Author Topic: Peracetic in DCM - dreams of success  (Read 8702 times)

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Chromic

  • Guest
Sure but a question
« Reply #40 on: June 09, 2002, 11:21:00 PM »
I want to preserve as much of the writing style as possible.. but I'll give it a try with the MM document.

P.S. I do not want to take the priviledge / responsibility of adding an acid/base extraction (ie giving appropriate amounts of solvents for maximal yields) to the MM document. The last thing I want to do is introduce a change that drops the yields. Maybe you could author that part.

Rhodium

  • Guest
Not having followed his procedure myself, I will ...
« Reply #41 on: June 09, 2002, 11:46:00 PM »
Not having followed his procedure myself, I will then only write "Add 25% NaOH solution until clearly basic to pH paper", as using "x ml" of such solutions can be unreliable in practice.

greeter

  • Guest
basification...
« Reply #42 on: June 10, 2002, 02:43:00 AM »
"Add 25% NaOH solution until clearly basic to pH paper"

Can the solution be 'over' basified (i.e. what impact would this have on the final product)?


A watched pot will indeed boil.

Rhodium

  • Guest
No such thing as overbasifying
« Reply #43 on: June 10, 2002, 03:19:00 AM »
No, you cannot really 'overbasify' an MDMA solution, the important part is only to get the pH over about 11, so that all of it is converted to the freebase form so that you can extract it effectively.

Storing a very basic solution of MDMA for extended time periods (24h+) may show more decomposition than if it was less basic, but on a timescales of minutes to a few hours, this is of no importance at all.

Francis_7

  • Guest
A few questions
« Reply #44 on: June 10, 2002, 09:01:00 AM »
Is it the glycol or the epoxide that is formed from the peracetic acid reaction?

Is the peracetic acid added drop by drop or all at once? 

Is this reaction exothermic in any way? 

When distilling the ketone, is there any forerun of epoxide or isoalkene or is the ketone the first and only fraction?

How were you able to control an MM reaction using 25 grams of ketone in a 500 mL flask?  Also, was the reaction performed under stirring?

Could you post or rewrite RoundBottom's isomerization technique here in this thread?  I can't find it.

Chromic

  • Guest
To Francis_7
« Reply #45 on: June 10, 2002, 09:32:00 AM »
The peracetic acid method makes a combination of isosafrole glycol and isosafrole glycol acetate ester. If it's fully buffered and done cold it also can be used to make isosafrole epoxide. In the end, since 15% H2SO4 is used to rearrange, it doesn't matter, and all forms result in isosafrole ketone (MDP2P).

Upon addition of the peracetic acid, there is an exothermic reaction. If a cold water bath is not used, the DCM will come to a boil. If a cold water bath is used, the DCM never heats up enough to boil. There is no need for drastic cooling. I recommend a cold water bath. Less heat means less by products.

The Methyl Man amination was not done. An Al/Hg with MeAmCl was conducted. 23.6g of ketone was processed in a solvent volume of about 300ml. The reduction of nitromethane, not done in this procedure, is normally an extermely exothermic reaction and was avoided for this reason. Also avoided was the large solvent volumes that I feel are a draw back of the MM procedure.

When distilling the ketone there was no forerun of safrole or isosafrole. There was a forerun of DCM up until about 150C or so. A viscous tar remained after the atmospheric distillation. The teflon on the stir bar was also somewhat melted. If this distillation is done repeatedly, you're going to go thru stir bars quickly. (hence my other post on rejuvenating stir bars)

Since the MM amination was not used, the amination was easy to control in a 500mL flask. However, I'm sure the solvent volume of a MM amination could be reduced if 1) thicker aluminum foil was used, getting all the tin foil required into a MM reduction would be a feat if it were Reynold's Heavy Duty wrap 2) an efficient reflux condenser is used.

RoundBottom's variation on the isomerization method proposed by Osmium can be found in

Post 277992

(RoundBottom: "Re: vacuum refluxing", Chemistry Discourse)
and

Post 278285

(RoundBottom: "Re: vacuum refluxing", Chemistry Discourse)
.

