Sulphuric Acid Ketone Liberation via Isosafrol Epo

[cheeseboy]

Cheese's friend SWIC is wondering if the Sulphuric acid treatment solution is too strong (too much H2SO4 added).

Here's what happens:
 
  After epoxidation of Isosafrole via Oxone the Epoxide is cleaned up with a few washes and tapped off (Since the epoxide lies on the bottom layer of the aqueous/epoxide solution) The Epoxide is a dark yellow.
 
   Next a 15% H2SO4 solution is made using dH2O/meOH/H2SO4<95%>). When the acidic acid solution is added to the epoxide ,it sinks and the oil floats.WTF?The epoxide oil was not digested in toluene either. After heavy stirring and refluxing for 2 hours, the oil is still floating on the top of the acidic solution and has turned a dark reddish brown. Upon flooding with dH2O the oil sinks, but how come it floats on the acidic solution? Cheese noticed that the Sulphuric acid is almost as thick as maple syrup (clear white) It is the lab grade stuff  and maybe there is too much in the solution therefor making it heavier than oil.

 Is this Normal, Or has cheese failed? The resulting oil smells creamier than the epoxide, like ketone smells, but still is crude and needs vacuum distillation to see if the yellow ketone is in there somewhere. Still a hint of Isosafrol in the smell of this supposed ketone. It all sounds like it's gone right except for the floating epoxide, that's wierd.Cheese thought that it was maybe the presence of toluene in the oil but this time NO toluene was used to extract oil, no non-polar at all was used anywhere. Anyone get the same results? It's got to be the density of the sulphuric acid solution being heavier than the epoxide/ketone. Cheese will be damned if more supposed ketone wastes good cyano/Ammonium acetate.  
Cheeseboy-a whiteboy with Soul Like a black guy without soul
May The Source Bee With You Always.

[cheeseboy]

Shit, this method MUST be new or something. NOBODY has had this occur or knows why this floatation happens?
Cheeseboy-a whiteboy with Soul Like a black guy without soul
May The Source Bee With You Always.

[terbium]

Well, 15% sulfuric acid would be significantly denser than water, perhaps enough that your epoxide/diol/ketone would float. Later I may get around to looking up the value.

[cheeseboy]

How do you calculate that? 15% H2SO4.. so then you need the density of both and then make both out as fractions and figure it out from there? Thanks for the help terbium, cheese isn't schooled in figuring out those kinds of equations yet, however simple they may bee!.
Cheeseboy-a whiteboy with Soul Like a black guy without soul
May The Source Bee With You Always.

[terbium]

For the density of sulphuric acid solutions I look in a table such as is in Lange's Handbook of Chemistry. This says that the density of 15% sulfuric acid solution is 1.102. The density of safrole is 1.096 so safrole would float. I don't know the density of the epoxide/diol/ketone but it is probably not any more dense than safrole.

[deludium]

safrole or isosafrole smell in the ketone isn't a good sign either. MDP2P has no smell like the starting oils. A good distillation is needed.

In epoxidation trials, the aqueous portion is always on top, and is milky with a tint of pink/yellow (depending on the acid quality). The lower epoxide layer is dark yellow or brown which gets darker as reaction continues.

Never seen it float on top like you describe. Unless it is in solution with toluene or something. Odd  


According to chemfinder, isosafrole density is 1.12 which should be the same for the epoxide

[cheeseboy]

Thanks for the help man, that clears things up a little, except  Pickler says his epoxide sinks to the bottom of the H2SO4 solution he makes, it must not be 15% sol.Thanks again terbium. Deludium :  the epoxide/ketone only floats when it's in the acid solution, all other aqueous solutions float on the epoxide/ketone. Like terbium said, the 15% solution is more dense than Safrole/Isosafrole/Epoxide.(well safrol yes, but most likely iso and it's epoxide)
Cheeseboy- a whiteboy with soul, like a black guy without soul
May De Source Bee Wit Chu

[cheeseboy]

Cheeseboy always measure's out the 15% solutions by eye, this means that the solution was probably over 15%. That explains it.
Cheeseboy- a whiteboy with soul, like a black guy without soul
May De Source Bee Wit Chu...Always

[Chromic]

Use 15% by weight. 15g H2SO4 and 85g H2O per 100g called for. Anything 15-20% should work fine.

[LaBTop]

I think you all missed this one:
""using dH2O/meOH/H2SO4<95%>). ""
He adds METHANOL, which has a density much less then water. That's why his epoxide floats first. LT/

PS: why still follow that damned addition of MeOH to a 15% H2SO4 solution? Redundant.
WISDOMwillWIN

[cheeseboy]

The damn MeOH is the culprit eh? Thanks LT. Cheese's vacuum isn't too strong, would sodium metabisulphite isolate the ketone from the crude oil/ketone mix (brownish red). Thanks again.
Cheeseboy- a whiteboy with soul, like a black guy without soul
May De Source Bee Wit Chu...Always

[PrimoPyro]

PS: why still follow that damned addition of MeOH to a 15% H2SO4 solution? Redundant.

