Bromosafrole-DMSO WTF???

[somniferous]

Okay,

There's a lot of contradictory information re. the DMSO route to bromosafrole. Half of the posters claim success with this method, half claim it's garbage. The precursors are SO readily available that SWIM had to try...

500ml DMSO was chilled(Frozen solid is more like it) and 39ml chilled conc. H2SO4 was added. It warmed up a little. To this was added 150g NaBr. Turned orange. hmm.... Welp, in for a penny, in for a pound. And in goes 30g washed sassafras oil, slowly... stirred, stirred stirred, orange color disappears. Can't help but think I'm making di-bromo, f*ck it. stir,stir,stir... let sit cold for 36 hours... cloudy as heck from all the salts, but getting slowly darker...
For kicks, I open the jar, phew, smells like commercial propane, yuck. 50 ml of the reaction contents are removed and 300 ml of ice cold dH2O is added, within minutes a little bit of gloppy cloudy yellowish liquid falls to the bottom. Now at this point, if I listen to strangelove, I'm doing great. But it' not red. I don't like that. I like pretty colors...

So, a few questions-
Most of the failures reported were with KBr, not NaBr. This makes sense, KBr would probably produce more Br2. Could stricter temperature control increase the amount of HBr produced/reduce Br2 formation when using NaBr?

Strangelove swears by H2SO4+2NaBr in DMSO gives HBr and Na2SO4. Others claim the HBr is destroyed by the H2SO4 to give water and Br2. One reaction would give us our bromosaf, the other seems to produce a di-bromo-saf. The product strangelove described(and SWIM has) sounds more like the di-bromo(yellow, cloudy, not red at all). However, he claims success getting MDA from this stuff? Is this possible? Or more specifically:  Did he actually make bromo? Or, could the Di-Bromo-Safrole reported by some from the DMSO method be converted to MDA/MDMA within the bomb via an unexplored reaction? Or, I may    have some experimentation data to share along this route soon as I figure out what the heck the cloudy yellow liquid is in the bottom of SWIM's snapple , um, reaction container.

At any rate, any feedback from someone with empirical experience would be wonderful, TIA.

Strung by a thin white hot wire,
burning with ecstacy

[somniferous]

Okay,

After the full 48 hours had elapsed, 4l cold dH2O was added, and a tan milky fluid fell to the bottom. So far, it looks like I've made Di-Bromo...
To this some methanol is added. After stirring, the methanol turns a deep purple(yes, like the band   ). So it looks like I made some bromosaf. The off white layer has lost some volume and is now white!!! It looks like it's at the lower end of it's liquid phase, so I warm some up(90C). It turns clear and darker brown. I let it cool and it whitens up, hmm.... no thermal breakdown yet. Seems like a homogeneous substance. I suspect it's Di-Bromo-Saf.

Since I don't have bromosaf(except maybe 5%-10% in methanol) I decide to play with my suspected Di-Bromo. I Heat some to 100C and it starts to bubble. I set up to distil, and get a dark brown-red, clear liquid. As I do this the alleged Di-Bromo Starts to darken. I let it cool, and it's greyish-white. Looks like some carbon is forming, thermal breakdown... Looks like I did make Di-Bromo!
That would make my dark brown liquid the 2,Bromo-propene. Whee!

So, Here's my thoughts-
1. The DMSO route to bromosaf is finicky, The reaction's main product was Di-BromoSafrole, not the desired 2,Bromo. Some 2,Bromo was formed. But not a lot... If I had to guess where it went goofy, I'd say batch size too large and not enough tempature control.

2. The DMSO/Bromo method to MDA/MDMA may be misunderstood. Hint, most reported failures used the Delepine rxn, not the bomb. Hint#2-Thermal Breakdown... I suspect the DMSO-H2SO4-NaBR method is valid(Flamebait, I know), but does not proceed as most think. Look for a post soon in the novel forum...  But, first, back to the kitch.  er lab.

Strung by a thin white hot wire,
burning with ecstacy

[somniferous]

Thanks,
If I dream that I'll probably bubble it through DMSO due to availability(farm country ). What I'm really trying to do is make sense of the H2SO4-NaBr thing and either prove or disprove the method(to myself at least). Even if I get nothing but garbage, I'll probably go at it again. I'm not really trying for product, just for knowledge. Acquiring the precursors is so ridiculously easy that even at 30% yield after amination, it would be economical. Plus, I suspect that people have actually made MDMA from Di-Bromo without realizing it, via the bomb. I've posted my idea over on the novel forum...

As far as making Bromosafrole via NaBr+H2SO4 in DMSO. I didn't make it work. But next time I'll be trying for Di-Bromo. (o.k.- I lied, I'm still trying for Bromosaf )

Strung by a thin white hot wire,
burning with ecstacy

[somniferous]

Well,
I'm back with another update.

Just tried to confirm my earlier suspicions about H2SO4+NaBr in DMSO.
Let me tell you about the dream I had-
60ml DMSO was frozen in a test tube. To this was added 4ml H2SO4. The DMSO immediately unfroze, and was chilled in Brine and ice for 15 min. Then 15g NaBr was added. No orange was evident upon addition of the NaBr! The Solids settled to the bottom and turned a light green. The DMSO remained absolutely clear. 2.5g safrole was added dropwise over 10 minutes. The solution remained clear and cool. About two hours have elapsed and it's starting to turn green!  So far, so good...