Btw, you asked a good set of questions!  :)

greeter

  • Guest
one other MM issue
« Reply #46 on: June 10, 2002, 09:58:00 AM »
I don't know if this is an error or what, but in the MM writeup he says basify the sludge with 35% NaOH solution, then gives a formula of 750mL H2O and 262.5g NaOH.  At least in the terms of solute that I'm used to, this makes about 26% NaOH solution.  262.5 is 35% of 750, not 35% of the total mass of the solution.


A watched pot will indeed boil.

Chromic

  • Guest
Yes, that's an error as well
« Reply #47 on: June 10, 2002, 10:50:00 AM »
>don't know if this is an error or what, but in the MM writeup he says basify the
>sludge with 35% NaOH solution, then gives a formula of 750mL H2O and 262.5g
>NaOH.  At least in the terms of solute that I'm used to, this makes about 26% NaOH
>solution.  262.5 is 35% of 750, not 35% of the total mass of the solution.

Yes. 262.5 / (750+262.5) = 0.259 = ~26%.

A 35% solution would be 262.5g of NaOH and 487.5g of H2O. Preparing a solution that concentrated requires external cooling while mixing the lye and water.

Osmium

  • Guest
When somebody cannot figure out how to perform an ...
« Reply #48 on: June 10, 2002, 12:45:00 PM »
When somebody cannot figure out how to perform an A/B after whatever amination reaction then that person didn't do his/her homework, and isn't ready for synthing anything.

I know that is a very unpopular opinion I am expressing here, but spoonfeeding people like this is not educating anyone. If you tell people every movement of your left pinky during something as simple as an extraction then you are generating a bunch of wanna-bee cooks, not people who understand what they are doing.

(Yes, I HATE 3000 word writeups of reactions when everything necessary can be said in 5 sentences. Awfully hard to read and understand.)

I'm not fat just horizontally disproportionate.

Chromic

  • Guest
Ok... this is really odd!
« Reply #49 on: June 10, 2002, 07:40:00 PM »
I think Entropy's writeup should be axed from the MM document. It's got a few obvious errors.

1) amalgam is not spelt amalgum
2) insufficient purification
3) 50mg (?) of MgSO4
4) Gassing is done in DCM
5) The reaction is done in a BEAKER (!!!)

I can't even attempt to fix that one. Although it's a fun story, this is a haphazardous writeup and probably should be nixed. I'll work on the MM document soon. I'll also incorporate a quick run down of the procedure as Os wants (and similar to the outlines I use).

greeter

  • Guest
Osmium...
« Reply #50 on: June 10, 2002, 09:05:00 PM »
spoonfeeding people like this is not educating anyone

Osmium, NOT spoonfeeding people is certainly not educating them either.  I agree with you that  with more information comes more wannabees, but with more information comes more safety and better technique.  I would much rather hear that some new chemist (such as swim) hurt themselves because they were told to do something and consciously CHOSE to disregard it (i.e. they are an idiot) than to hear that some bee hurt themselves simply because they didn't know what they were doing.

I look at it this way:  In a perfect world, drugs would be legal and easy to obtain, then NONE of us would be making any of these things.  Our toys would be made by highly qualified chemists and with the very best equipment in commercial laboratories.  However, in the world we live in right now, since the drug laws do not seem to reflect common sense, I think the most effective means of bringing about change is to make these drugs ubiquitous.  Already in the States and elsewhere the public opinion of marijuana is changing, simply due to the fact that it is everywhere.

The more chemists that are producing the people that will be doing and that is good for getting people to wake up and write new laws.

Osmium, over and over and over you write the best posts, I've learned so much.  You have truly mastered this art.  If you were to take the time to write a no-nonsense writeup that could be understood even by the most green beginner, imagine how much you would TEACH!!

EDIT:

BTW:  You do write great writeups Os, I just mean to say that if all the good "widely-followed" docs like MM's were written by people like you there would be a lot fewer errors and much better procedure.

