Author Topic: gassing in acetone worries..... acetone + HCl = phorone?  (Read 138 times)

NeilPatrickHarris

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gassing in acetone worries..... acetone + HCl = phorone?
« on: June 28, 2010, 07:53:21 PM »
tired of dealing with xylene/toluene that i can't get rid of from gassed crystals no matter how hard i wash them with acetone, i'm on the verge of one of two things, either gassing in acetone or going back to titrating

Moriarty shared an article over at PN where a lab in Indonesia was gassing mdma freebase in acetone, it was a megalab.  I'd always been worried about the reactivity of acetone.

What's the main worry about gassing in acetone, the formation of phorone?  Possibility of chlorine being introduced also?  All these reasons why gassing in acetone is a bad idea or is it really that much of a concern?  I have no idea how long it takes for these reactions to take place so i can't make a judgment call

Vesp

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Re: gassing in acetone worries..... acetone + HCl = phorone?
« Reply #1 on: June 28, 2010, 08:16:24 PM »
If allowed, you can turn acetone into 1,3,5-trimethylbenenzene, tons of other side products are made, and the steps taken to get there are pretty complex -- I do not believe it is that you only need to fear phorone, but a lot of others... it is probably best though to get some of these questions answered...

Does dry HCl cause condensation/dimerization of acetone, or does water have to be present to allow that reaction to happen at any appreciable rate? I.e does the HCl perhaps need to be ionized?

If it is kept cool, and you run the reactions fast, is it likely that any slightly significant amount of condensation products form?


Than another thing to consider is how much HCl will be present in the acetone considering solubility, the fact that the amines will be taking it out of the system, and also does the amine*hydrochloride also cause condensation products to form, or are those close enough to neutral to have no significant effect?

I would see how long it takes acetone to start reacting if it is very dry and very dry HCl is added too it - it might take a very long time?


It would be nice if you could give a source/reference -- such as those articles on PN.


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Naf1

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Re: gassing in acetone worries..... acetone + HCl = phorone?
« Reply #2 on: June 28, 2010, 09:05:25 PM »
Quote
It would be nice if you could give a source/reference -- such as those articles on PN

Quote
PROCESS FOR PREPARING (S)-(+)-CLOPIDOGREL BASE AND ITS SALTS
Patent application number: 20100016595

EXAMPLE 2

[0020]Clopidogrel base 5g [(I), R isomer 4%) was dissolved in acetone (50 ml), cooled and HCl gas passed till pH 1. The reaction mixture was stirred at 20-25.degree. C. for .about.16-18 hrs. The mixture was partly distilled and stirred for another 3 hours, filtered (R isomer as solid residue, 31%), & washed with acetone. Mother liquor was distilled off to get sticky solid 4.9 g (R isomer 2.5%). The reaction mixture was dumped into dichloromethane-water and to this was added 10% NaHCO.sub.3 solution (50 ml) at low temperature with stirring, pH was maintained at .about.8-9. Organic layer separated and aqueous layer extracted with dichloromethane. The combined organic layer was washed with water, stirred with activated charcoal (1.0 g) and sodium sulphate and hyflow filtered, washed with dichloromethane and distilled off at 50-52.degree. C. and traces removed under reduced pressure to get oil. The (S)-(+) Clopidogrel base was obtained as a pale yellow oil. (wt=4.3 g, R isomer 2.5%, chiral purity 97.5%)


http://www.faqs.org/patents/app/20100016595#ixzz0sBSRj8S4

Best Method for Hydrochloric Acid Gas
by Argox

'It was determined that IPA is superior to acetone.'

https://orgchembase.com/archive/Rhodium/chemistry/hclgas.argox.html

NeilPatrickHarris

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Re: gassing in acetone worries..... acetone + HCl = phorone?
« Reply #3 on: June 29, 2010, 02:39:37 AM »
FYI here's that article about the Indonesian lab.  All thanks for Moriarty for this find:

