PoohBear4Ever (Junior Service Representative)
10-04-01 02:06
No 220030
      Possible Peracetic Revision  Bookmark   

Already been asked, but I feel this topic could use a thread to itself:

MW: H2O2(34g); C2H4O2(60g); isostuffrole(162.12g).

1mol H202 + 1mol C2H4O2 ---H2SO4---> 1mol C2H4O3 + 1mol H20

So, if using 30% solution of H2O2 (1.11g H2O2/2.6g H20), we would need 110ml (30ml H2O2/80ml H2O). 

Now we have: 110ml H2O(30%) + 60g C2H4O2 ---> 76g C2H4O3.

The second oxidation goes:

1mol C2H4O3 + 1mol isostuffrole ---> 1mol stuffone.

So, the lesson learned here, only applicable if we lived in a perferct world, would be that for every 162g isostuffrole, you should use 110ml H2O2(30%) with 60g GAA, which is ~ 60ml. For every 100g stuffrole, we would need 68ml H2O2 with 37ml GAA.

It seems 1% catalyst suggested, but is this percent by weight or volume? Would assume weight, so it would be 1.2g per 114g GAA+H2O2, or 0.7 ml, correct? 

Here's the experimental (GAA/H2O2 + 0.33%; H2SO4 + 100%):

180ml H2O2 (30%) added slowly (~15min) to 100ml GAA, with 3ml H2SO4.  After stirring for 16hr, solution was slowly neutralized with 10g sodium bicarbonate. Next, 200g isostuffrone in 350ml DCM was slowly added to flask, and allowed to stir for 16hr. 

Semtexium, if we choose to use acetone instead of DCM, what do you think of the GAA/H2O2 ratios?  goiterjoe stated to me in a PM that Rhodium seems to have used Ritter's performic ratio in chems.  He also stated that Ritter seems to look more for a resulting product than for a perfect equation when synthing. 

When adding sodium bicarbonate, would it be best to add excess, making the solution basic, or just enough to neutralize?

A perfect ratio suggestion would gladly be tested by SWIP personally, and the results reported.  Perhaps not enough H2O2 was used in the past, resulting in not enough peracetic acid being formed in the first place.

Watcha think?

PB


*Also, could someone tell me what size stir bar is used for a 1L RBF when distilling/isomerizing?
 
 
 
 
    Chromic
(Hive Addict)
10-04-01 06:03
No 220108
      Re: Possible Peracetic Revision  Bookmark   

I can't find a reference to a successful HOOAc rxn using so little GAA. And, is anyone sure that H2SO4 is actually needed? Btw, seach Organic Synthesis on how much NaHCO3 to use. Your ideas look promising, report back how it goes. Btw, a 1.5" stir bar should suffice.
 
 
 
 
    PoohBear4Ever
(Junior Service Representative)
10-04-01 06:17
No 220115
      Re: Possible Peracetic Revision  Bookmark   

Already got that (NaCHO3) figured out the hard <yawn> way:

  NaC2H3O2= 72g/mol 
  NaHCO3=   82g/mol 
  H2SO4=    98g/ml   SD=1.8

Soooo,  if using 5 ml sulfuric (93-95%), you would have 9g, or ~ 0.091 mol. Multiply this by 2 and get 0.182, which is what you want of the NaHCO3 or NaH3C2O2. This amount to 15g baking soda, which is 15% more of the 13g of sodium acetate necessary to aceive this. 


Well, guess it could likely be why manufacturers decide to sell their peracetic acid solutions with acetic acid (H2O2 as well).  I'll just use the maximum amount my rxn vessel allows to ensure proper oxidation, but what about the H2O2 amount?  This would be if we wanted to convert all the acectic acid, but do we really want to...

PB

*Yes, sulfuric is needed as a catalyst, and I've seen several other sources that say so.
 
 
 
 
    Chromic
(Hive Addict)
10-04-01 06:30
No 220121
      Re: Possible Peracetic Revision  Bookmark   

H2O2 + HOAc <==> HOOAc + H2O.

It's an equilibrium reaction. I'd use 2mol of HOAc, 1mol H2O2, 1wt% H2SO4 to get your 1mol HOOAc. Looks like sulfuric acid is pretty common catalyst in preparing HOOAc. (just checked)
 
 
 
 
    PoohBear4Ever
(Junior Service Representative)
10-04-01 06:50
No 220130
      Re: Possible Peracetic Revision  Bookmark   

When we add the catalyst into the equilibrium, how much would it shift it to the right? Using you molar suggestion would just about make it a 1:1 ratio.

Checking around, it seems 40% peracetic solution is most common, so I'll assume this is what we want for out oxidation.  Using the above ratio, this is ust about what we would expect.


New Experimental:  Use goiterjoe's ratios, cuz doing the above comes out to just about that. He would have 2:1 ratio for peracetic, and enough acetic left over, and water created, to make a 40% solution.

Sorry for the waste of time,

PB
 
 
 
 
    Chromic
(Hive Addict)
10-04-01 07:01
No 220136
      Re: Possible Peracetic Revision  Bookmark   

Ok, I've got a better answer:

Shulgin says 34g 30% H2O2 (10.2g H2O2), 32.4g iso. Buffered performic uses 550ml DCM/230g iso (although Semtex uses 500ml acetone/325g iso). So I'd have to recommend that you use:

32.4g iso (0.2mol) in 50-80ml dcm

34g 30% H2O2 (0.3mol)
36g HOAc (0.6mol)
0.5g H2SO4 (1wt% of the mass of H2O2+HOAc)

I can't help you with buffering as this is definitely uncharted realms and it would likely introduce too many variables. You're already using 1/5 the amount of GAA that Semtex used, and substituting DCM for acetone. I know both of these things are minor variables, but I'd try this first and report back.

I'm tempted to avoid GJ's asarone writeup as he never checked his product with bisulfite or aminated.
 
 
 
 
    Chromic
(Hive Addict)
10-04-01 07:06
No 220140
      Re: Possible Peracetic Revision  Bookmark   

This definitely isn't a waste of time, please give a good writeup. smile
 
 
 
 
    PoohBear4Ever
(Junior Service Representative)
10-04-01 07:10
No 220141
      Re: Possible Peracetic Revision  Bookmark   

Cool, thanks.  I'll be using acetone instead of DCM (forgot to change in post), cuz Semtexium stated that the ketone didn't act right in the freezer (getting thick when it should stay free-flowing liquid). 

