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Author Topic: Jon's Method From Start To Finish *Update -- Failure*  (Read 894 times)

bjuice

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Re: Jon's Method From Start To Finish *Updated - Finkelstein complete*
« Reply #20 on: February 25, 2013, 12:10:09 AM »
I see what you guys are saying now.  That it would be best to be safe and make sure there is sufficient crowding on all molecules.  In fact, assuming my impurity is of lower molecular weight than the iodosafrole, it may be wise to use even more than the suggested 8:1.

I got some Vitamin E.  It's 80% alpha tocopherol in olive oil, which is the highest concentration I could find.  Shoulda seen me standing there at the store doing unit conversions, looking up molar masses, and figuring how much safrole I could treat with the bottle of the Vitamin E.  :P  Looks like olive oil contains mostly Lineoleic acid and Oleic acid.  Guess I'll be brominating a little bit of this stuff too but I don't see much harm in that.

So I'm going to get another bromo reaction going tonight.  I'll be adding 1-2% molar amount of Vitamin E and cooling the GAA when I add H2SO4.  Also going to make sure the salts settle before I freeze so I don't get that emulsion like last time.  Also going to use foil and low light.  I'll update with results.

Another thing I'm wondering -- when I do the finkelstein with this next batch, might it be better to mix acetone and bromosafrole, THEN slowly add NaI?  It seems to me that this would ensure I'm getting the NaI dissolved enough to react with the bromo since the solution won't be so saturated.

By the way Assyl, I like your idea of cooling a trap with dry-ice acetone to condense Br2.  Too bad I can't run that through a condenser....I don't think my water pump would be very happy about it.
« Last Edit: February 25, 2013, 12:28:53 AM by bjuice »

Whale

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Re: Jon's Method From Start To Finish *Updated - Finkelstein complete*
« Reply #21 on: February 25, 2013, 12:40:56 AM »
to quote jon on his original post:
Quote
you can scale that ad infinitum no probs 8 moles works fine the books say 10 but expiriment is king.
see if it would increase yields if you put it in an ice (maybe ice/salt) bath while adding the sulfuric, and that will work towards less Br2 gas being produced. In this route cooler is cooler  8) 8) 8)

bjuice

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Re: Jon's Method From Start To Finish *Updated - Finkelstein complete*
« Reply #22 on: February 25, 2013, 12:45:53 AM »
For sure.  I was saying a few posts back that an ice bath froze the GAA (I think it freezes at 17C), so I'll start off with just cold water then try to move to an ice bath as per Assyl's suggestion.  As the HBr content increases the melting point should decrease as well.

Just to clarify -- my above comment about cooling with dry ice acetone was in regards to a different topic: forming HBr gas in order to get HBr/GAA without mucking around with in-situ salts and h2so4.
« Last Edit: February 25, 2013, 12:48:46 AM by bjuice »

Assyl Fartrate

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Re: Jon's Method From Start To Finish *Updated - Finkelstein complete*
« Reply #23 on: February 25, 2013, 12:48:11 AM »
Sorry, gave you bad information - HBr actually boils at -66C, higher than anticipated - dry ice baths are -78C. But, Br2 boils at 58C, so you could just use a regular salt/ice bath.

Keep the order of addition the same, adding bromosafrole to all your NaI in acetone is fine. This all is actually not the way people typically run Finkelsteins anyway, though that's probably fine considering how precious safrole is. Typically, you'll pitch in 5-10 mol% of NaI as a catalyst and let the reaction go, sometimes at reflux if it's a difficult substitution. Isolation of the alkyl iodide isn't standard practice, but again, that doesn't mean it's a bad idea.

Have to suggest that you not get too impatient with starting up new runs until previous ones have been seen through. If you have safrole you can't replace, you have something truly precious, and you should be doing what you can to make the most of it. Be careful with excessively large batch sizes if you don't have much left. In chemistry, failures are simply the norm, so you probably want to get things figured out on a small scale so you don't burn through everything you have left before you get things optimized.
Someone Who Is Me

bjuice

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Re: Jon's Method From Start To Finish *Updated - Finkelstein complete*
« Reply #24 on: February 25, 2013, 12:54:11 AM »
Quote from: Assyl Fartrate on February 25, 2013, 12:48:11 AM
Sorry, gave you bad information - HBr actually boils at -66C, higher than anticipated - dry ice baths are -78C. But, Br2 boils at 58C, so you could just use a regular salt/ice bath.

