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Author: Subject: DDNP & related compounds: The über thread!
Rosco Bodine
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[*] posted on 21-2-2017 at 05:54


Quote: Originally posted by PHILOU Zrealone  
Quote: Originally posted by Rosco Bodine  
Rosco also believes that for DDNR the diazo-oxide forms straight across the ring as a para structure, not bonding with the hydroxyl that is ortho, adjacent as occurs for o-DDNP, but like the structure of the diazo-oxide found with p-DDNP. The tension across the ring bends the entire ring structure like a hexagonal spring wave washer being bowed by tension across its opposite vertices at para positions 1 and 4, and the diazo-oxide structure is the bowstring.

[Edited on 2/21/2017 by Rosco Bodine]

Simply ask and voilà added :D

The structure of trans-diazo is stil a bit mysterious...in reallity it must display a trans quinonoid structure so that both sides can bend onto the same side of the paper plane while the diazo connects to the opposite side...but connectivity is a bit hard to figure out. Into the book Traité de chimie organique Azoiques-diazoiques,.... they mention that the probable connectivity passes via a direct link between the N2 and the Cs on both sides thus without the oxygen being involved...a bit a cage structure related to DABCO(DiAzaBiCycloOctane) but with the Ns at other places and with unsaturations...anyway this is highly stressed...


DDNRs.jpg - 363kB

That looks good except for the first entry should be 2-diazo-(1-oxide)-4,6-dinitrophenol instead of the 3-oxide you show.

The middle compound is synonymous with what Klapotke called HODDNP

Looking at the last listing, the 6-diazo-(3-oxide)-2,4-dinitrophenol nomenclature would work there for the structure inverted and rotated counter-clockwise 30 degrees.

It is the stressed structure that accounts for the surprising energy as an initiator compared with an ordinary styphnate.

Anyway, the convoluted nomenclature is in part or completely explained by not associating the compound with resorcinol as a derivative.

I think that different researchers working from different precursors and not making the association with resorcinol is why the failure to make attribution to the earlier references about DDNR that trace back to Benedikt and Hubl in 1881.

It could be the NMR data is correct but is referenced to structure nomenclature for phenol rather than resorcinol, then having all the expected resorcinol associated position numbers made into alternate expressions. Also, Klapotke identifies ortho bonding with the adjacent hydroxyl to the diazo as occurs with the usual o-DDNP. But the scenario we have involving p-DDNP is more similar and strongly suggests a diazo-oxide that is the same as DDNR, even though it would seem either structure is possible.

[Edited on 2/21/2017 by Rosco Bodine]
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Marvin
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[*] posted on 21-2-2017 at 05:57


PHILOU, Where did 2-diazo-(3-oxide)-4,5 dinitrophenol / 6-diazo-(5-oxide)-2,6-dinitrophenol come from? I didn't write that. Who thinks that is the structure?
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Rosco Bodine
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[*] posted on 21-2-2017 at 07:34


Thanks to Louis for the synonymous expressions. In the context of the alternative synonymous naming for DDNR, the issue with the NMR data for the diazo position is reconciled as not being a problem about the NMR data but the differing nomenclature, recognizing the same NMR data could correspond with a diazo at position 6 or 4 described by different diagrams orientation corresponding to different long names and "parent" compounds. There is still a question about the diazo-oxide configuration, whether it is the hydroxyl oriented ortho or para to the diazo, that becomes an anhydride in forming the diazo-oxide.

The differing nomenclature for the same DDNR compound seems to be the best explanation why all the older prior art references were not included by Klapotke, and why the DDNR is being called a "hydroxyphenol" which is technically correct, but diverts attention away from the prior art for DDNR referenced as a derivative of resorcinol.

Making this still more confounding is that isomers are possible, for the DDNR, although in this particular case I believe the compound [8] identified by Klapotke is the same compound identified in 1881 by Benedikt and Hubl, later by Mendola and others.

I think the uncertainty of which hydroxyl (ortho or para to the diazo) is intact and which hydroxyl becomes the anhydride associated with the diazo has contributed to the confusion.

I think these 2 linked posts were the earliest posts where I was questioning the structure being identified, and saying I thought the hydroxyl and anhydride were transposed
http://www.sciencemadness.org/talk/viewthread.php?tid=439&go...

http://www.sciencemadness.org/talk/viewthread.php?tid=439&go...

