My Tibal Diaries. Part I: Atm0sphere

CannaBusiness
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So - the time has come. I feel manly and prepared to do a Tibal reaction. Yeah, the one with pyrophoric boom-boom on water contact. Li

I have a feeling US firefighting corps do I drill with this - but there are plenty of videos showing the ferocity of this catalyst.

As SWIM happened to have a kilo of this thing (in hexane, which gives me hope). I do not want it, but I don’t know how to get rid of it… ><
Not to through it away, heh?

  • it the original patent for dronabinol. A medical version of delta-9 THC, which I believe has helped so many people, including myself.

So TIBAL conversion it was then. But there is one thing. I live in an area with 82% relative humidity. And my access to glassware is rather limited.

Unfortunately, I do not have an access to a fume hood either. The one I have I made myself using a fire-protected metal closet with a hole drilled and a fan attached to it. But nowhere near having good clamps and (gosh) a shlenks line.

But I think I know how to do it.

Being unfamiliar with cannula techniques and sure that my hands would be far from being surguon-like.
I haven’t even seen a Shlenks line in real life, but I guess that is very convenient.

My precautions are somewhat limited to not smoking pot on the day and having a fire extinguisher nearby.

I have decided do build a set up in an Argon bag. Just make a plastic enclosed bad with positive pressure, and do all the Tibal manipulations inside it. They aren’t difficult… Are they?

piercing the 1l Bottles tiny hole with a syringe, purge once inside the bag.
getting some Tibal out with a syringe, and then put it in a prepared oxygen-water-free flasks.
Closing the flasks/creating a positive nitrogen with a balloon if needed.

Then take the balloon out and then just maintain positive argon state of the reaction.
Can I do that btw? Or I have to use the 2 connections ( 1 argon/1vacuum the whole time?)

Scared as fck to be honest. I have an analytical lab in the same building, and a fire is the last thing I’d want.

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I’d practice the cannula transfers with just the carrier solvent (hexane in your case) neat first, build up the confidence and muscle memory before you attempt to run in on the actual reagent bottle. Practice the procedure with just pure solvent alone until you can do it blindfolded(figuratively of course) and then go on with it. It doesn’t take much practice to get it down, it’s a fairly straightforward thing; a very basic thing in organic chemistry actually. It can be scary and intimidating(as it should be; never grow complacent) at first. Yet also dont be so afraid and unpracticed that your scared; you make more mistakes when your nervous/scared. Practice makes perfect, drill the procedure a few dozen times before you actually introduce the reagent into the mix and doing it with actual reagent will be way less scary.

Also a 1 mol solution isn’t that scary; 2mol, 5 mol solutions are way more nasty. None of them play nice though

Just practice you’ll be fine.

Also practice drying your glassware and feed stocks and whatnot. Operating anhydrously is the biggest challenge with this reaction.

To put things in perspective it takes roughly 54gs of water to quench 1L of 1mol Tiba. That ain’t shit in the grand schemes especially when you start your scale up. Keeping stuff anhydrous at scale is easier said then done.

Best of luck! Practice the transfer and then practice some more.

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So a long syringe wouldn’t do? I seem to have problems with finding a cannula. I have found only plastic-medical ones. I think sharpening the edges of an hplc tubing would do - but they are expensive and hard to replace. Anything else you think I would be able to use.

Yes, you are correct. It is indeed a 1m solution. As for the flask inside a BIG bag of agon? your thoughts? Highly appreciate the feedback though :slight_smile: I think Roguelab told me your were the n1 contact for all the papers :slight_smile:

I

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These are important because even Ph.D level chemists make flamethrowers regularly, unintentionally.

A big thing people tend to do is over think when nervous.

Taking these two points and combining them you may find out the hard way that if you heat a glass syringe body and panic rush to the bottle to ensure its dry, you might forget its still hot. If you pull a hyper volatile solvent into a hot tube its going to immediately expand. The only two ways it can go are out the cannula or by pushing the plunger out the back which both will result in ignition.