PB

BTW, the ratios you gave will create a 40.05% peracetic acid solution.  These are the numbers:

340g iso
375ml acetone

300ml H2O2
280ml GAA
3ml H2SO4 (1.9%)

Would slim it down some more, but SWIP thinks this is a good place to start. Hope it all goes well, and fits in a 2L flask.
 
 
 
 
    PoohBear4Ever
(Junior Service Representative)
10-04-01 07:41
No 220146
      Re: Possible Peracetic Revision  Bookmark   

How about the buffering?  What side rxns could possibly take place?  Could the peracetic react instead of only the sulfuric?  Would the sulfuric damage the isosafrole if left in?  Does a basic solution give higher yields than an acetic one?

PB

* Is a 40% peracetic solution too high?
 
 
 
 
    Semtexium
(Hive Elder)
10-04-01 08:04
No 220152
      Re: Possible Peracetic Revision  Bookmark   

Please keep in mind that the peracetic with acetone is likely to produce acetone peroxide which is a sensitive primary explosive!!!  SWIM's never had any problems with anything blowing up, but has noticed in the past some xtals forming in the ketone distillate and in the condenser which could have been acetone peroxide.  I think ethyl acetate has been mentioned as a possible substitute, SWIM doesn't have any at the moment so has been unable to try it out...

This warning WAS in the writeup on Rhod's page which has been changed/removed with the peracid review...

crazylaughsmiletonguewink    Mean People Suck    winktonguesmilelaughcrazy
 
 
 
 
    PoohBear4Ever
(Junior Service Representative)
10-04-01 08:10
No 220155
      Re: Possible Peracetic Revision  Bookmark   

Shit, damn it, fuck!

Back to the proverbial drawing board.  What's the chance of all the H2O2 not reacting with the GAA, and could one simply use dilute acetic acid solution for addition?  What about MeOH, like in the animation? 

PB


* Semtexium:  Being as knowledgable as you are on the subject, what tips have you to offer for someone attempting this synth? Any would help.
 
 
 
 
    Chromic
(Hive Addict)
10-04-01 08:52
No 220162
      Re: Possible Peracetic Revision  Bookmark   

I'd use DCM as all of the refs that I've read use. Btw, dilute H2SO4 won't hurt iso. You'll flood and extract with DCM anyways...
 
 
 
 
    foxy2
(Distinctive Doe)
10-04-01 12:51
No 220195
      Re: Possible Peracetic Revision  Bookmark   

I would try useing that acetone peroxide aka(dimethyldiroxane) to form the epoxide.  The literature says quantatative yeild if i remember correct.



Do Your Part To Win The War
 
 
 
 
    Rhodium
(Chief Bee)
10-04-01 13:01
No 220198
      Re: Possible Peracetic Revision  Bookmark   

Poohbear: A catalyst does not shift a reaction equilibrium, it just makes a mixture REACH equilibrium faster. I believe the HOAc + H2O2 => peracetic reaction is far to the right.

Foxy2: The explosive acetone peroxide is a cyclic trimer of dimethyldioxirane, and it detonates/deflagrates when scratching a few crystals under your shoe against a cement floor.
 
 
 
 
    Semtexium
(Hive Elder)
10-04-01 18:21
No 220268
      Re: Possible Peracetic Revision  Bookmark   

DO NOT use the Goiterjoe writeup, I have confirmation that what comes out of it is NOT ketone, it does NOT aminate, it's looking very similar to a run that was once tried, a modified buffered peracetic.  It gels up in the freezer, but comes over at the same temp as ketone would...  Back to the drawing board... frown

crazylaughsmiletonguewink    Mean People Suck    winktonguesmilelaughcrazy
 
 
 
 
    Semtexium
(Hive Elder)
10-04-01 18:33
No 220271
      Re: Possible Peracetic Revision  Bookmark   

Hey Rhod, didn't you mention in the past that you thought the rxn could proceed without acetone, as the GAA would possibly act as solvent enough...?

crazylaughsmiletonguewink    Mean People Suck    winktonguesmilelaughcrazy
 
 
 
 
    Rhodium
(Chief Bee)
10-04-01 19:05
No 220281
      Re: Possible Peracetic Revision  Bookmark   

Yes I did, the acetone is probably not necessary.
 
 
 
 
    Chromic
(Hive Addict)
10-04-01 19:10
No 220283
      Re: Possible Peracetic Revision  Bookmark   

Foxy, DMDO cannot be formed in situ.

Semtex, a buffered peracetic will work, just no one has done it. There's no risk of acetone peroxide, if anything DMDO would form, but the isosafrole epoxide/glycol is much more energetically favored.

Rhodium is right on the money as usual.
 
 
 
 
    Semtexium
(Hive Elder)
10-04-01 21:36
No 220324
      Re: Possible Peracetic Revision  Bookmark   

Rest assured that if I didn't think the modified peracetic would work I certainly wouldn't be getting SWIM to keep on trying.  Fact of the matter is that I have no doubt it can be made to work, as I have no doubt that the MDP2Pol route can be made to work given enough trial and error.  What I was pointing out was that the writeup given by Goiterjoe does NOT yeild ketone, that's all...tongue

crazylaughsmiletonguewink    Mean People Suck    winktonguesmilelaughcrazy
 
 
 
 
    PoohBear4Ever
(Junior Service Representative)
10-04-01 21:44
No 220329
      Re: Possible Peracetic Revision  Bookmark   

Because this bee would prefer not to leave himself open to possible detonation on his first dream of this type, could one of you more knowledgable bees suggest some numbers for this larva to use in his dream?  The only limit would bee his 2L flask, and he would prefer to have maximum ketone potential to be a factor.  After acheiving his isostuffrole, he will test acetic acid's suitability as a solvent, though having a backup idea would really be helpful. 

How many moles of peracetic acid would one desire to oxidize one mole of isostuffrole? 

Thanks,

PB

* Also, if peracetic acid is more more basic than performic, is there really any advantage if buffered, or is the sulfuric acid the reason why it would be favored to do so?
 
 
 
 
    Semtexium
(Hive Elder)
10-04-01 23:35
No 220373
      Re: Possible Peracetic Revision  Bookmark   

This is straight out of the peracid review that's on Rhod's site.  Simply omit the acetone, i.e. don't use any...  AFTER you successfully complete as written(minus the acetone)THEN modify it... wink

Peracetic acid Oxidation [5]
I became interested in the substitution of peracetic acid for performic acid for the oxidation of isosafrole to MDP2P because acetic acid is much more readily available than formic acid, and should be able to do the job just as good. It was inspired by a discussion in the Usenet newsgroup alt.drugs.chemistry in 1996 [6]. Improvements to the procedure outlined there was made by me, and it was tried out by Semtexium (aka Semtex Enigma), and the results follow here. An added improvement would be to neutralize the sulfuric acid used to catalyze the formation of the peracetic acid with 25 grams of sodium acetate before adding the isosafrole. Performic acid forms very easily just by mixing formic acid with hydrogen peroxide, but with acetic acid, it requires a strong acid catalyst and 12-16 hours standing[7].

