Ritter
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Phenyl-2-propanone (and heroin) from Ac2O
I'm moving this discussion from Energertic Materials. It has to do with the well-known use of Ac2O to produce phenyl-2-propanone.
| Quote: | Experimental
To a mixture of 136 g (1.0 mol) phenylacetic acid, 70 g sodium or potassium acetate, and 16 g (0.1 mol) anhydrous cupric sulphate is introduced 2000
ml anhydrous acetic anhydride* in 4000 ml flask. The mixture is refluxed 24 h. After cooling 500 ml of solvent (CCl4, CHCl3, CH2Cl2) is added and the
mixture is poured to a flask containing 2000 ml ice-water. After separation of layers upper layer is removed and lower layer is three times decanted
with water, separated, dried (Na2SO4, CaCl2), and distilled. The solvent is distilled off and fractionation column is placed on the top of the flask.
Remaining acetic acid and acetic anhydride is then removed, pure product is collected at 100°C/15mmHg. Yield 70-90 g (52-67%).
* The technical product, which contains water, can be dried by adding 10 g thionyl chloride.
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Source: http://www.erowid.org/archive/rhodium/chemistry/p2p.paa-aa-n...
Additional reference: JP59152342
Quite apart from this use of Ac2O, its DEA regulatory status is dealt with here:
| Quote: | | Because of its use for the synthesis of heroin by the diacetylation of morphine, acetic anhydride (known as 'AA' in clandestine chemistry circles) is
listed as a U.S. DEA List II Precursor,[6] and restricted in many other countries. The largest markets for diverted acetic anhydride continue to be
heroin laboratories in Afghanistan. |
Source: http://en.wikipedia.org/wiki/Acetic_anhydride
I apologize in advance if any aspect of this post is inappropriate & will gladly delete it if requested to do so.
[Edited on 27-7-2008 by Ritter]
[Edited on 27-7-2008 by Ritter]
Ritter
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\"The production of too many useful things results in too many useless people.\"
Karl Marx
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Sauron
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Generally, lead acetate is dry distilled with PAA to get crude P2P.
The DEA does not regard lead acetate as a "forbidden" chemical either. They are content with P2P and phenylacetic acid.
Show us the imaginary "forbiden list" Ritter.
List 1 and List 2 (DEA) chemicals are not restricted. The DEA just obliges the sellers to report sales above certain threshold values, and to keep
records. The onus is on the sellers.
So your proposition that Ac2O is forbidden ("on the forbidden list")as a meth precursor is simply and patently false. You should get your nose out of
the patent archives once in a while and get out into the real world.
There are many routes to P2P Ask Organikum, ask solo. That's pretty much their forte. Well, phenylethylamine chemistry in general.
I seem to remember one involving phenylacetyl chloride and diethyl malonate. No Ac2O anywhere in sight.
Another involving lithiation.
Still no Ac2O in sight.
Come on, Ritter? Where's your forbidden list? Is it in Joe MCCarthy's pocket along with his list of communists in the Defense Department?
It ought to be, as they are equally fictitous.
[Edited on 28-7-2008 by Sauron]
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Ritter
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| Quote: | Originally posted by Sauron
Generally, lead acetate is dry distilled with PAA to get crude P2P.
The DEA does not regard lead acetate as a "forbidden" chemical either. They are content with P2P and phenylacetic acid.
Show us the imaginary "forbiden list" Ritter.
List 1 and List 2 (DEA) chemicals are not restricted. The DEA just obliges the sellers to report sales above certain threshold values, and to keep
records. The onus is on the sellers.
So your proposition that Ac2O is forbidden as a meth precursor is simply and patently false. |
Here is what I posted:
| Quote: | | I believe Ac2O is on the forbidden list. |
Actually, Ac2O is tracked by the DEA regardless of its end use. Anything over 100 kgs gets scrutinized. Operation Topaz:
http://www.deadiversion.usdoj.gov/mtgs/chem_industry/conf_09...
And Ac2O is a known phenyl-2-propanone precursor. Attached is the English abstract of the Ube Japanese patent. They are a major producer of
phenyl-2-propanone, I believe.
[Edited on 27-7-2008 by Ritter]
Ritter
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\"The production of too many useful things results in too many useless people.\"
Karl Marx
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Sauron
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Tracked does not equal FORBIDDEN. You said FORBIDDEN. And when was the last time anyone around this forum ordered 100 KG of anything? 100 g is more
like it.
Stop spamming the board with nonsense, Ritter.
There are many routes to amphetamines that do not proceed through P2P at all.
I suggest you go to Kirk-Othmer or Ullmann's and look up the annual worldwide production of acetic anhydride sometime. It is a mass produced chemical
commodity. Many industries consume VAST quantities of it. The amounts used to produce heroin are trivial in comparison, and those to arguendo, produce
P2P even more trivial. I doubt there's a DEA agent parked inside every acetate resin plant or aspirin factory.