Good call there.  Now THAT I could run through a condenser.

Quote
Keep the order of addition the same, adding bromosafrole to all your NaI in acetone is fine.
Sure it wouldn't help to add NaI last?  It would ensure excess solvent and make sure that NaI dissolves enough to react.  Like you were saying before -- the addition of the oil probably caused a lot of it to precipitate.

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Have to suggest that you not get too impatient with starting up new runs until previous ones have been seen through. If you have safrole you can't replace, you have something truly precious, and you should be doing what you can to make the most of it. Be careful with excessively large batch sizes if you don't have much left. In chemistry, failures are simply the norm, so you probably want to get things figured out on a small scale so you don't burn through everything you have left before you get things optimized.
Agreed on that.  I'm just excited.  I should mention that I have over a liter of pretty pure sass and a domestic source if I run out.  I mean I don't want to get more because having that shipped always sketches me out, but I can if necessary.  Maybe I will do the next run with something like 15g though.  Thanks for the reality check.

Polonium

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Re: Jon's Method From Start To Finish *Updated - Finkelstein complete*
« Reply #25 on: February 25, 2013, 01:03:59 AM »
I have a feeling that you have a quite significant amount of unreacted safrole mixed with your bromosafrole. If you compare your photo's with those posted by xxxxx in his Halosafrole thread, your product appears significantly lighter in color.

http://127.0.0.1/talk/index.php/topic,1697.msg18854.html#msg18854
http://127.0.0.1/talk/index.php/topic,1697.msg19159.html#msg19159

He has his technique posted with photo's at http://127.0.0.1/talk/index.php/topic,1697.msg18798.html#msg18798

Anyways I really like your work and the pictures are great. Best of look with the amination, it really seems to be the place everyone is having trouble. Its quite critical that your IPA/methylamine solution is anhydrous as any water present will cause the iodosafrole to undergo E1 elimination rather SN1 nucleophilic substitution as desired. If your have trouble with the SN1 and want to recover some honey without elimation all your halosafrole to safrole I'd recommend looking at SN2 conditions. The yields are quite a bit lower, but should the conditions should be more forgiving and you will need to recover remaining safrole anyways.

I have given some more information about it in another thread (http://127.0.0.1/talk/index.php/topic,1833.msg31231.html#msg31231).

Happy dreaming

Assyl Fartrate

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Re: Jon's Method From Start To Finish *Updated - Finkelstein complete*
« Reply #26 on: February 25, 2013, 01:09:40 AM »
Yeah, it shouldn't make a difference regarding the order of addition of NaI, if anything it may be helpful that it crashes out first, as it's more likely to be in a finely atomized form, hence more reactive.

Good to hear you aren't running low - it's a hugely painful situation when a few failures means the end of the project. 15g runs will still give you plenty to enjoy with a few others (if you're successful), and you can always repeat and scale up.

Is this vitamin E 80% by weight? There will probably be some reactivity with the HBr, breaking that ether to give an alkyl halide, particularly - but it shouldn't be a problem. It has a phenolic OH on it and you will be able to extract it out with aqueous NaOH from your MDMA base, dissolved in DCM.
Someone Who Is Me

bjuice

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Re: Jon's Method From Start To Finish *Updated - Finkelstein complete*
« Reply #27 on: February 25, 2013, 01:09:59 AM »
Quote from: Polonium on February 25, 2013, 01:03:59 AM
I have a feeling that you have a quite significant amount of unreacted safrole mixed with your bromosafrole. If you compare your photo's with those posted by xxxxx in his Halosafrole thread, your product appears significantly lighter in color.
Agreed.  If I had to guess I'd estimate only about 15% bromosafrole.

