pickler (Stranger)
01-04-02 22:23
No 252700
      mdp2p from oxone  Bookmark   

I'm about to attempt this synth from rhodium's page(chromics method-oxidation of isosafrole to mdp2p using oxone) and a had a few questions about it. is this synth explosive at all? also in the addendumn by psycokitty, there seems to be some suggestions for some changes in the procedure. now if i follow the synths directions like they were originally written, will i yeild md2p(assuming i'm using isosafrole)?Is it really that easy to make mdp2p that way? i have used brightstar's synth before, but this seems much easier.
 
 
 
 
    Rhodium
(Chief Bee)
01-05-02 01:02
No 252747
      Re: mdp2p from oxone  Bookmark   

The synthesis is not explosive as long as water/methanol is present. Dry oxone may react violently when heated. Chromic's writeup will work as it is written, but Psychokitty had some ideas on how to improve it to make it even better - how much better is an exercise left to the reader.
 
 
 
 
    pickler
(Stranger)
01-05-02 02:35
No 252796
      Re: mdp2p from oxone  Bookmark   

thank you Rhodium. your always there to lend a helping hand to the less experienced bee.laughlaughlaughlaugh
 
 
 
 
    amalgum
(Hive Bee)
01-05-02 05:39
No 252842
      Re: mdp2p from oxone  Bookmark   

Yeah I like the epoxide routes, esp the oxone route.  So easy and OTC.  My problem isn't with the epoxidation though, it's with the hydrolization.  There has got to be a better way than the H2SO4 route.  I mean only a 50% yeild?  I would be synthesizing the epoxide all day with oxone if the hydrolization didn't suck hairy balls. Is there a better way?

Oh and by the way, does anybody have the MW of the epoxide?
 
 
 
 
    terbium
(Old P2P Cook)
01-05-02 06:58
No 252860
      Re: mdp2p from oxone  Bookmark   

does anybody have the MW of the epoxide?
= MW of safrole + 16
 
 
 
 
    amalgum
(Hive Bee)
01-05-02 21:49
No 252984
      Re: mdp2p from oxone  Bookmark   

Thanks
 
 
 
 
    Chromic
(Hive Addict)
01-06-02 03:48
No 253046
      Re: mdp2p from oxone  Bookmark   

I think these values are about right:
Species       isosafrole  anethole  asarone
1mol alkene   162.0g      148.0g    208.0g
1mol epoxide  178.0g      164.0g    224.0g
1mol ketone   178.0g      164.0g    224.0g
1mol A.HCl    215.2g      201.2g    261.2g
1mol MA.HCl   229.2g      215.2g    275.2g

 
 
 
 
    psychokitty
(Her Majesty, Stoni's Kitty)
01-07-02 04:13
No 253402
      Re: mdp2p from oxone  Bookmark   

If you are going to attempt the Oxone synthesis the way Chromic recommends, then the only two variations that I would suggest are as follows:

Do one or the other NOT both.

1.)  After the epoxidation reaction is over, add undiluted muriatic (pool) acid (31-32% concentration) to the solution so that you can skip the solid filtration step and go directly to extracting the goods.  (The HCl allows the solid to dissolve into the solution).  Oh, yes: 125 mL of acid solution for every 25 g of starting alkene (this ratio is for epoxidation; for glycolization, one can use less).

OR

2.)When the epoxidation reaction is completed, vac distill the methanol or ethanol (both work just fine. You should be left with a biphsic aqueous solution of your epoxide which will therefore be quite easy to extract.  I suspect that the precipitation of solids at the start of the reaction is caused by the addition of the methanol.  Following this logic, all solids should redissolve once the methanol is gone.  This is also a good way of recycling one's methanol.

As for the explosion factor, going the epoxidation route, I don't think it even exists. Here are my reasons: 

By the end of the epoxidation reaction, ALL of the oxone--that is according to the 1991 ref--is used up.  That means that all that is left in solution is your epoxide, water, potassium bisulfate, mabe some sodium bicarbonate, and your alcohol.  I can see no reason why distilling off the alcohol, even at atmospheric pressure, would cause any danger. 

Let's say, however, for the sake of arguement, that there is still some oxone left in solution.  SO WHAT.  The alcohol is still in excess over the oxone and once you start distilling, it is going to react with it to form either acetaldehyde or acetic acid which will both be carried over with the alcohol (or it will stay in the distilling flask dissolved in the water).

For those that are concerned about the notion of heating aqueous oxone solutions with organic substances and the rumored explosive danger in doing so, refer to the original oxone JOC article wherein the authors synthesize MANY organic compounds by reacting oxone with various substances under much more rigorous conditions than those used in the oxone epoxidation synthesis. 

Rhodium, that article is a real treasure!  In it are experimental details to synthesizing ethyl acetate and other goodies from oxone and various other OTC items.

Anyway, if anyone has questions, feel free to ask. 
 
 
 
 
    pickler
(Stranger)
01-07-02 06:18
No 253439
      Re: mdp2p from oxone  Bookmark   

thank you very much Psychokitty. It was a lot easier for to understand what you were talking about( being as i'm not to knowledgeable about chemistry terms).thanks again for clearing everything up for me.
 
