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           Oxidation of propenylbenzenes to P2P's using Oxone 
                                 by Chromic
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This method is 100% OTC. It is awesome for a first time chemist not interested 
in yields or time constraints, but rather in producing an active product without 
the purchase of suspect chemicals.

Running the reaction
Setup a 1L or 2L flask for reflux, optionally monitoring the temperature.

1. Add 100mmol alkene (eg 16.2g isosafrole, see note)
2. Add 200mL MeOH
3. Drop in a 2" stir-bar and start the stirrer
4. Add 500mL distilled H2O.
5. Add 200mmol KHSO5*1/2KHSO4*1/2K2SO4 (~72.7g Oxone)
6. Slowly add 290mmol (24.4g) NaHCO3 

This will form a swirling white brew of chemicals in your flask.

Let this reaction run 5h with no external heating.

Extracting the goods
Turn off the stirrer, and let the mixture settle. The sediment will drop to the 
bottom. Pour off as much as possible into a beaker without getting any solids in. 
Suction filter the rest. The crystals will be off-white. A lot of your product 
will remain in the crystals. Rinse the crystals with fresh methanol to try and 
get as much product out as possible. The crystals should be bright white after 
rinsing twice.

Load into your 1 or 2L sep funnel and extract 3x100ml (or 4x60ml) with DCM.

Recover the DCM by simple distillation on a water bath.

React the oil as usual, to get ketone. If you don't know how to do the usual 
reaction, read the small section at the end. Purify the ketone by vacuum 
distillation and/or forming the bisulfite adduct, then the ketone plug into 
Methyl Man or Osmium's reductive amination... and away you fly!

Pool chemicals rock. The war is over.

Observations
The temperature will quickly rise to ~35(C after mixing the chemicals. The 
color will change from a swirling mix of white solids in a colorless and clear 
liquid to white solids in a light yellow liquid. As the reaction comes to 
completion, the temperature will drop to room temperature.

If using anethole:

1. The glycol oil will be a clear yellow (instead of clear and colorless, as 
   with anethole) and no longer smell of licorice, rather like root beer... 
   and it has maybe incorporated the smell of burnt rubber.
2. The ketone will have a stronger non-licorice smell-similar to, but stronger 
   than the glycol / epoxide... less similar to root beer, and more medicinal 
   and smelling like burnt rubber / fruity. Your phenylacetone will be a 
   light-brown oil!

If using isosafrole:

1. The glycol oil will be a darker yellow (instead of clear and colorless, as 
   with isosafrole) and will smell more like root beer after this... the same 
   sort of burnt rubber smell is present. The yellow color won't be totally 
   extracted by the DCM.
2. The ketone will have a stronger smell, losing the hints of root beer, and 
   will have that medicinal burnt flower smell. Your phenylacetone will come 
   out dark-yellow. In my experience, all phenylacetones have a similar smell, 
   but each is subtly different. Some yellow color won't be able to be extracted 
   by the DCM when extracting the ketone. The ketone is a dark red before NaOH 
   washings which really clear up the color.

Trials

1. 1.5g anethole (10mmol), the crude yield of ketone after steam distillation 
   was 0.6g (3.7mmol), 37% yield.
2. 3.0g anethole (20mmol), the crude yield of ketone was 2.2g (13.4mmol), 
   66% yield
3. 14.8g anethole (100mmol), the first step crude yield was 16.4g epoxide 
   (100mmol), 100% yield, and the crude yield after hydrolysis and washings 
   was 12.6g ketone (77mmol), 77% yield.
4. 24.3g isosafrole (150mmol), the first step crude yield was 22.4g epoxide 
   (125mmol), 83% yield (sloppy technique), and the crude yield after hydrolysis, 
   washings and vacuum distillation (~60mmHg, 190-92(C) was 13.4g ketone (75mmol), 
   50% yield.
5. 32.4g isosafrole (200mmol) (300ml MeOH, 750ml H2O, 45g NaHCO3, 145.4g Oxone), 
   from which the first step crude yield was 30.7g epoxide (171mmol), 86% yield.

Qualitative Analysis

The product from a Methyl Man or Osmium reductive amination is unmistakably 
active. Recrystallisation from IPA, followed by a rinse with acetone yields 
a bright white odorless crystal that is soluble in warm alcohol, insoluble in 
acetone that is not hygroscopic and completely melts below 200(C. It tests 
purplish-greenish black with Marquis reagent (liberating hydrogen chloride gas), 
and burns cleanly. 150mg will produce a smooth high complete with empathy, eye 
jitters, jaw clenching and pupil dilation. TLC, MS, IR or NMR has not been done 
for confirmation on the product.