Perhaps he is not versed in chemistry, and was only doing what he should have done to be successful: He followed the writeup he chose verbatim. If this is so, then I don't grudge him the slightest bit for not knowing. If this is so, I say to him, "Thanks for using your brain and following directions like so many others should learn to do."

#1 reason why people generally suck at sciences, especially chemistry and physics: They can't follow directions.

It may seem very simple, but it's true. Although many people consider chemistry to be rocket science, it is based on one big assumption, that is often incorrect for most people, causing them to fail: That you have the very basic ability to follow explicit directions when they are given to you.

There are so many people that will be able to cook themselves a steak from scratch when hungry with not so much as a piece of paper for help; using only their common sense, memory, and instincts. But when supplied with very detailed directions on how to prepair a boiling water bath, they will choke every time. The average person's inability to follow directions is truly amazing.

                                                  PrimoPyro

Vivent Longtemps La Ruche!

[cheeseboy]

Greenhorn said he adds MeOH to the epoxide BEFORE the 15% H2SO4 solution, his oil sinks, how come? Is it becuase the meoh is trapped inside the oil and is not a part of the ACID Solution?
Cheeseboy- a whiteboy with soul, like a black guy without soul
May De Source Bee Wit Chu...Always

[deludium]

I would think the MeOH would stick in the water, since there isn't alot added according to Chromic's writeup. Still, even with methanol added, I've never seen the epoxide on the top layer. The epoxide is denser than the sulfuric solution, as is the ketone.

[cheeseboy]

Well terbium stated above that 15% sulphuric solution has a density of 1.102 and safrole has a density of 1.096. So safrole would float on the acidic solution. But what cheese was trying to say before is, his eye was not on mark when adding the 96% Sulphuric acid to the dH2O. Cheese will make up the EXACT 15% solution next time and see what happens (Without methanol!!!!)Thanks again. Cheese has a feeling that ketone was made. All the color changes occurred to the book(dark yellow epoxide, dark brown reddish krude ketone) and the smell is definatley of ketone, but still can't get a strong enough vacuum to distill out the MDP-2-P at 180°C. Would these color changes occur if the Isosafrole used happened to be safrole due to a failed Isomerization? How about if the Oxone was bunk Oxone? These color changes are related to the 2-alkene epoxidation only right?What cheese wants to know is if the color changes would happen with 1-alkene too, psychoketty was saying she had a failed run due to failed isomerization but the safrole was fully recovered, was the safrole dark brown after the H2SO4 treatment?   Curiousness killed cheeseboy. Cheese tried aminating his first failed ketone run and nada (duh). But that ketone was greenish yellow, not dark brown (krude ketone) and was obviously Glycol.What a waste of cyano/aa. Cheese doesn't want to wreck the ketone with too much heat, all the water is out of the ketone and no solvents are in there either so a sodium metabisulphite addition will hopefully precipitate the ketone out, as a crystal or an oily mass.Cheese just knows there's ketone in there, because there is the same creamy smell as the MDP-2-P compton had which cheese aminated successfully. It's like a subtle safrolly type smell, much more pleasant, creamy is the only way to describe it in cheese's palate of words. MaDMAx says that bisulphite does indeed work and Strike said it works fabulously, but Strike's ideas haven't all been peachey keen.
Cheeseboy- a whiteboy with soul, like a black guy without soul
May De Source Bee Wit Chu...Always

[Rhodium]

One would think that cooking skills are related to chemistry skills but that is definitely not the case. I have in vain tried to learn a master cook to do chemistry, but it was impossible. He had too much of the "a little bit of this and a little bit of that" mentality - and the converse is also true, I truly suck in the kitchen (ask Fractal) as there is too many variables to keep track of when making food, there is no such thing as standardized equipment, the reaction times when cooking are never consistent, and ACS grade beef is never available.

[Chromic]

Rhodium, seriously? I personally think the two skills go hand-in-hand and it's just a matter of when to apply each mentality.

I remember seeing undergrads using a graduated cylinder to measure out 100.0ml of solvent for their reaction. Sure it says 100ml, but it's a solvent, anything +/- 5% for a solvent is perfectly fine. That's the mentality of a cook making a chemist more efficient.

But then there's times for careful procedure with cooking. I've seen under-experienced cooks in the kitchen throwing on what they think is approximately 1 tsp of cayenne pepper, and it turns out a disaster! In that situation, you make sure to measure with a fair degree of accuracy. That's when the precision of a chemist makes the cook better.

[humidbeing]

That was funny as hell, rhodium!
nipples and buttocks and crotches with wings these are a few
of my favorite things

[cheeseboy]

Ya Big R it sucks when you add too much Sodium Chloride to your porage in the morning, a quick reflux only evapourates more water to make the oate even saltier, the only solution is to add more reagent (Oats). Cheese isn't a master chef but can find his way around a kitchen OK. A Gourmet chef's job is nowhere as interesting as Dr. Shulgin's job....good 'ol Sasha eh!!@%&*#$@
Cheeseboy- a whiteboy with soul, like a black guy without soul
May De Source Bee Wit Chu...Always

[wacko_reaco]

anyone got any physical data on the diol-color, bp, smell etc?
wacka wacka wacka

[Rhodium]

I know there is data about this in the search engine.