 
 
 
    noj
(Hive Bee)
01-08-02 22:43
No 254125
      Re: mdp2p from oxone  Bookmark   

Ok, I need some help understanding the terms, or some clarification as to what they mean. Assuming one were using isosafrole and potassium monopersulphate complex, what are meant by 1-alkene, 2-alkene, diol, epoxide, and glycol?

I have my assumptions, but want to make certain.

No One's Jurisdiction
 
 
 
 
    Rhodium
(Chief Bee)
01-09-02 00:45
No 254152
      Re: mdp2p from oxone  Bookmark   

For simplicitys sake, I will just draw some phenylpropane derivatives to illustrate the point.

A 2-alkene has its double bond between carbon no 2 and 3 on an alkyl chain, while a 1-alkene has it on the first carbon (between carbon 1 and 2).
An epoxide is a compound which has a three-membered ring somewhere, where two of the atoms are carbons and one is an oxygen.
Finally, a glycol is a compound where two OH groups are situated on carbon atoms next to each other. Is it all clear now?



 
 
 
 
    noj
(Hive Bee)
01-09-02 02:51
No 254190
      Re: mdp2p from oxone  Bookmark   

So in this example, the safrole is the 1-alkene, isosafrole is the 2-alkene. After the reaction with oxone, the extractant is known as an epoxide and a glycol. Hydrolysis is refluxing in H2SO4 to form the ketone, MDP-2-P, from the epoxide. Correct?

Psychokitty mentions that following hydrolysis there were 3 fractions: epoxide, the desired ketone, and the diol, in the order of distillation temperatures. This was what I also experienced and didn't catch the fractions seperately due to my lack of understanding. It is also mentioned that it will require a longer duration of hydrolysis than the stated 2 hrs.

Would the hydrolysis occur at ambient temperatures at say 8 hrs, or is the heat (reflux) necessary? Would too long a duration (8 hrs) degrade or harm the ketone?

What is the diol?

Forgive my ignorance. I am kicking myself in the ass for not taking any chemistry courses.

No One's Jurisdiction
 
 
 
 
    terbium
(Old P2P Cook)
01-09-02 05:19
No 254262
      Re: mdp2p from oxone  Bookmark   

Probably better here to use the term rearrangement than the term hydrolysis.


Here is another oxone epoxidation ref. This one uses just water sans any cosolvent.
http://www.nccp.org.tw/pdf/con199614.pdf
 
 
 
 
    Chromic
(Hive Addict)
01-09-02 06:20
No 254278
      Re: mdp2p from oxone  Bookmark   

Well, 1-alkene (safrole) to 2-alkene (isosafrole) by heat and KOH. Then we go onto the oxidation with oxone:

If it's buffered (ph near 7): the 2-alkene becomes the epoxide
If it's unbuffered: the 2-alkene becomes the glycol

Then when that's extracted and put into the H2SO4 mixture, if it's the epoxide, then it's hydrolysized to the glycol (addition of water, which opens that little epoxide ring). Then the glycol is dehydrated and rearranged by H2SO4 to the ketone by H2SO4. 2hrs of reflux (with stirring) seems to be enough time, yields have always been pretty good.
 
 
 
 
    noj
(Hive Bee)
01-09-02 06:56
No 254287
      Re: mdp2p from oxone  Bookmark   

1.)  After the epoxidation reaction is over, add undiluted muriatic (pool) acid (31-32% concentration) to the solution so that you can skip the solid filtration step and go directly to extracting the goods.  (The HCl allows the solid to dissolve into the solution).  Oh, yes: 125 mL of acid solution for every 25 g of starting alkene (this ratio is for epoxidation; for glycolization, one can use less).


Doing this worked in getting the solids back into solution, but... it created a messy interphase of bubbles which would not totally disappear after an hour at rest. Will try distilling the methanol out next time.

edit: Actually, IPA was used instead of methanol.

No One's Jurisdiction
 
 
 
 
    Rhodium
(Chief Bee)
01-09-02 10:02
No 254336
      Re: mdp2p from oxone  Bookmark   

Noj: The glycol is the diol.
 
 
 
 
    halfapint
(Ubiquitous Precursor Medal Winner)
01-09-02 16:08
No 254405
      Re: mdp2p from oxone  Bookmark   

Kitchen chem implementations to Terbium's ref on the water/oxone oxidation (without PTC, buffer, cosolvent or catalyst) could bee as simple as excessively fast stirring, which produces splashing in the flask. Or an aquarium bubbler type pump operated on overdrive. Or manual working with a whisk, done with amphetamine enthusiasm. An optimal amount of oxone (to prevent salting out) for each rxn may be determined experimentally, then noted down and communicated to fellow beez. Pool chems rule! It don't get no better than this.

Combined with thermal rearrangement in place of acid mediated rearrangement, which I believe has been demonstrated for both the diol and the epoxide, and we're giant steps closer to the "one-pot" OTC synth which could prove general for propenyl benzenes to 2-propanones. Even the so-touchy asarone. I have in mind boiling out the water, filtering off the salts, returning the washed organic phase to the flask and then just keep on heating until ketone conversion is achieved. If this is then vacuum distilled, it's not really one pot, but still hugely simplified over previous methods.

