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Author: Subject: Searching for Beilstein-synthesis of picramic acid
Mephisto
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[*] posted on 14-4-2003 at 05:20
Searching for Beilstein-synthesis of picramic acid


I am searching for the synthesis of picramic acid from picric acid, ammonia, H2S and acetic acid. I am quite sure, that it is in Beilstein, but I can’t check it. It would be nice, if someone, who has an access to Beilstein could post the synthesis here.

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FireFly
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[*] posted on 29-4-2003 at 11:03


I don't know the Beilstein-synthesis as you questioned, but The Preparatory Manual Of Explosives has it has follows...

Preparation of Picramic acid

Materials: 26.8g glacial acetice acid & 100g ammonium picramate.

Procedure: Dissolve 100g of ammonium picramate in 1000mL of cold water while stirring the water (if some of the ammonium picramate fails to dissolve, add an additional 400mL of cold water). To this solution, add drop wise, over a period of ten minutes, 26.8g of glacial acetic acid. After the addition of the glacial acetic acid, filter-off the product, wash with 400mL of cold water, and then dry in an oven at 80 Celsius for 1 hour.

~NP

Hazards: Wear gloves when handling glacial acetic acid. Glacial acetic acid can cause skin burns.

[Edited on 02-20-03 by FireFly]
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Krypton
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smile.gif posted on 29-4-2003 at 19:31


FireFly,

what says the manual to the starting material
of the TNA synthesis ?
The same like the way from 1,3,5,7-tetraiodoadamantane with
O3 in the presence of silica gel ?

Why do you not use a foomhood when making something
with glacial acetic acid ?




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Haggis
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[*] posted on 30-4-2003 at 07:49


Lookee here, a Picramic synthesis found in our very own library. http://www.sciencemadness.org/library/picramic.pdf
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Krypton
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[*] posted on 1-5-2003 at 18:56


Have you try out perform a reduction in 4 ?
for instance:
1-hydroxy-4-amino-2,6-dinitrobenzene
and the salts of it




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Mephisto
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[*] posted on 4-5-2003 at 05:51


FireFly: Thank you for your help. I couldn’t aswer sooner, because I wasn’t online. The Beilstein-Synthesis uses H2S and not sodium sulfide to reduce the picric acid. Your book looks very interesting. How is the synthesis of ammonium picramate described? I think that might be the right synthesis. :)

If someone else is interested in „The Preparatory Manual Of Explosives“: here you can find a overview of the synthesis. And here you can download Chapter 11. I think it's a real shame, that only this chapter is online available :(

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[*] posted on 4-5-2003 at 23:26


NH4-picramate is easy just partially reduce picric acid with NH4HS ( or (NH4)2S ). Just as easy as preparing sodium picramate ! But the thing is that the difficult step is the partial reduction of picric acid.
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mad.gif posted on 5-5-2003 at 03:33


Mephisto,

the Chapter 11 of the manual, i hope it`s not the
correct chapter of the manual. Some synthesis wouldn't
work correct with the described conditions.
The wittiness is, this part is circling in the wwww,
i `ve found the part on other servers any months ago.




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Mephisto
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[*] posted on 11-5-2003 at 02:19


Krypton: It seemed to me, that the file was correct, but I didn’t read it completly, sorry. What mistakes do you mean?

I want to use H2S and ammonia instead of the expensive ammonium hydrogen sulfide. But how I know, that I add enough of H2S to the picric acid + ammonia solution? Is there a change of colour or pH, which says me, when to stop the addition of H2S?

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mad.gif posted on 12-5-2003 at 03:26


Mephisto,

i think the "big manual" is for ducks,

gag gag gag.

:P




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[*] posted on 13-5-2003 at 10:39


I’m neither responsible for the manual nor for the online-chapter.

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[*] posted on 13-5-2003 at 12:24


Krypton: I didn't read the manual either, but could you please state what is incorrect? From the first impression and from what other people said I came to the conclusion that these books are okay, so it would be good to know what's wrong.
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[*] posted on 14-5-2003 at 10:10


The only synth I have used out of the book, has been the synth for picric acid/TNP, and had good results. Something of interest is in one of the synths for TNT listed in the book, requires 30% fuming sulfuric acid. Is there such a thing as 30% being fuming?
~NP
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[*] posted on 16-5-2003 at 06:54


FireFly,

i can`t found the synth diparabenzenehexanitrate
on the site.
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[*] posted on 16-5-2003 at 07:58


Quote:
Originally posted by Krypton
FireFly,

i can`t found the synth diparabenzenehexanitrate
on the site.


On the "site" which site are you referring to?
~NP
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[*] posted on 16-5-2003 at 22:02


30% fuming translates as 30% free SO3 oleum.
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wink.gif posted on 17-5-2003 at 06:29


I mean at
http://www.cannonfuse.com/explosives/

A goog manual contains a synth of
diparabenzenehexanitrate family.
I will writing down this in my :mad:book !!!

:mad::D:mad::D:mad::D:mad::D:mad::D:mad::D:mad::D




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[*] posted on 17-5-2003 at 11:00


Quote:
Originally posted by Krypton
I mean at
http://www.cannonfuse.com/explosives/

A goog manual contains a synth of
diparabenzenehexanitrate family.
I will writing down this in my :mad:book !!!