Org.Syn. has a pep of P2P using a vapor phase reaction of PAA over thorium nitrate on pumice in a tube furnace, so you want to call thorium a
precursor of amphetamines? Go ahead and get laughed out of town.
If you go back a couple-three steps from P2P by all possible routes you get a LONG list of precursors, fella.
If you go back the same number of steps from PAA you get to toluene.
Toluene - benzyl halide - benzyl cyanide - phenylacetic acid
And that's not the only way.
Get a grip.
Calling acetic anhydride a precursor of meth is like calling 2-propanol (rubbing alcohol) a precursor to sarin.
Technically correct and of no practical significance at all.
Anyway, the central issue is your characterization of Ac2O as FORBIDDEN.
Wrong!
Widely used, and watched to some extent above a 100 Kg threshold. I think we can agree that 100 Kg is an industrial quantity. Well industry buys it
by the multiple tons.
[Edited on 28-7-2008 by Sauron]
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Ritter
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| Quote: | Originally posted by Sauron
Tracked does not equal FORBIDDEN. You said FORBIDDEN. And when was the last time anyone around this forum ordered 100 KG of anything? [Edited on
28-7-2008 by Sauron] |
I stated what I believed to be the case & in reality the DEA closely monitors Ac2O which can be used to make phenyl-2-propanone. So your
point is?
You are quibbling about a point of semantics just as you were quibbling in the CL-20 thread about the aesthetics of my graphics files versus yours.
I suggest we drop this & go back to talking about interesting things.
[Edited on 27-7-2008 by Ritter]
[Edited on 27-7-2008 by Ritter]
Ritter
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\"The production of too many useful things results in too many useless people.\"
Karl Marx
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Sauron
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What irks me about you is your stubborn pigheaded refusal to admit you were simply wrong.
I just looked up the annual production capacity for acetic anhydride. from Ullmann's.
"The production data of recent years, as far as they are available, are given in Table (3). Recent annual capacity data for acetic anhydride are as
follows: Western Europe (1978) 357000 t, (1980) 362000 t; United States (1980) 905000 t, (1982) 929000 t. The start of operation at the new
Tennessee-Eastman plant (Halcon Process) with a capacity of 227000 t should not change the total capacity in the United States significantly, because
it is expected that a corresponding capacity from the ketene process will be shut down in the next few years. No data for the mixed anhydrides are
available."
Almost a million TONS annually in the US alone.
About the same for rest of the world.
Now, how much of that is required to process the annual opium yield from the poppy fields in South Asia and South East Asia and let's not forget
Mexico?
I'm sure DEA and/or UNDP have got stats available.
But is should be obvious that the amount of acetic anhydride required is a tiny fraction of one percent of the global acetic anhydride production.
Now, since the heroin production increases annually while the price drops, does it sound to you like DEA and their colleagues are doing a very good
job at interdicting this traffic. including the diversion of Ac2O? It ought to be obvious that trying the stop the diversion of say 0.0001% of a mass
manufactured chemical commodity is an impossible task and the results (dismal failure decade after decade after decade) bear this hypothesis out.
Now, you want to characterize Ac2O as a meth precursor, where diversion for that purpose is MINISCULE in comparison? Well go right ahead and say what
you like but your position is a JOKE. And you are well on your way to being one too.
[Edited on 28-7-2008 by Sauron]
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Sauron
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From a Dept of Justice site:
"Heroin is produced from opium poppy cultivated in four foreign source areas: South America (primarily Colombia), Mexico, Southeast Asia, and
Southwest Asia. Estimates of worldwide potential opium and heroin production increased considerably between 2001 and 2002. According to the Crime and
Narcotics Center (CNC), worldwide potential oven-dried opium production estimates increased from 1,345 metric tons in 2001 to 2,249 metric tons in
2002, resulting in an increase in estimated worldwide heroin production over that period from 134 to 246 metric tons. Worldwide production estimates
rose primarily because of a resurgence of cultivation in Afghanistan in Southwest Asia, but the heroin from this area generally is consumed in Asian
and European drug markets. Estimates for Colombia and Mexico--the sources of most of the heroin available in the United States--as well as for
Southeast Asia decreased. Heroin from both Southeast and Southwest Asia is available in U.S. drug markets in lesser amounts."
Morphine represents c.10% of opium by weight.
Therefore we can approximate the total annual morphine base production at 225 metric tons.
The conversion to heroin is a rather lossy process.
So as a very rough estimate let's say 100 MT heroin.
The stoichiometry is simple. Two mols Ac2O to 1 mol morphine. The MWs are known. I haven't looked up the MW of morphine base but it is in Merck. And
it is a large multiple of the MW of Ac2O.
Actually it takes c 80% (224 g vs 284 g) the mass (not molar mass) of acetic anhydride to convert the morphine base. So we are talking 160 MT Ac2O to
convert the entire annual morphine base produced..