In fact, hasn't there been some discussion that 1,2-epoxidation of the allylbenzenes may also produce the 2-ketone?? Will the isomerization step also fall by the wayside?

These are exciting times in which to bee!

Sans Marx, sans Jess. Daniel Cohn-Bendit
 
 
 
 
    Rhodium
(Chief Bee)
01-09-02 20:17
No 254453
      Re: mdp2p from oxone  Bookmark   

1,2-epoxides are much harder to form, but as soon as you have them prepared, they can be rearranged with LiI to the ketone.
 
 
 
 
    noj
(Hive Bee)
01-09-02 21:01
No 254461
      Re: mdp2p from oxone  Bookmark   

Ok, the epoxide was extracted with 2x200mL DCM (doing a 3x scale here) and DCM distilled out. Extraction was repeated 3 times, distilling the DCM out and reusing. Each extraction took more and more yellow out of the solution. After 3 times, it seems that there is still more to get, DCM was yellow, but paused because the solution being distilled, the epoxide, was getting noticeably more brown. Is it possible that it is rearranging from the heat alone? The H2SO4 hydrolysis will be done nonetheless just to make certain.

No One's Jurisdiction

After 3 hrs refluxing with H2SO4, extraction was washed 3x with 5% NaOH. Vacuum distillation yielded 24.6g of the yummy smelling ketone. Pretty low yield from 49g of isosafrole. However, since it worked there is only room for improvement.
 
 
 
 
    RollWitMe
(Hive Bee)
01-10-02 04:33
No 254614
      Re: mdp2p from oxone  Bookmark   

What's Oxone again? I don't think we're talking about any peracids. How about using an Ozone generator to do the oxidation. fun fun!

I like to cook! . . . but some dudes in blue vests with yellow letters took my kitchen.
 
 
 
 
    Chromic
(Hive Addict)
01-10-02 04:39
No 254621
      Re: mdp2p from oxone  Bookmark   

RWM: Oxone is a peracid, ozone will cleave the double bond... HP: I never could get the 1991 JOC ref to work with isosafrole, neither could improv_chem... psychokitty said he had success, but said his yields were low (and I'm not sure if he ever reported that he made mdma out of mdp2p)...
 
 
 
 
    noj
(Hive Bee)
01-10-02 05:57
No 254664
      Re: mdp2p from oxone  Bookmark   

potassium monopersulfate is what I used, cost US$7 for 2 lbs. Much cheaper than benzoquinone and palladium chloride. And OTC as chlorine free "shock-it". Many many thanks psychokitty and chromic!

No One's Jurisdiction
 
 
 
 
    backburner70
(Stranger)
01-10-02 16:25
No 254782
      Re: mdp2p from oxone  Bookmark   

(my first post!)

What type of yields are normal from the H2SO4 hydrolysis? I know Chromic mentions 50% in the writeup, is that typical? I was wondering if it was worth the effort to capture the epoxide/diol fractions and throw them back in the mix the next time around. What is the stability of these two for storage purposes?

bb 7.laugh
 
 
 
 
    Rhodium
(Chief Bee)
01-10-02 17:02
No 254785
      Re: mdp2p from oxone  Bookmark   

Typical yields using the performic reaction is 50-60% and with the buffered performic 10-20% more than that.
 
 
 
 
    Chromic
(Hive Addict)
01-11-02 04:01
No 255024
      Re: mdp2p from oxone  Bookmark   

I saw something like 60-75% overall.
 
 
 
 
    noj
(Hive Bee)
01-11-02 05:51
No 255072
      Re: mdp2p from oxone  Bookmark   

Amalgamation worked! Not certain of yield yet but it definitely has the right taste.

No One's Jurisdiction
 
 
 
 
    Chromic
(Hive Addict)
01-11-02 18:25
No 255310
      Re: mdp2p from oxone  Bookmark   

I meant 60-75% from isosafrole -> mdp2p. Overall is something like .90 * .60 * .75 = ~40% overall molar yield of mdma.hcl from safrole.
 
 
 
 
    Rhodium
(Chief Bee)
01-12-02 00:31
No 255448
      Re: mdp2p from oxone  Bookmark   

Only that it does not require formic acid.
 
 
 
 
    noj
(Hive Bee)
01-12-02 02:28
No 255476
      Re: mdp2p from oxone  Bookmark   

Or 35% H2O2.

