Hi,

Just planing to make som other MDxx compounds after last sucess with MDMA ( Thanks Vespiary!!!
but there seems to be problems with ketone.
There is very little about ketone stability and what effects it on the net.
I just looked at my ketone batch and I am afraid something might go wrong!

Most interesting thing is that my first batch I ever did 3-4 months ago is still green,
viscous when frozen,has same smell and gives great MDMA yields,while batches I made few days ago and month ago turned
totally yellowish from original green colour and smell more like safrole than MDP-2-P.
No further synthesis were done with this new ketone since most chemicals are consumed now, but it will be done ASAP.
Also, feather like crystals were noticed at freezer temperatures in all batches.

Only difference I did in my first synthesis was that I made only two NaOH 10% washes,
while I did more washes (3-4) in late batches than changed appearance.
Xylene was used for the first batch that is still great and DCM and toluene for the latest batches.
I realize that pH and exposure to light(not factor in this cace) might change color of some organic chemicals,
but does anyone have any similar experience!?

Is there any known method or additive to keep ketone fresh for longer time(expect making some MDxx and freezing)!?
Quantitative tests on MDP-2-P are highly appreciated!

I know about bisulfite, and NaI seems to work even better, but this seems to be somehow messy and complicated...
Is there anything to just add in, like food preservatives are added or something like that!?

What might be cause of such behavior of ketone!?
(one batch stays OK, and other goes weird.)

Now you are screwing me arround...
You mean NaI and bisulfite!?
I know it can be used to make adduct,it is on Rhodium,but it is not case here,it is too dirty,labor intensive and results in impure ketone that needs further purification.
Many pople tend to have futher problems with this method...

Storage in freezer is great way for me,but I don't understand why older ketone is still same while newer one undergo rapid change!?
That is real problem here...what causes it,how to stop it and determine how bad it really is.

If there is some simple method to determine ketone contest and is it decomposing or just changing colour,just give me a link,I am sure I saw it somewhere but can't find it now.

I doubt i would ever succeed in making final product w/o critical thinking skills!
Open mind(other ways to get same thing) is what plunged me in this trouble in the first place!
You misunderstood mine problem, that is probably because of my inferior English grammar skills.
I understand basic scientific method, I am just asking for EXACT known causes of the
presented problem,so I can eliminate them one by one...

(Had similar problem with Al/Hg reductive amination, when most people said it can be done in EtOH
successfully with same method that involves MeOH, BULLS..T it CAN'T!
It inhibits amalgation,has too high b.p. and acts weird when NaOH is added. )

Of course, only reason why is it degrading is environment or pollution.
Excluding environment we are searching for pollution.

I used vacuum fraction distillation every time, and re-distilled ketone that started to spoil,
so only pollutant might be iso-olefin but it is spoiling again!
Now I am thinking that reason might be:
1) olefine-ketone auto-catalytic reaction
2) too many NaOH washes(but don't know why)

I find out that extractions done with DCM haw bigger tendency to spoil, my conclusion is that DCM doesn’t carry away   
water and basic water soluble crap like xylene does in lower fractions, purifying ketone form these before it reaches
higher temperatures of ketone b.p.(hence faster spoiling) Only part of DCM tends to distill under normal pressure and than It makes mixture
of all fractions at once in receiving flask if not heated really slowly under vacuum...

Toluene is much better but it sometimes starts to boil into receiving flask under high vacuum due the low b.p.
an than screw vacuum rig.

Xylene works perfectly for me.

Sure,I will do only 1-2 NaOH ashes in the future and use xylene if available, but I need to save ketone I got now so
this is reason why I ask help.

Problem is in chemicals, peracids are strictly watched here and hard to come by.
I accidentally come by 1l of 99% formic acid,but more steps,smelly and much longer procedure
putted mine interest out of this method. I must try it at least once...
Now when I have more PdCl2 than needed for industrial scale it is bitch to change method :-(
Unfortunately p-benzoquinone, hydroquinone become even harder to come by recently...
I am considering O2 gas as oxidants for wacker Wacker but have no idea haw to make non-magnetic pressurized apparatus
that can be mixed with magnetic stirrer and won't kill me!