Notes

1. 0.1mol (100mmol) alkene is 14.8g anethole or 16.2g isosafrole. 0.1mol 
   (100mmol) epoxide is 1.6g heavier than each alkene.
2. 1991 ref said 1g Dupont Oxone contains 2.75mmol KHSO5, although 1985 ref said 
   0.2mol is 61.5g Oxone (ie 1g contains 3.25mmol KHSO5). I went with the info 
   from the 1991 ref... who really cares anyway, as the reagent is used in excess.
3. The whole idea of buffering is to keep the pH only weakly acidic... note that 
   the molecular formula for Oxone is 2KHSO5·KHSO4·K2SO4, so there's .3 mol of 
   acidic hydrogen for .2 mol of KHSO5... which means we'd need less than .3mol 
   of bicarbonate to leave this slightly acidic. Luckily, if too much bicarbonate 
   is added, the pH will not exceed 8.3 due to the weak dissociation of bicarbonate 
   ions, this is why I prefer it to sodium carbonate .
4. After the bicarbonate is added to the Oxone, the solution must quickly used 
   (<10 min). It will start to liberate free oxygen and lose strength. 
5. NaHCO3 available as baking soda. MeOH available as methyl hydrate for alcohol 
   stove fuel. Oxone available as Oxyshock for pools (to raise active chlorine or 
   bromine). Alkene found or derived from essential oils. Water is found distilled 
   at a grocery store (tap water will liberate chlorine if you add Oxone, this is 
   undesirable). DCM is available as "methylene chloride" as a paint stripper and 
   to bond Lucite.
6. The reflux condenser is more of a safety / odor control device than anything 
   else, if you don't mind the smell, an Erlenmeyer flask will work fine. You can 
   optionally run this setup with a Claisen adapter with a thermometer to monitor 
   the temperature.
7. If you don't have a large sep funnel (say if you're doing this 2-50x scale), 
   find a large carboy or glass flask for shaking. Even HDPE plastic containers 
   work well. Load the reaction mix and DCM, and shake it. Let it settle, pour 
   off most of the water into another container, and then load the rest into your 
   sep funnel. Get as much of the DCM as possible, then return the contents to the 
   other container, load back into your shaker, and repeat. Yes, it's a bitch, but 
   is it worth it for this purely OTC method? You be the judge.
8. The amount of MeOH and H2O have been successfully reduced, look at the trials 
   section for more information. Yields may go down, there isn't enough information 
   yet.
9. Good stirring is absolutely necessary, the faster the better.

Refs: J Org Chem 1985, 50, 1544-45
J Org Chem 1991, 56, 7022-26

The usual workup from the gylcol
Thanks to Strike, Semtex Enigma, Rhodium and the all-wonderful Shulgin

The more usual 65g batch is what most small-scale chemists do (after Shulgin, 
I suppose). In our case, we're just working with a mere 15g. Once you distilled 
out the DCM from the 250ml flask keep the glycol in and add:

1. 25ml MeOH
2. 120ml 15% H2SO4

Change the setup for reflux, and lightly reflux the mixture for 2h using 
a boiling hot water bath. The water bath should be kept at a light boil, 
and the reaction vapors will have a temp of around 65(C.

The epoxide mixture will go from a light yellowish color to more of a 
darker brown color. 

Let it cool. Load it into a sep funnel and pour off as much of the more 
dense ketone as possible (both PMP2P and MDP2P are more dense than water). 
Now extract with 3x20ml DCM.

Wash extracts with 3x80ml 5% NaOH

For the first wash, simply rock the sep funnel back and forth. For the last 
two washes, shake vigorously. The sodium hydroxide washes will take away a 
lot of the yellowish-brown impurity color with anethole ketone, and will take 
away some of the reddish-brown impurity color with isosafrole ketone.

Now distill off the DCM in a water bath, or an oil bath if you're going to 
later vacuum or steam distill the ketone.

Notes

1. 1kg of 15% H2SO4 is made from 150g H2SO4 and 850g H2O
2. 1kg of 5% NaOH is made from 50g NaOH and 950g H2O
3. Stirring is not absolutely necessary, but beneficial. The reflux provides 
   sufficient agitation if you don't own a hotplate/stirrer.
4. H2SO4 available as a high-strength drain opener (hardware store). NaOH is 
   available as lye (soap shop, hardware store, grocery store). Info on finding 
   DCM, water & MeOH is as above.

Preparation of Anethole

1. 206.5g star anise oil fractionally distilled to 191.0g at 145-60(C at ~60mmHg
2. Distilled again, now 178.5g at 145-48(C under ~60mmHg

Preparation of Isosafrole

1. 250ml clear yellow sassafras oil is (optionally) fractionally distilled at 
   145-50(C under ~60mmHg to clear colorless safrole.
2. Vacuum refluxed in a 2L flask (w/no stirring, no boiling stones) with 1.5wt% 
   ground KOH flakes a la Osmium for 6 hours, the mix turns black
3. Distilled and tossed first 15ml back with unprocessed sassafras, collected 
   over 200ml clear colorless isosafrole at 160-62(C under ~60mmHg.
4. Checked isosafrole by bringing to a reflux at atmospheric pressure and saw 
   that the isosafrole boiled at 254(C. Successful conversion!

Thanks

Thanks go out to Psychokitty for discovering the awesome 1991 ref which lead me 
to the almost as awesome 1985 ref on which this method is based. Props go out to 
improv chem (thank you so much for your experimentation), as well as to Osmium 
and Rhodium for letting me know how to figure out if I really had the goods 
amongst my doubts. Thanx also go out to Bright Star, Methyl Man, Ezekill, 
Eleusis and Shulgin for raising my awareness and inspiration.

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