No One's Jurisdiction
 
 
 
 
    Vibrating_Lights
(Hive Bee)
01-12-02 23:18
No 255702
      Re: mdp2p from oxone  Bookmark   

Hello every one.  It has been a while since swim has been here.  the holidays are a busy time around our city a  we will say that this was the best new years we have ever had.  Our hats go off to Chromic again.  He is the shit. We all know that the Oxone procedure works pretty fool proof.  we have not yet done the research althought chromic might have about diffrent Ph levels.  It is their understanding that oxone will epoxidise under weakly  acidic conditions.  swim thinks that any one experiencing low yeilds with this procedure are dealing with an OTC pool store oxone source with the ingrednce listed as 85%monopersulfate compound and 15% inert.  Well those inert ingrediants are not inert for our purposes.  The so-called inert ingrediants in those 85%mixes are sodium Carbonate and sodium metaBisulfite.  Monopersulfate is an acid by itself in a saturated solution it will definatly carry a high PH.  Now the companies that mix up the oxone are doing so in a that the formula that they sell is buffered by the sodium carbonate in the same way that chromic buffers his oxone with Sodium bicarbonate. The proper ammount of 85% Monopersulfate solution to use on a 200mmole of isosafrole is around 167 grams or so that is including inert ingredients and all straight out the bag. They think peope could be getting bad results because they are adding the amount of bicarbonate that chromic suggests and the Ph goes to high lowering the solution's epoxidation capabilities. Swims recomendation is that when using 85% Monopersulfate  OTC pool formulas moniter the Ph while adding the bicarbonate and even check it before adding and aim for around a PH of 6.9  We think this might improve the yeilds for some bees experiencing this problem.Also the other ingredient Sodium sulfite will not affect the rxn.  We hope this instills cofidence in using Otc pool chems. Just check your labels.  Also Thermal Rearrangement of crude isosafrole epoxide  67% yeilds 245.c heavy stirring 2Hr reflux time with  2.5gallons of water with 500grams of ice through the recirculated through the condensor  temp was monitered at the base of the kneck and the cold water keeps most of the vapor in the flask.  moniter the progress under a black light.  As soon as you witness it under a black light you will understand. They suspect that reaction times may very depending of the ammount of side product during the epoxidation and the purity of the starting isosafrole.  They suspect that yeilds will improve greatly perhaps with the thermal rearrangement with vacume distilled epoxide. The thermal rearrangment will provide superrior yeilds because ther is no acid around to chew on the molocule which is the cause of the red coloration with the typical H2SO4 rearrangement.We believe that up to around 80% yeilds are possible with distilled epoxide. yeilds might even be higher if the Ph of hte oxone run is kept at 6.8-7 yeilding only epoxide and no glycol. they suspect that the loss in yeild might even be that glycol is not converted by either method of rearrange ment and with H2SO4 is destroyed and with thermal it it just not converted.   When they send swim their exact quantative data Swim will post.

VL_
 
 
 
 
 
    cheeseboy
(Hive Bee)
01-13-02 09:38
No 255866
      Re: mdp2p from oxone  Bookmark   

Tanks for da meal!

May The Source Bee With You....Always.
 
 
 
 
    Vibrating_Lights
(Hive Bee)
01-13-02 19:44
No 255980
      Re: mdp2p from oxone  Bookmark   

Chromic,  was there any indication of glocol being present when you did tlc analysis of the epoxides. we know you keep the proper PH.
 
 
 
 
    Chromic
(Hive Addict)
01-14-02 06:40
No 256135
      Re: mdp2p from oxone  Bookmark   

I didn't do TLC, I did NMR. There were two chiral centers, a mixture of R and S epoxides (I figured). I doubt any of it was glycol (when buffered with bicarbonate). Anethole epoxide rearranged very nicely to anethole ketone and the yields were excellent (both of the amination and rearrangement), and I'm sure isosafrole would do the same. I attempted it and got excellent yields of suspected mdp2p, however, I screwed up on the amination and got piss-poor yields (enough to celebrate news years eve... but not enough to post at the hive recommending this procedure to the general hive populace...)
 
 
 
 
    Stroke
(Stranger)
01-14-02 07:54
No 256154
      Re: mdp2p from oxone  Bookmark   

But if it was the amination that was quasi-botched and the yields of epoxide oil and finally ketone oil were good then it's fair to say that the OXONE method works well to epoxide-->ketone(MDP-2-P). No Formic OR 35%H2O2! Yum Yum
 
 
 
 
    noj
(Hive Addict)
01-14-02 16:00
No 256230
      Re: mdp2p from oxone  Bookmark   

Chromic, yields for swim turned out to be 9g of salt from 25g of ketone. This is consistent with any amalgam swim has done so it is apparently my method causing the yields. I'm not sure if it was just the 6 month absence of useage or what but that was a potent 150mg dose.

I think the commercial imports must be cutting their pills down to 40mg of MDMA because there was nothing but balls-to-the-wall reviews.

we are we are
 
 
 
 
    Vibrating_Lights
(Hive Bee)
01-14-02 22:12
No 256381
      Re: mdp2p from oxone  Bookmark   

swim would say that european pills are average 80-90mg israile middleeast 65-70.  poeple neeed to get #4caps and fill em full 126mg.
Vl_
 
 
 
 
    Chromic
(Hive Addict)
01-15-02 05:03
No 256521
      Re: mdp2p from oxone  Bookmark   

What amalgamation did you use? Your yields sound a bit low, but if it's for personal, then that's tons... Yeah, 150mg of pure mdma.hcl is fucking amazing for me too as I use only 3-4 times a year.
 
