Oxone yeilds

[SuperStar]

SWIM found this information once before but cannot relocate.  Looking for typical yields in grams from

1. safrole
2. iso
3. epoxide (via Oxone)
4. ketone
5. mdma

If you don't have all the numbers please post the steps you do have.  Not looking for details just the basics to use as a yardstick.
Pardon my friend officer, He's a little slow.

[Chromic]

>safrole

depends on the oil, usually 75-90%. (by the way, this isn't truly a percent yield, it's more of a "percent recovery")

>iso

95%

>epoxide (via Oxone)

95%

>ketone

65% of epoxide.

>mdma

if you've purified your ketone well, then about 80% via Al/Hg. (I'd also like to add that poorly purified oxone ketone, for me, has always resulted in pitiful yields)

[Rhodium]

= 35-40%

Could somebody who's got the time calculate how much liquid/solid waste is produced per gram of finished product? Just add the weight of all reagents/solvents used in each step (only excluding water) and subtract the weight of finished product, then divide this amount with the weight of the product.

[Osmium]

You have to include the water, especially when bees are working with halogenated solvents.
I'm not fat just horizontally disproportionate.

[goiterjoe]

lets assume were staring with 100g of Safrole

to that we add 5g of KOH, and get about 95g of isosafrole and 10g of tar back.

forming the epoxide via Oxone of the remaining 95g of Isosafrole, we need 1.2L(1kg) of methanol, 3L(3kg) of water, 450g of Oxone, and 150g of sodium bicarbonate.  You will also need 450g of DCM to extract if you wash your water afterwards(optional, but recommended for yeild.  You better be reclaiming all of your DCM!)

to rearrange the 85g of epoxide to ketone, we will need ~1L(1.15kg) of 15% sulfuric acid, 700ml (600g?) of ether, 2L (2kg) of water and ~50g of sodium hydroxide for washes.

reductive amination of ketone to MDMA is the real killer though.  We'll base our numbers around a nitromethane Al/Hg on 55g ketone return from before.  you'll use 116g of aluminum foil, 45ml(50g) of nitromethane, 2L(1.6kg) of methanol, and 400mg of HgCl2 (ouch!).  for extraction, you will need 1.5L(1.5kg) of water and 550g of sodium hydroxide, 1L(900g?) of toluene(which will be reclaimed), 6L (6kg) of water and 50g of NaCl for washes.  After adding ~20g of muriatic acid, you will have ~40g of crystals.

Time to recap:
100g of safrole
5g of KOH
1000g + 1600g Methanol
3000g + 900g + 2000g + 1500g +6000g Water
450g Oxone
150g Sodium Bicarbonate
150g Sulfuric acid
600g ether
50g + 55 g sodium hydroxide
50g nitromethane
115g aluminum
0.4g mercuric chloride
20g hydrochloric acid
50g table salt

so to make 40g of MDMA, you produce ~18kg of waste.  not counting water (all water get contaminated when waste is disposed of recklessly, so it's kind of a mute point), we end up with ~4.4kg of waste for 40g of MDMA, or a ratio of 110:1 product to waste.

In other words, that retard playing the rave video game is working harder than OPEC to fuck up the environment.

[cheeseboy]

Cheese could be wrong but isn't it 1% of safrole to KOH? So if 100g of safrole were to be isomerized, 1 gram of KOH would suffice....no?  5 grams would be WAY too much.... no?
May De Sorce Bee Wit Chu-Always

[goiterjoe]

it won't hurt to use too much.  the last couple of times I isomerized safrole, I use CaO with KOH instead, which I believe to be an easier way to do it(I work fulltime and go to school fulltime as well, so time is expensive.)  When going this route, it is recommendable to use excess KOH if you are having trouble stirring effectively, as the black tar formed by the calcium hydroxide will cover your KOH and render it useless.

[SiLiCoN7]

Hard working bees have known these numbers.

