I went about this route for a good 4 months with no success producing HCL salts. I'm 80% sure that I produced bromosafrole and iodosafrole from TLC -- but the amination has confounded me relentlessly. 

This thread details some of my dreams with this route -- jon was there.
http://127.0.0.1/talk/index.php/topic,3405.0.html

This stoichiometry that worked for me was as follows:

50.0g  sassafras oil x .95 =   47.5g of safrole

47.5g  safrole x (1mol saf/162.19) =.2929mol safrole

(2.2mol NaBr/1mol saf) this will form a little over 2mol HBr/1mol safrole

.2929mol safrole x (2.2mol NaBr/1mol saf) x (102.894g NaBr/1mol NaBr) = 66.295g NaBr

66.295g NaBr x ( 1mol NaBr/102.894g) x (1mol H2SO4/1.1mol NaBr) x (98.079g/1mol H2SO4) = 57.448 g H2SO4

For 98% H2SO4

(57.448g H2SO4 / (57.448g H2SO4 + Xg H2O) ) = .98

X = 1.1724g H2O

1.1724g + 57.448g = 58.62g

So 58.62g of 98% H2SO4 total

Now for the GAA, at 40%

( 47.392g HBr/ (47.392g HBr + Xg GAA))=.40

X = 71.088

He did 

1mol safrole
2.2mol NaBr
2mol sulfuric acid

how much GAA?

I never had a problem getting the acetate I used gaa in stoichiometric amounts then heat and vacuum to drive off the excess ipa and acetone gave the goods.
I know this route works I know for a fact did the yellow oil have that biting amine smell?

Pbinter: did you calculate the methylamine you had in solution then add 1/8th the iodosafrole?
if you didn't you can make quat amines and the hcl salt would be soluble in them too.
make sure your 8:1 on that methylamine stoich it doesn't have to be 15% 10 will do.
also you said it was nacl that crashed out on gassing I highly doubt it it would likely be methylamine hcl

I told you to use a trap in the bubbler I always did to prevent suckback the carried over naoh can e2 eliminate the hx of iodosafrole.
it may be that the reactants carried over say some leftover halo safrole is interfering with crystallization I've seen that happen with bromo safrole.
I remedied it by adding acetone if you got suckback you got water that will ruin it.

Bump*!

Dope Amine

I've been wanting to do this for efficiency's sake at least.

When you use this method, do you have to filter, and then keep adding IPA/HCL soln? When I gas the toluene directly I have to gas 4 times to get all the freebase converted.

Thank You!
Pbinteger

the sulfuric acid doesn't oxidize hbr at room temp in GAA I know this for a fact many have tried this bromination and it works like a charm, just don't agitate it let the salts remain on the bottom very little bromosafrole will soak into and you can work up the salts and the GAA separately it's what I do it works.
just try it.'
 and pbinterger I never gassed it I used equimolar gaa then vacuum evaporation then the alcohol acetone recrystallization you got the yellow substance with a biting amine odor this proves I am correct and not bullshitting you are just having problems making crystal this can be the harderst thing to do sometimes in organic chemistry is to get pure crystal it is a very common problem.

the sulfuric acid doesn't oxidize hbr at room temp in GAA I know this for a fact many have tried this bromination and it works like a charm, just don't agitate it let the salts remain on the bottom very little bromosafrole will soak into and you can work up the salts and the GAA separately it's what I do it works.
just try it.'
......

Like a charm? Obviously not for those who try, except the archetypical dutch who always shows up in such cases to prove the correctness.
Being some time on this kind of boards makes me resistant against such old foul tricks.

Try it? Why should I try something what was ruled ot as unsuited 15 years ago after lots of trials by people more skilled in the art then me and you? Thats called stupid except you want to prove something and why?
A chimp can make anhydrous HBr in quantitities and quantitativly from bromine and tetraline, just vent it in no salt no oxidation no free bromine but bromosafrole. Real bromosafrole.
No tetraline? 45% HBr is dehydrated by either anhydrous HCl or H3PO4 (better metaphosphoric) and such it works.

There is a reason why your infamous safrole destruction by sulfuric acid/HBr is not state of the art, you know?
No, you know better.

Untested, halfbaked, verbally optimized, etc....

But the bromosafrole route is still a good one.
Not like you describe it though.

And btw. 4-MAR does not induce seizures in humans with a halfway stable constitution, but of course an elderly epileptic junkie with a history of drug-induced strokes who thinks mainlining 100mg is a splendid idea will suffer seizures. Like he probably would from a nougat bar too because of the sugar shock.

And here the stories connect again: Jon thinks mainlining untried compounds into his drug-rotten body in huge amounts is a good idea.
And he thinks bromination with H2SO4 and a salt of bromine is a good idea.
Nevertheless, despite what Jon thinks it is just stupid. Plain, outright stupidity fueled by an overblown ego.

Hail Jon!
Golden calf of the wasps!
Hail!


/ORG

Quote from: jon on May 10, 2013, 12:51:07 AM

the sulfuric acid doesn't oxidize hbr at room temp in GAA I know this for a fact many have tried this bromination and it works like a charm, just don't agitate it let the salts remain on the bottom very little bromosafrole will soak into and you can work up the salts and the GAA separately it's what I do it works.
just try it.'
......

Like a charm? Obviously not for those who try, except the archetypical dutch who always shows up in such cases to prove the correctness.
Being some time on this kind of boards makes me resistant against such old foul tricks.

Try it? Why should I try something what was ruled ot as unsuited 15 years ago after lots of trials by people more skilled in the art then me and you? Thats called stupid except you want to prove something and why?
A chimp can make anhydrous HBr in quantitities and quantitativly from bromine and tetraline, just vent it in no salt no oxidation no free bromine but bromosafrole. Real bromosafrole.
No tetraline? 45% HBr is dehydrated by either anhydrous HCl or H3PO4 (better metaphosphoric) and such it works.

There is a reason why your infamous safrole destruction by sulfuric acid/HBr is not state of the art, you know?
No, you know better.

Untested, halfbaked, verbally optimized, etc....

But the bromosafrole route is still a good one.
Not like you describe it though.

And btw. 4-MAR does not induce seizures in humans with a halfway stable constitution, but of course an elderly epileptic junkie with a history of drug-induced strokes who thinks mainlining 100mg is a splendid idea will suffer seizures. Like he probably would from a nougat bar too because of the sugar shock.

And here the stories connect again: Jon thinks mainlining untried compounds into his drug-rotten body in huge amounts is a good idea.
And he thinks bromination with H2SO4 and a salt of bromine is a good idea.
Nevertheless, despite what Jon thinks it is just stupid. Plain, outright stupidity fueled by an overblown ego.

Hail Jon!
Golden calf of the wasps!
Hail!


/ORG

You brought up some valid concerns; it's too bad you decided to go off topic by attacking jon's character, which is completely irrelevant to this discussion.