02-17-04 02:10
No 489179
Hey bees swim has few questions before swim tries the Iodosafrole route to mda/mdma. The halogenation is fine; swim will use the NaI in DMSO + H3PO4 to make HI and gas the chilled safrole as it says in the doc for halo safrole on rhodium’s pages.
#1 is the DMSO still required when using phosphoric instead of H2SO4? DMSO was mentioned on rhodium’s halo safrole docs when using H2SO4 as it has the habit of making iodine in this process, phosphoric wont do this will it?? Swim is using a gas generator instead of putting it into the safrole, and piping the gas ala HCl gassing at the end.
#2 the HI gas (Oh Oh), how can swim pipe it? Swim has visions of any kind of tubing disintegrating on contact and swim getting lovely acid burns over 90% of swim’s body, but is swim wrong? Can tubing take it?
Swim is making methylamine.HCl ala hexamine, HCl and water, then dropping this into the Iodosafrole and reflux, this part is fine in practise but….
#3 Swim has found in organic chem text swim had lying around that amination of halides (does not specify primary of secondary) with secondary amines does not stop after one run, ie: The MeNH2 will goto MDMA then the nitrogen will kick off another hydrogen and grab another Iodosafrole, making a monster compound consisting of two methoxy’s hooked to the one nitrogen making a tertiary amine compound. ??????? RHODIUM, BRIGHTSTAR, ANYONE, HELP!!!!
Can someone confirm/deny this? and give swim options for a way to stop it doing this??? swim was thinking that changing the order of addition; add the iodo to the amine may work to reducing this product being formed?
Or is it that this happens only with primary halides and not our beloved secondary halide?
The rest of the process is well documented; swim is ok with the next parts.
If swim is happy with the method after some bees re-assure swim with answers to the questions then swim is going to be doing a photo assay and full write up with yields to share with the hive on this process. Please if swim has mistaken anything or left something out tell swim and swim can post it.
POKE HOLES IN SWIM’S METHOD IF THERE IS ANYTHING WRONG PLEASE!!! Rather it is wrong on paper than in practise, also swim has looked on TFSE and found nothing concrete, seems to be a lot of confusion re Iodosafrole.
Swim thanks all bees who help.
(LinguisticBee)
02-17-04 04:03
No 489199
the whole beauty of the proceedure is that the HI is produced in-situ, negating the need any tubing (or you being exposed to it). The HI is dissolved in the DMSO that way, until it reacts with your safrole.
Better to get a rxn to work for you as written first and then start modifiing it after you have some sucess under your belt.
As far as the finklestein swap (sp?) goes the MeNH2 swaps with I atom and thus MDMA is born, leaving elemental Iodine (i think) in solution.
good luck
We are all just witnesses.
(Stranger)
02-18-04 15:11
No 489534
Yeah ok, well that was what is written all over the place here but is there any problem with adding all in the one pot? Safrole, DMSO, h3po4, ki (using ki, easier to get where swim is). As far as swim can see h3po4 shouldn’t touch the safrole? or will it make mdp2pol as with h2so4? And the ki won’t do a thing with safrole... (it shouldn’t should it?)
Heres what swim was thinking:
1mol safrole, 1mol KI, 1/3mol h3po4, DMSO solvent.
The ki is in enough DMSO to dissolve it then the safrole is added, h3po4 is added to start the ki turning into the HI which will react with the safrole, i guess a side reaction of making mdp2pol wouldn’t be too bad as the HI would displace it anyway….
Iodosafrole and water (reaction by product) swim would want to make sure Iodosafrole is water free right? Dry the h3po4 before reaction and dry the DMSO too? Or just do it after reaction via the extraction?
So is that a better alternate?
(Fragile ego)
02-18-04 19:08
No 489566
using ki, easier to get where swim is
As long as it scaled for the proper # of moles that shouldn't bee an issue.
Dry the h3po4 before reaction
I don't know, maybee you could try it both ways, this reaction hasn't been documented very well as far as I remember. You could make a valuable contribution. Take good notes and post your experiences. The merck index says Phosphoric acid heated/boiled to 150C becomes anhydrous. Keep in mind that its melting point(anhydrous) is ~42C.
dry the DMSO too?
This link has good info on drying DMSO and really good all around DMSO info.
http://www.gaylordchemical.com/products/
Its a sad day that free debate is stifled on the Hive. Fragile egos destroy societies.
(Stranger)
02-19-04 09:43
No 489698
Excellent! thanks, swim was thinkin that shouldnt be a prob but had the inital idea to create a separate generator to eliminate any such problems, but that ended up causing more than it solved.
yeah mol amounts are altered correctly to suit reaction ratio.
The only other thing swim can think of is when adding methylamine.hcl into Iodosafrole in basic conditions as the swap works it will produce nacl (from the hcl in menh2), nai (from the Iodosafrole) and water… swim was thinking the nai could be re-used in more runs but with equimolar amounts of nacl and nai being dropped out it becomes a bit dodgy… now is swim wrong in the mechanism for this rxn? Or is there some way nacl and nai could be separated?
Swim cant think of anything else at the moment, nothing else seems to bee an issue, the amination worries swim had were found out to bee not such a prob with sec halides, does happen but only in a little amount.
(Fragile ego)
02-19-04 20:08
No 489776
Or is there some way nacl and nai could be separated?
Yes, NaI is soluable in (ethyl i think) alcohol(0.5 g/mL) and NaCl is only slightly soluable in alcohol. According to Merck.
Its a sad day that free debate is stifled on the Hive. Fragile egos destroy societies.