The significance of what I am trying to say is that Klapotke's compound [8] and DDNR are one and the same.

Based on experiments reported by nitro-genes there is a niche reaction condition that allows for (probable) DDNR to be formed from a paracetamol precursor, without having to first further acetylate paracetamol to a diacetyl derivative.

The interesting and bizarre story here is that over a period of 134 years, four or five different researchers have made the exact same compound, (DDNR) by different methods and called it by different names, "reinventing the wheel" as if it were invented for the very first time :D And it seems nitro-genes has added another chapter to the story, not yet fully sorted out.

[Edited on 2/21/2017 by Rosco Bodine]
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Rosco Bodine
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[*] posted on 21-2-2017 at 15:55


While the niche reaction conditions for best yield of DDNR from paracetamol not further acetylated before nitration are an interesting unexpected development reported by nitro-genes, how efficient will be that approach is unknown and may not ever work as well as proceeding from paracetamol acetate, which is Klapotke's compound [5].

It appears likely to me that the N NMR data identifying a diazo at position 6 for compound [8] of the Klapotke article is explained by nomenclature semantics that have inverted and rotated positions so that Klapotke's position 6 diazo for Klapotke's compound [8] (and likewise for unrecognized [8] is DDNR) is synonymous with what I am calling position 4 for the same diazo and is the same compound, DDNR, with confusion over nomenclature arising at compound [5] in the Klapotke article where p-aminophenol is converted to a diacetyl derivative that is O,N-diacetyl-p-aminophenol, or paracetamol acetate, or 4-Acetamidophenyl Acetate, but is identified synonymously by Klapotke as N-(4-Acetoxyphenyl)acetamide, which inverts the subsequent ring position numbering and causes the nomenclature confusion thereafter. Other confusion of the structure numbering would have occurred for nomenclature like 4'-Hydroxyacetanilide Acetate.

For example, in the alternative, if Klapotke's compound [5] had been named O,N-diacetyl-p-aminophenol and obtained as at least 100 grams yield from 97 grams of paracetamol substituted for the 35 grams of p-aminophenol described which yielded only 50 grams instead, everything to follow would have been simplified, efficiency would have improved and the nomenclature confusion about the 4 versus 6 diazo would have been entirely avoided. :D ;) :D

Likewise, it is the potassium derivative of Klapotke's compound [8] that is of particular interest for testing initiator properties identified by Von Herz and physical properties identified by Benedikt and Hubl, Meldola, et al, in order to ascertain if indeed the compound [8] of Klapotke is DDNR as I believe it is.

Klapotke's compound [8] 6-diazo-3-hydroxy-2,4-dinitrophenol (HODDNP) is I believe the same DDNR identified by Benedikt and Hubl and Meldola and others.

Klapotke route of synthesis from p-aminophenol to DDNR.bmp - 256kB

Klapotke DDNR tests.bmp - 738kB

Here attached again are the two Klapotke articles

Attachment: Synthesis & Energetic Properties of 4-Diazo-2,6-dinitrophenol and 6-Diazo-3-hydroxy-2,4-dinitrophenol.pdf (286kB)
This file has been downloaded 33 times

Attachment: Synthesis and Initiation Capabilities of Energetic Diazodinitrophenols.pdf (754kB)
This file has been downloaded 36 times

[Edited on 2/22/2017 by Rosco Bodine]
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PHILOU Zrealone
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[*] posted on 21-2-2017 at 19:17


Quote: Originally posted by Marvin  
PHILOU, Where did 2-diazo-(3-oxide)-4,5 dinitrophenol / 6-diazo-(5-oxide)-2,6-dinitrophenol come from? I didn't write that. Who thinks that is the structure?

You indeed wrote:
6-diazo-3-hydroxy-2,4-dinitrophenol aka 6-diazo-2,4-dinitroresorcinol
and
4-diazo-2,6-dinitroresorcinol.
(*)

Those are ambiguous names as seen in the practice by all of us when trying to understand each others between forum members, but also when trying to understand and correlate the research of Klapote's team and previous early works from the past.(**)