 
 
 
    noj
(Hive Addict)
01-15-02 13:50
No 256657
      Re: mdp2p from oxone  Bookmark   

The typical MM variety. The mercuric chloride was self made and the ketone may have been impure. I did notice that after checking pH while adding the sodium bicarbonate to the oxone that the amount specified made it too basic (pH 8) so that will have to be worked out. I can't imagine why the manufacturer would buffer it since it will be added in 1 lb.(as directed) to 10,000 gallons of water.

we are we are


If one were having trouble with the solids while extracting the glycol with DCM, would toluene work if the solution was made slightly basic?
 
 
 
 
    Chromic
(Hive Addict)
01-15-02 17:44
No 256720
      Re: mdp2p from oxone  Bookmark   

Yeah, toluene would work fine. I used DCM because it's more easily recovered than toluene.
 
 
 
 
    Vibrating_Lights
(Hive Bee)
01-15-02 18:36
No 256734
      Re: mdp2p from oxone  Bookmark   

Also if you strip off your methanol by appling vacume to the  mix the solids will dissolve back in the water allowing you to skip the filteration step.
VL_
 
 
 
 
    noj
(Hive Addict)
01-16-02 17:43
No 257234
      Re: mdp2p from oxone  Bookmark   

Will a duplicate hydrolysis/rearrangement harm ketone? Someone forgot to label a flask and was thinking of refluxing in 15% H2SO4 to make certain.

BTW, toluene is very ineffective as a substitute for DCM. In this instance anyway.

crucify the ego before it's far too late
and you will come to find that we are all one mind
 
 
 
 
    Rhodium
(Chief Bee)
01-16-02 19:56
No 257266
      Re: mdp2p from oxone  Bookmark   

Yes, running the acid hydrolysis twice as long, or two times in a row wil hurt yields.
 
 
 
 
    Vibrating_Lights
(Hive Bee)
01-16-02 22:35
No 257300
      Re: mdp2p from oxone  Bookmark   

Chromic,  what are your thaoughts on adding (aq)saturated oxone dropwise to alkene in meoh like with the modified peracid techniques.  earlier you said that there was no unreacted alkene just over oxidation products in the post rxn mix.  It seems that rxn would be less prone to side products if  full ammount of oxidiser was not present for the durtion of the rxn.
VL_ 
 
 
 
 
    Chromic
(Hive Addict)
01-16-02 23:54
No 257313
      Re: mdp2p from oxone  Bookmark   

The yields are already near 100% so I don't see how that would help improve anything...?
 
 
 
 
    noj
(Hive Addict)
01-18-02 16:20
No 257915
      Re: mdp2p from oxone  Bookmark   

Man I really like the outcome of this procedure. Someone had a strange accident in which while distilling the solvent out before vacuum distilling the ketone, the whole flask foamed over leaving someone with what ressembled foaming beer. Taking it back out and doing a few more basic washes and filtering the nasty emulsion... left someone with a very nice light yellow liquid. Well someone is distilling this none the less, and all is okay now. This could be a method for people without a vacuum to perform and see good results! If the ketone can be cleaned up so well with 4-5 basic washes, it may work out in an amalgam.

crucify the ego before it's far too late
and you will come to find that we are all one mind
 
 
 
 
    Chromic
(Hive Addict)
01-18-02 16:55
No 257930
      Re: mdp2p from oxone  Bookmark   

In addition, vacuum distillation is only necessary to see your true yields. I've distilled epoxide at atmospheric pressure (epoxides turn to ketones at high temperatures) and amalgamated and it was OK. I'm very sure it works with isosafrole (as I successfully did it with isosafrole epoxide as well... but never got high yields do to a messed up Al/Hg)... more experimentation is needed in that area.
 
 
 
 
    noj
(Hive Addict)
01-18-02 17:04
No 257935
      Re: mdp2p from oxone  Bookmark   

I've distilled epoxide at atmospheric pressure

Explain that... you didn't reflux for 2 hours as in thermal rearrangement? Simply distilling the epoxide resulted in ketone coming over? Man, someone is starting to see some very wet dreams ahead.

crucify the ego before it's far too late
and you will come to find that we are all one mind
 
 
 
 
    humidbeing
(Hive Addict)
01-19-02 01:36
No 258105
      Re: mdp2p from oxone  Bookmark   

Shit! Nothin like a little suspense!tongue

excons make wonderfull employees
 
 
 
 
    Chromic
(Hive Addict)
01-19-02 01:39
No 258109
      Re: mdp2p from oxone  Bookmark   

Thermal rearrangement is heating the epoxide to about ~260C and holding for a few minutes, cranking the heat, and distilling it... it comes over somewhere around 300C (I didn't have a thermometer that went above 260C). What distills over is not epoxide, it is ketone. The crude yield is about 80%, the flask is relatively hard to clean afterwards. It has not been verified to give a good purity, but I know it works, and I think the purity is decent.
 
 
 
 
    humidbeing
(Hive Addict)
01-19-02 03:55
No 258174
      Re: mdp2p from oxone  Bookmark   

Bump!
 This is as interesting as it's likely to get right now!

" It's the smell!.......I feel saturated by it...
 