1. safrole - 150gr
2. iso - 129.6
3. epoxide (via Oxone) - 108gr
4. ketone - 96gr
5. mdma - 50.8gr

Will post a complete writeup soon.
 
the 21st of the 12th 2012......

[chem_123]

goiter...those numbers look bunk...according to:

Oxidation of propenylbenzenes to P2P's using Oxone
by Chromic
on rhodiums site...why?

Dreaming of the sweet honey  

[SiLiCoN7]

Safrole is only really "recovery" as Chromic stated. So is the iso yield because SWIS7 keeps the middle fraction and recycles the rest. Saff and iso aside, SWIS7 got these yields in a buffered oxone a'la Chromic at 8x scale.

Trile and error adjusting for local filtered water pH and oxone pool mix pre-buffering found that the right amount of buffer was 110gr Sodium bicarbonate.
The reaction proceeded with.
580gr oxone
1200ml MeOH
3000ml H2O
129.6gr isosaffrole
Stirred 5 hrs.
The resulting epoxide was refluxed for 3.5 hrs in methanol and 864ml 15% H2SO4. Then the ketone extracted in DCM and suction filtered through silica gel then evaporated to yield 96gr light amber/yellow oil.(Chromatography ROCKS!)
The ketone was split into 4 portions then amalgamated in 4 methyl man style reactions and extracted together, washed, dried and gassed to produce 50.8gr MDMA.HCL

Dose this make sense??
Ahhh, back to washing the glassware!

the 21st of the 12th 2012......

[goiterjoe]

the epoxidation reaction was scaled off of the oxone writeup, but the hydrolysis rearrangement numbers were taken from shulgin's PIHKAL #109.  I've had problems with the hydrolysis step in the past, so I don't like using other people's reduced numbers for that step.

You ever tried saving all your lab waste from safrole to X?  it's a hell of a lot more than you might think.

[lablozer]

SiLiCoN7,
Was your oxone 100% pure? Im wondering about the 110gr buffer with a 80% oxone product.

Thanks

[pickler]

If your oxone is 80%, just adjust your ratios and don't add a buffer. Buffer is only needed with 100% oxone.
We'll soon find out if I'm a chemist or not!

[lablozer]

The resulting epoxide was refluxed for 3.5 hrs in methanol and 864ml 15% H2SO4

Does SWIP remember how much methanol?

Thanks,
Pickler: Thanks for confirming my % question.

[goiterjoe]

you should use ~140ml of methanol.

I may be completely wrong about this, but it is my impression that the purpose of the methanol was just to lower the reflux temperature of the reaction so that the ketone is not degraded as fast.  It also might play a small part in helping the epoxide/glycol distribute more evenly in the sulfuric acid mix and thus helping to speed up the hydrolysis.  Don't quote me on that, as I've been proven wrong more than enough times on this board.

[pickler]

goiterjoe is on the mark about the menthol being ~140ml. Swim has no prob just scaling everything up by just doubling or tripling etc.
We'll soon find out if I'm a chemist or not!

[SiLiCoN7]

180ml MeOH i think, scaled from chromic.
the 21st of the 12th 2012......

[SiLiCoN7]

The oxone must be only slightly buffered already because oxone and H2O is still very acidic (off the pH paper scale). However oxone runs with the perscribed amount of bicarb added where too basic and resulted in crap yield and the following reactions ran poorly.
So after testing a few times, like SWIS7 said the right amount of buffer was worked out.
Where can SWIS7 get pure 100% oxone anyway?
the 21st of the 12th 2012......

[pickler]

^{Reffering to}

The oxone must be only slightly buffered already because oxone and H2O is still very acidic (off the pH paper scale).


Swim's oxone is 85% oxone and 15% other crap and ph is always at 7. No need for additional buffer. There are many different brands that contain oxone in different amounts. Swim has seen as low as 40% and up to 85% and everything in between.
We'll soon find out if I'm a chemist or not!

