otto
(Hive Bee)
04-14-02 13:31
No 296778
      buffered performic - a deeper look
(Rated as: excellent)
 Bookmark   

otto had some 50 ml of anise oil in the fridge(1). encouraged by the recent posts about PMMA he decided to give it a try.
GC of the anise oil showed three peaks. one of these is about 90area% of all peaks. otto assumes that this is anethole. on TLC there was only one spot visible under UV-
light as well as with permanganate (RF 0.8 - 0.9 with Hexane/EtOAc 4:1).
the oil was subjected as is to a buffered performic using the following proportions(2):

50 ml anise oil
100 ml DCM
15 g NaHCO3

this was put together with a stirring bar into a 500 ml erlenmeyer flask. then

45 ml 30% H2O2 (~ 50 g)
70 ml 85% HCOOH

where mixed and set aside for 1 hour. the performic acid was added then slowly and under stirring to the mixture in the erlenmeyer flask so that the DCM doesn't boil. the stirring was continued 17 hours at r.t. (flask losely stoppered).
the DCM layer was separated, the aqueous layer extracted twice with 50 ml DCM and again twice with 50 ml EtOAc. the evaporated extracts show 3 major peaks (very close to each other)(3) in GC. also there are minor peaks of anethole, PMP2P (already!) and of one of the other constituents of the oil (one of the three peaks from first GC), which apparently remained unchanged(4).

the residue was transferred into a 1 l RBF, 100 ml methanol and 300 ml H2SO4 were added and the flask was put aside for 1 week (otto had no time). the organics formed a bottom layer. GC of this layer showed 2 major peaks totally different from those of the raw performic product(5). and: the area of the PMP2P - peak was increased (comparison
to anethole and the other oil constituent)!
otto thought, that the rearrangement can take place at lower temp than 80C or reflux, so he heated the mixture to 65C for 30 minutes under stirring to see the resulting GC.
it worked. area of PMP2P-peak is now about 1/3 of area of the two diol-peaks. some peaks of heavier products occur (6).

2 hours at 80C converted almost completely to the ketone. almost means, there are still 5 - 10% diol unchanged (7).

the mixture was cooled, the organic phase separated, the aqueous layer extracted 3 times with 50 ml EtOAc and the combined organic phases were dried with MgSO4 and evaporated in vacuo. of the product obtained, about 70% is PMP2P (8).

vacuum destillation yielded two fractions. first fraction (pale yellow) was collected at 63-63C at 1.7 mbar (9), total 5.5 ml. second fraction (pale yellow) was collected at 70C at 0.8 mbar, total 35.5 g.
remainder was a thick black oil, total 5-10 ml.
GC of each fraction tells:

fraction 1: about 50% unchanged constituent of the essential oil, 20% anethole, 20% PMP2P and some minor peaks.
fraction 2: 98% PMP2P.
residue: about 5% PMP2P and a lot of other compounds but no diol(10).

isolated product: 35.5 g (71%) of a pale yellow liquid. bp 70C at 0.8 mbar. TLC RF = 0.3 eluent Hexane/ethyl acetate 4:1 (11).

marks

(1) according to literature anethole melts somewhere around r.t. it would not surprise otto, if this can be used for its isolation from the essential oil. see also the thread
can't get safrole?-FREEZE IT in the newbee forum.

(2) the proportions were taken from rhodiums site and only scaled down.

(3) none of which was the epoxide, as confirmed by an external sample.

(4) this other constituent of the anise oil has a lower bp than anethole. on some websites it is stated that it would be methyl chavicol (the p-MeOallylbenzene).
however, it is not affected by the performic.

(5) apparently either of these peaks is from diol since the only rearrangement product is PMP2P. in the literature there are described 2 different diols (the alpha and beta - isomer) having different m.p.

(6) these peaks of heavy molecules are then found in the residue of vac-dest. the PMP2P peak has increased to 1/3 area of the diol peaks. no quantitative conclusion can be drawn from here since PMP2P was present before.

(7) in the attached reflux condenser there was little condensate. otto put it into GC, too.
it was mainly methylformate.

(8) as in most cases, otto assumes, that area ratios in GC correspond to weight ratios, which is not always the case. in other words: otto hopes that 1 g of PMP2P gives the same peak area as 1 g of any other compound. so the 70 % are not a super exact value.

(9) at such low pressures destillation takes a much longer time than normal.

(10) the flask could be easily cleaned using ethanol.

(11) anethole is very active in UV. TLC is thus a good proof of proper separation.
RF: anethole 0.8 - 0.9, PMP2P 0.3 in Hexane/EtOAc 4:1.


conclusions

about 70% of isolated yield have been obtained by otto which is in good correlation to other reports at the hive. it seems that a 70 - 80% yield range is general for this technique as stated many times before.
from the remaining 30% a few yield% of PMP2P are in the other fractions and the rest formes heavier products. these products resulted mainly from the rearrangement.
so, IOO (in otto's opinion) rearrangement is the yield limiting step in buffered performic.

this procedure works fine with raw anise oil. the non reacting constituent has to be removed at some stage though.