 
 
 
    noj
(Hive Addict)
01-19-02 13:45
No 258299
      Re: mdp2p from oxone  Bookmark   

If nothing comes over between the 260 and 300 mark, could it be that the epoxide is rearranged to ketone after a few minutes? All one would need is to let cool and distill under vacuum to yield perhaps 67% as V|_ mentioned with his thermal rearrangement. Guess someone will have to try this.

crucify the ego before it's far too late
and you will come to find that we are all one mind
 
 
 
 
    humidbeing
(Can't SWIM)
01-25-02 06:54
No 260633
      Re: mdp2p from oxone  Bookmark   

Any results?

singel wite intejunt male
 
 
 
 
    noj
(Hive Addict)
01-25-02 11:11
No 260695
      Re: mdp2p from oxone  Bookmark   

I would, but the current setup limits me to 270C.

Real men cook naked.
 
 
 
 
    cheeseboy
(Hive Bee)
01-27-02 01:41
No 261270
      Re: mdp2p from oxone  Bookmark   

cheese will try....cheese will try...cheese will try. Did cheese mention the cheese will try. OK

May The Source Bee With You....Always.
 
 
 
 
    humidbeing
(Can't SWIM)
01-27-02 01:55
No 261279
      Re: mdp2p from oxone  Bookmark   

Good deal cheesy. Waiten!smile

Honey? Where's my little black medical book?
 
 
 
 
    uemura
(Hive Photographer)
01-28-02 16:26
No 261827
      Re: mdp2p from oxone  Bookmark   

Chromic and all other bees...

Thermal rearrangement is heating the epoxide to about ~260C and holding for a few minutes,



Browsing thru the mail of the last three weeks, Uemura recognises that thermal rearrangement of epoxides is now an established method in the communitysmile

Now, there seem to bee a bit a confusion how long or if at all you have to reflux the epoxide. What uemura did was the following:

Put a high temp termomether inside the boiling liquid (use a 2-neck flask, 1 neck for the thermo, 1 for the condenser). Then watch the temp! In case of anethol epoxide you will recognise that boiling starts around 240DegC, then the temp climbs up slowly up to about 265DegC when it seizes at that level. Then add 5 minutes to complete the conversion. Replace the condenser by the usual destillation setup for normal pressure. The ketone Uemura got froze in the freezer.


Carpe Diem
 
 
 
 
    cheeseboy
(Hive Bee)
02-01-02 04:21
No 263519
      Re: mdp2p from oxone  Bookmark   

Failure....can you say "burned cheese"? Cheese will try again. Fascinating!

Cheese is using 100% OXONE from the hardware store. Sold under the label "Oxy-Clear" by DuPont. If DuPont makes it, it'sa the shit, no chlorine no nuthin' pure Oxone. $6.50 kg. The war IS over.

May The Source Bee With You....Always.
 
 
 
 
    sYnThOmAtIc
(Hive Bee)
02-01-02 10:39
No 263716
      Re: mdp2p from oxone  Bookmark   

Uemura,   None of the ketone pinky ever dealt with ever froze in the freezer though all his already had the nitro added with the proper nitro to ketone ratio ready for use in the al/hg. What is the mp for reference? Havent seen anyting but a bp.

Cheese,(or shoud I say COMPTON?) did yours fail in the epoxidation or the rearrangement?
 
 
 
 
    UKBEE
(Stranger)
02-01-02 11:15
No 263724
      Re: mdp2p from oxone  Bookmark   

You guys might find this useful ?

http://www.dupont.com/oxone/applications/index.html



I love the smell of Ketone in the morning.
 
 
 
 
    amalgum
(Hive Bee)
02-05-02 06:06
No 265329
      Re: mdp2p from oxone  Bookmark   



Uemura,   None of the ketone pinky ever dealt with ever froze in the freezer though all his already had the nitro added with the proper nitro to ketone ratio ready for use in the al/hg. What is the mp for reference? Havent seen anyting but a bp.




Well, the more diluted your ketone is in a solution, the lower the b.p. has to be for it to freeze.  Also, since you said you added nitro to your ketone, I assume your talking about MD-P2P.  Where as Uemura was talking about p-MeO-P2P made from anethole.

 
 
 
 
    SuperStar
(Stranger)
02-11-02 23:10
No 268177
      Re: mdp2p from oxone  Bookmark   

Cheese: You said you got a product called "Oxy-Clear" from the sto?  This wouldn't happen to be homebase?  What is it used for, trying to locate but need more info?

Pardon my friend officer, He's a little slow.
 
 
 
 
    SuperStar
(Stranger)
02-11-02 23:27
No 268183
      Re: mdp2p from oxone  Bookmark   

Found this. Let me know if this is inappropriate

Some major brand name products for the swimming pool that contain xxxxx Oxone potassium monopersulfate are
xxxx "xxxxxx,"
xxxxx"xxxxxxx,"
xxxx "xxxxxxx,"
xxxxxxxx,"
xxxxx "xxxxxxxx,"
xxxx "xxxxxxx,"
xxxxxx"xxxxxxxxx" and
xxxx "xxxxxx.""

