bluealcoholflame
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Dipipanone Synthesis Questions
I've been looking around at all of the published methadone synthesis that are about, and most are actually pretty complete. So I started poking
around the opioids that were similar to methadone. Funny enough, I can't find a complete reaction for dipipanone anywhere. I've checked in "Opioid
Analgesics" by Paffit, as well as Paul Jansens seminal text on the subject. All of these basically just say to do the same methadone synthesis but
sub-out 2-dimethylaminoethyl chloride instead of 2-dimethylaminoisopropyl chloride. Anyways, my actual question is what are the intermediate
aminonitriles formed by this reaction? In the case of methadone, you have a high melting and low melting nitrile, which one will recrystallize from
cold hexane first. Any idea if 2 amino nitriles are formed with dipipanone synth? Also, is one the useful product and the other not, or can they
both, with the help of grignard, create the isomers of dipipanone. Also, if one is not useful, what is the standard method of separation? Is it
similar to the cold hexane crystallization (and which one is the useful product, the initial crystallizing solid, or the one that crystallizes last)?
Thanks for your help- these questions have been bugging me like crazy-
-bluealcoholflame
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zed
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Such discussions aren't common here. Try the Vespiary.
Though you have clarified something. The outright purchase of Dimethylaminoethyl Chloride(and salts thereof), has for many years been "touchy".
I now understand why.
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bluealcoholflame
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Thanks for the suggestion- I wasn't really sure where to post. It seems like such a throw back question- at least in the US. Dipipanone has been
Schedule 1 over here for a couple of decades, so most research/chemistry into it stopped years ago.
Also- I think that the reason chem companies are "touchy" over 2-dimethylaminoethyl chloride is for 2 reasons:
1. It is an environmental toxin
and, their highest concern;
2. It can be used to make mustard gas.
Some indexes refer to 2-dimethylaminoethyl chloride as one of the "half mustard" agents. I know it is monitored by the UN, but not sure about
domestically (in the US at least).
-bluealcoholflame
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zed
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Not especially hard to make. But, even 35 years ago, it was touchy buying it outright.
Handy for the 3-alkylation of Indole Grignards, but that reaction was not very widely known in those days.
Precursor for the synthesis of Opioids and Chemical weapons? Yeah, that would raise some eyebrows, even in those easygoing days of yore.
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bluealcoholflame
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A little update-
I found an article from the Royal Chemistry Society ("Search for New Analgesics, Part IV, Variations in the Basic Side-chain of Amidone (w/ a Note on
Some Pharmacological Results)", Ofner and Walton, RCS 2158, 1950) that has the original synthesis included (as well as many other similar opiods).
It's a fantastic article- if anyone is interested in a copy, please let me know. The answer to my question is that yes, there are 2 different
aminonitrile products. And yes, the active aminonitrile is crystallized from hexane (@ 0 deg C) as the second crystallizing product (in basic form)
and as the first crystallizing product (as a halide salt). The conversion with grignard is not as easy as methadone, though, because of a stable
intermitent ketimine. Apparently prolonged acid hydrolysis is
needed (they used HBr, although i'm pretty sure HCl would be suffiecient). I would still appreciate any practical advice or thoughts on this.
Thanks!
-bluealcoholflame
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andy45
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HELLO bluealcoholflame
iam very interesting in the dipipanone synthesis can you give the copy of the artIcle?
thaks
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jon
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i am also interested in that article can you somehow provide a link to rapidshare.de???
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bluealcoholflame
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Sorry for the long wait- work and family have been overwhelming...
Anyways- just an update...
I have uploaded the article on dipapinone synthesis to Rapidshare (as well as attaching it to this message, for both users and non-users alike)...
here is the link-
http://rapidshare.com/files/444765751/JR9500002158.pdf
If anyone could answer a question for me...
SWIM synthed then left an appreciable amount of Methadone in it's final hydrolysis product for almost 2 months (comprised of h2o, mgcl, ~10%hcl)- it
was silly, but SWIM was sleepy after being up so long synthing
anyways- when SWIM ran into hard times, SWIM did a work up on what was left- and after a bit of work, SWIM was left with nice needles of what should
have been methadone. now what SWIM can't figure out is that this stock seems to work, but just barely (SWIM takes around 300 mgs of methadone a day)
and he has to take almost 2 G of the extracted product for the sickness to subside, but mostly he just gets sleepy. It is not just weak- he did a
recrystalization and another full work up because of how weak it was, but SWIM knows it's something- maybe something similar to NORmethadone
(something with about 1/5th the potency of methadone). if anyone has any ideas- let me know. I can't figure out how prolonged HCl hydrolysis of
methadone hcl could have caused anything like this.
SWIM's was very happy with the rest of his original batch- swim will prob try dipapinone if he can figure out what the other precursor is- the text is
vague and i can't find anything anywhere else. any thoughts would be appreciated for both questions!
thanks-
-B.
[Edited on 27-1-2011 by bluealcoholflame]
Attachment: JR9500002158.pdf (244kB)
This file has been downloaded 1139 times
[Edited on 27-1-2011 by bluealcoholflame]
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turd
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Please don't use SWIM - not only is it quite embarrassing, it also makes the text terribly hard to read. I could barely figure out what you are
talking about. If you want help it should be your first priority to make yourself clear. Just use the typical impersonal style of scientific papers.
