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Firstly, you need DCM (dichloromethane aka methylenechloride) it is sold as paintstripper and as brush de-hardener.
In the country where SWIM lives, they only sell paint stripper with a wax binder which sucks, so he found that the brush de-hardener didn't contain any wax binder, so he distilled the brush de-hardener.
It contains: DCM, methanol, solvent-naphta, hydrogenated naptha.
Both the napthas have a boiling point greater than 100 *C, the methanol 65 *C and the DCM 39-40 *C.
So without a vigreux colomn he distilled the DCM, and it came over at 39 *C until 41 *C.
The mixture itself was 55*C and the gastemperature was 39 *C and at the end 41 *C the mixture contained 65% DCM.
The addition funnel is to get the DCM in the 1 liter round bottom flask.
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All the DCM is added to the flask (500 ml) and it is ready for the heating, so SWIM turned on the heat and started to distill off the DCM.
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Boiling brush de-hardener.
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Quite some DCM came over quickly, at least enough to use as a solvent for the epoxidation reaction.
To do the peracetic acid epoxidation reaction, the isosafrole needs to be dissolved in a solvent to make it mix with the peracid, alcohol can be used, but due to alcohol containing water easily it is not a good choice. Acetone is also quite a lot used, but SWIM didn't want to use it, because you need to distill the mixture after you are done with the MDP2P reaction.
And acetone can form acetone peroxide with hydrogen peroxide and an acid (acts as a catalyst). Acetoneperoxide is a high explosive, which detonates from heat.
So guess what happens if you used a bit too much H2O2, and then you are going to distill that mixture Acetoneperoxide are white needle like crystals by the way.
Anyway, to make the peracid one should do the following:
Pour:
- 55,8 ml of 99-100% glacial acetic acid
- 55,2 ml hydrogen peroxide 35%
- 0,66 ml sulfuric acid 96%
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H2O2 and acetic acid.
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Sulfuric acid 96% with a 1,00 ml pipette.
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Everything mixed, set this aside for 4 days, and swirl every day for a couple of times.
All together in a flask, let this react for 4 days, it doesn't heat up, just stink like acetic acid very badly. And let it react for 4 days to get to it s equilibrium, and then it can be used.
Dissolve 33 ml of isosafrole in 51 ml DCM.
Add this slowly to the peracetic acid, and let the temperature not rise over 40 *C.
You should place the flask on a magnetic stirrer in an icebath while doing this.
After everything is added, let the ice-bath come to roomtemperature by itself, and leave it to stirr overnight, with some foil over the top of the flask.
The color will go from yellow to orange to deep red, distill off the DCM and distill off the acetic acid.
A dark, thick syrup will remain.
Dissolve this syrup in 51 ml methanol and add to this 250 ml 15% H2SO4 solution.
Let this reflux mildly for 3 hours.
Then when it has come to room temperature, drain off the acid layer, and keep the dark layer.
Pour the dark layer in 125 ml of water and then extract the syrup again.
Then wash it with 125 ml of NaOH solution of 5%, this last wash is difficult to see so use a flashlight to see where the phases separate.
Now pour in 5 g of MgSO4 (epsomsalt) which is completely dry, dried in oven at 300 *C for 4 hours.
Filter off the MgSO4 again and wash the MgSO4 with DCM.
Distill the resulting liquid, this is your pure ketone.
Here are the pictures:
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Here you can see 51 ml of dichloromethane mixed with 33 ml of safrole, it does not mix when just poured onto each other, SWIM sucked the mixture up with his pipette and blew it back into the rest of the liquid to mix it, until it was mixed well, it was quite easy to mix.
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Here you can see the icebath with the isosafrole and DCM mixed in there, while the peracetic acid is being added to it slowly.
As you can see, it is in an icebath as mentioned above, this is to prevent the liquid becoming too hot, and get to a boil.