Francis_7

  • Guest
You still haven't answered all of my questions
« Reply #51 on: June 10, 2002, 10:02:00 PM »
1.) Was the peracetic acid solution added drop by drop or all at once under cooling? 

2.) Was the amination done under stirring?

Btw, I don't really understand RoundBottom's post.  What is the purpose of applying the vacuum for 30 minutes?  Why not just stir the KOH and alkene for 20 hours at a temp of 160 instead?

Could you please just state what YOU did to make things easier.  Please include all weights and measurements.  RoundBottom's diagram was just plain confusing to me.

One more new question:

1.) What are the ratios of methanol/MeNH2-HCl/Al/ketone and how long did the reaction last before it was time to process the final product?

Here is a link that describes a similar peracetic reaction to yours:

http://l2.espacenet.com/espacenet/bnsviewer?CY=ep&LG=en&DB=EPD&PN=US4393242&ID=US+++4393242A1+I+



Thanks.

Chromic

  • Guest
A perfect world?
« Reply #52 on: June 11, 2002, 02:15:00 AM »
>In a perfect world, drugs would be legal and easy to obtain, then NONE of us would
>be making any of these things.

Really? I disagree. Some of the chemists are here because they are interested in the chemistry and not interested in making any money.

>Was the peracetic acid solution added drop by drop or all at once under cooling? 

It was sitting in the fridge and them poured into the flask.

>Was the amination done under stirring?

Yes. The epoxidation, rearrangement, distillation and amination were all done with magnetic stirring.

> Btw, I don't really understand RoundBottom's post.  What is the purpose of applying
>the vacuum for 30 minutes?  Why not just stir the KOH and alkene for 20 hours at a
>temp of 160 instead?

That's what he does. The initial vacuum is to remove the water present in the KOH, otherwise you're
not going to affect the conversion of safrole to isosafrole and you risk destroying the safrole.

>Could you please just state what YOU did to make things easier.

I recited the general technique in other posts. Freezing and isomerization is hardly rocket science.

>Please include all weights and measurements.  RoundBottom's diagram was just plain confusing to me.

Get him to clarify it then.  :)

>What are the ratios of methanol/MeNH2-HCl/Al/ketone and how long did the reaction
>last before it was time to process the final product?

It went 5hrs.

The reaction details are novel, and are a combination of a variety of information already publically available. No synthesis that I could find uses prepares HOOAc from H2O2/acetic acid and does the oxidation in DCM (to the best of my knowledge). If you want my references for this reaction, I invite you to read:

EP patent 1,140,788

http://l2.espacenet.com/dips/viewer?PN=EP1140788&CY=gb&LG=en&DB=EPD

(pg27)

J Chem Ed, Volume 73 (6), 555 (1996)

https://www.thevespiary.org/rhodium/Rhodium/chemistry/2-phenylpropanal.html



US patent 3,028,398

http://l2.espacenet.com/dips/viewer?PN=US3028398&CY=gb&LG=en&DB=EPD



Organic Syntheses, CV 4, 860

The amination was:
133mmol mdp2p in flask A. 29.8g MeAmCl + 30mL water in flask B. 53ml water + 17.7g NaOH in flask C. In an ice bath, flask C is added to flask B. In a 500ml flask 185ml MeOH, 0.1g HgCl2. Stirred. Added 11.9g Al foil. Left stirring until it starts to bubble. Added flask B then flask A. Rinsed flask A with 10ml MeOH, added to rxn. Let run 5hrs. Basified with 89g NaOH in 210mL water. Extracted with 250ml toluene. Washed with 250ml 5% NaOH. Filtered toluene to remove chunks of foil. Washed with 250ml 5% NaOH. Washed with brine. Extracted with acidic water (titrated to pH 4). Washed with acetone. Took yield. Then went on to recrystallize. (no A/B or freebase distillation was done, I'm sure Rhodium & Osmium disapprove!)

If you need more details, read up more. I think all the essential details have been covered in these posts.

goiterjoe

  • Guest
Isn't it already basic?
« Reply #53 on: June 11, 2002, 02:17:00 AM »
When you run an Al/Hg reductive amination, isn't the resultant slurry already basic from the aluminum hydroxide present?  I thought the purpose of adding that much sodium hydroxide afterwards was just to finish eating up the aluminum and making the mixture easier to separate out.