The dean of our chemistry college states that he did this once and ran the syringe through his lab spewing flames until he could get to his reaction. Somehow he was able to insert it into the reaction which was inert blanketed and in a fume hood, which quenchd the flame and allowed him to discharge the remaining contents into the flask.

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Distill solvents off of sodium metal for perfect dryness.

At UO we had one lab with these solvents “on tap” and if you needed it really dry you’d just walk over to that lab and get a cannula transfer,

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So pastic syringe isn’t an option?

Molsieves in HPLC grade solvent would not do?

Distillation is really a step of complexity :slight_smile: I could barely call myself a chemist.

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The sodium metal acts as a mol sieve (drying agent) in this situation.

The distillation step is also probably not what most envision on this website. You boil as much as you need, take your sample or volume of solvent, and drop the rest back into the distillation flask that holds the drying agent, be it sieves, metals or hydrides. Its more of a forever setup for organic labs that use these dry solvents commonly.

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Yeah, that’s exactly the setup i’m referring to.

Sodium gets to lower trace levels than mol sieves do. Just a matter of how extreme you need. ppb, ppt, ppq…

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Glass syringe 100ml

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What solvent are do you want to use ?

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you can use a syringe however its much easier to make mistakes with syringes; the plugers like to pop out because your pulling out of a “pressurized” (low pressure don’t pressurize the bottle) environment; and it doesnt take much over pressurization to pop the plunger. practice practice practice with neat solvent before running the actual transfer.

also make sure you pull in some Argon (from the headspace of the reagent bottle) into the syringe when your pulling the needle out of the reagent bottle to clear the needle tip of solution. if there’s solution in the tip; (the very tip) it can be quenched by atmospheric moisture in humid conditions and hydrolyze to aluminum hydroxide, which can then plug up the needle. usually it can be pushed out; and doesn’t offer much resistance; but when practicing fine chemistry; that’s an introduced catalytic impurity. this is a very minor risk but something to keep in mind.

personally I prefer cannulas; but depending on the volume of reagent required a syringe might be more ideal; its certainly easier to meter. one must also consider the heavier gauges(smaller gauges are also available but prone to kinking/clogging) of a transfer cannula is more detrimental/damaging to the septa of a reagent bottle then the smaller gauges of a needle and a septa can only take so many penetrations before its compromised. also be sure to tape the septa up well in parafilm and electrical tape after the fact.

lol yeah dont do that; terrible oversite by the operator, should be common sense but shit happens and its easy to forger how low BP some of the solvents out there can be, especially in a rush!!

Store your dried glassware in a desiccator. only use glassware at RT.

but yeah like i mentioned above a syringe introduces a whole new set of complexities; but again, nothing that cant be trained and drilled into muscle memory.

glass forsure.

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I think you’re largely exaggerating the risk of using a 1M solution of triisobutylaluminium in hexanes for this reaction. Anyone who has used a 1M solution will know what i’m referring to, the triisobutylaluminium is dilluted enough at that concentration that you shouldn’t have much to worry about as long as your air free teqnique is on point.

Look into purchasing a schlenk line and then start at benchtop scale with the triisobutylaluminium reaction. Exercise caution and proper reagent handling and you’ll be fine.

Anyone looking for a consultation regarding d9 reactions with triisobutylaluminium feel free to hmu.

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Yust start your runs on dcm
Will give decent yield if reagent is added stepwise slowly
Run it at roomtemp Wich will give you plenty of time to take your time
16 hours run time should suffice

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This is the first post I’ve made in months.

I just wanna say—don’t do that. Dispose of it immediately before you die a horrible death or disfigure yourself beyond recognition.

Edit: if you’re actually gonna go for it tho, the advice above is pretty solid. I’ve never messed w organometallic catalysts and I don’t plan on it—plenty of accomplished chemists have seriously fucked themselves up messing w organometallics. Just my $0.02

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I once managed to blow up a Blast unit, a hood, all of the surrounding glassware, the hallway outside, and the windows in the atrium between two buildings doing this.