Although it should not exceed 40 *C, DCM is used as a solvent, so you also need not worry about explosives peroxides(since you need to distill this mixture) when using acetone make sure you do not add too much H2O2, since if not everything is used up by the acid it will peroxidize your solvent if it is peroxidizable (such as ether and acetone).
Below you can see the color change, the first picture is after everything is just added, the 2nd after an hour and the third after 2 hours and so on, on the third it is capped with Al foil, and left to stir for 16 hours.
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As you can see, the color changes from clear to yellow to orange to red to dark black-red.
Now the 16 hours has passed.
It is time for the DCM to be distilled off.
Thus SWIM poured his mixture in another round bottom flask and set it up for distillation, see below.
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The color is like orange juice, in some syntheses it is said to be dark red.
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Well, this is what happened in the epoxidation reaction:
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When the peracid forms this happens in general:
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Now it is time to get rid of the acid, that is done by adding NaOH solution SWIM used around 3 g of NaOH in 150 ml water, and used it all to neutralise the peracetic acid he made. Below you can see pictures of a wash with ether after it was neutralised, this was done twice.
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You can see the layers quite badly, although you can see an upper layer which is slightly darker than the other layer, ether will float on top since the density is a lot lower than that of water.
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Here it is separated by a separatory funnel, here again it isn't seen well, but the layer is underneath the text 250 ml in blue on top of the funnel, not where the big part goes over in the smaller part.
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Here is a close up of the ether(which contains your isosafrole glycol) layer and the water with sodiumacetate layer.
The peracetic acid gets neutralised with NaOH so it forms water and sodiumacetate.
Anyway, the layer on the bottom can be getting rid of, but SWIM washed it again with ether and combined that ether layer with the previous ether layer, the one that is on top in the picture above.
The ether is distilled off at 39*C, and pure isosafrole glycol is what you have in the flask then. This needs to be turned into MDP2P, you can see the reaction mechanism below.
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You need to pour as much methanol together with the isosafrole glycol, as you used solvent for the isosafrole.
In SWIM's case that was 51ml, so now he uses 51ml methanol to dissolve the isosafrole glycol in, and adds 255 ml (5 times as much as the methanol) 15% H2SO4 to it.
If you take 99% sulfuric acid, that is the most common to buy as draincleaner, one could also buy battery acid. That is 37.5% sulfuric acid, dilute it 2,5 times with water to get 15%, but if you couldn't figure that out, you didn't get this far with the synthese, although you should read this whole thing before beginning anyway.
When using 99%, you need to dilute it 6,6 times.
When using 96% (also quite common instead of 99% as draincleaner), you need to dilute 6,4 times.
The density of H2SO4 when concentrated is 1,84 g/ml, so you need 1,84 g with 6,4 times as much water.
1,84 g*6,4 g = 11,78 g water. 11,78 g/0,998 g/ml = 11,80 ml water.
1,84 g = 1 ml
So for every milliliter H2SO4 you need 11,80 ml water.
You need 255 ml sulfuric acid, 255/11,80 ml = 21,61
((19,92*11,80)/0,998)= 234,53 ml = 234,06 g
((19,92* 1,84)/1,84) = 19,91 ml = 36,63 g
234,06 g / 36,63 g = 6,4 times as much.
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This is what it looks like just plain, not with a lamp underneath it, this is only the first wash by the way. The next wash will be added to this, and then the ether is distilled off and the pure isosafrole glycol remains, and then you should add the methanol and the sulfuric acid (mix the sulfuric acid ahead with water).
Reflux this mixture for 3 hours and no longer else, the yield will go down, now you have raw MDP2P.
Now let it cool down to ROOM temperature, now pour off as much of the water as possible, and pour new fresh water in there, so the flask is filled half or 2/3rd and mix well, and let the layers separate and decant of the water.
Do this 4 times, this should be good enough to remove the last traces of sulfuric acid left in the oil.
Now, for the last time adding water decant off the water, and attach distill head etc. onto the flask, and start to distill the MDP2P.