[Vibrating_Lights]

Diol is yellow and smells like floral  candy only slight hint of base. if vac distilled it will freeze.  when vac distilled it is a clear light yellow with green tints. Don't have bp data thermo was broke.  thermo was broke and observations were taken from vac distillation of an unbuffered oxone run ph 2-3 after 2.5hrs.
VL_

[cheeseboy]

The Diol's BP is higher than the ketone's BP. Isn't that what psychokitty said?
Cheeseboy- a whiteboy with soul, like a black guy without soul
May De Source Bee Wit Chu...Always

[Rhodium]

Definitely - according to Os, at a vacuum where MDP2P distills at about 85°C, the isosafrole glycol distills at 100°C.

[cheeseboy]

Now that's a killer pull for a vacuum, must be one of those refridgerator vacuum pumps eh?!
Cheeseboy- a whiteboy with soul, like a black guy without soul
May De Source Bee Wit Chu...Always

[Chromic]

Fridge pumps pull a really shitty vacuum my my experience...

[El_Zorro]

I'd like some clarification.  For the diol and the glycol to be hydrolized to the ketone, a strong acid is needed.  Not specifically sulfuric acid, just a strong acid.  Alright, here we go.  The glycolization step, (using performic acid) according to LaBTop, if nearly quantitative.  The only losses in the conversion of isosafrole to ketone is in the hydrolization step, right?  Now, I read in an earlier post(fuck!  I can't find it with TFSE!  I'm using the exact same search words I used before,(eugenol, cleave, methoxy) but now I don't even get 1 match!  Were some posts deleted?), that safrole and it's derivatives are energetically polymerized by sulfuric acid.  Is this the reason behind the yeild losses?  Is there another acid that could be used that didn't polymerize the diol or glycol?  I don't think formic would work, it would only convert it to the glycol.  So what, HCl?  Nitric even?  Any ideas?
I sell crack for the CIA

[cheeseboy]

Hey EZ, cheese was reading up in TS II about other acids being used to salt out. Not sure , but maybe Oxalic acid would be a contendor, just a guess though. Cheese can't wait to actually figure out why all this is... Ya, so hydrolyzing with Oxalic acid yields the monoxalic salt . Cool eh? BTW performic acid isn't easily purchased if at all right? Performic is made by adding Peroxide (H2O2) with formic acid.Per-Formic acid, in other words, a peracid.HCl is used most often due to the fact that it's the most common of acids. Cheese thinks that H2SO4 is the shit for salting. No water, just goods, BigR?
Cheeseboy- a whiteboy with soul, like a black guy without soul
May De Source Bee Wit Chu...Always

[Chromic]

It is possible to use p-tosic acid aka p-toluenesulfonic acid aka tosic acid aka 4-methylbenzenesulfonic acid to hydrolyze the epoxide/glycol/glycol ester (ie whatever comes out of the peracid technique).

Read Scooby_Doo's ref,

Post 264135

(Scooby_Doo: "Ref on Isosafrole to diol via electro", Novel Discourse), conversion from the epoxide was done in ~85% yield.

The problem with making this an OTC method is that p-tosic acid made from toluene and 90% sulfuric acid is hard to get sufficiently dry so you can use it in a solvent like toluene (or heaven forbid, benzene) which is very intolerant of water. Blobs of wet p-TsOH will just float around if it's not dry enough.

[El_Zorro]

Hey cheese, I wasn't talking about salting out, at least I don't think so.  I was talking about the hydrolysis of the diol or glycol to MDP2P.  If you used Oxone, then you would end up with the epoxide.  But I was talking about if you used performic acid(made from formic and H₂)₂) to oxidize the iso, then you would eventually end up with the monoformyl glycol.  I was thinking that using LiI would give better yields, but you could only use with on the Oxone procedure, because it wouldn't convert the glycol to MDP2P, just the epoxide.  Does anyone know of anybody using HCl as in the hydrolysis step?

I guess I'm just chasing a quantitative safrole->MDP2P synth.
I sell crack for the CIA

[cheeseboy]

So Solly! Can't believe it was misinterperated. Cheese wouldn't know the answer to that 'yet'. But H2SO4 is used for a reason. It's usually very high in concentration [%95+], where as HCl doesn't get higher than 38% without vaporizing right? The oxone route is amazing you know. If you don't mind losing a few mls of product, the whole procedure from Isosafrole ---> crude MDP-2-P can be done without the use of any non-polars to digest them. Just collect the oil in sep funnel after each step, however you will be losing some of the oil floating around in the aqueous portion, just let the layers seperate really well. Oxone is the shit. OTC, cheap, close to odorless, strong oxidizer, rxn done w/o extra heating or pressure. Cheers, and thanks for all the replies on this one, it was a blast.
Cheeseboy- a whiteboy with soul, like a black guy without soul
May De Source Bee Wit Chu...Always