Chemicals:

Peracid:
1500ml of Glacial Acetic Acid
325ml of 30% H2O2
5ml of H2SO4
Olefin:
500ml Acetone
325g of Isosafrole
Solvents:
7500ml of Water
1500ml of DCM
500ml of MeOH
H2SO4 (15%):
368g (200ml) of concentrated H2SO4
2300ml of Water
Wash(s):
1250ml of Water
1250ml of NaOH 5% solution
Drying:
50g of Anhydrous MgSO4
Distillation:
100ml of Cooking oil to prevent scorching
Procedure:

Mix the peracetic acid chemicals together in an appropriate sized flask (3L), swirl or stir solution until thouroughly mixed and let stand for 12 hours.
Combine the olefin chemicals and place into the freezer to chill.
Bring the peracid solution down to 5C with the help of an ice/salt/water bath. While magnetically stirring this solution sitting in the ice bath, add the now chilled olefin solution to the peracid solution at such a rate that the mixture stays below 40C. After all of the olefin has been added, let the solution stir for 16 hours, letting the ice bath melt away and the solution come to room temperature on it's own.
After the 16 hours of stirring has elapsed, pour the solution into 7500ml cold water, mix thouroughly, and extract this mixture with 3x500ml DCM. The extractions are combined and the solvent removed via distillation to yeild a thick, dark red syrup.
This syrup is taken up in 500ml methanol and added to the 2500ml 15% H2SO4 solution and lightly refluxed for two hours, after which time the flask is cooled under running water and/or the use of an ice bath, do not proceed until solution has reached room temperature or lower.
Using a large sepratory funnel or by simply pouring off the acid layer collect the dark bottom layer BEFORE extracting this mixture with 3x400ml DCM (you did reuse the DCM from the first extraction, didn't you?). Combine the extracts with the dark layer which was first collected and proceed.
Wash this dark mixture of ketone/solvent with 1250ml of water, then with the 1250ml of the 5% NaOH solution which was made previously. Please note that the separation with the second wash will be difficult to see, therefore the use of a flashlight is favorable to determine the different layers.
Dry organic phase over 50g of anhydrous MgSO4 (made by baking epsom salts at 300C for a couple of hours, let cool, then grinding into a powder) making sure to filter off the MgSO4, and washing the filter cake with a small amount of DCM. The solvent is removed and kept for a later run, the resulting residue is combined with 100ml of vegetable cooking oil and distilled under vacuum to yield ketone (>200 grams) [That is a 56%+ yield].


crazylaughsmiletonguewink    Mean People Suck    winktonguesmilelaughcrazy
 
 
 
 
    PoohBear4Ever
(Junior Service Representative)
10-04-01 23:50
No 220380
      Re: Possible Peracetic Revision  Bookmark   

Thanks for the ref, and SWIP has reviewed said procedure prior to posting.  Going back to moles, it appears that the amount of H2O2 would produce 3mol peracetic acid for 2mol isostuffrole, leaving 1300ml GAA unreacted.  Is this for proper solvation of the isostufrole, for it would be a more dilute concentraion if, say, we used 800ml GAA.  Would higher concentraion peracetic give higher stuffrone yields,  or would that concentraion be too unstable? 


PB 
 
 
 
 
    Rhodium
(Chief Bee)
10-05-01 00:10
No 220388
      Re: Possible Peracetic Revision  Bookmark   

The rest is for the solvation of the isosafrole and the formed glycol. For stability reasons, never make a peracetic acid solution stronger than around 30%. Below that, the amount of GAA can be changed at will, I believe, and only experimentation can tell how low you can go with the amount of solvent and still obtain the same yield.

I really encourage people to diddle with this, as the peracetic oxidation isn't at all perfected yet, as it is relatively new.
 
 
 
 
    PoohBear4Ever
(Junior Service Representative)
10-05-01 01:07
No 220420
      Re: Possible Peracetic Revision  Bookmark   

Thanks for the info.

If SWIP used 4mol H202, in 30% solution with 320g H2O,  with 15mol GAA, he would end up with a 28.8% solution of peracetic acid.  Would the remaining 11mol GAA (650ml) be suitable to dissolve 200g isostuffrole, if no addition solvent with iso is used?  Would be 2mol less than the writeup above using same amount, though there would exsist 1.3mol more peracetic acid. 

Thanks if you can answer any of the above,

PB  
 
 
 
 
    Rhodium
(Chief Bee)
10-05-01 01:42
No 220435
      Re: Possible Peracetic Revision  Bookmark   

I belive that would work. However, with less solvent volume, the temperature must be CLOSELY monitored, as there is not much excess solvent to absorb the generated heat. Preferably, you should cool the reaction with an ice-bath, and make sure the reaction temperature NEVER exceeds 40C. Otherwise a runaway reaction may occur, or the high temp lowering yields. Don't forget to report back on this experiment.
 
 
 
 
    foxy2
(Distinctive Doe)
10-05-01 01:43
No 220436
      Re: Possible Peracetic Revision  Bookmark   

What DMDO cannot be formed in situ???

EPOXIDATION PROCESS WITH A PARTIALLY NEUTRALISED CARO'S ACID SOLUTION
This invention concerns a process for the epoxidation of alkenes.

Alkenes represent convenient starting materials in the synthesis of organic chemicals because they are often readily available in good purity and at relatively low cost. Much of their utility arises from the presence of a relatively reactive functional group - the carbon - carbon double bond - within the molecule. Additional or alternative functional groups can conveniently be added to the aikene by reaction at this site.

One common way of introducing functionality is to employ an epoxidation of the double bond(s). Many reagents and processes have been proposed for carrying out such epoxidations. In recent years, one particular class of reagent that has attracted much interest comprises dioxiranes on account of their relatively high reactivity. Dioxiranes can conveniently be formed by contacting a suitable oxidant with a ketone, and two distinct methods of employing them as reagents can be identified. The first is to preform a solution of dioxirane, usually as a solution in the corresponding ketone. This solution can then be stored until it is desired to employ it in a reaction. Such processes are less favoured because dioxiranes are generally not very stable, and readily decompose on storage, even at low temperatures.

