jon,

I'm having trouble finding where you specifically reference your most up-to-date work up suggestion for the finklestein swap..

How do you suggest working it up?

Finkelstein success!

I had to take a pestle to these huge rocks of KI to get it to go, but definitely a color change..and definitely a change in the crystalline structure. In solution of acetone it has more of that brownish iodine color and turns more of a purple hue as you evaporate the solvent.

After evaporating the Acetone more bromide salts crash out -- these have to be separated and the oil extracted... I'm having a bit of trouble getting all of the acetone out.. I'll attempt to finish evaporating tonight before extracting with DCM, water and brine..

Jon is the only one who will *rightfully* toot his own horn about his work

So -- while the yields weren't perfect, this reaction DOES work making Iodosafrole directly

What is the actual yield ? Did you isolate, purify and characterized your assumed iodosafrole or are you just saying that based on color aspects ?

I extracted with water, DCM, basic solution, washed multiple times with brine to break emulsions -- dried the solvent / oil layer with anhydrous Na2so4, Evaporated the solvent w/ a rotovap and measured the resultant oil which has the EXACT same hue, smell, and viscosity as what I yielded from the Finkelstein rxn from Bromosafrole.

It also reacts the same way when dropped onto cold h2so4...

Yields were 31% of original Safrole that went into the reaction -- Safrole or isosafrole was also recovered as a fraction during separation

I need to get set up for TLC on this stuff.. I have a very old Infrared Spectrometer that I got from University surplus that probably still works but no salt plates...and those fuckers are expensive.

It would really confuse the shit out of me if this WASN'T Iodosafrole, but without TLC, IRSpec, or GCMS it is just a thorough hypothesis. I suppose an attempt to aminate it would provide some proof if freebase oil was obtained.

Well, looking forward to your upcoming posts then as it is nice to see somebody really  serious about getting quantitative, and reproducible, results about methylamination of halosafroles. Wasting so much methylamine and getting mediocre yields in order to lessen the amount of work always made me cringe and overall I always was too chicken shit to consider experimenting on it. Its nice to see that somebody is willing to do so and share the results. Thanks!

31% from the direct iodination?
you need to save your aqeuous layers and back extract them i never got such shitty yeilds doing this.
remember when you set up to saturate ipa it has to be dry 0C is acceptable you can get 12-15% conc. this way and the reaction will work at that concentration.
you need to drip conc. NaOH onto methamine crystal not the other way around because when water hits solid NaOH it steams off fucking things up for you. (i've used slugde before it does'nt have to be all that pure)
the reason you do this is it is'nt exothermic make sure you have a suckback trap and a gas dispersion fitting at the end of the tubing.
so the gas dissolves drip it slowly because the gas escapes fast and there is an induction period where there is'nt much gas generating then it goes off like a volcano do it in a chanpangne vase or something metal because as it dissolves it heats up and the metal transfers heat well allowing for rapid cooling.

The 31% yield he mentions is not pertaining to his yield of amine from halosafrole, but of iodosafrole with direct halogenation of his safrole from earlier trials.

oh ok i never got 31% out of a finklestien more like close to quatitative i'm not bullshitting on this here.
i never attempted HI directly i forsaw problems maybe he cleaved some of the md ethers

Cleavage of Ethers by HI or HBr. http://www.chem.ucalgary.ca/courses/351/Carey5th/Ch16/ch16-3.html

HI is preferred over other hydrogen halides in polar protic solvents because the iodide ion is a much better nucleophile than bromide or chloride, so the reaction can take place at a reasonable rate without much heating. The large iodide anion is less solvated and more reactive in polar protic solvents and thus causes the reaction to proceed faster because of stronger partial bonds in the transition state. http://en.wikipedia.org/wiki/Hydrogen_iodide#Key_reactions

Hydrohalogenation is the addition of hydrohalic acids such as HCl or HBr to alkenes to yield the corresponding haloalkanes. The subsequent reaction proceeds by an SN1 mechanism due to the presence of the electrophilic carbocation and a nucleophilic halide anion.
http://en.wikipedia.org/wiki/Hydrohalogenation
http://en.wikipedia.org/wiki/Alkenes#Hydrohalogenation

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Hydrohalogenation is a SN1 reaction.
Cleavage of Ethers depends on the structure of the alkyl groups, the reaction can be SN1 or SN2 like. Primary and secondary alkyl ethers react by an SN2 mechanism, while tertiary, benzylic, and alcylic ethers cleave by an SN1 mechanism.

The SN1 reaction rate WILL be faster for hydrohalogenation than for the Cleavage of Ethers at 1-2 oC. As the hydrohalogenation reaction proceeds faster, the moles of HX (X = Br, I) are diminished, and therefore the concentration of HX (X = Br, I) is less.

As the concentration of HX (X = Br, I) is less, and at low temperature, the reaction rate of ether cleavage is negligible to nil.

I'm skeptical about this direct iodination approach. First off using H2SO4 oxidises part of your HI and secondly, from my experiments more than 10 years ago, where I was gassing cold acetic acid solutions of safrole with dry HI(g), isosafrole was the main product so iodosafrole was formed but elimination happened at the same time.

When using 47% aq HBr, Fester's variation by gassing a solution of safrole and 47% aq HBr in acetic acid with dry HCl(g) to dehydrate it is said to really work, it was confirmed by at least one trustworthy member of the Hive (Ritter). I haven't tried it myself. The same principle works when reducing l-ephedrine in aq. HI in presence of red phosphorus. If the homemade aq. HI < 50% dehydrate by gassing with HCl(g). It works really well.

Wait... I take that back

After giving it some more time it looks like a rather miniscule amount of free base was obtained. After a few hours of settling droplets of yellow oil were noticed above the aq layer after ph was brought to 11-12. I extracted the aq layer with ether and the ether is bright yellow. I will evaporate the solvent and see what I get...

Terrible yields though. I really do think I got water in the solution. Next time I will try a very cold condensor during the gassing and 3A mol sieves after gassing.

how cold was your ipa?
was it ice bath temps in that case it would'nt have dissolved more than 12-15% at best methylamine.
so if it was at that temp and you say it was 30% concentrated more than likely you were gassing in water vapor.
if you got it cold enough about -20C you could get it to up to 35%.
(dry ice acetone) you would have to seal it afterwards as it was reacting because your methylamine would escape at room temp pretty fast, in fact you would'nt realize it and that could have adverse impact on your reaction too.
another thing is i never took 20-30 minutes to bubble in methylamine it took me more like 5 minutes at the most.
as soon as you drip conc. naoh onto that methylamine crystal methylamine comes over instantly (there is an induction period at first as it dissolves) but once bubbling occurs your not going to get anymore in solution by letting it sit there for 20-30 minutes or heating it to drive the last of it off forget about that.
your just driving water off at that point.
i always made it a point to cool my naoh solution and cool the generator vessel to avoid any exothermia but there was'nt much exothermia going on if you used that order of addition anyway if you driped methylamine solution onto naoh solid it would be a different story altogether with steam being driven off and your reaction would fail most of the time.