So your wrongly named and ambiguous 6-diazo-3-hydroxy-2,4-dinitrophenol is the same as 6-diazo-3-hydroxy-2,4-dinitrophenoxide (an ortho diazo-oxide derived from 4-amino-1,3-dihydroxy-2,6-dinitrobenzen); while your wrongly and ambiguous 4-diazo-2,6-dinitroresorcinol is in fact refering to 4-diazo-3-hydroxy-2,6-dinitrophenoxide (a para diazo-oxide derived from the very same 4-amino-1,3-dihydroxy-2,6-dinitrobenzen)

As I exposed by drawing:
From trinitroresorcinol (1,3-dihydroxy-2,4,6-trinitrobenzen) by monoreduction of a NO2 group you only get two possible isomeric amino-dinitroresorcinol:
1°) the amino comes from reduction of the nitro trapped between te two NO2
--> 2-amino-1,3-dihydroxy-4,6-dinitrobenzen
2°) the amino comes from reduction of one of the two others NO2 that are next to one OH (in ortho) and in para of the other OH...and those only provide one isomer by degenerescence linked to the symetry of the molecule (the axis being between the two OH)...so reducing the 4 or the 6 nitro will always lead to 4-amino-1,3-dihydroxy-2,6-dinitrobenzen

From 1°) aka 2-amino-1,3-dihydroxy-4,6-dinitrobenzen
by diazotation you will get only one isomeric 2-diazo-oxide because the -N=N-OH may react (anhydrize) with the -OH in position 1 or with the -OH in position 3 what is the same (again degenerescence) also because of the inter-OH molecular symetry...
So in fact:
2-diazo-(1-oxide)-3-hydroxy-4,6-dinitrobenzene
is equal to
2-diazo-3-hydroxy-4,6-dinitrophenoxide (not phenol because the OH in position 1 is not present anymore and phenoxide means implicitely that the oxide is in position 1)
what is equal to
2-diazo-(3-oxide)-4,6-dinitrophenol (the OH in position 1 implicitely)
and if you flip along the free OH axis this is equal to
6-diazo-(5-oxide)-2,4-dinitrophenol (cf supra)

From 2°) aka 4-amino-1,3-dihydroxy-2,6-dinitrobenzen
by diazotation you will get only two isomeric 4-diazo-oxide because the -N=N-OH may react (anhydrize) with the -OH in position 1 (thus in para position vs itself) or with the -OH in position 3 (what is ortho position vs itself)...
So in fact:
para case
4-diazo-(1-oxide)-3-hydroxy-2,6-dinitrobenzene
is equal to
4-diazo-3-hydroxy-2,6-dinitrophenoxide (not phenol because the OH in position 1 is not present anymore and phenoxide means implicitely that the oxide is in position 1)
what is equal to
2-diazo-(5-oxide)-4,6-dinitrophenol (the OH in position 1 implicitely)
and if you flip along the free OH axis this is equal to
6-diazo-(3-oxide)-2,4-dinitrophenol (cf supra)

ortho case
4-diazo-(3-oxide)-1-hydroxy-2,6-dinitrobenzene
is equal to
4-diazo-(3-oxide)-2,6-dinitrophenol
what is equal by flipping along OH axis to
4-diazo-(5-oxide)-2,6-dinitrophenol
what is equal to
2-diazo-(1-oxide)-5-hydroxy-4,6-dinitrobenzene
what is equal to
2-diazo-5-hydroxy-4,6-dinitrophenoxide
what is is equal to
6-diazo-(1-oxide)-3-hydroxy-2,4-dinitrobenzene
or
6-diazo-3-hydroxy-2,4-dinitrophenoxide

Yes you start to feel dizzy and suffer from vertigo...your brain is overheating and fuming :D:cool::);):P and this gives you a better view of the problem...

(*) So what you wrote implicitely is exactly what I wrote explicitely...
I deliberately noted the oxide place and number to make things clearer...because this is the main source of confusion...
I really think that everybody here should always do so...to be sure what we speak about.

(**) If there is little ambiguity (***) when dealing with DDNP beause the diazo can only form a single diazo-oxide with the only OH present; when dealing with dihydroxyphenol (resorcinol)...confusion arises and speaking about DDNR becomes a problem.
In common usage for the future we should refer DDNP to be Diazo-Di-Nitro-Phenoxide and not Diazo-Di-Nitro-Phenol because the -OH is inexistant into the molecule...for analogy it is like saying that CH3-O-CH3 is methyl-methanol...while it is an ether (dimethyl-ether).
(***)The tiny ambiguity may come from the various true isomers and from the effective numerotation/nomenclature used...
so a little molecular drawing is never too much.