Products for the spa or hot tub that use Oxone include xxxxx,"
xxxxxxx" (used with xxxxxx") and xxxxxxx."


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

YEAH he's fuckin SLOW, NO SOURCES posted ever!!! Normally this means a ban, so I'm in a good mood today, let's presume... LT/
 
 
 
 
    LaBTop
(Daddy)
02-12-02 08:30
No 268441
      Re: mdp2p from oxone  Bookmark   

Didn't you think the posts from Cheeseboy and UKBEE weren't informative enough?
And if in doubt, we have a PMachine. LT/

WISDOMwillWIN
 
 
 
 
    Vibrating_Lights
(Hive Bee)
02-12-02 09:52
No 268481
      Re: mdp2p from oxone  Bookmark   

ON TOP OF THAT vL_ HAS ALREADY TOLD EVERYONE THE COMMON 85%MIX CAN BE USED STRATICHT OUT OF THE BARRREL.
vl_
 
 
 
 
    SuperStar
(Stranger)
02-12-02 20:51
No 268681
      Re: mdp2p from oxone  Bookmark   

Sorry about that.  It won't happen again.

I was under the thought that brand names were different that sources.  Like I said. Won't happen again.

Pardon my friend officer, He's a little slow.
 
 
 
 
    SiLiCoN7
(Stranger)
02-15-02 12:56
No 269959
      Re: mdp2p from oxone  Bookmark   

Has anyone else tried a H2O wash on the DCM/glycol extracts?

Just one wash really cleaned up the glycol immensly with only about a 2-3% "loss" in yield. It also resulted in a much cleaner product in following steps.

Pool chemicals rock! I love is reaction, no heat, no smell, just find yourself a BIG bucket and BIG suction filter and the sky's the limit.
 

If you're not talking to your kids about drugs who is?
 
 
 
 
    cheeseboy
(cheese head)
03-01-02 08:40
No 275194
      Re: mdp2p from oxone  Bookmark   

sYnThoMaTiC my man! Failure was in the rearrangement due to impure isosafrole (don't ask, it was harsh nano to begin, some shit got in, it very well may have worked but cheese burned it in the ketone distillation, weak aspirator, HIGH temps. baaad News)  And NO cheese aint compton. Cheese has a feeling compton was on the breast of a comeback, as he put it, then got nabbed even harsh by a bee he ripped off. You know compton, sheeit, hell compton be scammin' ,snakin', doggin', decin' around Beantown like he some white boy Foo with da ketone to go. Compton took the wrong bee for a ride and there ain't NO way that fool could govern himself THAT high. Hell NO cheese ain't compton, shit.Dog? c'mon?
 Cheese's just glad he didn't place no second orders with that fool. Cheese dripped all over his plans he had for cheese.(Say Cheese!) teehee That old game he tried to play wasn't as old as cheese is...er yes it is...tongue

         May The Source Bee With You...Always. Cheese is a White Boy with SOUL! (as opposed to a Black Guy without soul)
 
 
 
 
    cheeseboy
(cheese head)
03-12-02 00:39
No 280823
      Re: mdp2p from oxone  Bookmark   

SUCCESS!!.   Thermal rearrangment of the glycol oil worked just fine. Glycol oil was an antifreeze, see thru green. After  heating to 260C for 1 1/2 hours the glycol (now ketone) oil became darker, see thru brownish in color, heating mantle was turned down, time passed to cool down  oil, then full vacumm was applied and an opaque yellowish green ketone came over at arounf 214C Approximatley 25-30 higher than the Isosafrole precursor.smilesmilesmile. Thank you - thank you, no please, sit...sit please , applause isn't necessary!! No Really!

 Cheese will work with 100gm of Isosafrole from now on. Not sure scaling this up too much is good for the Iso.??
Thanks to Vibrating Lights, Noj, Pickler, Chromic, PooBearForever, Psycokitty, Rhodium, Locrian, El_Zorro,sYnThOmAtIc and last but not least... The Big R. (Let's not forget Sasha, Strike, and all the mods on the Hive for making it possible.) This acceptance speech has got to end soon.......this ain't the academy awards

Cheeseboy-a whiteboy with Soul Like a black guy without soul
May The Source Bee With You Always.
 
 
 
 
    PoohBear4Ever
(Junior Service Representative)
03-12-02 01:18
No 280849
      Re: mdp2p from oxone  Bookmark   

Congradulations on your eminent success smile!  When will SWIC be dreaming his reductive aminations?

PB
 
 
 
 
    pickler
(Greenhorn)
03-12-02 01:54
No 280863
      Re: mdp2p from oxone  Bookmark   

Way to go cheesy!laugh

We'll soon find out if I'm a chemist or not!
 
 
 
 
    Chromic
(Hive Addict)
03-12-02 05:14
No 280986
      Re: mdp2p from oxone  Bookmark   

Yes, I believe this is KEY to rearrangement. You must keep the epoxide at a high temperature for a fair time before finishing the distillation.

Congratulations! I'm so happy to hear this worked out like this. Save half of your oil and try a MM reduction with the other half.

Good luck!
 