From another synthese I read, the MDP2P comes over as a yellow to brown oil at 115-170*C with an aspirator vacuum, and then redistillation gives yellow oil (MDP2P) at 140-150*C.
At SWIM the MDP2P came over at 158 °C with vacuum, SWIM collected 15 g of MDP2P that is a yield of +/- 45%, which was yellow golden in color, and when held against the sunlight it has a greenish look from some sides depends on how one looks at it.
Another method to collect your MDP2P would be (and also to test if it is real MDP2P) with sodiumbisulfite.
One would make a saturated solution of sodiumbisulfite, and drop a bit of what should be MDP2P into it, and if a preticipate forms, it is a ketone, and most likely MDP2P, since it just happens to be a ketone.
It is a somewhat well known fact that sodium bisulfite will add to the carbonyl group of a ketone to form a crystalline addition product. If the parent ketone is of large enough molecular weight, the product will be insoluble in water. The parent ketone can then be recovered at a later time by decomposition with sodium hydroxide. This is a doubly good trick in that it gives us an excellent way to get pure ketone from an impure reaction matrix, and it also allows the long term storage of an otherwise unstable ketone prior to its use.
Now, this doesn't *eliminate* the need for a proper (vacuum) distillation of the ketone, but it does make such a process much more pleasant in that when recovering from the bisulfite, there will be little tar and/or polymerized crap to deal with. This means greatly reduced cleaning for those precious flasks, and, possibly, higher yields. The bisulfite addition is a fairly general process, and may be adapted to different ketones (keeping the molar ratios in proportion), however, there are going to be some ketones which will either not react or react to a low extent (mainly ones in which there is significant steric hindrance to the carbonyl carbon). In cases where the carbonyl carbon is on an aliphatic side chain to some other funky ring structure, there is little steric hindrance, and so the reaction proceeds quickly and nearly quantitatively. Finally, there is the limitation that ketone (or ketone containing slop) be reasonably freed of acidic or basic impurities, as these will interfere with the formation of the addition product.
1) Preparation of the bisulfite reagent
(This must be prepared just prior to use, as it will autooxidize within hours if left to it's own devices.)
Add 52 g sodium bisulfite (NaHSO3, .5 moles) to approximately 90 mL of distilled water at room temperature with vigorous stirring (slightly more water may be used to get it all into solution). Add a volume of denatured alcohol of about 70% of the solution's volume (i.e.- if you end up with 100 mL of solution, add 70 mL of alcohol), then add more water to just dissolve the precipitate (~60 mL).
2) Reacting with the ketone
Slowly drip .25 moles of ketone(*) into a beaker containing the bisulfite solution, with vigorous magnetic stirring. The 2:1 molar ratio insures that all the ketone will be converted. Let sit on the stirrer for an additional 30-45 minutes, then filter on a vacuum Buchner funnel. Wash the crystals with 20-50 mL of denatured alcohol. Dry in a vacuum dessicator or open tray, then store in a stoppered glass bottle until needed.
(*) If adding an impure reaction matrix, add as much solution as you expect to contain .25 moles of ketone.
3) Recovering the ketone
Add the ~.25 moles of bisulfite addition product to a separatory funnel, then slowly pour in 105 mL of 10% Sodium Hydroxide solution (w/w). Separate out the aqueous layer (which may be on top or on bottom depending on the ketone), saturate with salt (NaCl), and extract with 50 mL of ether (toluene or benzene ok if the ketone is of high enough bp). Combine the extract with the ketone layer and strip off the ketone by distillation (condense and reuse!). Distill the ketone residue, preferably under vacuum (if you're making what I think you're making), to yield up to 90%, depending on the purity of the starting ketone, of course.
Refs to chase: A. Vogel, "Practical Organic Chemistry"
Now one has MDP2P, if one wants to store it do so in the freezer it will become a very viscous liquid and will be storable for LONG times.
Now will be outlined how MDP2P, can be synthesized with the wacker oxidation and p-benzoquinone a la Methylman.