wacko_reaco (Stranger)
05-07-01 09:27
No 189761
      isomerisation success (x2)  Bookmark   

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
 
 
 
 
    baalchemist
(Hive Bee / Eraser)
05-08-01 12:29
No 192653
      Re: isomerisation success (x2)  Bookmark   

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
(Chief Bee)
05-08-01 14:36
No 192662
      Re: isomerisation success (x2)  Bookmark   

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
(Hive Addict)
05-09-01 01:51
No 192769
      Re: isomerisation success (x2)  Bookmark   

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
(Stranger)
05-09-01 03:37
No 192800
      Re: isomerisation success (x2)  Bookmark   

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
(Chief Bee)
05-09-01 03:52
No 192806
      Re: isomerisation success (x2)  Bookmark   

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
(Stranger)
05-09-01 04:03
No 192809
      Re: isomerisation success (x2)  Bookmark   

Oh pooh.  Well, back to the books.
 
 
 
 
    rangmang
(Stranger)
05-09-01 08:13
No 192852
      Re: isomerisation success (x2)  Bookmark   

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
(Hive Bee / Eraser)
05-09-01 11:37
No 192904
      Re: isomerisation success (x2)  Bookmark   

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
(Hive Addict)
05-09-01 13:46
No 192922
      Re: isomerisation success (x2)  Bookmark   

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
(Stranger)
05-10-01 04:32
No 193129
      some extra notes  Bookmark   

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
(Stranger)
05-10-01 05:50
No 193145
      Re: isomerisation success (x2)  Bookmark   

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 smile.
 
 
 
 
    Rhodium
(Chief Bee)
05-10-01 13:40
No 193234
      Re: isomerisation success (x2)  Bookmark   

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
 
 
 
 
    firecracker
(Newbee)
05-10-01 18:42
No 193284
      Re: some extra notes  Bookmark   

wacko,

So "straight from the bottle" isomerization worked?

1) 100g KOH was ground w/ mortar n pestle.
2) 1600mL of chinese sass oil mixed w/ KOH in a flask.
3) Mixture was heated and stirred for 12 hours at 140C.
4) Post reaction mix was washed once w/ dH20. (and possibly filter because of "chunkiness")
5) Vacuum distill to get 1400ml iso.

2 questions:

1) Wouldn't a 5% NaOH wash at the beginning be useful as well? It would get rid of some of the solids.
2) Why 140C?  Why not hotter/faster?

Thanks for the input,
fc


Snap, Crackle, Pop
 
 
 
 
    wacko_reaco
(Stranger)
05-11-01 07:49
No 193447
      Re: some extra notes  Bookmark   

Yes that is all true, i wanted to leave it overnight so i didn't want to subject it to conditions too severe, so I only programmed it to 140C, the post washing iso is very murky when the distill begins, alot of water comes off and the mix clears right up, there seemed to be practically no safrole forerun but sometimes it's hard to see (good vac source).
I dunno, try running it hotter and shorter and see how you go, maybe plasma phase at 3600C for 8msec, ha ha ha, a scientist joke.
Anyway, i do suggest to all those with the means to buy some RuCl3, i ran it at lower than the patent  concentrations but hotter and for longer, it was so easy.
bye now


wacka wacka wacka
 
 
 
 
    Osmium
(Stoni's sexual toy)
05-11-01 10:58
No 193456
      Re: some extra notes  Bookmark   

You used quite a lot of KOH. It will work with much less, and you can skip filtrations and washings etc.
Grinding in a mortar is not necessary either. It will only pick up more H2O from the air, at those temps the KOH flakes will disintegrate on their own anyway.

It's good to see that things like RuCl3 work, but at that cost I doubt I'd consider that reaction. The KOH way gives almost quantitative yields (only limited by your distilling abilities) when starting with pure safrole.
 
 
 
 
    Osmium
(Stoni's sexual toy)
05-11-01 14:38
No 193482
      Re: some extra notes  Bookmark   

A shy lurker bee asked me to post the following:

> Ruthenium(III)chloride hemihydrate (1.68g, 7.75 mmol) was ground to a
> fine powder and added to safrole (450g, 2.75 mol) in a 1000ml RB flask
> fitted with a reflux condenser and the solution, which soon turned a
> greenish black, was stirred at 150C for 4h. The resulting black oil was
> distilled at the water pump to give 45g of safrole at 110-117C, and the
> bulk of the oil distilled at 118-121C yielding 360g of crystal clear isosafrole
> (90% yield based on the reacted safrole).

Some of that supposed safrole forerun will be cis-isosafrole, so I suggest you save it for the next isomerisation and not use it for a reaction requiring real safrole.

> I just wanted you to know that I tried the RuCl3 isomerization method, and
> it worked better than expected. The yield was 90%, higher than I've ever
> gotten from any other method (I've tried your vacuum reflux thingy, the
> KOH/CaO method and KOH/Aliquat 336). The safrole wasn't distilled, only
> crystallized, half-melted and sucked dry on the buchner, followed by complete
> melting, which may contribute to the fact that 10% of the oil never distilled
> in the desired temperature range, and formed a black tar in the flask (but it
> was soluble in acetone, while the crud left from KOH isomerizations is not).

Alcohol and water washes will dissolve that residue. Also distilling to dryness is not recommended (but can be done without ruining the flask), but since you can use it for at least another isomerisation the mechanical losses aren't that big.