Quote
Anyways I really like your work and the pictures are great. Best of look with the amination, it really seems to be the place everyone is having trouble. Its quite critical that your IPA/methylamine solution is anhydrous as any water present will cause the iodosafrole to undergo E1 elimination rather SN1 nucleophilic substitution as desired. If your have trouble with the SN1 and want to recover some honey without elimation all your halosafrole to safrole I'd recommend looking at SN2 conditions. The yields are quite a bit lower, but should the conditions should be more forgiving and you will need to recover remaining safrole anyways.
Thanks for the tips.  I'm going to go with the SN1 though.  I don't think I'll have any issues getting my IPA sufficiently dry.  I'll be starting with 99% and drying with Lithium.

Polonium

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Re: Jon's Method From Start To Finish *Updated - Finkelstein complete*
« Reply #28 on: February 25, 2013, 01:13:49 AM »
Are you going to try dry your methylamine/IPA solution with lithium metal. Just drying the IPA solution at the start might not be sufficient as water is generate when your neutralize the Methylamine.HCl with NaOH.

bjuice

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Re: Jon's Method From Start To Finish *Updated - Finkelstein complete*
« Reply #29 on: February 25, 2013, 01:16:10 AM »
Quote from: Assyl Fartrate on February 25, 2013, 01:09:40 AM
Yeah, it shouldn't make a difference regarding the order of addition of NaI, if anything it may be helpful that it crashes out first, as it's more likely to be in a finely atomized form, hence more reactive.
Ok I'll go with your suggestion.

Quote
Is this vitamin E 80% by weight? There will probably be some reactivity with the HBr, breaking that ether to give an alkyl halide, particularly - but it shouldn't be a problem. It has a phenolic OH on it and you will be able to extract it out with aqueous NaOH from your MDMA base, dissolved in DCM.
Couldn't say for sure if it's by weight.  It's 21 g Vitamin E per 30 mL of oil.  Not sure yet how much the 30 mL weighs.

bjuice

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Re: Jon's Method From Start To Finish *Updated - Finkelstein complete*
« Reply #30 on: February 25, 2013, 01:18:39 AM »
Quote from: Polonium on February 25, 2013, 01:13:49 AM
Are you going to try dry your methylamine/IPA solution with lithium metal. Just drying the IPA solution at the start might not be sufficient as water is generate when your neutralize the Methylamine.HCl with NaOH.

I see what you're saying but jon has reported 80%+ yields using dry IPA.  I'll be keeping the NaOH/CH3NH2.HCl flask in an ice bath to prevent water from vaporizing.

Polonium

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Re: Jon's Method From Start To Finish *Updated - Finkelstein complete*
« Reply #31 on: February 25, 2013, 01:21:15 AM »
I may be wrong, but I recall him claiming 80% yield when he dried the IPA after the addition of methylamine. If you can pick up some 3A molecular sieves they should be able to dry the IPA for you and they are reusable. Good luck with your dreams anyways!

bjuice

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Re: Jon's Method From Start To Finish *Updated - Finkelstein complete*
« Reply #32 on: February 25, 2013, 08:23:15 AM »
Quote from: Polonium on February 25, 2013, 01:03:59 AM
If your have trouble with the SN1 and want to recover some honey without elimation all your halosafrole to safrole I'd recommend looking at SN2 conditions. The yields are quite a bit lower, but should the conditions should be more forgiving and you will need to recover remaining safrole anyways.

Btw Polonium, not trying to be nitpicky by any means, but an e1 on 2-iodosafrole would result mainly in isosafrole. See when the base goes to pull off the proton it's going to take it from the most substituted carbon (because a secondary carbocation is more stable than a primary) -- in this case 3rd from the end. Those free electrons then snap down to the carbocation where the Iodine used to be and create the double bond. There will be some safrole formed, but much less than iso. It's called Zaitsev's rule. Just thought I'd give a heads up :)

Good call on the 3a sieves. I'm thinking about getting some.
« Last Edit: February 25, 2013, 08:25:47 AM by bjuice »

bjuice

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Re: Jon's Method From Start To Finish *Updated - Finkelstein complete*
« Reply #33 on: February 27, 2013, 03:39:02 AM »
Ran another bromo rxn using these guidelines:

Quote
I'll be adding 1-2% molar amount of Vitamin E and cooling the GAA when I add H2SO4.  Also going to make sure the salts settle before I freeze so I don't get that emulsion like last time.  Also going to use foil and low light.  I'll update with results.