That is out of the worldwide production of about 2 million MT Ac2O.
QED.
To summarize:
1. Ac2O is not forbidden, it is just watched. In some parts of the world it IS restricted but not in the West.
2. On the contrary it is a major mass produced chemical commodity. Made to the tune of 2 Million metric tons annually, that is 2 BILLION Kg.
3. I have made a rough estimate of the demand for diverted Ac2O to produce heroin from morphine, It is c.160 MT, a trivial amount compared to
production.
4. I believe that it is this disparity that makes monitoring so difficult, and demonstrably a long term failure.
Now as to amphetamines:
There are many routes to amphetamines and not all or even most go through phenyl-2-propanone
There are many routes to P2P and not all or even most go through Ac2O
Ac2O therefore is if anything a minor "precursor" to amphetamines, one of many many.
Oh, if I were the DEA I would be watching 4-DMAP as were I a heroin chemist I would certainly like to use it to improve yield and shorten reaction
time and/or allow milder conditions.
[Edited on 28-7-2008 by Sauron]
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Ephoton
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thats a horrible way to p2p ritter my uncles dog could wipe it up quicker than that from
paint thinner ;P
acetic anhydride is only dangerous if you have the means mind and purpose to use it
for evil (ie what the goverment think is evil).
use it for good and you can publish my friend and all the pats on the back are yours.
please do not use some ones nick then say there into this or that. its rude unless
some one asks you too  . common manners my man.
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bash-2.05#
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Sauron
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ephoton, go read Orgie's threads and solo's posts and draw your own conclusions.
Common sense, old man.
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ScienceSquirrel
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Give the resources available to the large scale clandestine drugs trade the diversion of acetic anhydride on the scale that Sauron is talking about is
a fairly easy matter.
Front companys can be set up or legitimate companys can be 'bent' to buy from the manufacturers or their agents.
Even if there is an elaborate system of checks in the USA, the stuff is exported on a large scale elsewhere in the world.
Many developing nations have sizable chemical industries as well, this is only a partial list of manufacturers worldwide
http://www.thomasglobal.com/search/heading.asp?new=Y&hid...
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Nicodem
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I'm moving this thread to Legal and Societal Issues section since it obviously does not belong to Organic chemistry.
Ritter, when you open a new thread, please take a minute to describe the topic start a discussion. Your autistic way of thread forming is a bit
annoying (I already told you this as a forum member and now I'm telling you as a moderator). I honestly don't know what kind of discussion is a thread
supposed to be starting when all you do is copy/pasting some text without commentary. Even if not on purpose, you make your self look like you are
just post whoring. Not to mention that we already have threads dealing with list of watched chemicals and related topics. Acetic anhydride in EU is
certainly not "scheduled" or however that status is called in the USA, however when buying it one has to sign the end user declaration due to the
danger of it being diverted to Afganistan and other countries where the acetylation of morfine is done.
…there is a human touch of the cultist “believer” in every theorist that he must struggle against as being
unworthy of the scientist. Some of the greatest men of science have publicly repudiated a theory which earlier they hotly defended. In this lies their
scientific temper, not in the scientific defense of the theory. - Weston La Barre (Ghost Dance, 1972)
Read the The ScienceMadness Guidelines!
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Sauron
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The infamous Golden Triangle of Laos, Burma and Thailand adjoins India and China and it is very likely that the Ac2O needed comes from those sources.
The South Asian trade adjoins India as well, and also several former Soviet republics. Also Pakistan and Iran.South American and Mexican heroin
refining, I know nothing of its logistics and so will not speculate.
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MagicJigPipe
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I think Ritter was just simply trying to point out that an individual would have a difficult time acquring acetic anhydride in the US without
problems/opposition. Many things aren't "forbidden" but are nevertheless risky to attempt to purchase or possess.
I certainly wouldn't risk buying it (in the US) even if the risk is low. Remember, alkali cyanides are high volume chemicals that are used
occasionally in the production of drugs yet there have been stories popping up about people being watched for purchasing it.
I don't think chastizing him for his "mistake" is very becoming. But, then again, I'm not extremely familiar with his posting history.
This observation is based on what Sauron said about what Ritter said as Ritter has apparently deleted much of his original post. I just thought I
would attempt to put it in perspective.
All that aside, if you haven't noticed I've been absent from the site for a while. School seems to get in the way of everything else.
"There must be no barriers to freedom of inquiry ... There is no place for dogma in science. The scientist is free, and must be free to ask any
question, to doubt any assertion, to seek for any evidence, to correct any errors. ... We know that the only way to avoid error is to detect it and
that the only way to detect it is to be free to inquire. And we know that as long as men are free to ask what they must, free to say what they think,
free to think what they will, freedom can never be lost, and science can never regress." -J. Robert Oppenheimer
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