Conclusion- Scale and temperature seem to be the key components with this reaction. Small and cold is the rule.(The first try, the DMSO/H2SO4 was well below 75°C but formation of Br2 was evident. The guidlines for aqueous HBr production don't seem to follow with DMSO. If you add the NaBr, and see orange, cool it off some more.)

I'll post the complete results of the dream in 48 hours. Same Bat Time, Same Bat Channel.

p.s.- Thanks to everyone here! I've found this site invaluable.

Strung by a thin white hot wire,
burning with ecstacy

[LaBTop]

That's a fine example of independent, logical thinking, and then checking your thoughts on nanoscale, and not spoiling gram- to kgmoles on not fully understood reactions. Waiting for the final test of the endproduct, LT.
Well done! New name: TestTubby!

WISDOMwillWIN

[yellowjacket]

Funny, SWIM went round and round with that DMSO buisness a while back, and got identical results: brown reddish goo that some bee said was Di-Bromo. The whole process is stinky and somewhat frustrating because the results seem to vary every time you try it. By the By, some sources here list Hbr as watched. SWIM changed his tack worked instead on MMs method and the Baalchemist/Ritter patented performic Al-Hg One Two Combo. SWIM has found everything needed OTC.  

marijuana is the flame, heroin is the fuse, LSD is the bomb!

[somniferous]

Howdy,

HBr is definitely watched...

But Ca3O8P2+3H2SO4+6H20 --> 2H3PO4+3(CaSO4 - 2H2O)

and H3PO4 and NaBr will produce HBr gas! All OTC from-

Phosphate rock(fertilizer)
H2SO4(Drain Opener)
NaBr(Spa Sanitizer)

H3PO4 can sometimes be bought as a rust remover as well. But Hypophosphoric acid is more common where I am. (Managuador specifically .

Strung by a thin white hot wire,
burning with ecstacy

[yellowjacket]

Hey somniferous, howabout a quick writeup? Sounds useful...

marijuana is the flame, heroin is the fuse, LSD is the bomb!

[somniferous]

Well, here's the (mixed) results of the nano-scale dream(or nightmare, You must decide  Nothing to do now but DANCE!(Hey, it's my dream. Sue Me!)

After cleaning up, the remaining DMSO mixture is mixed with around 5 times it's volume of cold water. The aqueous portion is then poured off to reveal perhaps .75g of pink clear slime with a fruit loopy odor, distinctly different than the scent of the safrole. Not enough to aminate, but an encouraging result nonetheless. Stay tuned for the next psychotic episode.

667 - Neighbor of the Beast

[somniferous]

I haven't ever done the phosphoric acid to HBr conversion but SWIM has and I'm assured that it works. The H2SO4+phosphate rock method of H3PO4 production is widely used and well documented.

As far as a write-up goes, another time perhaps. Anyway, it's all hypothetical until someone loses an eye.

Sweet dreams...

I Drank What? -Socrates

[CaSpErTRiPPS]

Anyone ever think about trying the iodosafrole instead? you use sodium iodide to iodonate it, and then aminate this with hexamine, its supposed to work better for large rxn's than small, i heard its a process used in the netherlands as well. Anyhow its supposed to work a lot faster and at more normal temps closer to room. Anyone have any info on it?

[improv_chem]

Yes, SWIM tried it with DMSO, NaI, and then tried that funky delephine with some hexamine.  No luck. 
The initial Iodosafrole rxn was very messy and stunk way more than the HBr in the DMSO from the NaBr.  I think that too much iodine is created (even worse than the Br2 formed in the DMSO).  The NaI is more easily turned into I2 than NaBr is to Br2, therefore making the corresponding rxn with NaI out of the question.  That had to be the most messy rxn that SWIM has ever done!  And SWIM got a total of fuck all after stinking up the apartement!
Hey somniferous, do you still have that small bit of product left.  If you got any NaN3 around try that rxn to make the azide and then reduce.  You could do it with a very small amount of bromo if you have some NaN3. 
SWIM is very interested in hearing about this rxn because SWIM has played with it quite a bit but always seems to have bad luck.  Keep up the good research!
--improv

--Preventing odors from escaping to nearby noses is essential.....

[somniferous]

NaN3 huh? Yeah, I do have the smidge of bromosaf from the previous rxn(in my dreams ). But more importantly, I think I've got this whole reaction down! I'm 36 hours into a larger scale dream now. Look for an improved write-up in this thread. After 1 failure and 1 accident DMSO is looking promising again!

I'm still wondering what the best amination process is. 40%aqueous methylamine at 10% in methanol(for a week) is an option, as is the bomb. Also, I've absolutely no experience with MW chem. Would it be possible to run the amination at atmospheric pressures in the microwave? I'm told that many reactions run at reduced temperature/increased speed in the MW.(A pipe dream I'm sure, but Bromosaf to MDMA in 15 minutes would be cool!) Any input would be appreciated.