This time when I flooded I didn't have two oil layers.  Instead it was all one dark purple layer at the bottom of the funnel.  After extracting and washing it was definitely darker than the first run.  Got a 58% yield.  Again, density of 1.11 g/ml.  I can't help but wonder if when jon reports 93% yield he's going by weight and not by molar mass.  Doesn't seem like the type of thing he'd do as he seems up on his stoichiometry, but I can't image why I'd be getting substantially lower yields than him when I'm doing the procedure *exactly* like he says.  I also can't help but wonder how accurate ChemSpider's density estimate is (estimates 1.48 g/ml for bromosafrole).  I'll be doing the H2SO4 test on both batches.

Anyway, it's going through the finkelstein right now.  Sorry, no pics as everything is pretty much the same as last time except for the differences noted above.

I'm all set for the amination this weekend.  Can't wait!

bjuice

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Re: Jon's Method From Start To Finish *Updated - Finkelstein complete*
« Reply #34 on: February 27, 2013, 04:00:48 AM »
Gotta admit I'm feeling a little discouraged right now.  Part of me wonders if the procedure is even legit.  I mean he goes around the net touting it like it's the best thing since sliced bread -- but I haven't seen one single person replicate it successfully.
« Last Edit: February 27, 2013, 04:15:17 AM by bjuice »

bjuice

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Re: Jon's Method From Start To Finish *Updated - Finkelstein complete*
« Reply #35 on: February 27, 2013, 04:58:12 AM »
Something to note for anyone else trying this: After the finkelstein be sure to extract well with your DCM.  That acetone really likes to hang on to the oil.  I had to extract with 4 volumes of DCM and spent about 30 minutes rocking and mixing before the aqueous layer was colorless.  I was NOT this thorough the first time around, so I'm hoping the finkelstein yield will be higher this time.  It helps to use a larger separatory funnel so you can really dilute things down with a lot of water.  It helps to break the interaction between oil and acetone.

Another thing -- don't spill acetone on your scale!  You'll have a hell of a time trying to tare it when the buttons are fused with the casing.  ::)  ;D

Sneak

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Re: Jon's Method From Start To Finish *Updated - Finkelstein complete*
« Reply #36 on: February 27, 2013, 09:27:31 AM »
Yeh haha I have memories of similar.  I fused a beaker of cocaine hydrochloride to my scales once. Messed em up reet proper. Plumes of white smoke were not a good sign and I almost knocked the shit over in the fuss!
If you really want to enjoy a pure, clean product the only way... is to make it yourself...

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carbonated

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Re: Jon's Method From Start To Finish *Updated - Finkelstein complete*
« Reply #37 on: February 27, 2013, 09:45:49 AM »
Nice work bjuice, this is some quality OC! I'm curious, what are your anticipated yields for this run (percentage-wise, with regards to your 50g of safrole)?

myhero

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Re: Jon's Method From Start To Finish *Updated - Finkelstein complete*
« Reply #38 on: February 27, 2013, 10:14:35 AM »
sneak ahaha i can imagine, the golden becker..... ahahhaha i remember having special care of  extracted Cocaine Hydrochloride solutions given the value of the prioduct

bjuice

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Re: Jon's Method From Start To Finish *Updated - Finkelstein complete*
« Reply #39 on: February 28, 2013, 12:31:40 AM »
76% yield from the second Finkelstein.

I want to be ready to aminate on Friday or Saturday.  Should I dry my Iodosafrole?  I want to but am concerned about mechanical loss when I filter.  If I do dry it, should I mix with DCM to give everything some wiggle room?

Something to note, I'm going to do a separate amination on each Iodosafrole batch.  Mostly because it will be nice to have two chances in case I screw something up, but also because I suspect the first batch is of lower purity and I don't want that to interfere with anything.

By the way, I have less methylamine than I thought.  I'm going to do NH3 on the first batch and MeNH3 on the second batch.


Ok, the workup.  Here is my plan:
-After amination, vacuum distill to remove IPA
-Add water
-Basify to pH 12
-Extract with DCM
-Dry with Na2SO4
-Gas with HCl.  HCl gas will be bubbled through H2SO4 to dry it.

Any benefit to using Toluene over DCM for salting?  I'd rather use DCM because of its low BP.  Anything else I'm not thinking of?

Allmost there!  ;D
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