> Perhaps you could post it in the "Safrole Isomerization success (x2)" thread
> for me?

Sure honey smile wink
 
 
 
 
    improv_chem
(Hive Bee)
05-11-01 19:34
No 193563
      Re: some extra notes  Bookmark   

SWIM tried to make isosafrole with only washed safrole and using ipa as the solvent at atmospheric.  Distillation was done at atmospheric and got 80% yeild of isosafrole after 3hours.  The key was to make sure that the KOH in ipa and the Safrole in ipa were dried with MgSO4 and everything was anhydrous.  No CaO was used. 
Short rxn times are possible (did it in under 3hours) if the ipa is slowly allowed to evaporate by periodically removing the reflux condenser to concentrate the solution and raise the temperature.  Distillation of Safrole and vaccume are not necessary to do this process.
Have Fun!!!
-improvsmile


--Preventing odors from escaping to nearby noses is essential.....
 
 
 
 
    Rhodium
(Chief Bee)
05-11-01 21:19
No 193594
      Re: some extra notes  Bookmark   

How much safrole was used? How  much KOH and in how much IPA? Was there any safrole forerun collected, or did the other 20% become tar?


http://rhodium.lycaeum.org
 
 
 
 
    goiterjoe
(Hive Bee)
05-11-01 22:50
No 193604
      Re: some extra notes  Bookmark   

here's one for you Rhodium:

240g distilled safrole
3.5g KOH flakes
refluxed for 18 hours with a high vacuum oil pump
initially started refluxing at 88C; at end of reflux temperature was around 83C.  end product was distilled directly out of the boiling flask to yeild 236g of a clear oil with a sweeter smell than the starting safrole and a boiling point about 5C above the boiling point of the starting safrole using the same vacuum(with the oil changed before each run.)




If pacman influenced us, we'd glide around dark rooms eating pills and listen to repetitive music.
 
 
 
 
    LaBTop
(Daddy)
07-11-01 10:21
No 189965
      Re: isomerisation success (x2)  Bookmark   

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
(Hive Addict)
07-11-01 11:20
No 189967
      Re: isomerisation success (x2)  Bookmark   

This is awesome news. My vacuum pump will breath easier. cool
 
 
 
 
    GlaseIs
(Stranger)
07-13-01 04:50
No 190263
      Re: isomerisation success (x2)  Bookmark   

Would this proces work equally well with Sassafrass Albidum?


"Humanity's first sin was faith; the first virtue was doubt"
 
 
 
 
    goiterjoe
(Hive Bee)
07-13-01 08:19
No 190294
      Re: isomerisation success (x2)  Bookmark   

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
(Hive Elder)
07-13-01 18:59
No 190395
      Re: isomerisation success (x2)  Bookmark   

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


crazycrazy
 
 
 
 
    Antibody2
( )
07-13-01 19:19
No 190400
      Re: isomerisation success (x2)  Bookmark   

Wacko - No shit? cool 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
(Chief Bee)
07-13-01 20:26
No 190417
      Re: isomerisation success (x2)  Bookmark   

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

The Hive - Clandestine Chemists Without Borders
 
 
 
 
    PoohBear4Ever
(Junior Service Representative)
09-26-01 05:06
No 217237
      Re: isomerisation success (x2)  Bookmark   

So, it has been said that NaOH may bee used for isomerization, though at least 2% of safrole weight.

If one simply took their sass, boiled at 120C to get rid of the aqua, cool down, then heat back up to boil and use the 99.999% NaOH without allowing any water to enter.  Then, why not just go ahead and use the CaO or MgO for better aqua insurance, and distill on over the isosafrole without filtering, using HCL to clean all glassware of crud.

Better chance at success, or has anyone tried anything similar? How clean should the iso bee if using peracetic?  Distilled 2x?

PB 
 
 
 
 
    Chromic
(Hive Addict)
09-26-01 17:30
No 217378
      Re: isomerisation success (x2)  Bookmark   

Single distilled iso is fine, it doesn't have to be very clean to go into the peracetic. If I had to isomerize again, I'd add 1% KOH in alcohol (just enough to dissolve it), then add the safrole... distill off the alcohol, reflux with no vacuum, and fractionally distill. Other methods work, but this appears to be the easiest/most OTC.
 
 
 
 
    PoohBear4Ever
(Junior Service Representative)
09-26-01 22:54
No 217443
      Re: isomerisation success (x2)  Bookmark   

Ya'll keep scaring me with that 'fractional distill' shit.  Can one kinda ghetto such without a proper column (vigreux) by boiling off the alcohol (anhydrous isopropyl, or MeOH?) without vacuum, and then collect the second run (unreacted safrole) by slowly turning up the heat?  Change out receiving flask once more, and then shoot for the stars (i.e. higher temp)?

Has anyone had repeatable success by drying out reagents, and if so, how long should the reflux bee maintained?

Thanks,

PB
 
 
 
 
    zooligan
(Hive Addict)
09-27-01 15:59
No 217717
      Re: isomerisation success (x2)  Bookmark   


Has anyone had repeatable success by drying out reagents




Had questionable results drying KOH.  Stick with the hydrated form and boil openly until steam is gone, then attach condenser and vac or atm reflux.

z


"And if we don't get some cool rules ourselves, pronto, then we'll just be bogus too!"