isomerisation success (x2)

[wacko_reaco]

5g RuCl3 ground with a mortar and pestle and added to 1600mL of chinese sass oil (~95% safrole) and was stirred at 150C for 12 hours. 1400mL of isosafrole was vacuum distilled off (confirmed by IR)
-bingo this method works
not liking the rational for the vacuum reflux
1600mL of the same chinese sass oil was stirred at 140C with 100g of KOH for 12 hours in an open topped vessel. Again 1400mL of iso was vac distilled and confirmed by IR.
We can all now lose the vacuum and lose the safrole distillation step.
Bow bow bow
caio

wacka wacka wacka

[LaBTop]

What was your KOH percentage? 99 or 80/85% ? Flakes or pellets?
A lot better and easier than the messy Aliquat method. LT/

WISDOMwillWIN

[Chromic]

This is awesome news. My vacuum pump will breath easier.  

[GlaseIs]

Would this proces work equally well with Sassafrass Albidum?

"Humanity's first sin was faith; the first virtue was doubt"

[goiterjoe]

what were the post reaction byproducts like for the KOH stirring method?  a long high vacuum reflux was very clean, but hell on a vacuum(not to mention the slight noise.) 

damn if feels good to be back.  without this place the only site on the web worth visiting is the patent office.

If pacman influenced us, we'd glide around dark rooms eating pills and listen to repetitive music.

[Semtexium]

Is the catalyst re-usable and how is it for price, rather expensive...?

 

[Antibody2]

Wacko - No shit?    no relfux, condenser probably still a good idea to keep the neighbors from cluing in though, huh? Wonder now by how much the 12hrs stirring can be reduced.


bravo wacko

"All those memories lost like rain..."

[Rhodium]

The RuCl3 catalyst should be reusable, and yes, it is pretty expensive (Aldrich: $100/5g).

https://www.rhodium.ws

[baalchemist]

Back a couple years ago,SWIM posted some reaction details on iso'ing chinese sass straight out of the bottle with KOH. It definately works, as does numerous other KOH involved iso-reactions without vac. Vac refluxed iso tends to be a higher percentage of trans-iso(if not all trans), which  leads to a more potent end product. Yields are highest also, with 3000mls>safrole, SWIM will receive ~2900mls>iso after vac distilling. If maximization doesnt appeal to one & chooses to do it w/o vac, youre better off running it closer to the reflux temp. Then you only have to run it for 1-2 hours and its finished.

[Rhodium]

There is *no* difference whatsoever between MDP2P prepared from either cis- or trans-isosafrole, so there is no difference at all in the end product. The statement in TSII that there is a difference between the isomers is just plain wrong.

http://rhodium.lycaeum.org

[Chromic]

Cis should be expected to form the epoxide easier, anyways. Rhodium, nowhere in your isomerisation writeup does it detail a method w/just KOH. Are you planning to include some procedural details in your FAQ?

[Neron]

So this method replaces the distillation and the benzo-wacker in one step?  Cool.  Would this work with any safrole containing oil, or does it have to be high purity?

[Rhodium]

Chromic: Yes, I will include procedural data as soon as I have gathered professional writeups of all the featured procedures. I haven't seen anyone using just plain KOH without any solvent (or vacuum) before, that's why it is not included on my page.

Neron: Absolutely not. You have gotten it all wrong.

http://rhodium.lycaeum.org

[Neron]

Oh pooh.  Well, back to the books.

[rangmang]

Neron: Gonna let you in on a little chem info.  Isomerization, in this context, is referring to the cis and trans forms of Isosafrole.  Your talking about an oxidation process to make the ketone.  Read up my friend

[baalchemist]

Never read TSII, dont own it. My statement on trans-iso was merely a pet theory SWIM had. It was based on end users experiences with product made from different iso-mixtures. Early on, SWIM usually had the standard cis/trans iso-mix, which fared a good end product. After switching gears to vac-iso'ing,which produced a predominantly trans-iso result. The end users have commented that its psychadelic'ish properties seemed more enhanced/intense than before. Psychsomatic hogwash on their part? Well that blows another theory all to hell. Is there any reading material in the cyber-jungle on isomer research relating to this?  Chromic, the straight KOH method is Osmiums iso-route contribution from way back. I believe its over there at Rhodium's. The only thing SWIM does differently is that the post iso-reaction mix is filtered through a fritted buchner(fine)funnel prior to distillation to remove the excess solids.
prior to distilling

[Chromic]

Baal, I meant no initial safrole purification, no vacuum, no CaOH, 1wt% KOH, with optional reflux, temperatures 150-250C, rxn times 4-12h (?). I'd love to do this, especially if I didn't have to run my compresser for a few hours...

[wacko_reaco]

rhodium, thanks for finally killing that cis-trans folklore, it was rather amusing/frustrating (not an nice emotional mix) seeing it all the time (waste of time me posting against it as you need a name around here for anyone to take notice (this is good though in a way)). Is there any real empirical data on if the trans is more reactive anyway, there seems to be an anomoly here anyway, if longer reaction times in the isomerisation produce more trans this would imply that is was the more stable and therefore less reactive, i am oversimplifying the whole thing really with this though.
Anyway about the KOH w/o reflux, the KOH was ground, but the real killer is that the whole mix required water washing post isomerisation/predistillation b/c if distillation was attempted w/o the washing a foam was produced that allowed the iso to diffuse up the column, over the still head etc etc.
The RuCl3 method is beautiful, i am kicking myself as i used all my RuCl3 but didn't bother trying to filter/reclaim it to see if it worked over and over, I really wasn't expecting it to work that well. is it wactched?
Anyway hope that clears things up (pun) and yes no ketone was produced during any of these isomerisations.
bow wow
ruff ruff
woof woof


wacka wacka wacka

[Neron]

You know, now that I'm more awake and sober, I can see what a silly post I made up there.  I'll try and refrain from doing that again   .

[Rhodium]

The RuCl3 should be reusable, but you will probably have to purify it after a while, as you will be accumulating a lot of tars in your reaction flask after a few runs. RuCl3 is absolutely not watched, it is just expensive, but considering the ease of the reaction and the excellent scale-up possibilities it might well be worth it. Perhaps even less RuCl3 can be used than in the patent if the reaction time is increased like in your example.

http://rhodium.lycaeum.org