Energetics-testin
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P-DDNP Synthesis using HNO³ for the diazonation
I've been following the paper posted on here by NitroGenes and for the diazotation he has 3 method..Two of them consist of a solution of NaNO2 being
used as the diazotation agent and the last method uses 68% nitric acid which is easy to make compared to converting sodium nitrate into nitrite and
use that to follow the normal procedure.
I've folowed his procedure (the third one) and when it came time to crash the DDNP in ice..it vanished from existence and the ice turned piss
yellow...
when washing the beakers used in the synth,the color of the water changed from yellow to red,when diuting it even more it became orange..after that
if I added more water it turned back to the piss yellow that I had when I crashed the solution.
I was wondering if anyone here has tried the third method,if yes i appreciate any feedback and would like some help figuring out where I ''fucked
up''.
Is it better to just use one of the 2 other procedure or the HNO3 one works fine ?
Attachment: Synthesis of 4-amino-2,6-dinitrophenol (isopicramic acid) and p-DDNP from acetaminophen version 1.pdf (1.3MB)
This file has been downloaded 331 times
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AngelEyes
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Are you sure it says nitric, and not nitrous...?
As far as I am aware, you need the NO2 ion to perform diazotations. Usually the NaNO2 is in an acid solution which makes nitrous
acid in situ
\'Silk and satin, leather and lace...black panties with an Angel\'s face\'
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Tsjerk
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I checked the write-up and does say nitric, but I don't see how that could work.
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Energetics-testin
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[/rquote]s far as I am aware, you need the NO2 ion to perform diazotations. Usually the NaNO2 is in an acid solution which
makes nitrous acid in situ[/rquote]
Yeah I know thats why it seemed weird to use HNO³ but eh i didn't think twice about it and followed the paper..it lead me to disappointment and
wasted reagents.
I made more isopicramic sulfate and tried both procedure and they work fine.
I still have some isopicramic sulphate in solution,I'll try the third procedure again but i dont expect much.
[Edited on 26-9-2022 by Energetics-testin]
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njl
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I also checked the paper and it doesn't make sense. All I can think, and I may be out of line for this, is that Roscoe Bodine (one of the authors) was
banned for several things, among them spreading unreliable procedures.
Reflux condenser?? I barely know her!
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Tsjerk
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There was nothing wrong with his procedures, the contrary. His rants about what probably only he could understand were the problem.
Edit: well, if you ignore the last decade of his posts, I can remember I always skipped the posts written by him.
[Edited on 28-9-2022 by Tsjerk]
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PHILOU Zrealone
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In a book from an organic chemistry collection of encyclopedic nature written by the famous Victor Grignard (and friends), I also noticed that strange
diazotation procedure from dilluted HNO3.
The books (into a good collection of 25 or more volumes (IIRC)) is about chemistry of 1850 up to 1950 or so...it is in French and has very detailed
chemistry synthesis, chemical reactions, identifications reactions and various monographies of chemical compounds... really a must have and read
collection for real chemistry lovers. Hopefully I'm a natural born French speaker and (bio)chemical engineer specialized in organic chemistry so I
have no problem to read and digest that kind of litterature.
This books that I have amongst some others is dedicated to azo-, diazo-, hydrazino-, hydrazines, azido- compounds (and also poly-nitrogenous chain
compounds (3,4,5...)) for sure a marvelous treasure for an energetic lover like me... and yes it speaks about aryl but also alkyl compounds of the
kind... each book is about 1000-1500 pages of delightfull (to me) informations...
Sometimes hard to imagine it is a collection that is more than a century old.
I have found reactions that were used then... and rediscovered after the years 2000-2010 to put patents on it... while it was common public knowledge
then... sadly internet and digitalisation of books doesn't go that fast and far into the past... so new patents have no right on those already
published inventions or processes.
The principle is easy and works relatively logically... para-diphenol, para-diaminobenzene, para-hydroxy-aniline (or para-amino-phenol) all share in
common an easy and strong reducing power by oxydation into para-quinonoides... and exposure to dilluted HNO3 (an oxydizer) allow for reduction to HNO2
thus generated in situ...this means nitrosoamine is formed from the amino group (-NH2 --> -NH-N=O) and quinonic resonance provides -N=N-OH
(diazonium hydroxide) while the hydroxy (ph-enol) at the opposite side of the molecule (para) turns from its enolic form to its ketonic quinon form
(most people dont read the evidence: phenol is an enol and as such can turn into a discrete keton).
The process of natural oxydoredox runnaway was used back in those 1900ish ages to make aryl diazonium industrial batches for vat dying for fabrics
(artificial colors were often based onto aryl-diazonium skeleton).
The use of aminobenzene and HNO3 to make diazonium proved to be economicaly viable and effective in those times... Rosco Bodine was, like me, a big
fan of those lost receipes and old books full of wonders and hindered in plain sight under our eyes  ...if only we knew where to look...under the dusty layer of 1 cm thick... of some forgotten unread anymore
books...  
[Edited on 16-1-2023 by PHILOU Zrealone]
PH Z (PHILOU Zrealone)
"Physic is all what never works; Chemistry is all what stinks and explodes!"-"Life that deadly disease, sexually transmitted."(W.Allen)
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Hey Buddy
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I have read about dilute HNO3 being reduced to HNO2 in situ in several procedures for various energetics. In some cases the mechanism isnt well
understood, so it isnt brought to attention or can seem under the radar and unusual. Recently Ive been reproducing Sabanejeff oxidation experiments
which reduce dilute HNO3 to HNO2, or at least that is one of several theories on the mechanic. The end result is the same as HNO2 so it is generally
accepted that is what occurs. Id imagine anyone writing a DDNP procedure will not make errors between diazo and nitro because they are both used in
DDNP and anyone designing a DDNP procedure will be acutely aware of the difference and the reagents to cause their formation.
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