Unless the dioxirane solution is used relatively quickly, the solutions can therefore suffer from significant loss in activity.

A more convenient method is to employ dioxiranes generated in situ in the reaction medium. This avoids the need for low temperature storage units for dioxirane solutions and allows the use of more stable oxidants which can be more readily stored.

 
 
 
 
    foxy2
(Distinctive Doe)
10-05-01 03:45
No 220473
      Re: Possible Peracetic Revision  Bookmark   

Dioxirane mediated steroidal alkene epoxidations and oxygen insertion into carbon-hydrogen bonds
Tetrahedron Letters
Volume 32, Issue 4
21 January 1991
Pages 533-536

Dioxirane generated in situ from reaction of ketone with KHS05 at O-5C in aqueous phosphate buffer/methylene chloride containing Bu4NHS04 - pH maintained at 7.5 by pH stat controlled addition of 5M KOH.




Do Your Part To Win The War
 
 
 
 
    Chromic
(Hive Addict)
10-05-01 10:30
No 220604
      Re: Possible Peracetic Revision  Bookmark   

I stand corrected. All of the refs I've read up to this point have always isolated it. Good news.
 
 
 
 
    PoohBear4Ever
(Junior Service Representative)
10-07-01 14:43
No 221226
      Re: Possible Peracetic Revision  Bookmark   

Noticed that Shulgin uses 40% peracetic acid (in acetic acid) extensively in his synthesis (epoxidations?), and I wonder at the fesibility of creating this concentration without decomposition if GAA and H2O2 are allowed to mix in a fridge, at say 10C. This percent seems LG standard, no? 

PB

* BTW, is technical grade celite sufficent for filtering, or must it be analytical?
 
 
 
 
    Rhodium
(Chief Bee)
10-07-01 16:32
No 221243
      Re: Possible Peracetic Revision  Bookmark   

That 40% peracetic acid is made by adding strong (over 50%) H2O2 to acetic anhydride, which makes it not only strong, but also anhydrous. Some stabilizing agents are probably also added to the commercial product.

Shulgin uses it primarily in the bayer-villiger oxidation of aromatic aldehydes to phenols.
 
 
 
 
    PoohBear4Ever
(Junior Service Representative)
10-08-01 03:14
No 221429
      Re: Possible Peracetic Revision  Bookmark   

Could one dissolve isosafrole in peracetic acid prior to addition in flask, or would the two react in the addition funnel, and produce too much heat?  How viscous is isosafrole?

PB
 
 
 
 
    Rhodium
(Chief Bee)
10-08-01 03:52
No 221447
      Re: Possible Peracetic Revision  Bookmark   

No, they would react in the addition funnel. The viscosity is lower than olive oil.
 
 
 
 
    PoohBear4Ever
(Junior Service Representative)
10-08-01 04:35
No 221464
      Re: Possible Peracetic Revision  Bookmark   

Alrighty, well besides DCM and acetone, SWIP can't think of any other NP solvents suitable, and will proceed without.  Here's the experiment:

325g Isostuffrole (~2mol)
1150ml GAA (~19mol)
450ml H2O2 (30%) (~4mol)
9ml H2SO4 (~ 1% )

Should get a 20% peracetic acid solution, which is 2x mol necessity.  In the review, the concentration was 12%, so this is 8% stronger.

PB

  
 
 
 
 
    Chromic
(Hive Addict)
10-08-01 18:20
No 221684
      Re: Possible Peracetic Revision  Bookmark   

Rhodium, have you ever handled isosafrole? It's a heavy colorless white liquid that has a viscosity like water. It doesn't evaporate easily (unlike water) and hence, doesn't "cool down the hands". It has most of the properties of GBL in those respects, however it has a distinctive smell that is unlike safrole but quite similar.

PB, I would cut back on the H2O2 to what is recommended. I would try and scale back the amount of acetic acid that Semtex used because it's just more solvent that will have to be extracted and is present in a very, very healthy excess. I'd still go with:

325g iso (2mol) in 500ml dcm
340g 30% H2O2 (3mol)
360-720g HOAc (6-12mol)
5g H2SO4 (1wt% of the mass of H2O2+HOAc)

The DCM should have in theory kept the temperature around 30-40C, however I found that mixture didn't boil until it got considerably hotter than 40C.
 
 
 
 
    PoohBear4Ever
(Junior Service Representative)
10-08-01 20:01
No 221720
      Re: Possible Peracetic Revision  Bookmark   

Ok, thanks for the tips an suggestions.  Just last night, I came across the the thread in which your dreams were discussed (Chromic).  I noticed that only a few bees (3 maybee) used DCM in peracetic, goiterjoe being one. He didn't get his desired ketone; however, he also used sodium acetate to buffer, which could also have been a factor.  It seems that DCM has been used successfully in performics, so it shouldn't really be any different in the peracetic, right?

The only problem I saw in cutting back the HOAc would be going over the 30% concentration rule. Will try to get my original 20% solution still, and will likely scale back the H2O2 to your suggested ratio. When mixing the peracid, would it be best to slightly cool in fridge while mixing for 12hr to advoid decomposition, or have most used room temp when doing so?  Should one use stirring during this time frame, or just upon addition of chemicals?

Also, it seems in the above post I was figuring the catalyst without compensating for the water in the H2O2.

Thanks for the help,

PB
 
 
 
 
    Rhodium
(Chief Bee)
10-08-01 20:41
No 221736
      Re: Possible Peracetic Revision  Bookmark   

Chromic, that GBL similarity is a good example. It is also less viscous than olive oil, but more so than water.
 
 
 
 
    PoohBear4Ever
(Junior Service Representative)
01-06-02 04:16
No 253066
      Re: Possible Peracetic Revision  Bookmark   

Here's what SWIP is dreaming of dreaming in a few weeks:



A) Distill
Add .5g Hg  to each (8) tincture bottles for 3days min.
1) Use grease on joints, insulate up to column with foil, room temp water through column, give air-leak when heating without vacuum.
2) Add 250ml stuff with to 500ml RBF, 250ml RBF receiving.
3) Slowly bring stuff to 130C to boil off water, with stirring, till no steam is left, then bring up to 234C (BP of stuffrole), and let cool to room temp.
4) Begin vacuum slowly, with heavy/fast magnetic stirring, then slowly bring to ~121C (depends on vacuum; see bottom).
5) Try to get 5-10 drops a minute, and do not go above 160C (try to keep 5 degree range for distillate), do not distill dry.
6) Use safflower oil bath, in aluminium or copper bowl with stir bar in oil bath, along with one in flask, flask not touching bowl.
*About the first 7-10% of the distillate is crap, the next ~85% is stuffrole, and the deep red shit in the boiling flask is more crap.