OK,we determined that adduct is best way for storing ketone,will do in the future,thanks...
But is there simple qualitative or quantitative test for mpd-2-p like there is one for MDMA?!

It doesn't matter,I would make adduct same day,but this puzzles me...
How come can it be less stable with this method when there are less polutants in O2 Wacker than in p-benzo Wacker?
One of our members has(or at least had,can't connect right now ) wab-page with complete Wacker using O2,
yields are higher than those with p-benzo and I think that reaction must be much cleaner since there is no hydroquinone/quinohydrone crap left.
Yes,I know p-bezoquinone is more selective and keeps double bond of alkenes in place,but this is important only during reaction,not after it became something else in reaction,right?! Hydroquinone became totally unavailable here, like p-benzo was for years! Only problem I have with O2 Wacker is reaction flask,
really don't have idea what to use to withstand pressure and that can be stirred magnetically.

Will send you link of successful O2 Wacker with stirring when I find it.
It would be interesting to try potassium peroxymonosulfate in addition to sodium as source of oxygen
in Wacker oxidation, pity it is hard to find them here...

And about adduct, should KI work same as NaI!?
I mean this is all about I- anion or!?

Interesting...are yields higher than those with formic acid!?

Nice,thanks!

First method seems great,unfortunately it is only theoretical,do you know if anybody tried it actually!?

Never had problems with ketone stability made using the Wacker process. There is for sure something wrong in your procedure (probably distillation), since you have feathers-like crystal in your product. The ketone melting point is well below freezer temperature...That means you have a contaminant in your product, since it freezes at those temps.

this is sheer speculation but it seems a number of different things effect the ketone color.  from the temp the ketone is distilled at, to the concentration and amount of NaOH washes.  never seen any varying in ketone color due to the extraction solvent (toluene vs dcm) before though, the crude undistilled ketone will be a different color yeah but after vacuum distillation it's all looked the same when using different extraction solvents.

lugh has it right, the ketone produced via peracid is higher purity because the wacker oxidizes to other ketones, etc, but it's in very very small amounts.  the only problem i've heard regarding ketone stability is from ketone produced via o2 wacker.  never heard of any problems from benzo wacker or peracid ketone.

yes it gets thicker consistency when kept in the freezer for awhile but the ketone will not freeze at regular home freezer temps.

Anyway the problem doesn't seems to be from the synthesis itself, as much as from the work-up/distillation....There should not be crystals in the ketone.

I don't know why, but I never had ANY safrole/Isosafrole comes over with the wacker oxidation.

Don't think Iso-olefin crystallizes when frozen...it may have just been that some of the original olefin from the very beginning did not convert (this could even happen if not enough oxidizing agent was used) and came over early on with the distillation, got into the 'tone, then crystallized at the bottom of the 'tone...where it will then begin to grow upwards. Sounds like it was some kind of contamination that does crystallize, that's for sure. If eugenol was left in, it will oxidize and go all the way thru the entire process yet it does not crystallize if it is still mixed in with the 'tone, it just causes a portion of inactive particles to result after an amalg. Even though it is inactive and tangy instead of super bitter...it does cause body load and some amount of body hangover. It sounds like just some of the original olefin got in there. A wacker is not perfect, even after reading the forensic studies, they found 5 to 10% of iso-olefin is always created. It's a very small percentage, but it is usually always there in some tiny amount.

Here is the only post I've ever seen on getting ketone to crystallize, this is from the old Hive:

Hellman:

In hindsight I believe that there was no need to crystalize the mdp2p, I believe its purity was sufficient. But i had to try it, next time I wont bother.