As far as an A/B extraction, It would be easy to add that step at the end of the writup after the NP extraction.  Just add ~15% hydrochloric acid to your MDMA freebase/NP mixture until acidic, extract the water layer, wash with NP, then add 25% NaOH solution until all of your freebase has separated out.  Then you could take your oil, dissolve it in IPA, and titrate in concentrated hydrochloric acid until neutral.  You could then reclaim your MDMA crystals.  You could further wash them with a NP solvent.

greeter

  • Guest
blip
« Reply #54 on: June 11, 2002, 02:35:00 AM »
Chromic:

    I completely understand about doing it for the love of Chemistry, but are you saying that when it comes to drugs you wouldn't rather be putting some FDA approved USP grade drugs in your body?  I'm not saying there's no need for home Chemistry, it's just that if you could get a pharmaceutical grade tab of MDMA for $5 at the grocery store then what would be the point of creating it yourself (other than maybe once to learn)?  I think doing research chemistry (say synthing analogues) would be much more intriguing (not to mention within the law).  Anyway, $.02 from the peanut gallery.

goiterjoe:

As far as an A/B extraction, It would be easy to add that step at the end of the writup after the NP extraction.

    I think this is what is being talked about (with respect to additions to the MM writeup), but I think it's necessary to do a water wash (at the very least one, maybe even two or three) in addition to carefully filtering the sludge prior to making it acidic.  Otherwise there's just too much grit and sludge in there.



A watched pot will indeed boil.

goiterjoe

  • Guest
That's what I implied
« Reply #55 on: June 11, 2002, 03:20:00 AM »
I was implying that; it would be stupid to skip the bicarbonate washes and water washes.  You would start with the A/B steps right before the MM paper instructs you to gas your product.

Besides, this A/B wash would be just as quick as gassing for recovering crystals, and would be well worth the effort.

RoundBottom

  • Guest
ISO
« Reply #56 on: June 11, 2002, 07:50:00 AM »
um... diagram?  did i write a diagram?  it was a long weekend, pls tell me the post number and i'll try explaining it.

also, chromic is correct about the "sucking" out of the water, that is what SWIM was attempting.  i believe i updated the writeup later on to indicate that i didn't use a column while running the vacuum.  make sure you use a vacuum trap, as it won't help your pump any to suck any water (or solvent) into it.

do it any way you want.  experimentation is just that.

i learned a thing or two from charlie dontcha know.

Rhodium

  • Guest
The PRIDE of being able to
« Reply #57 on: June 11, 2002, 06:56:00 PM »
I'm not saying there's no need for home Chemistry, it's just that if you could get a pharmaceutical grade tab of MDMA for $5 at the grocery store then what would be the point of creating it yourself

Speak for yourself only. If you already have all the lab supplies, the chemicals used for synthesizing 125mg MDMA and purifying it to USP standards are just a few cents, and that's just the economic argument. Then - isn't it something special about knowing that the compound that made the experience for you and your friends possible was a creation of your own mind and own skills?

That's just the beginning - novel analogs are even more exciting, knowing that you are the first human to experience the effects of a certain analog, which is also your own creation - that beats sex and everything else on the planet...

humidbeing

  • Guest
yeah!
« Reply #58 on: June 11, 2002, 08:51:00 PM »
With that staement you've really shown where your
heart lays rhodium!  You're a true believer.

CG I miss you sweety, I really do.

Antoncho

  • Guest
Yes.
« Reply #59 on: June 12, 2002, 02:11:00 AM »

isn't it something special about knowing that the compound that made the experience for you and your friends possible was a creation of your own mind and own skills?





Rhodi...i almost cried when i read this :)

have to confess that for that very reason i'd hate to see certain things to bee government-approved :) ........ :) ......... not for my children, maybee, but definitely for myself..... :)

Sorry for offtopic ;)



Antoncho