B) Isomerize
       *Start peracid sometime 12hr prior to being done.

1) Fit flask with reflux condenser with vacuum attached as per distillation.
2) Add 3g KOH in small portions to 200g stuffrole, then bring to reflux under vacuum (130C) with damp-rid in condensor and receiving flask.
3) Reflux for 10-12hr (boiling will be smoother when finished), and then turn off heat, let cool 2hr.
4) Heat stuffrole to BP, then allow flask to cool, and change receiving flask and  wash with acetone.
5) Begin vacuum slowly, and distill isostuffrole at ~ 136C (15C over stuffrole; ~ 240C bath temp).

C) Oxidation
1) Add 650ml AA(90%), 140ml H202 (25%), and 8ml H2SO4(32%), to 3L RBF, stopper flask, and shake thoroughly.
2) Once well mixed, let sit 11hr, then chill 1hr in fridge to 20C min.
3) Add 140g isostuffrole with 220ml acetone, then chill in freezer (~5C).
4) An ice/salt/water bath used to keep flask cool, ~ 5C.
5) Slowly add isostuffrole/acetone solution to flask (~35min), with good stirring, keeping temp below 20C (temp stabilizes after ~1hr).
6) Remove ice bath, let stir for 16hr (keep flask temp 20-30C).
7) Add flask contents to 3.6L water, then separate glycol/epoxide, and extract this with 3x with 210ml DCM (may break down into three portions; if emulsion forms with DCM, use a little salt to break up).
8) Wash with dH2O, strip off DCM and save for step 11, then add syrup to 2L flask with 200ml MeOH, and gently heat to ~ 80C. 
9) Bring 1.1L H2SO4 (15%) to 80C, then quickly dump in this syrup, with hard stirring.
10) Lightly reflux only for 2hr (75C-80C; steaming, but not boiling), then allow flask to cool, then flood with 500ml dH2O, and set in cold water bath for 20min.
11) After at room temp, add to sep funnel and seperate off crude stuffrone (on bottom; D=1.2), and extract acid in funnel with 3x180ml DCM, and combined with other seperation. 
12) Wash once with 500ml dH2O, then once very, very easily shaken with 500ml NaOH (5%) (use black light to determine layers; stuffrone green, on bottom).
13) Strip off DCM, then distill stuffrone at 25C more than isostuffrole temp (135C-150Cmax).

D)  Animation
1) Carefully add 60g aluminium and 1.5L MeOH to 3L RBF, and heat to ~ 55C (made before hand by adding 2x tincture bottles to 500ml dH2O + 500ml MeOH with 60g Al, allow 17-30min to react, until grey precipitate forms, likely to be 30 mins,  decant liquids, wash foil with dH2O, then with MeOH; do not expose to air after, store in 1.5L MeOH).
2) Carefully pour 40ml MeNO2, then 80ml MeOH, then 50g stuffrone to addition funnel, and set into position.
3) Place 500ml condenser with, optional steel wool, into position; run off heat; start drip rate at 3dp/sec carefully, letting stirrer stay on constantly, 2dp/sec set after.
4) Try to come to the peak, back off a sec, and then finish addition before amalgamation is done (~ 30min)(try not to let rxn run-away;  there is little un-dissolved Al when done).
5) After 2hr from initial addition, may need to add more MeOH, then let contents reflux for 3hr, then cool for 30min.
6) Make NaOH (35%) (mix 530g NaOH per 1500ml water or ice), make sure cool, and slowly add to flask with use of addition funnel.
7) Let stir for 1hr, then add 900ml xylene to 4L flask, or split into two batches, then decant xylene, and wash contents of flask once more with 200ml more xylene.  
8) Chill xylene in freezer for 30 min, then decant, leaving garbage in flask.
9) Wash out sep funnel, then add xylene solution, then wash 3x dH2O (1L) or until clear, then 2x with brine (1L), then once more with dH2O.
10)   Add 60g MgSO4 to xylene in container and shake, then let sit 30 mins.
11) Filter out MgSO4, wash filter cake with fresh xylene

Crystallization
1) A/B extract (50ml dH2O + 5-6drops muratic (pH 6), dry until syrup, crash out with ice cold acetone, followed by 2x ice cold acetone washes.
2) (*Optional): Dissolve in minimal amount of hot, anhydrous IPA, let cool to room temp.
 3) Add 2x acetone, then seal and place in freezer for 12hr.
 4) Filter out crystals.



Any last words of advise? Should he buffer peracid with sodium bicarbonate, or could this induce any side-rxns?

PB

<Snow Rulez!>
 
 
 
 
    unnilhexium
(Stranger)
01-06-02 08:11
No 253149
      Re: Possible Peracetic Revision  Bookmark   

Well, old unnilhexium, in a profound state of mind at the time of this writing, is going to take advantage of his mental clarity to post EVERYTHING HE KNOWS ABOUT PERACETIC!!!!  Not to mention how we can make it better.

>SWIM believes that the reason that a buffered peracetic doesn't (to the best of my knowledge) work, is that the buffer salt would neutralize the h2so4.  This might sound like a good thing, but wouldn't that stop the further formation of peracetic acid?  Swim believes so.  SWIM feels that the solution is to A)Use a lot of external cooling instead, or possibly, B)Start dripping in a buffer solution at oh... the 8 hour point(untested).

>Peracetic acid is MUCH more brutal to isosass than we give it credit for.  Where else do the yields go?  SWIM doesn't get an iso forerun.  It seems that destruction of iso is not solely related to ph.  Swim plans on testing the ph of a buffered performic, and trying to use an excess of acetic to bring it closer to the same ph at the finish of the addition, for research purposes, and then go from there.

>The obvious flaw of peracetic is, the slow formation.  SWIM is as we speak experimenting with more h2so4, to hopefully catalyze the peracetic more completely in the 12 hour standing time.  SWIM does not believe it will fuck up yields at all.

>From swims experience, it seems that while 2 hours of 75-80C is hot enough for performic h2so4 rearrangements, SWIM thinks it might be better for cleaving the acetyls with a longer/hotter reaction.  SWIM always ran his a little hot, but one time, exactly 2 hours, carefully monitored at 75-80C temps, yielded some obviously fucked up ketone, which was aminated for shits and giggles, and yielded NOTHING.