I created a cooling chest by slowly heating a drinking glass 500ml in the oven to about 300c(this can be done, the trick is o do it slowly) With this heated glass I submerged it ino a 20cm CUBED BLOCK of polystyrene(I was going to ozonate this styrene, but I will leave that to another day) Into the glass which had cooled-(smile), I poured my Co2/acetone/salt/ slurry, and ino that i placed my testube containing roughly 50ml clear as water Mdp2p,.
Being not a professional in crystallizing, It took me a while to get a seed crystal to start.

I furiuosly went through vogels, and realized that letting the substance warm just a little, then scratching it with a glass rod produced the seed that i was after,. Back into the ice chest it went, and back into the freezer,. And with 2 hours after that the whole testube was a crystalline solid, WOW,.(or for you american dudes-Neat-) I let it warm jst a bit drained the oil and refroze,.So, Yes you can crystalize Mdp2p, but after steam distillation, I don't believe that it really makes that much difference.

Good Info on melting points, and excellent question on whether any of them can precipitate out of solution.

i dunno but on a very good frezzer (dry frezzer) ketone got froze  might have to send pictures.
dunno what happened but getting ketone thats freezing 2 froze.... (its more like a slurpe in USA) so got blue slurpe, and now green slurpe.
didnt test the green slurpe but the blue one yield me 70% at al/hg. so i doubt thats isosafrole that froze or even water.
any thoughts?
peace

why some ketones are freezin? they become like a slurpe...like meshed up ice you know.... yield fine at al/hg.
it goes back to oil form very fast after take off freezer.

just wondering, why its happening, why its freezing. if it was really safrol or isosafrol my yilds on nitro al/hg wouldnt be around 70-80% i guess. seem many posts but no real conclusion. why the ketone is freezing. and just got blue ketone for the second time huahauha 

i just made some note.... when i got a complete reaction with p-benzo i have absolutly no left over p-benzo!!!! at all, only pdcl2. nothing besides pdcl2 to be filtered.
now.... sometimes i got some left  over p-benzo at final of reaction, (which led me to conclude that the reaction wasnt 100%).
*well, here, when i have a post benzo reaction with NO p-benzo left over.... the ketone "freeze" (like 7eleven slurpe)!!!
*the reactions that i had p-benzo left over.... the ketone doesnt freeze at all!!  maybe that will help  more knowladgeble bees to solve the matter. is afecting purity of ketone?

apreciate any thoghts..
peace

lugh sorry maybe you understood me wrong!!!
ive always know about isosaf being a side product os benzo wacker.....
what im saying is that if i have 100ml of ketone and around 70-80% is ketone, what i mean, is that the other 20% possibly isosafrole wodn´t be enought to crystalize so much, see the whole thing gets very thick with crystals, its hard to swirl even, i might be wrong but i dont think 20% isosafrole would make the solution so thick and so many crystals.
other ketone that i had crystals were like snow flakes and werent enought to make solution that thick! i hope i made myself clear.

and what i said is that the ketone thats freezing yield just fine like MM al/hg around 70-80%. so it cant be that much isosafrole. thats just what i think, ive read alot about these cristals, actually on this very same topic we stand on!!! thats why i posted here!! im just curious about the crystals formation and ive made a point that maybe is valuable about the p-benzo being all consumed or not, im very limited in chemistry, just though the info i had could be valuable!

for the ketone being like that would need at least 50% iso 50%ketone, but if that was the case the al/hg qouldnt yield 70%. am i right?

but i can see that you also have no idea why its freezing! thanks anyways!

peace!!

alright!!
i will try to give more detais next time, thank you.

 i distilled the ketone, my iso start coming at  135 so i let go up to 145 let it sit for a couple minutes,always collects the first maybe 70ml, then replace flask and continue destilation. so since i dont do a fractional destilation at least i try to catch some isosaf.
i will check the temp of my freezer, but i have to tell you, i have a ketone in the same frezer that has not froze at all!!! but others did. this is something that its not bothering me too much but i wonder the reasons behind it. ill try to colect more data as possible!!

thanks anyways!!

peace