[lablozer]

SWIMMER saw that that SiLiCoN7 had some good results so he tried the same procedure. SWIMMER had an oxone at 85%, so no bicarb was added. To a bucket the following was added.

580gr oxone(85%)
1200ml MeOH
3000ml H2O
130gr isosaffrole
Stirred for 5 hrs.

The epoxide & 140ml MeOH & 870ml of 15% H2S04 where then refluxed for roughly 3.5 hrs. Extracted in DCM and vap'd off to yeild 90.4gr of golden liquid. SWIMMER has no idea why the yeild was so low, chalk it up to experience.
The golden liquid was then used in a Bucket Reduction via MM Al/Hg Nitromethane. Yielding only 35gr of jaw-jittering, eye pop'in fun.

This is surely an easy OTC route when used in conjunction with MM Al/Hg Nitro. The 90.4gr + 9.6gr from previous batch, where split into 2 two buckets reductions. 35.6gr of product the first time, 36.9gr second time. Anybody can improve on those yeild. Lack of equipment and experience are why the yeilds are low.

Lablozer

[goiterjoe]

Are you not distilling your ketone?  if not, how can you possibly be bitching about yeilds!?

[lablozer]

vap'd off = distilled

Sorry SWIMMER should be more specific when drunk.

[Vibrating_Lights]

The buckets make great rxn vessels don't they.  Just remember it is possible to get a 8-10gallon bucket similar to a paint bucket.
VL_

[SuperStar]

Hey VL or someone,

When doing the oxone in the bucket. 

Are there any good tricks or tips for getting the epoxide out of the bucket with minimum DCM?

What about filtering the oxone solution before hand?

Guessing to get 2 or 3 buckets and try to filter back and forth between the two until the solution is clean. Then starting DCM, dunno, need some ideas?

You guys using a 5gal or a mop bucket (3 gal) for the 10x oxone.
Pardon my friend officer, He's a little slow.

[goiterjoe]

Has anyone tried flooding the post reaction mix with, say, 4x the amount of water to get the mix to separate better?  I've wondered if the salts that fall out of solution will go back in if the methanol concentration is lowered substantially.  Anyone willing to try?

[Vibrating_Lights]

When the rxn is flooded with water it does help to get the epoxide out to the bottom.  On a large scale  let the oxone solution settle. put 50% of your DCM in another bucket.  Then Pour the oxone liquid into the second bucket and either stirr or pour back in forth in another bucket.  Then do like chromic says and wash the crystals with some MeOH and add it to the dcm/toplayer.
VL_

[SuperStar]

Hey VL,

When you say put 50% of your DCM in another bucket, what are you doing with the other 50%?  SWIM knows this is stupid question but got confused.
Pardon my friend officer, He's a little slow.

[GOD]

seeing how VL has supposivly ducked out, can anyone give a theoretical awnser to the last question?  Swiy is fixun ta give the oxone a whirl and is 'studying up' for pointers etc...would the other 50% get used to washout the other bucket after its been emptied?
when someone asks what the sound of one hand clapping sounds like, you should smack them in the ear.

[SuperStar]

VL, must be doing the 50% in a bucket twice. Sort of like extracting 2x50% DCM

Just a guess.
Pardon my friend officer, He's a little slow.

[SiLiCoN7]

Don't worry about the other 50%, Extracting the oxone is easy. Just filter then extract the whole lot together at least 3 times with DCM. Two big 5L DH2O bottles are good, just shake, settle for at least 5 min, decant the majority into the other bottle then transfer to the sep funnel for seperation. The DCM is almost clear on the 4th extract.

Combine extracts and wash once with about half the volume of DH2O to wash away any oxone remnants then evap the DCM.

If you don't filter the oxone before the reaction, the white powder will continue to percipitate with each extraction, even after post reaction filtration. SWIS7 believes that this is a result of the pH changing as the epoxide is removed. Is this correct? Anyway, don't worry about the percipitate, it will dissolve with just one wash at the end.

the 21st of the 12th 2012......