Hadn't thought about the azide, might have to check that out.



Gimme some sugar baby! -Ash, Army of Darkness

[somniferous]

After one large scale failure and encouraging results with a nano-scale experiment(not enough bromo to aminate, but a fruit loopy odor for sure!), my recurring dream of bromosafrole from H2SO4 and NaBr in DMSO was back. I really need to stop eating sweets right before bed. This time the dream went like this- (I must at this time stress that this is all hypothetical. I have been having these kinds of recurring dreams for years. My hope is that by talking through them, I can make them stop. Also: DMSO has the unique property of carrying substances straight through the skin and directly into the bloodstream. Even minor skin contact with the mixture described below could cause blood poisoning/death. In layman's terms- If you so much as touch this shit you will probably fucking die!!! You have been warned.)

150 ml DMSO(99% pure) was frozen and 11ml conc. H2SO4(est. 93-95%) was added. This liquified the DMSO which was then chilled to 10°C in an ice water bath. Below 9°C the DMSO/acid started to freeze. 45 grams of NaBr(99% pure) was then added all at once. The solution turned a pale green then into yellow(almost urine) color. The salts settled at the bottom and caked together. They were (carefully) broken up with a glass rod and the solution stirred for one hour.  Roughly 7 ml washed sassafras oil was then added dripwise over 10 minutes. with the solution in a water bath at 10-12°C. Upon the addition of the Safrole, the solution turned a clear dark green. The salts were broken up again and the solution stirred at 10-12°C. Within minutes it has turned blue-green and I finally get it. They lied! This is NOT a room temperature reaction. Or at least room temperature is the upper limit.

My god, it's full of stars!!!

(I may allow the solution to come up in temperature a bit after 24 hours has passed. I haven’t decided yet. If the reaction follows what I’ve read on HBr in GAA, then it should eventually turn orange or red…)


12 Hours In-
The solution was stirred repeatedly and kept in a water bath. It was never allowed to exceed 12°C and remained liquid all the way down to 3 or 4°C. (I was curious to see how cold I could get it without it freezing.) At 12 hours, it is a refreshing  minty blue-green color, like mouthwash. If Fester is to be trusted

Gimme some sugar baby! -Ash, Army of Darkness

[yellowjacket]

Are you sure you want to use methylamine HCl in the rxn? Most writeups this bee has seen recommend basifying the salt first, and then bubbling the gasious methylamine into cold methanol. 

marijuana is the flame, heroin is the fuse, LSD is the bomb!

[somniferous]

Yeah,
I've seen room temperature write-ups with aqueous Methylamine*HCl and write-ups using anhydrous methylamine. I've seen successes and failures with both methods. My decision to go one way versus another was arbitrary and based mostly on the lack (for now) of a workable "bomb". Even a 10% yield would be o.k. for now, as I'm just evaluating methods...

i.e.- Now that I've got a handle on the bromosafrole, I can figure out the best amination method at my leisure.  

Gimme some sugar baby! -Ash, Army of Darkness

[improv_chem]

I don't think you could do it that easily because the NH3 or MeAm would boil off with the heat. 
the amination can be done at room temperature with MeAm (so i've read) but will take a long time.  If you had iodosafrole it might be quicker.  mabe try swaping the Br for an I by heating the bromosafrole with some NaI in acetone for a while and then putting the iodosafrole in the MeAm/MeOH solution and stir for like a week or something??
sweet dreams;
--improv

--Preventing odors from escaping to nearby noses is essential.....

[somniferous]

Hey,

From what I've seen on MW chem, people are using pyrex and leaving the lid a little loose so pressure won't build up. Since the glass is MW transparent, the top of the container remains cooler. Which might help condense the gas. I'm sure some methylamine would escape. But it's mixed at 10x molar, so there's a lot there. It's academic until I find a cheap, thrift store microwave to play with. (Not to mention a place to try, as I'm sure the reaction will stink to high heaven.) I'm really just wondering whether, under MW radiation, the correct reaction would even take place.

i.e.-It would really suck to do the reaction and make isosafrole.

If I get the chance to play I'll post results in the novel discourse. (With my luck  this will probably include at least a fire or two and maybe even an explosion. So it would be a good read.)

Instant X- You gotta admit, It'd be cool...

There's no business like the Devil's business! -Tibet 93

[Osmium]

Using MeNH2*HCl will not work.
And heating substances to 100°C to dry them isn't recommended either, especially not with such delicate molecules as bromosafrole.

[somniferous]

Thanks, I'd already surmised that the HCl salt wasn't going to work. I'm dreaming it with MeAm gas now...
I'll post the results.

As far as heating the 'Bromo'- I was only heating a small sample to see whether it'd break down at the same temp as my suspected 'di-bromo'.(It didn't.) Call it a sacrifice to the gods of chemistry... )
possible, as an unintended side rxn?


If so that would really suck. It would also explain some things...

Any ideas anyone?

Next dream I'm either keeping the everything cold for the whole 48 hours. That, or say "Fuck it!" and bubble the HBr into the DMSO...

There are three kinds of people - Those who can count and those who can't.