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Q: Fritz Haber and MDMA ( Answered 5 out of 5 stars,   0 Comments )
Question  
Subject: Fritz Haber and MDMA
Category: Science > Chemistry
Asked by: dcp-ga
List Price: $30.00
Posted: 13 Nov 2002 06:20 PST
Expires: 13 Dec 2002 06:20 PST
Question ID: 106799
When, if ever, did Fritz Haber synthesize MDMA?

[background : a search via Google gives dates variously of 1891, 1892
and 1898. The synthesis doesn't appear, as far I can tell, in his
Ueber einige Derivate des Piperonals (Berlin G. Schade, 1891),  the
first (and only???) edition of his doctoral dissertation in
Charlottenburg Technische Hochschule in Berlin.]
Answer  
Subject: Re: Fritz Haber and MDMA
Answered By: scriptor-ga on 13 Nov 2002 13:00 PST
Rated:5 out of 5 stars
 
Dear dcp,

This question is, indeed, very hard to answer since the only source
that could give a defitive answer would be the dissertation in which
Haber reportedly published the method for MDMA synthesis. This
dissertation, howerver, has never again been published after 1891 - I
checked it at the Deutsche Bibliothek, who are bound to have, similar
to the Library of Congress, at least one copy of every publication
printed in Germany. But obviously, no publisher has ever been
interested in this dissertation. This might be so because, as I found
out during my research, it was not a masterpiece according to Haber's
own opinion (Stoltzenberg, p. 31f.). As a website proves, at least a
single copy of Haber's dissertation still exists, but it is not said
where it is located:

MDMA.net: Fritz Haber - Ueber einige Derivate des Piperonals
http://mdma.net/fritz-haber/inaugural-dissertation.html

In the context of this website, the dissertation from 1891 is listed
among the references. So if the authors of MDMA.net have done careful
research, they got their information directly from the original
source. Sadly, they did not add reproductions of the pages reportedly
including the paragraphs about synthesis of MDMA.

Anyway, one thing is very important to note: It is absolutely possible
that Fritz Haber really sythesized MDMA while working for his
dissertation. As his biography tells:

"[For his dissertation] Haber got from Liebermann the assignment to
verify a reaction on piperonal, an aromatic substance with heliotrop
aroma, similar to the first step Baeyer's and Drewsesn's indigo
synthesis. (...) [In the dissertation] Haber also described (...)
various other derivatives of piperonal." (Stoltzenberg, p. 31)

And MDMA is indeed a derivative of piperonal. So it is not impossible
at all that among the "other derivatives", there has also been
methylenedioxymethamphetamine. However, though this would have been a
completely new substance, it was not in the center of Haber's or his
examiners' attention and remained rather unnoticed. But this does not
change anything concerning the question: Is it likely that Fritz Haber
was the first one to synthesize MDMA? He definitely had been able to.

If Haber discovered the new substance, the only possible date is 1891.
His works from other years mentioned in some sources seem not to have
any connection to derivatives of piperonal or the synthesis of related
substances. In 1892, he spent half the year working in his father's
chemical factory in Breslau, and the other half in Jena as assistant
of professor Ludwig Knorr and guest auditor at lectures at the
university. There is no evidence that he did any experiments related
to his dissertation topic in that time. And in 1898, he worked nearly
entirely on electro-chemical experiments. (Stoltzenberg, p.42-47,
58-70)

The patent for MDMA was issued to the Germany pharmaceutical company
E. Merck in 1914. Two of their chemists, G. Mannish and W. Jacobsohn,
had created MDMA as a by-product while attempting to synthesise
hydrastinin in 1912. Very likely, they did not know at all about Fritz
Haber's possible discovery. But even the Merck company did not really
notice the potential of the newly found substance. It seemed rather
useless and remained forgotten for several decades. Most sources
attribute the synthesis of MDMA to the Merck chemists, which might
count as evidence that the Haber dissertation does not include any
mention of MDMA. But this is, of course, no proof yet.