Quote
The DEA Singapore Country Office and DEA Special Testing and Research Laboratory (Dulles, Virginia) recently assisted in the seizure of a very large MDMA/amphetamine operation in Tangerang, Jakarta, Indonesia. The laboratory was seized by the Indonesian National Police, and consisted of a chemical synthesis laboratory and a separate tabletting operation. The synthetic route to MDMA involved reductive amination of 3,4-methylenedioxyphenylacetone (MDP2P or PMK) with methylamine and sodium borohydride; the hydrochloride salt was produced by gassing an acetone solution of the free base with commercial hydrochloric acid gas.
h**p://www.justice.gov/dea/programs/forensicsci/microgram/mg0103/mg0103.html  <- be careful with that link

i do also recall the hive post "Processing 1 Mole Ketone Using Nitromethane" by Abacus who came up with the method of reducing nitro via the al/hg first, isolating the MeAm and then running a standard MeAm Al/Hg.  Abacus was a big advocate of gassing in acetone, he distilled his freebase and use 4x v/v acetone to freebase.  i know that doesn't say anything but i figured i'd toss it out there.  here is the link to that post
http://127.0.0.1/rhodium/Rhodium/hive/hiveboard/methods/000382493.html

From that same "Processing 1 Mole Ketone Using Nitromethane" stated above, Osmium came through and said "I can also recommend the following crystallization procedure: dissolve freebase in IPA, gas with HCl, and then crash out the product with excess acetone. Store at -20°C for some time and filter. Save those mother liquors, still some goodies in them!"

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Yeah Vesp there are quite a few possibilities depending on your technique, seems like a lot of different by-products that could be produced, some of them are crystalline and probably difficult to differentiate from your amine salts too.  granted i'd imagine it would take more time than what's used in a simple gassing to obtain these by-products, it's just a really scary thought and personally i'm one that's big of piece of mind for knowing my solvent won't react to form something unexpected.  at the same time i'm tired of tasting xylene/toluene.  i had always worried IPA was too polar to work well for gassing MDMA HCl but maybe not?  i guess it just depends on what the dielectric constant drops to at < 0C.  it'd be great if someone had a reference for IPA's dielectric constant at 0C

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Naf1 thanks for that article!  There are indeed lots of worries about using acetone if one plans to store the acetone with HCl in it for any length of time, that idea alone makes me want to stray away from gassing in acetone altogether.  My main worry is MDMA HCl and MDA HCl's slightly higher solubility in IPA than acetone.  does anyone have the dielectric constant of acetone and IPA at 0C and 25C for comparison?  these numbers below are the closest i could find:

taken from here h**p://clippercontrols.com/pages/dielectric-values
Acetone (77° F) 20.7
Acetone (127° F) 17.7
Acetone (32° F) 1.0159
Iso-Propyl Alcohol (68° F) 18.3
Toluene (68° F) 2.4
Xylene (68° F) 2.4

so combine your freebase with 4x v/v dry, freezer cold IPA and gas away.  the freezer cold IPA will ensure HCl having a higher solubility in the IPA.  BTW the 4:1 IPA to freebase volumetric ratio was pulled out of my ass, it just sounds like a roundabout nice volumetric ratio to use and is not based on HCl(g)/IPA solubility vs stoichiometric HCl to freebase amount like it should be based on.  i must admit it would be really nice to find out HCl's solubility in subzero temp IPA so one could prepare a pregassed IPA solution, store in the freezer then add the right volume of it to your freebase (in excess of course).
« Last Edit: June 29, 2010, 02:44:14 AM by NeilPatrickHarris »

jon

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Re: gassing in acetone worries..... acetone + HCl = phorone?
« Reply #4 on: June 29, 2010, 03:51:07 AM »
***BTW the 4:1 IPA to freebase volumetric ratio was pulled out of my ass***

it's okay neil with all this talk of assatone and gas it was inevitable that  would happen.
we forgive you.

NeilPatrickHarris

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Re: gassing in acetone worries..... acetone + HCl = phorone?
« Reply #5 on: June 29, 2010, 12:03:20 PM »
***BTW the 4:1 IPA to freebase volumetric ratio was pulled out of my ass***

it's okay neil with all this talk of assatone and gas it was inevitable that  would happen.
we forgive you.

lol jon with the steady eye for details