so check it)

what about if we substituted pyridine in the transition metal halide demethylation
with picoline or another substituted pyridine derivative. This might even remove
some of the dangers involved with working with pyridine (long term health issues)

so back to my origonal idea

eugenol in DCM with gas head ( must be dry).
burnt wood or some other carbon source borax heated in a vessel with chlorine being bubbled through it.
I must find a way to dry BCl3 so as it does not move water into the demethylation
reaction and in a way that does not brake BCl3 down (I think BCl3 is quite reactive
maby even so reactive it will react with all of the water anyway working as its own
drying agent)
then pipe gas into DCM from borax melt.
next we need a indicator so as we can tell when the reaction is compleate.
any ideas Smile

hope I have been of some help will keep on looking into this route

Lego · Mon Jul 04, 2005 9:56 pm

Eur. J. Org. Chem., 2003, 19, 3745-3743
http://dx.doi.org/10.1002/ejoc.200300174

Demethylation with LiCl in DMF

LiCl (292 g, 6.89 mol) was added to a solution of eugenol (354 mL, 2.30 mmol) in DMF (3.7 L), and the mixture was refluxed for 44 h, with additional portions of LiCl (292 g, 6.89 mol) being added after 4 h, 22 h and 29 h. The reaction mixture was allowed to cool down to room temp., and diluted with toluene (2 L). The formed precipitate was filtered off and washed with toluene, the washings were combined with the organic solution and concentrated in a rotary evaporator. Silicagel FC (Et2O/pentane, 1:1, Rf = 0.37) provided 4-allylpyrocatechol (173 g, 50%).

DMF is OTC and so is LiCl.

joe_aldehyde · huxleys associate

very good find. i wonder if the amount of DMF can be decreased, or maybe the ratio is fixed as to the solubility product of LiCl. i just happen to have all components handy Smile

but only 1.5 liters of DMF.
does the paper mean the addition of LiCl after the mentioned periods as "each time 292g" or "292g in total"?

was there any notice about the yields to be expected?

Lego · Tue Jul 05, 2005 2:13 am

joe_aldehyde · huxleys associate

swim certainly will, even though he has a reliable source of piperonal and nitroethane. 50% isn't so bad, considering that the solvents could be recovered (can they? is it essential to have anhydrous conditions?) oh i just found some di-iodomethane, fukin A!!

if you're thinking about alcohol, try the following thing: get a coconut, put in freezer for an hour, drill a hole in it, mix 2 teaspoons of brown sugar with 96% ethanol (food grade of course) and pour that inside. stick straw in it and be drunk in seconds! hooray for summertime!

Lego · Tue Jul 05, 2005 3:26 am