[Edited on 22-2-2017 by PHILOU Zrealone]




PH Z (PHILOU Zrealone)

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Rosco Bodine
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[*] posted on 22-2-2017 at 03:59


It is frustrating and confusing what is the nomenclature derived issue and trying to do the mental algebra to translate what is being described at one time in history using an "original language" kind of nomenclature and associated ring position numbering, with the changed naming language of a different time in history where the same compound is subjected to a different naming convention. Often the naming chosen to be used follows a pattern that is an association with the trivial name for the precursor compound used in synthesis of a product compound that is then regarded as a derivative "offspring" child of the "parent compound". The trivial name for the derivative or some acronym adopted is then not formally correct, as Louis pointed out regarding DDNP which is not actually any longer a phenol but a phenol anhydride resulting from the diazo-oxide bridge that has displaced the hydroxyl hydrogen of the parent phenol. Even so, DDNP will forever be called DDNP simply because every chemist knows the historical name even though it is not precisely technically correct.

In common usage what is the compound DDNP is understood to be "the diazo compound of Griess who discovered and published the origin of diazo chemistry",
so the acronym is not formally correct but is a historical trivial name for what is a compound every chemist knows as a "basic compound" no matter what long name it may be given.

In my opinion it is likewise the case for the compound DDNR, which analogously is "the compound of Benedikt and Hubl" and is another historical trivial name and acronym that has a historical basis that should be understood by every chemist what structure is DDNR, no matter what long name it may be given.

The subject of this nomenclature issue was discussed earlier
http://www.sciencemadness.org/talk/viewthread.php?tid=439&go...
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[*] posted on 24-2-2017 at 08:25


It is hard to believe there really exists a N=N-O bond for diazophenols:

1. The ring strain produced for pDDNP would be really immense for an aromatic and perhaps more importantly, much higher compared to oDDNP. Yet, the difference in energy release and initiating properties between the two seems very similar. (Although the latter still needs proper verification, I would say pDDNP is somewhat more energetic, but perhaps also seems so due to mono-nitro present)
2. One would expect that Tdec would be lower for pDDNP due to increased ring strain, while the opposite is true
3. In all likelyhood, both DDNP's dissolve in strong acids to form a diazonium salt
4. Even moderately strong nucleophiles can easily react with the diazogroup leading to substitution, even under (almost) waterfree conditions
5. No other compounds containing a R-N=N-O-R group have been found (fafaiaao), while diazotates are charged (behaving more like a OH- salt IIRC)

I think depending on conditions, DDNP's represent something between a zwitterionic and quinoid structure. In very strong concentrated acids it can behave as the former, but the electrons are not completely sure where they should reside the most. :D

So where does the extra energy for pDDNP come from in Klapotkes calculations? From assuming the NNO bridge?

[Edited on 24-2-2017 by nitro-genes]
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Rosco Bodine
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[*] posted on 24-2-2017 at 11:30


In the case of the p-DDNP the diazo-oxide bridge has only one path to form which is straight across the ring, since there is no other hydroxyl available. And I think the nitros on each side of that para hydroxyl amplify the attraction and steer that diazo-oxide linkage formation there sort of like magnets steering an electron beam. And I think the combined effect of those "steering groups" is stronger than the attraction of an adjacent hydroxyl as a prospective target, particularly if that hydroxyl hasn't formed yet because it is a nitro at 3 and must decompose to a hydroxyl subsequent to the formation of the para diazo-oxide linkage across the ring. I could be wrong, but that is my guess what is occurring. If the second hydroxyl was already present before the diazo-oxide linkage formed, then it might preferentially form the linkage with the adjacent hydroxyl similarly as is the case for o-DDNP. There is an uncertainty about these reactions and sequence that could make possible different isomers. To sort out what is the whole true story would require performing different paths of synthesis and comparing the products to see which are the same and which may be different.

I think the extra energy for the p-DDNP comes from the para diazo-oxide bond and added stability comes from the symmetry.

Thanks to Boffis for the file for the Klapotke article that is published. We have been discussing what was information in an early preview draft that had not yet published so there may be unknown changes or corrections. Attached is the file for the article as published.

Attachment: 4-Diazo-2,6-dinitrophenol and 6-Diazo-3-hydroxy-2,4-dinitrophenol.pdf (432kB)
This file has been downloaded 27 times

I already see what I believe is a problem in the NMR data table figure description.