>DCM and Acetone.  As far as swim can tell, the reduced reaction/surface area of dcm, does wonders for performic, but probably makes it a little to hard for peracetic to function.  Acetone on the other hand, seems to lead to side reactions in performic, and is overkill on the peracetic as well.  Not to mention the risk of acetone peroxide WHICH SWIM STILL HAS NEVER SEEN!!!!  SWIM still feels acetone is the answer, but thinks that using a very small amount (barely enough to co-solvate the peracetic/iso solutions together) might bring us to a high yielding happy medium.

And please, everyone with knowledge, experience, or ideas, contribute what you know to this thread.  Formic is a hard to get for those lacking the courage to buy it, and I am positive that peracetic has not reached its potential yet.  I think the biggest flaw is that all posted synths try to substitute it for formic, rather than treat it by it's own properties.

106
 
 
 
 
    Rhodium
(Chief Bee)
01-06-02 09:01
No 253158
      Re: Possible Peracetic Revision  Bookmark   

Unnil: You speak about very probable error sources. Especially that the formation of peracetic takes time. However, the acetone peroxide formation is very real, it is just a matter of chance if it crystallizes or not. Using MEK or THF instead of acetone should take care of that problem. Their peroxides are not so easily crystallizable (and hence not as shock sensitive).
 
 
 
 
    unnilhexium
(Stranger)
01-06-02 09:47
No 253169
      Re: Possible Peracetic Revision  Bookmark   

Rhodium:  I don't quite follow what you are saying about "peracetic taking time."  However, I think that MEK would actually work very well, and it is just as easy to get stateside(even though SWIM has thus far perceived a low risk factor from acetone).  I just wanted to ramble off some new ideas, based on the observations of the peracetic oxidations swim has done(quite a few).  Nothing in that post is referenced, or based on anything other than personal(fictitious) observations and experiences.

106
 
 
 
 
    Rhodium
(Chief Bee)
01-06-02 11:50
No 253191
      Re: Possible Peracetic Revision  Bookmark   

After mixing H2O2, Acetic acid and H2SO4, the mixture must be allowed to stand for at least 12h for the peracetic acid to form.

I really think someone should try to substitute MEK for the acetone in both the peracetic and performic reaction and report back if there was any difference in workup/yield using that solvent. It is VERY similar to acetone, but with the difference that it doesn't form a crystalline peroxide easily.
 
 
 
 
    noj
(Hive Bee)
01-06-02 15:32
No 253215
      Re: Possible Peracetic Revision  Bookmark   

On a second attempt at the peracetic following the writeup at Rhodium's site, I ended up with an extremely viscous fluid that looked like the ketone, but had little smell. It was too thick. I had to dilute with methanol to pour it out at room temperature. It also would not aminate. The reaction wasn't buffered and acetone was used as a solvent, albeit less than the writeup purposed. A crystalline substance appeared in the condenser that would only rinse out with acetone. The peracid was allowed to form for 16 hrs before use. I'm not certain what is going wrong.

No One's Jurisdiction
 
 
 
 
    Rhodium
(Chief Bee)
01-06-02 15:57
No 253220
      Re: Possible Peracetic Revision  Bookmark   

Have you performed the H2SO4 hydrolysis of the crude reaction product, done the extraction and distilled the oil?

If so, what color is it, what temp/pressure did it distill at, and what was your yield? How thick is it?
 
 
 
 
    goiterjoe
(Hive Addict)
01-06-02 16:14
No 253224
      Re: Possible Peracetic Revision  Bookmark   

This is the first time I've read this thread, and I think I missed out on a lot of good information.

Semtexium, thanks for confirming my results.  SWIM ended up with an oil that boiled like ketone, but became syrupy in the freezer.  it didn't aminate correctly, instead resulting in a plasticized looking substance that was thrown out. 

Rhodium, wouldn't substituting MEK for acetone still result in MEK peroxide being formed which is also a powerful sensitive explosive?

Sed quis custodiet ipsos custodes?
 
 
 
 
    terbium
(Old P2P Cook)
01-06-02 19:12
No 253248
      Re: Possible Peracetic Revision  Bookmark   

Rhodium, wouldn't substituting MEK for acetone still result in MEK peroxide being formed which is also a powerful sensitive explosive?
From personal experience, the MEK hydroperoxide polymer is a very sensitive explosive. I have not seen it in solid form though. Perhaps Rh's point is just that the MEK peroxide doesn't drop out of solution as easily and is thus more likely to stay diluted in solution where it is less dangerous.
 
 
 
 
    PoohBear4Ever
(Junior Service Representative)
01-06-02 20:37
No 253269
      Re: Possible Peracetic Revision  Bookmark   

Check out this info on acetone peroxide: http://www.xinventions.com/main/pyro/ap.htm

I wonder what the maximum amount of this could likely be produced from the peracetic rxn, and what amount of energy such an amount possesses.  If we are only talking about loosing an arm or a leg, no big deal; however, I am somewhat attached to the rest of my body smile.

PB 
 
 
 
 
    Rhodium
(Chief Bee)
01-06-02 20:54
No 253276
      Re: Possible Peracetic Revision  Bookmark   

Yes, my point is to use MEK instead of acetone because MEK peroxide (while still being as explosive as acetone peroxide) will not crystallize out of the solution, and thus will be much less likely to detonate from impact/friction, as it stays diluted in the organic solvents. 
 
 
 
 
    noj
(Hive Bee)
01-06-02 22:37
No 253316
      Re: Possible Peracetic Revision  Bookmark   

Rhodium, yes. Everything as written on your review of peracids. The post rearrangement product was thick, like motor oil, but looked fluorescent yellow. It came over 25 higher than safrole under vacuum, over a 10 range. My only guess would be the wood bleach peroxide was not pure. Will try it again in a few days with reagent grade chemicals. Will also try buffering.

No One's Jurisdiction
 
 
 
 
    Osmium
(Stoni's sexual toy)
01-07-02 02:34
No 253372
      Re: Possible Peracetic Revision  Bookmark   

> The post rearrangement product was thick, like motor oil,
> but looked fluorescent yellow. It came over 25 higher
> than safrole under vacuum, over a 10 range.

and

> ended up with an oil that boiled like ketone, but became
> syrupy in the freezer.  it didn't aminate correctly,
> instead resulting in a plasticized looking substance

You guys didn't hydolyse/rearrange for long enough, sounds like the glycol to me.
 