And I had a fucking inert atmosphere glove box - with 5 years of practice - with all the support of a loving professor, surrounded by other graduate students, excellent GLP training with well written laboratory procedures. With laboratory grade distilled solvents. And I wasn’t wondering what kind of syringe to use. :wink:

At the time 31 publications in - including many working with complex explosive and pyrogenic organic compounds. <3

So yeah - it can happen to you - just like it happened to me, with all the tools, knowledge, experience, and guidance I had. The advice above is okay - I didn’t see anything wrong with it except…

Just don’t do it. You don’t have the appropriate stuff. Could you do it and not get hurt and not hurt anyone else, possibly, maybe even probably. But why do you want to do this? Why would you want to put yourself and others at risk, when not having done this work before, not being sure of the work you are trying to do, and being in less than ideal conditions?

Ask yourself if there is any other thing you can do instead. If that other thing is safer - then why not do that.

Phil is so right here. Why do this thing? Why do this thing when you don’t need to do this thing?

If its just for giggles - try to remember that you might not be laughing when you are done. <3

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I haven’t touched pyrophoric reagents but in the process of getting a bachelor’s in chem I’ve done enough lab work to have the proper fear put into me. And I’ve got to mirror what the last two posts say: don’t do it. A proper fume hood, with a rated blast shield, in a building with proper ventilation and fire suppression for serious chemistry to be done are a minimum for working with this. Ideally you’ll also have someone who has done this before consulting you on the exact process and your exact setup (like if not in person, over video, in a lot of specific, step-by-step detail). If you’re making money and can work up to this type of proper setup later, then store the TiBAl and wait until you have the infrastructure. If you won’t have the right stuff and will be tempted to use it, ditch it now.

No batch of cannabinoids is worth your health and safety.

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I never worked with this stuff but this advice is worth taking. :octopus: Stay safe.

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I echo the sentiments of everyone else here, it’s not worth the risk if your not properly equipped; which you’re not!

Approaching organometallics with a cavalier attitude is a surefire way to ruin your day! Regardless of their molar concentrations.

but by all means if your curious about air free transfer techniques, practice with neat solvent, get a feel for the process! Learn a bit! But before you run a reagent make sure you know what your doing and your properly kitted for the task; this is not a realm where you can/should cut corners.

that said; running a process like this successfully also requires a lot of foundational knowledge; it’s more then just the transfer. At the very least; and I touched on some of this briefly, ya gotta know how to run anhydrous, ya gotta know how to achieve and maintain inert reaction conditions, ya gotta know how to quench and do the work up/postprocessing. Nevermind solvent recovery and distillation.

If this is your first attempt at cannabinoid cyclization/isomerization then your doing it wrong and this could be a trial by fire that ends badly.

Start with baby steps; try some of the other methods out there first, learn to run inert, learn to run anhydrous, learn to quench etc etc on more forgiving reagents, and the down the line once you’ve built all the foundational skills required to do something like this safely and successfully, and you’ve built out a proper kit, send it!

Best of luck

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There’s actually a paper somewhere ive seen here that talks about how if its diluted enough in solvent it wont catch fire itll just smoke

Ive taken a 100 ml of 1m tri and broke it on the ground outside and all it did is smoke there were no flames

Not saying to fuck around or anything though you still need to respect these compounds

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I’ve ran hundreds of liters of 1mol solution. It’s not that bad.

Seen a bottle break, seen a pressure equalizing addition funnel leak at the stopcock, it was quite a beautiful phenomenon, streaks of smoke trailed as the drips fell. Seen a few other accidents, never seem spontaneous ignition of 1mol. Doesn’t mean it can’t happen. all organometallics should be treated with respect regardless of concentration.

For the funzies once we broke a bottle with like 15ml of 5mol DIBAH left in the parking lot instead of storing it after some r&d resulted in a nice little fireball.

Growing complacent when doing organometallic work is dumb, being loose and fast because you think it can’t ignite is surefire way to fuck your shit up.

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