The first thing you should do is take a reliable melting point of your analytically pure (recrystallized) sample. Leaving an organic compound in
strongly acidic media for 2 months is generally not a good idea, especially given the fact that methadone has a ketone functionality. I'm surprised
that you got anything at all and not only a dark red mess!
HTH
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ScienceSquirrel
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If you keep on SWIMing you will find that quite a few people on here will ignore you.
I will discuss chemistry, I do not discuss making bombs or cooking your own drugs!
You should at least do a melting point or do TLC in with two different solvents and a reference standard on any drug you make before taking it.
Poisoning yourself is not a clever move!
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madscientist
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SWIM = someone who is me, and everyone - the courts included - knows it.
No use of SWIM, please.
[Edited on 28-1-2011 by madscientist]
I weep at the sight of flaming acetic anhydride.
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DDTea
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Brainstorming a bit here.
Strong acid solutions can protonate ketone groups and activate them toward nucleophilic addition reactions. Although these can be finicky with regard
to pH when it comes to adding an amine to a carbonyl, it is hypothetically possible. In this case, I'm going to speculate that, if normethadone is
left in acidic solution for a long time, the amine may have undergone some intramolecular annulation by adding to the ketone group, forming a cyclic
enamine. Add that to the list of possible compounds!
Besides melting point and TLC, some wet chemical test for either primary or secondary amine may be useful here (after separating the components of
this mess, of course).
"In the end the proud scientist or philosopher who cannot be bothered to make his thought accessible has no choice but to retire to the heights in
which dwell the Great Misunderstood and the Great Ignored, there to rail in Olympic superiority at the folly of mankind." - Reginald Kapp.
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bluealcoholflame
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Sorry for SWIMing- I have been out of the game of online chem forums for the last 8 years (since the hive went down). Still trying to get a handle on
what is enough and what is too much. I suppose instead of SWIMing, it's just better to just not talk about such things.
Chemistry only- got it.
I actually did a melting point test on what should have been the HCl salt of Methadone- came out 248c (which is 3 deg over the proposed melting
point).
I have since scrapped everything that wasn't what it should have been as soon as I realized that I had obviously made a mistake.
On to the social issue here- don't know how many of you are in the same predicament, but being a junky will bring down your standards (especially
when dope sick). I am a relatively successful middleaged professional- most of time I look like someone that you wouldn't think twice about asking
for a ride when your car breaks down. But there is a chunk of time where I find myself doing things that are a odd and/or desperate- but only when
sick.
A sick junky would drink what COULD be poison if only it MIGHT contain a portion of a narcotic. And I'm talking about what would seem to be
intelligent people. I personally have very tight set of principles- I don't steal, I don't hurt anyone else, and I don't violate anyone else's
privacy or do anything that would harm them in my pursuit as a junky. I spend all day managing a department (doing whatever it is I do- think
design/engineering professional) and my habit is my reward. I can't control it- I would be still "rewarding myself" even if I did nothing but sit on
a street corner all day squeegying people's car windsheilds with a newspaper. I don't kid myself though- a junky is a junky is a junky- none of us
better and none of us worse. I've been to the point of being on the street- but methadone has been a great help- it's just so damn expensive.
I know the rant is off topic- just thought a little background was necessary. I don't think that you can seperate the concept of freedom of
individuals to talk and promote chemistry without some thoughts of the ethical implications. There are some people with similar dispositions as me
that don't care about themselves or others- and there is an obvious need to protect society from their actions (see the Junky Code of Conduct (JCoC)-
which I made up but will someday have to put to paper).
I don't delude myself- I have a problem- but as long as it's just my problem (and not anyone elses) then I will continue on (into the wild yonder).
I know that no one gets things shut down for everyone but irresponsible drug addicts. Junkies love to ruin a cool little secret by overexploiting it
(because they are, well, junkies). Better to not have them on the forum, probably.
Except I do have a thourough genuine interest in chemistry- especially enanomers/stereo chemistry and grignards (from my college days of taking
Organic Chemistry labs- I was only required 1 advanced chem class, but I took 4 b/c it was just so damn interesting.
Will come back with actual clarification on the Dipipanone synthesis- I have a friend who is very familiar with Jansen's work- hopefully we will have
some further clarification on the secondary precursor as well as the step of HBr hydrolysis (it seems to me that aq HCl hydrolysis would work just
fine, but the synth speaks about a stable ketimine).
Will keep everyone updated (and sorry for the novel- just thought it would be good to get some things out in the open).
-B.
~
This is a strange and wonderful time that we live in.
~
[Edited on 28-1-2011 by bluealcoholflame]
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ScienceSquirrel
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Most of us are quite happy to discuss chemistry and drug synthesis from a theoretical point of view and give some practical advice.
I worked as a synthetic organic chemist before getting involved with computers and I know a quite a lot about drugs of all kinds as well as
pesticides, etc as they are valuable products.
I would describe myself as a liberal with a social conscience. The sort of thing that I really dislike are people coming on here and their first post
is a request for an A plus B recipe to make GBH from essence of glue plus toilet cleaner.
Not only are there the risks of making something that you intend to consume using this type of methodology and very little skills but GBH is a nasty
compound that has landed quite a few people in hospital and has been used for date rape.
You seem like a genuine person and I think people will be glad to help you out.
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andy45
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are you looking for the precursor to make 2-chloro-1-piperidinopropane?
By the way you can just replace 1-dimethylamino2-chloropropane by 2-chloro-1-piperidinopropane and do the methadone synthesis to get dipipanone.
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