 
 
 
    LaBTop
(Daddy)
03-12-02 06:13
No 281033
      Re: mdp2p from oxone  Bookmark   

Whut the Fuck is this:
""After  heating to 260C for 1 1/2 hours the glycol (now ketone) oil became darker, see thru brownish in color, heating mantle was turned down, time passed to cool down  oil, then full vacumm was applied and an opaque yellowish green ketone came over at arounf 214C Approximatley 25-30 higher than the Isosafrole precursor.""

How the hell can you get rearranged ketone coming over under FULL VACUUM at 214C ?????????
It should come at 120-130C at high vacuum. I HOPE it's a typo, and you meant 114C !!! LT/

PS: don't give me a heartattack!

WISDOMwillWIN
 
 
 
 
    PoohBear4Ever
(Junior Service Representative)
03-12-02 06:25
No 281039
      Re: mdp2p from oxone  Bookmark   

Maybe not a typo;


...but cheese burned it in the ketone distillation, weak aspirator, HIGH temps. baaad News




PB

 
 
 
 
    LaBTop
(Daddy)
03-12-02 06:55
No 281056
      Re: mdp2p from oxone  Bookmark   

If this is working well in any amination, then THIS day the Hive made HISTORY again! LT/coollaughcool

WISDOMwillWIN
 
 
 
 
    noj
(Hive Addict)
03-12-02 08:23
No 281088
      Re: mdp2p from oxone  Bookmark   

The ketone was opaque? Or just colored? And did you say your epoxide was green? Something sounds awry. Maybe I'm just sleepy.

Everyone falls down. It's how fast you get back up that is important.
 
 
 
 
    LaBTop
(Daddy)
03-12-02 08:54
No 281095
      Re: mdp2p from oxone  Bookmark   

Greenish colors can be picked up by totally burned teflon stirrbars, exposing the metal, thus infecting the reaction with Fe ions. It can also appear when using SS overhead stirrer propellors.
He's going high in temps, remember that, and his aspirator vacuum seems to totally suck, he better buy a new one very soon, now from SS. The synthetic ones tend to dissolve or wear off over time, especially the thin stream jet opening inside. Use then a filter in front of it, you will be surprised how much metal or plastic scrap or sand you will find in there every week, that scrap will damage your venturi very fast when it is pressed through it by the high water pressure.

You see how eager I am, to see this RRRREALLY happen?! LT/, waiting for a bio essay report.

WISDOMwillWIN
 
 
 
 
    noj
(Hive Addict)
03-12-02 09:55
No 281107
      Re: mdp2p from oxone  Bookmark   

The product from the buffered performic should be able to be rearranged this way as well, correct? Would the yield increase there as well? Not that I'm complaining with it now of course.

Everyone falls down. It's how fast you get back up that is important.
 
 
 
 
    cheeseboy
(cheese head)
03-14-02 07:54
No 282383
      Re: mdp2p from oxone  Bookmark   

FAILURE:

   Amination via cyano reduction yielded nothing. Damn. And that yellowish green oil must have been diolprobably. Or maybe this method is BULLSHIT. Cheese isn't going to waste the rest of his iso on this method. Time to get some Formic. has ANY bee had successfull aminations using OXONE yet? just curious. Like LabTOP says--> "lot's of bees input on thermal rearrangment but no amines yet?"  WTF eh?! That cherry red oil sure did look yummy though.

 Question:  Does the Formic acid route yiled the epoxide as well, or is it a completelt different intermediate? Thanks again for all the hel, even if ti was unsuccessful, it was a 'FUN RUN" cool (Don't you hate it when you pour freebase/DCM into your sep funnel when the stopcock's open!! LOL)shockedmadtongue

Cheeseboy-a whiteboy with Soul Like a black guy without soul
May The Source Bee With You Always.
 
 
 
 
    cheeseboy
(I'm not Cheesie)
03-15-02 08:58
No 282897
      Re: mdp2p from oxone  Bookmark   

Back to the 'ol drawing board. LabTOP was right, cheese's stirbar is half gone and the magnetic metal part is exposed on one half , from spinning with sillicagel for MDA runs.(using Lab Grade ketone) The last attempt was  right to the point using the Chromic method at 16.2 gm of Iso. Everything went by the book, until after H2SO4 treatment, the now brown oil sank to the bottom of the solution and it was separtaed.(12.4gm) This oil was brought to a boil and water came out(11.9gm), thus clearing it up and making it even more darker brown. Cheese has problems with his heating source and has to wait until it's repaired to vacuum distill this brown oil. But cheese tried distilling it on a hotplate, and it came to a boil but in quick bumps, NO steady boils, and no vapours. Cheese didn't have the patience to wait any longer, after half an hour of these quick bumps.Wierd. maybe this IS ketone and the proper hetaing source with vacuum distill the yellow ketone out of this dark brown oil. We'll see, but cheese's 3rd attempt was right by the book and if it isn't MDP-2-P then something IS awry.Thanks labTOP. And all the other helpfull bees.

Cheeseboy-a whiteboy with Soul Like a black guy without soul
May The Source Bee With You Always.