 
 
 
    noj
(Hive Bee)
01-07-02 02:56
No 253379
      Re: Possible Peracetic Revision  Bookmark   

So perhaps one should go longer than the 2hrs? A stronger acid solution?

No One's Jurisdiction
 
 
 
 
    PoohBear4Ever
(Junior Service Representative)
01-07-02 03:07
No 253380
      Re: Possible Peracetic Revision  Bookmark   


From swims experience, it seems that while 2 hours of 75-80C is hot enough for performic h2so4 rearrangements, SWIM thinks it might be better for cleaving the acetyls with a longer/hotter reaction.  SWIM always ran his a little hot, but one time, exactly 2 hours, carefully monitored at 75-80C temps, yielded some obviously fucked up ketone, which was aminated for shits and giggles, and yielded NOTHING.




Isn't this what unnil was just talking about?  I wonder what parameters he uses when wishing to aminate for reasons other than "shits and giggles?"


PB

 
 
 
 
    Chromic
(Hive Addict)
01-07-02 04:24
No 253408
      Re: Possible Peracetic Revision  Bookmark   

I made a post on a peracetic acid in DCM... it works wonderfully. It is necessary to give the H2O2/acetic acid nearly a week to come to equilibrium (mind you, it stores very well in a fridge, make up extra...).  Ever mixed GBL/water together? Ever noticed how long it takes to come to equilibrium of GHB/GBL/H2O? (nearly a week...) Anyways, I never had success on the peracetic until I had some vidid dreams of an old man that guided me towards success. Try it, you won't be displeased.
 
 
 
 
    goiterjoe
(Hive Addict)
01-07-02 06:45
No 253447
      Re: Possible Peracetic Revision  Bookmark   

What would be the recommended length of acid reflux hydrolysis then?  It's been a while since swim last did this, but he remembers letting it go for 2 hours.  Would a 2x stronger acid concentration with a 3h reflux be good or excessive?

Sed quis custodiet ipsos custodes?
 
 
 
 
    goiterjoe
(Hive Addict)
01-07-02 07:06
No 253449
      Re: Possible Peracetic Revision  Bookmark   

would the glycol be fairly soluble in methanol or a methanol/nitromethane mix?  And if the plasticized post amination product were still around somewhere, is there a simple test that could be performed on it to see if was indeed the glycol that was used as the starting material?

Sed quis custodiet ipsos custodes?
 
 
 
 
    Osmium
(Stoni's sexual toy)
01-07-02 10:54
No 253500
      Re: Possible Peracetic Revision  Bookmark   

TLC.
 
 
 
 
    unnilhexium
(Stranger)
01-08-02 09:08
No 253929
      Re: Possible Peracetic Revision  Bookmark   

The original Fugasawa/Deguchi performic synth called for a 3 hour rearrangement, but now every synth I see calls for 2 hours.  Whose idea was it to shorten the time?  Was the shorter time shown to yield more ketone(or maybe just more distillate?)?  SWIM believes that the longer time would yield purer ketone, as it seems a lot of the glycol is left over after only 2 hours.

106
 
 
 
 
    Rhodium
(Chief Bee)
01-08-02 10:45
No 253948
      Re: Possible Peracetic Revision  Bookmark   

I don't believe there was anyone in particular who told us to shorten the acid reflux time (except perhaps Ritter in Post 41983 (Ritter: "Re: Modified Performic", Methods Discourse)).
 
 
 
 
    unnilhexium
(Stranger)
01-09-02 03:01
No 254201
      Re: Possible Peracetic Revision  Bookmark   

That damn ritter thinks he knows everythingsmile  LOL ritter, you are my idol.  SWIM just tried lengthening the h2so4 reflux in a peracetic dream, to 2 hours and 20 minutes.  The result: narrower distillation temp range, and a more flourescent color to the ketone.  The subsequent amination dream failed, but SWIM is certain that the failure was due to other factors(problems with amalgamation, and using the MeOH/MeNO2 azeotrope instead of pure MeNO2).  SWIM is going to go for the full 3 hours next time.  In that post, ritter says that methanol is not necessary, so without the use of methanol, the reaction would run considerably hotter, and 2 hours probably would be sufficient for the rearrangement to take place, IMO.   

106
 
 
 
 
    goiterjoe
(Hive Addict)
01-20-02 05:59
No 258547
      Re: Possible Peracetic Revision  Bookmark   

SWIM decided to be ballzy and test out the plasticized crystals, and sure enough they worked they had a delayed taste to them, but then the taste was undeniable, and the effects were definitely undeniable(extreme empalthy, dilated eyes in light, talkative, loss of appetite, etc.).  SWIM guess this could be the beginning of a new era, as he can now say that the peracetic in DCM definitely works.  it's just a question of where the yeilds got so wrong.  as was said earlier, the acid hydrolysis should have been run for at least 3 hours instead of barely 2.

If Pacman had influenced us, we'd run around dark rooms eating pills and listen to repetitive music
 
 
 
 
    foxy2
(Distinctive Doe)
03-04-02 13:43
No 276639
      Peracetic Information
(Rated as: good read)
 Bookmark   

Thought I would add this reference to a similar epoxidation.
Patent EP1140788

The epoxidation of an optionally substituted trans-cinnamic alcohol of formula:

to give an epoxide of formula la can conveniently be carried out using a suitable epoxidizing agent, for example, vanadic anhydride and hydrogen peroxide, vanadium (acetylacetonate) 2 and tert-butyl hydroperoxide, or a peroxy acid such as perbenzoic acid, m-chloroperbenzoic, peracetic acid, pertrifluoroacetic acid or mono-or di-peroxy-phthalic acid. The reaction can be carried out in any suitable solvent or combination of solvents, for example, in a hydrocarbon, a halogenated hydrocarbon, a linear or branched ether, a carboxylic acid, or an ester. Specific solvents include benzene, toluene, chloroform, methylene chloride, diethyl ether, dioxane, acetic acid, and ethyl acetate. Preferably the reaction is carried out in methylene chloride or ethyl acetate. More preferably in methylene chloride. The reaction can be carried out at any suitable temperature from the freezing point to the reflux temperature of the reaction mixture. Preferably the reaction is carried out at a temperature in the range of about 0 C to about 50 C. More preferably at a temperature in the range of about 5 C to about 25 C.