So the final conclusion is: Fritz Haber could easily be the person who
found MDMA. His work for his dissertation was concentrated on a highly
specialized area of chemistry, and the process of synthesizing belongs
in this very area. The only possible timeframe for this would be the
first months of 1891, before he submitted his dissertation. But
neither the dissertation nor excerpts of it are available online or in
other sources, except some very rare original copies of unknown
location. Without a chance to read it, no one could provide a final
answer.

Sources:

Fritz Haber - Chemiker, Nobelpreisträger, deutscher Jude. By Dietrich
Stoltzenberg. Published by Wiley-VCH, 1998. ISBN: 3-527-29573-9

Thema Drogen: MDMA (in German!)
http://www.thema-drogen.net/Drogen/Syn/Syn_MDMA.html

Jack Tracks: Ecstasyverbot und Unrechtsbewußtsein (in German!)
http://www.jacktracks.de/300/302/014/30201428.html

Ausmaß und Entwicklung jugendlichen Drogenkonsums, by the Austrian
Ministry of Social Security, 1999 (in German, Acrobat Reader file!)
http://www.bmsg.gv.at/bmsg/relaunch/jugend/content/jugendforschung/downloads/drogenkonsum_ecstasy.pdf

MDMA.net: Mental Health in the Third Millennium - MDMA and Beyond
http://mdma.net/

Deutsche Bibliothek
http://www.ddb.de/

Humboldt State University: The Chemestry of MDMA, by Jennifer McNeil 
http://www.humboldt.edu/~morgan/ecstacy/MDMAjen.html

Search terms used:
haber mdma:
://www.google.de/search?hl=de&lr=&ie=UTF-8&oe=UTF-8&scoring=d&q=haber+mdma&sa=N&tab=gw
haber mdma dissertation:
://www.google.de/search?hl=de&ie=UTF-8&oe=UTF-8&q=haber+mdma+dissertation&meta=
haber mdma doktorarbeit:
://www.google.de/search?hl=de&ie=UTF-8&oe=UTF-8&q=haber+mdma+doktorarbeit&meta=
haber derivate piperonals:
://www.google.de/search?hl=de&ie=UTF-8&oe=UTF-8&q=haber+derivate+piperonals&btnG=Google-Suche&meta=
piperonal mdma:
://www.google.de/search?q=piperonal+mdma&hl=de&lr=&ie=UTF-8&oe=UTF-8&start=0&sa=N

Though I could, alas, not give you a definitive "yes" or "no", I hope
that the results of my research are of any value for you.

Best regards,
Scriptor

Request for Answer Clarification by dcp-ga on 13 Nov 2002 17:25 PST
Thanks again scriptor.
Haber's dissertation is scanned in below.
Alas I don't speak German, but I can't see MDMA (unless I'm missing
something obvious), so I'd wondered if the German language sources
that credit Haber were drawing on other material -  published or
otherwise.

http://www.mdma.net/fritz-haber/temp/5.jpg
http://www.mdma.net/fritz-haber/temp/6-7.jpg
http://www.mdma.net/fritz-haber/temp/7-8.jpg
etc
up to
http://www.mdma.net/fritz-haber/temp/76-77.jpg
http://www.mdma.net/fritz-haber/temp/78.jpg

very mysterious!

DCP

Clarification of Answer by scriptor-ga on 13 Nov 2002 18:01 PST
Dear dcp,

I have read the dissertation as carefully as I could. I am, I admit,
not a chemist. Nevertheless, I did not find the German term for MDMA -
3,4-Methylendioxymethamphetamin - anywhere. It may hide behind a
different expression or formula than C11 H15 NO2, but in that case I
would never find it. The closest thing is C11 N9 NO2 on page 74; but
that may be miles away from MDMA. And the rare German sources
mentioning Haber in connection with this substance do never give other
resources than this dissertation. It is indeed extremely mysterious.

Best regards,
Scriptor
dcp-ga rated this answer:5 out of 5 stars
Absolutely superb standard.

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