Chromic`s peracetic problem- help needed

[BieneMaya]

Swim has a real big problem with chromic`s peracetic oxidation.

After trying to destill the desired ketone some colorless shit came over.
The boiling point was 98-100 C with vacuum. Safrole comes over at 90C at the same vac.
Ketone made via Benzo Wacker comes at 125-140 C and has a yellow colour, doesn´t freeze
and smells beautiful.

But this little piece of shit smells only a little bit after ISO and freezes at -16 C.

So what could that be Swim had produced?

Here my setup:

Cromic´s version was scaled down to the half of the org. amounts (26,35)
-ISO was made via KOH and heating at 150 C for 12 hours.
 ISO came over at 105C at same vac as above. It smells less than Safrole.
-selfmade peracetic acid aged 12 days (instead 5-7) was used.
-Then dumping the acid into the DCM/ISO/NAHCO3 solution no warmup appeared.
 Nevertheless the solution turnt into a light yellow after 5 hours.
 But it was stirred another 4 hours due to no time to go on.
-After washing it with 5% NaOH the second wash ate a lot of the yellowish colour.
 Swim was a litlle confused what there was happening but he went on.
-So the DCM was destilled off and the residue was reacted with 15% H2SO4
 at reflux for 3 hours.
-Wash with DCM with a reddish colour change of the solvent
-Again washing 3 times with 5% NaOH. The first one ate nearly the whole reddish colour.
-Destilling off the DCM
-Then the shit (absolutly no ketone) came over at 98-100 C at vac.


So what the holy fuck can this be?
Maybe converted to some other shit? Alcohol?

Why does the NaOH eat nearly all of the yellow colour?
In this step the yellow colour indicates for the Epoxide, doesn`t it?

Another question?
Will in the fist step a yellow colour be formed even with plain Safrole?
Is the yellow colour an indication that the reaction went right?

Any bee who can help, please take the time....
Many thanks in advance.
The Hive with all of your bees is the best community
---THANKS FOR THAT in the name of holy Jesus Christ---

[ApprenticeCook]

dont know what it could be coming over at 98-100, colourless??? some iso maybe... wouldnt be ketone, bp to low, more than likely its iso. refraction extent? more info on distillate.

As for proceedure:
iso distilled out ok? correct bp for iso? smelled and looked like what its been described as..?
peracids of this kind (formic and acetic) have to be aged (1hr for formic, ~90hrs for acetic) but also have a used by date, thats why the proceedures say fresh peracid, i dont think it would have gone bad after 12 though, its not that bad... where was it stored for the 12 days, conditions? container? Did you use fresh peroxide and GAA? thats a common problem, esp with acetic peracid formation, did you include the sulphuric catalyst for peracetic formation, chromic does not have it on his page but the sulphuric should be removed after its used?
Addition, SLOWLY add the peracid to refluxing mixture, but it must be on a VERY HIGH stir... reflux the mix with addition of the peracid under high stir for the time period. You dumped it? meaning what?
Extended reflux time is no problem, just as long as its going for 5hrs+.
Ok, so you now have a refluxed mix of peracid, iso in dcm and carbonate... the naoh wash (1) "ate" the colour? what didi it look like after it was eaten...? did you seperate the aqueous layer and re-wash the dcm organics with more naoh? then seperate again...
distill off the dcm and use sulphuric or even better the HCl method of rearrangment... reflux them, ahh maybe reflux for a bit longer, 5hrs+ is good, but still would expect some should have been made at t+3hrs.... hmmmm.

As for the distillate.... anyone???
Cant do peracid with safrole, you wont make ketone... must be iso.

My thoughts, use FRESH 30% peroxide and formic acid (oxalic acid + glycerol ref rhodium.ws) to make performic, stand for 1 hour and use it... also double distill the iso.
Look at the review document on rhodiums site to do performic, its really good ref, buffered performic that is. And utfse for ref for HCl rearrangment.

I dont know what you have made but try and distill in the hope of getting back some iso....
Dont know if thats helped but its what i think...  

-AC

[Bond_DoubleBond]

try redistilling that fraction without vacuum and note the temp.  might give you a better idea.

[tweek_ez]

plain safrole straight out of the bottle will react in a way that it seems like it is iso. maybe due to the small iso content? swit heard it will go beatiful yellow or orange and then redish after h2so4. It will also blow a geiser of smelly shit all over the ceiling if too much peracetic is added and left unatended. at least thats what swit says!

[BieneMaya]

Thanks bees for the effort

refraction extent? more info on distillate
14g. 53% its in the expected yield
colour like safrole
smell very light like iso



conditions? container? Did you use fresh peroxide and GAA
stored in a labority brown glass bottle
in a dark cool cupboard
the H2O2 was bought 2 month ago
Didn`t used GAA but liquid acetic acid (purity ~ 95%)
It was bought at the same time as peroxide

blue]iso distilled out ok? correct bp for iso? smelled and looked like what its been described as..?[[/blue]
It was my first experience with iso.
smelled as described. looked the same as safrole
can´t check with bp point(atmospheric) because I have only an oil bath as heat source


did you include the sulphuric catalyst for peracetic formation, chromic does not have it on his page but the sulphuric should be removed after its used?