United States patent 5,068,433 and related United States patent 5,391,735 disclose that an epoxide of formula Ib can be prepared from trans-cinnamic alcohol using a suitable oxidizing agent, for instance vanadic anhydride and hydrogen peroxide, or a peroxy acid such as, e. g., perbenzoic acid, m-chloroperbenzoic, peracetic, mono-or di-peroxyphthalic, or peroxy-trifluoroacetic acid. At Example 1, these patents specifically exemplify the preparation of an epoxide of formula Ib by the oxidation of trans-cinnamic alcohol with m-chloroperbenzoic acid. The oxidation of trans-cinnamic alcohol with m-chloroperbenzoic acid was also reported by P. Melloni et al. Tetrahedron, 1985,41, no. 7,1393-1399.
m-Chloroperbenzoic acid is expensive to use on a commercial scale. Thus, a different epoxidation reagent would be preferred for the commercial scale production of a compound of formula (A). Studies with mono-peroxy-phthalic acid have shown that this reagent can be used to prepare epoxide Ib on a commercial scale. However, the preparation of mono-peroxy-phthalic acid from phthalic anhydride and hydrogen peroxide is time consuming. Additionally, the epoxidation reaction with mono-peroxy-phthalic acid generates a large amount of solid phthalic acid by-product that must be filtered from the product mixture. This filtration step is time consuming and generates a large amount of aqueous and solid wastes. Thus, m-chloroperbenzoic acid and mono-peroxy-phthalic acid are not ideally suited for the commercial scale epoxidation of trans-cinnamic alcohol.

It has been discovered that the epoxidation of cinnamyl alcohol can conveniently be carried out on a commercially scale using peracetic acid. Peracetic acid is less expensive and, as a liquid, is easier to handle on a large scale than m-chloroperbenzoic acid, which is a solid. Additionally, the use of peracetic acid reduces the time required for preparing epoxide Ib, by eliminating the need to prepare mono-peroxy-phthalic acid; peracetic acid also substantially reduces the amount of aqueous and solid waste generated by the epoxidation reaction compared to the reaction with mono-peroxy-phthalic acid.

Accordingly, the invention provides a method for preparing an epoxide of formulala:

comprising oxidizing a corresponding optionally substituted trans-cinnamic alcohol with peracetic acid. The epoxide la is highly sensitive to decomposition by strong acids.

Commercial peracetic acid is stabalized with sulfuric acid. Accordingly, the peracetic acid should be treated with a suitable base (e. g. sodium or potassiun acetate) prior to use; or the reaction can conveniently be run in the presence of a suitable solid base (e. g. sodium or potassium carbonate). Preferably, the reaction is carried out on a commercial scale.

Preferably, the reaction is carried out in methylene chloride and at a temperature below about 30 C.


Example 1. (2RS, 3RS)-2,3-Epoxy-3-phenylpropanol (I).

Sodium carbonate (224 g) and trans-cinnamyl alcohol (200.0 g) were mixed with 2L of methylene chloride. a slow nitrogen sweep was maintained through the vapor space of the flask and the mixture was cooled to 15-20 C with a cold water bath. Peracetic acid solution (35%, 381.2mL) was added over a 3 hour period, maintaining the internal temperature below 25 C. After the peracetic acid addition was complete, the mixture was stirred for 2-3 hours until complete, as shown by HPLC analysis. The mixture was cooled to 10 C with an ice bath, and a solution of sodium sulfite (160g) in 1200 ml water was added slowly over 90 minutes, keeping the temperature below 30 C. The phases were separated and the aqueous phase was extracted with methylene chloride (200 mL) to give a solution of the title compound.

Make a Difference Donate Now!! (http://www.lp.org/drugwar/)
 
 
 
 
    Rhodium
(Chief Bee)
03-04-02 14:04
No 276641
      Re: Peracetic Information  Bookmark   

Can a cinnamic alcohol epoxide (3-phenyl-2,3-epoxypropanol) be turned into someting useful? I feel that it should be possible, but I don't really know how.
 
 
 
 
    foxy2
(Distinctive Doe)
03-04-02 14:12
No 276646
      Re: Peracetic Information
(Rated as: good read)
 Bookmark   

German Percarboxylic Acid Epoxidation Patent
A German Speakering Bee(hest) could scan thru here and see if there is anything interesting, I can't tell.
Patent DE19849527

Abstract
The invention relates to a method of epoxidizing olefins with percarboxylic acid in a reaction mixture consisting of an aqueous phase and an organic phase. According to said method, the percarboxylic acid in the aqueous phase is formed in situ from hydrogen peroxide and a carboxylic acid or a carboxylic acid anhydride and the olefins in the organic phase are dissolved in an organic solvent. The epoxidation is carried out in several steps. Each step is carried out with a fresh aqueous phase each and after each step the aqueous phase is removed.

Make a Difference Donate Now!! (http://www.lp.org/drugwar/)
 
 
 
 
    Rhodium
(Chief Bee)
03-04-02 15:05
No 276660
      Re: Peracetic Information
(Rated as: good read)
 Bookmark   

Multiple stage peracid oxidation of alkenes (DE 19849527)

They state that the total reaction time is considerably shortened from overnight stirring to a few hours. The yield of epoxide is also increased, as the two-phase reaction and shorter reaction time reduces the incidence of acid-catalyzed ring-opening and other side reactions. The discarded aqueous phases still contain excess HCOOH/H2O2, and this should be recycled. By choosing toluene as the non-polar reaction solvent, the water and formic acid forms azeotropes with the solvent, and are thus removed first by simple distillation, leaving only an anhydrous toluene solution of the epoxide, which can be further purified by vacuum distillation. The same is also true using xylene or dichloromethane. The concentration of the hydrogen peroxide is not so critical, but use no less than 25% peroxide, calculated from the total water content of the acid and the peroxide solution.

Example 1

In a 2000ml RBF, 336g 1-dodecene (2 mol) and 46g 99% formic acid (1 mol) was dissolved in 800g toluene and heated to 90C. To the vigorously stirred mixture was added 136g 50% hydrogen peroxide (2 mol) during 20 minutes, and after that the mixture was stirred for a further 20 minutes,  and the aqueous phase was then discarded.

For step 2-4, the designated amount of formic acid is added in one portion, and the designated amount of hydrogen peroxide (same concentrations and temperatures as above) is added during five minutes, followed by 20 minutes of stirring and dicarding of the lower aqueous layer. In step 2, use 0.5 mole formic acid and 0.5 mole 50% H2O2, and for step 3-4, use 0.3 moles of each.

The crude product was analyzed with GC to reveal the following composition:

93.2% 1,2-Epoxydodecane
 1.1% 1-dodecene
 2.1% 1,2-dodecanediol
 1.6% 1,2-dodecanediol monoformate
 1.6% 1,2-dodecanediol diformate