:mad::D:mad::D:mad::D:mad::D:mad::D:mad::D:mad::D


When will your book be out? If it will be out for sale, e-mail me some info and a price, I might want to buy it. If your wanting that synth, I'll look it up when I get back to my house, I'm not sure if it's in that manual or not, but I probably have it saved on disk, or in another book.
~NP
e-mail is HE246C7H5N3O6@aol.com
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[*] posted on 18-5-2003 at 09:47


FireFly,

you have to good connection with the
email adress. ;);)




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smile.gif posted on 4-6-2003 at 04:16


(NH4)2S can idees as NH4SH be used to perform monoreduction of polynitroaromatics.
No mather there is a sight excess reduction won't attack a second NO2 group!

In the case polyreduction is wanted, go for Fe/HCl, Zn/HCl or SnCl2/HCl ... then all NO2 will be reduced!

Unfortunately the reduction of TNP by sulfides is quite specific to the ortho position; to get 2,6 dinitro paraaminophenol one would need to pass via another synthetic way.

NH2-C6H5 + Cl2 (1 equivalent) + AlCl3 --> NH2-C6H4-Cl + HCl (mostly para, a then ortho and very little meta).
NH2-C6H4-Cl + CH3-CO2H -reflux->CH3-CO-HN-C6H4-Cl + H2O
CH3-CO-HN-C6H4-Cl -H2SO4/HNO3-> H2N-C6H2(NO2)2-Cl + H2O + CH3-CO2H
H2N-C6H2(NO2)2-Cl + NaOH --> H2N-C6H2(NO2)2-OH + NaCl
(thus we get 2,6 dinitroparaaminophenol).

The fact they give you a sample doesn't mean it is bullshit; it is simply marketing in action:
"Come one sweeties see how good is chapter 11; no,no to get the 19 other chapters you will have to buy teh book".
Anyway all the reactions described in that chapeter are 100% true...I have synthetised at university:
trichlorotrinitrobenzene almost the same way; except that to increase speed of reaction, we have use a little more concentrated H2SO4 (30% SO3).But when you have time, and you don't care for 90% instead of 100% yield reaction, it is no problem - this was of course not the case as usual for university research.




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cool.gif posted on 4-6-2003 at 23:55


PHILOU,
when "all the reactions described in that chapeter are 100% true",
then you don`t breaking your university rules when you posting
about explosives, or it`s true you posting nonsense !

:P




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sad.gif posted on 6-6-2003 at 10:55


I don't understand your point?

Benzene is hard to trinitrate
chlorobenzene is about the same
metadichlorobenzene is a little bit easier
1,3,5 trichlorobenzene is much easier to nitrate than benzene (almost like toluen to TNT).
So what do you find wrong with the book experimental conditions or reactions of chapter 11?
Did you tried it?

Maybe it was a dream and non-sense to your eyes...but it looked pretty real to me and to the teachers of the university that graduated me...
We have synthetised:
Trichlorotrinitrobenzene by the method I have exposed before; then we have turned all Cl into NH2 (Sanger reaction) in liquid NH3 (-30°C) to get triaminotrinitrobenzene.
A final critical step was to react triaminotrinitrobenzene dry in dry liquid NH3 with solid sodium (very delicate since no excess is allowed) under N2 atmosphere to get the air and moisture sensitive hexaaminobenzene (by reduction of all nitro).

NH3 was boiled off into a CO2/aceton cold trap.
Then dry glyoxal (2 equivalents to 1 HAB) was introduced in the reaction vessel and heated on water bath to perform cyclisation reaction and extension of aromatic sheet...(Schiff's base / imine formations).

The final product was diaminotetraazaphenanthrene (DiaminoTAP).
It was essential building bloc to my project research (end study work for graduation) the synthesis of a core photoactivable Ru(II) complex of polyazaaromatic rings.
The core of the dendrimere was PheHAT --> Ru tris PheHAT --> Ru(PheHAT)3(2+)
PheHAT = phenanthrolinehexaazatriphenylene
(A plannar ligand/chelatant fully aromatic that contains 7 aromatic rings aside of each other in the shape of a bone...the ligand contains 8 nitrogen atoms (all heteroaromatic) and responsible of the chelating habilities.
The ligand displays 4 chelating sites and the problem was to get all 3 identical ligand fixed by the same side to 1 single Ru(2+) atom...we have solved that.

Free University of Brussels (ULB)
Science Faculty
Departement of Physical Organic Chemistry
Academic year 1997-1998
"Conception and synthesis of new polymetallic compounds of Ruthenium (II) of the dendrimeric kind-Research in the field of new materials wich display controled photophysical properties"

What was the use of that weird molecule?
*Photoactivation of strong electric oxydoreduction to produce H2 from water and sunlight.
*Strong affinity for DNA would allow photoactivable anticancerdrug.
*Being a symetric core with a lot of external chelating sites to continue building of dendrimere and allow energy circulation from outside to inside or directed at will following synthesis sheme --> light transformation into electricity for nanomachines.

You want more explanations?Or proofs?
I can expose you 80 pages of borring HNMR, UV and IR spectrum, Flash laser photolysis, luminescence and phosphorescence decay.

But I won't.I have showed enough to my sense.

:):):)




PH Z (PHILOU Zrealone)

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