Yes used H2SO4. Never heard of removing it....

You dumped it? meaning what?

added it in ~0,5 minute

Extended reflux time is no problem, just as long as its going for 5hrs+.
never got any reflux. Have used cold water.
The flask did`t warm up not even 1 C.

the naoh wash (1) "ate" the colour? what didi it look like after it was eaten...? did you seperate the aqueous layer and re-wash the dcm organics with more naoh? then seperate again...

The NaOH sol. looked the colour as the DCM before. (yellow)
The DCM looked a little milky white.
I´m familiar with extraction methods.
NOTE: The second NaOH wash ate the colour.
Washed the DCM with water to get rid of remaining NaOH.
Didn´t dry it because water is used in the afterwards reflux step anyway.  

Cant do peracid with safrole, you wont make ketone... must be iso

Yes it´s plausible. I meant if the colour changes to
yellow even with safrole. Or does the yellow colour change
show that iso was used....

Thanks AC
Will try it with formic acid some day.
Will better wait for some Hydrochinone to make Benzo.

Double Bond:
try redistilling that fraction without vacuum and note the temp.  might give you a better idea.

I have no heating mantle to reach those temps.

Tweak
plain safrole straight out of the bottle will react in a way that it seems like it is iso. maybe due to the small iso content? swit heard it will go beatiful yellow or orange and then redish after h2so4

So it´s very possible now that swim had no iso..

[tweek_ez]

[ApprenticeCook]

i said REFRACTION EXTENT not reaction... how much does the product bend light when its passed through it.

storage is good... keep the place dry too....

peroxide should be good... and as for AC instead of GAA.... ahhh i only ever heard it works with GAA, how do you know the % of yours? calculated it? best to utfse for thread on purification of AC to GAA and try again with that, follow exactly what is written in synths that work and you wont have a problem (shouldnt).

check bp of iso with nomograph at vacuum bp and strength of vacuum, its pretty accurate, but dont rely on it.

remove the sulphuric... its on rhodiums peracid review.

added it in ~0,5 minute

Does that mean added all in 30s??? thats way to fast.... when you do it again make it wwwwwaaaaaaayyyyyy slower.

you do realise your supposed to heat the flask to reflux right??? it wont get there on its own....

no idea whats happening with the hydroxide...

dont rely on colour too much... its very fine line on colours and varies alot... just as long as its close to the liturature.. eg ketone is shown in a few writeups as being red-orange-yellow-green-blue so thats just an example how not to rely on it... rely on the disto temp.

-AC

[BieneMaya]

Yeah allright.
Just saw the fraction in it and thought it has something
to do with destillation....
By the way never learnt optics in physics.
As soon as I´m back to my lab I will report it,
about the Refraction.

In case of that GAA... It´s just nearly anhydrous
AC, isn`t it. So the H2O2 has a lot water anyway.
Doesn`t make a sense to use GAA.
Chromic refs to AC, too.
Maybe I`m wrong- correct me

I have an old Vacuummeter but it´s very inexactly.
I have compared both boiling points at the same vac.
With that

https://www.thevespiary.org/rhodium/Rhodium/chemistry/equipment/nomograph.html

it was then calculated to say its a 6 torr
vacuum. So at 6 torr sassy comes at ~90-95 C and

and Iso 105-110 C. This is exactly what I had.
So I thought it`s ISO and gave it a try.

Yes I realised to heat the flask. But Chromic`s writeup
didn`t tell of it. Next time I will bring it to reflux
with extern heat and will add the peracid slowly.
Maybe a addition funnel could be useful.

Thanks again AC for your help.

Tweak:
It`s really hard to understand what you`re talking about.
But I guess I got the meaning.
Anyway I don´t want to spend too much time on that peracid route. I will try one time again with performic.
If it doesn`t work then I`ll give a fuck to it
spend all my time with Benzo.
Nevertheless thanks for help

[tweek_ez]

[ApprenticeCook]

Got the point on GAA so hmmm, dont know, but in the past swim has dreamed with success processes which are exactly what is written in proven synths and its worked, use the materials and amounts it says and the equip it says and follow the processes exactly and there was no probs... just a thought.  

dont add while its refluxing!!! the temp to reflux the iso is WAY higher than the bp of the peracid so you will lose it when you add it.... just stir and a tiny bit of heat to warm the mixture a little more than RT. add the peracid and stir for a few more mins tehn apply reflux heat...

performic works.... just follow the synth on rhods review page exactly, buffered performic... home-made formic as with the glycerol/oxaclic synth and it is ok.

-AC