17 hours were not sufficient for full consumption of all anethole used.

two diol isomers have been formed.

the rearrangement can be run at lower temp.

2 hours @ 80C left some 10% of diol unchanged.

some of the methanol added is converted to methylformate.

questions / outlook

are there higher yielding rearrangement proc's? what is the methanol added for and is it necessary at all?
the anethole should be isolated by freezing prior to reacting it. TLC should be used in the performic (disappearance of anethole) step to check for full conversion. time for rearrangement should be increased a little.

otto
 
 
 
 
    Chromic
(Hive Addict)
04-14-02 14:50
No 296799
      Answers to some questions  Bookmark   

1) higher yielding rearrangement -> toluenesulfonic acid in toluene.
2) methanol is not necessary in the rearrangement, I think the function of it is to lower the BP so that it refluxs at 80C.
3) did you see any diformate? (or just the two isomers of the monoformate?)
4) freeze purifying anise oil is easy (almost too easy as slow crystallization is important)... it's also very easy to get a seed crystals.
5) PMMA sucks, PMA sucks even more.


 
 
 
 
    otto
(Hive Bee)
04-14-02 23:34
No 296914
      questions to Answers to some questions  Bookmark   

hi chromic,

thank you for your fast response.
otto knew that this might bee of interest to you since you've actually run the reactions on anise oil and posted before.
to your points:
1) has anybee actually done the rearrangement in toluene?
the proc. sounds promissing, but then the H2SO4-way is known to be simple (no isolation of diol required) and behaves well.
2) so thinks otto. also some formic acid can be removed this way (via the ester), but this doesn't seem necessary to otto, who also thinks that MeOH can be omitted at all.
3) otto saw three peaks, none of them diol nor epoxide, all very close to each other. he can't say to what compounds these refere. maybee two monoformates and one diformate or only monoformates of the two isomeric diol forms or...
4) all of ottos anise oil was solid in the fridge and he didn't consider to purify first. did you purify it this way (freezing) once? how is it like to do?
5) otto has no idea about PMMA. he read some discussion and some bees tell that its very good. some tell that its crap or evil. what to do then, how to know...?

otto
 
 
 
 
    Vibrating_Lights
(Hive Addict)
04-15-02 02:24
No 296960
      Drying of ketone/DCM  Bookmark   

What is the purpose of drying the DCM/Ketone solution before removal of the solvent and distillation.  Is it just to avoid having to change the recieving flask.It seems that all the water would come out as soon as it is hit with vaccume after the solvent is gone. Kind of off topic but was just curious.
VL_
 
 
 
 
    Rhodium
(Chief Bee)
04-15-02 02:36
No 296965
      Why dry?  Bookmark   

Yes, it is to make sure that the only fractions coming over is the solvent followed by the ketone. Also, many oil vacuum pumps do not like contamination with water.
 
 
 
 
    Chromic
(Hive Addict)
04-15-02 04:40
No 297008
      Q&A to Q to A to some questions  Bookmark   

>1) has anybee actually done the rearrangement in toluene?

Read up on Scooby Doo's post in Novel Discourse (J.Org Chem 1984, 49, 1830-1832) Post 264135 (Scooby_Doo: "Ref on Isosafrole to diol via electro", Novel Discourse). In that reference they use a conc. of 1g tosic acid to 100ml of benzene to do the rearrangement. I'm sure toluene could substitute as a solvent, and the concentration of the acid catalyst left the same but the concentration of the intermediate raised. (ie use 1g p-tosic acid, 100ml toluene, 100mmol processed alkene) I'm working on getting OTC p-tosic, but I keep running into little problems. My biggest problem right now is removing the aqueous phase from the mixture without a dean-stark trap... I get this nasty reaction mixture after reacting conc. h2so4 / toluene, but there's a not-viscous lightly colored phase, and a very viscous dark colored phase. Oh well, that's for another thread! smile

>the proc. sounds promissing, but then the H2SO4-way is known to be simple

No isolation is required for the p-tosic acid method either.

>4) all of ottos anise oil was solid in the fridge and he didn't consider to purify first.
>did you purify it this way (freezing) once? how is it like to do?

I have frozen the oil, but just for the fun of it, I didn't consider that method to purify it. Read up on safrole purification from sassafras. The gist is to put a small amount in the freezer, and you'll get a seed crystal. Chill the star anise down to just below the freezing point of anethole (ie 15C or so), then drop in the crystals. Wait a few hours for it to crystallize and pour off what doesn't freeze, thaw the oil, and repeat to purify.

However, I used vacuum distillation to purify my oil.

>5) otto has no idea about PMMA. he read some discussion and some bees tell that
>its very good. some tell that its crap or evil. what to do then, how to know...?

Try it out yourself. Keep your dosage low and don't expect much. smile
 
 
 
 
    otto
(Hive Bee)
04-15-02 18:58
No 297234
      hi VL, actually the PMP2P is volatile with water.  Bookmark   

hi VL,

actually the PMP2P is volatile with water. one would lose some ketone to the water fracion. sometimes water causes problems in dest of organics. otto just wanted to be sure thats why drying was applied.

otto