Eleusis's safrole isomerization

[chemrat]

Hallo !

I read eleusis document  eleuisos, about isomerization of safrole : boling it whith CaO and KOH, alleged reference CA 47 art. 9360.

I tried to perform this reaction. failing several times (incomplete isomerization).
I read in several post on the hive that this method is ineffective, plus, looking for references I found something totally unrelated to isosafrole :  some info about a german patent  (see above).


Who know more ?
Are eleusis docs unfounded ?


CA 47  art 9360
(Transcript from a fax)


Scifinder scholar
Sulfur containg organic compounds.  Raichle, Karl; Rossig, Lisa;Zorn,
Hermann (Badische Anilin & Soda Fabrik (I.G.  Farbenindustri  Akt.-Ges
"In Auflosung")   (1952)   DE840239  19520529      Patent language
unavailable    CAN47:9360    AN  1953:9360  

Patent family information

Patent  No.                   Date                   Application  No.
DE  840239                  19520529          DE


Abstract
S-contg. org. compds.  of the general formula  RX.CS.S.R".S.CS.XR' (where X is S or O; and R and R' are aliphatic, cycloalifatic, aromatic or heterocyclic radicals; R" is an alkyl, cycloalkyl, aryl,
arakyl or heterocyclic group) useful as softening agents in the laquer industry, are prepd. by treating alkali-metal xanthenates or the corresponding tri-thiocarbonates with halo compds. contg. at least 2 Cl atoms bound to C atoms, preferably in aq. soln.  or in water contg
org. solvents heating of iso-AmOCS2K 1010 in water 200 and
tetrahydrofuran (I) 800 with (CH2Cl)2 247 for 10 hrs at about 80, and removing I by distn. and the salts by washing with water gives as residue ethylene bis (isoamylxanthate) 790 parts.  1,4-(Butanediol bis(ethylxantate) is similary prepd from  EtOCS2K and Cl(CH2)4Cl.

[Rhodium]

For some reason, the volume and/or article numerical identifiers in CAS Online is often dissimilar to the ones in the printed edition (at least in the old days). I have no idea why that is the case - could anybody enlighten me on this matter?

[moo]

I haven't personally checked this but according to a librarian the older issues of Chemical Abstracts had two columns both indexed by the same number, which gave some troubles in the process. This might have something to do with why they have adopted the CAN numbers instead of CA. It would be nice if there was a way to do a conversion.

[placebo]

I learnt the hard way...

Use KOH pellets or flakes not evapped KOH solution (hydroponics shit)

Make sure you get rid of all the H2O or nothing will happen.

[Lilienthal]

KOH and NaOH turn into K2CO3 and Na2CO3 upon exposure to air (to CO2 to be more specific).

[Rhodium]

This is the full text from Chem. Abs. Vol 47, 9360c (1953) and as you can see, it is not especially verbose. If you retrieve the original japanese patent it refers to, you can probably learn more about the details.



A related patent, summarized below in Chemical Abstracts, Vol 47, 10005h (1953), where they pre-dry the safrole by passing it hot through some calcium oxide before heating it together with KOH and a far lesser amount of CaO than in the procedure above. This is probably more suitable for large-scale endeavours.

[chemrat]

Sorry, I'm wrong !

[ApprenticeCook]

For placebo's comment on KOH pellets instead of hydroponics store stuff....

Is it really that bad? the stuff swim has is not powder or any such, it is small flakes... last time swim dreamed it was pellets which swim found someplace.
Flakes ok or not for process?

[amine]

Swim has had good luck using flakes.
The general method used:

Vacuum set-up for glassware
1700ml of sassasfras oil in the rxn vessle.
150g of KOH (waaaay to much I know)

Heat at 150C for 2 hours.
Pulled a slight vacuum to make sure the water was gone.
Then continued heating for another 16 hours.
Isosafrole was distilled ~90-95C.  Smelled like licorice.

Performic rxn worked and so did oxone .

[ApprenticeCook]

possibly the major excess worked due to some of the flakes turning to carbonate as decribed above? pellets would convert less than flakes. The excess flaskes allowed for a certain % of conversion in the flakes. Thanks amine.

EDIT: Amine, sassy oil, and not safrole? huh?

[placebo]

A_C, pellets or flakes are fine, my point, as stated, was not to use a solution of KOH/water as it turns into shit upon evaporation, as Lillienthal stated, and I learnt the hard way that it if you use it, it doesn't work and fucks your safrole.

[ApprenticeCook]

thanks placebo, thats what i was thinking you meant... but had to ask.

[amine]

A.C the proceedure I outlined should work, it was recommend to me by other bee's during my isomerization difficulties.. thanks to them I produce 26g of product today....and then placed that 26 almost dry grams in the oven and killed 21g of it...(don't ask....) but the product produces was sparkling white from the initial gassing.  I had never seen anything more white in my life. Also I recommend using the HCL method for th hydrolysis outlined by chromic, I ran the rxn at 4x using the methanol @ reflux (the solution stays around 85C) for 2.5 hr.

Good luck with all your endevors and use the lamp...don't try to rush things with the oven.
~Amine

[chemrat]

How much a good agitation is important for this reaction ?
It's a magnetic agitator a good choice ?

[amine]

for the isomerization you NEED to keep stirring nonstop.

[ApprenticeCook]

Stir is ESSENTIAL.... and at a high speed too.... keep the safrole from bumping too much and keep the KOH moving about.. Any kind of stirring is ok, overhead or magnetic whatever as long as you agitate the mix, as rhodium says on his iso review if your using over 1000mL of safrole to make iso mag stir is no longer viable and a stream of air is your better choice.

Bigger reactions than 1000ml of safrole that have the tendency to bump violently, apparently magnetic stirring isn't good enough anymore. For our industrially oriented bees: using a capillary to introduce a stream of air bubbles, comparable to good old-fashioned vacuum distillation should work to circumvent the batch size limitation.

https://www.thevespiary.org/rhodium/Rhodium/chemistry/isomerizafrole.html

-AC

[zoloft]

can this isomerization procedure take place without the CAO?  If someone dreamt about the BP reaching that of isosafrole, but didn't add the CAO, it still would be isosafrole, correct?

[abacus]

This has been discussed so many times its bordering on the ludicrous.

1.  Yes, Simply heat with KOH and stirring.  The higher the temp that shorter the reaction, the lower the temp the longer.  CaO is NOT required. 

2.  UTFSE, read, and you will find more than enough information to make this work for you.

3.  While your at it, go to rhodium's page, download and happily read away until you get it.

Abacus