The first two compounds based on identification of structure diagrams appear to be transposed. The legend shows compound [7] as the middle compound, but the structural diagram is for iso-DDNP which is compound [4]

Likewise for the first structural diagram shows compound [7] but the legend for the table says it should be compound [4].

So the table legend for Figure 3 is wrong for the first two compounds. I am pretty sure the top graph is for [7} and the middle graph is for [4].

Klapotke article as published.bmp - 714kB


[Edited on 2/24/2017 by Rosco Bodine]
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Rosco Bodine
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[*] posted on 24-2-2017 at 18:24


Okay I think I have sorted out what has been puzzling about this Klapotke article and why his reported compound [8] may differ from Meldola's p-DDNR structurally with regards to the diazo-oxide appearing as an ortho linkage to the adjacent hydroxyl to the diazo, instead of appearing as a para linkage diazo-oxide to the hydroxyl across the ring directly opposite the diazo.

If what Klapotke is reporting is accurate, (and I now believe it is), then it is possible to produce either isomer depending upon the method of diazotization applied to the compound [7] which is 4-amino-2,3,6-trinitrophenol. Following the method of diazotization of Klapotke depends upon the decomposition of the nitro at 3 to diazotize the amino, so that sequence makes available the ortho hydroxyl adjacent to the diazo as soon as it forms. In that case, if that is what does occur then indeed HODDNP could be the result.

In an earlier post linked here Meldola used a different means of diazotization applied to the same 4-amino-2,3,6-trinitrophenol, and used small portions of solid nitrite added to a solution of the 4-amino-2,3,6-trinitrophenol in cold H2SO4, under conditions where the 3 nitro remained intact as the diazotization was
performed. In that circumstance there was only one hydroxyl available for the formation of the diazo-oxide bridge and that would be the para, just the same scenario as occurs for p-DDNP.
http://www.sciencemadness.org/talk/viewthread.php?tid=439&go...

Meldola actually isolated the 4-diazo-2,3,6-trinitrophenol(1-anhydride) as a dense yellow microcrystalline powder precipitated from dilution of the soluble diazonium sulfate. Boiling that material with a strong solution of sodium acetate decomposed the 3 nitro and produced the sodium salt of p-DDNR, even though it is clear Meldola was not certain himself of the structure, and did not positively identify one isomer. Given the reaction sequence as the most logical influence, it would be likely that Meldola was describing the para isomer variant different from the ortho diazo-oxide DDNR of Bendikt and Hubl. The DDNR of Benedict and Hubl has the ortho hydroxyl already present, as would other diazotization schemes applied to styphnamic acid. So evidently the ortho bridge for the diazo-oxide would be the usual, "normal" structure for DDNR and is the exact same compound as Klapotke's HODDNP.

Klapotke's HODDNP = Benedikt and Hubl's DDNR

Meldola describes what would be an iso-DDNR or p-DDNR variant that has the same para diazo-oxide bridge as p-DDNP.

So the normal, more usual diazo-oxide bridge is the same ortho structure for DDNP and DDNR. The classical DDNP of Griess is o-DDNP and the classical DDNR of Bendikt and Hubl is o-DDNR.

The para variant of DDNR would then be the para "iso" structure for the p-DDNP and for the p-DDNR. The enhanced energy and stability that appears for p-DDNP would reasonably apply also for the p-DDNR.

So at this point, the logical hypothesis for me to make is that depending upon the method of diazotization applied to Klapotke's compound [7] 4-amino-2,3,6-trinitrophenol it is possible to obtain either isomer desired. Following the method of Klapotke the product will be HODDNP, o-DDNR, but in the alternative, following the diazotization method of Meldola and hydrolyzing the product will be p-DDNR, or iso-DDNR, obtained as the sodium or potassium salt, with the free acid p-DDNR obtained by acidification with HCl or other acid.

So I think ...the mystery is solved!!!! See how easy that was :D:D;):P

Hey it was so much fun ...let's do it again :D

To summarize what has been distilled from the study of the available references, the nexus which I had identified for the compounds described by Benedikt and Hubl, Von Herz GB207563,
Hagel and Redecker US4246052, and Klapotke compound [8]
appear to be all DDNR ....and about that nexus I was correct.

However, all of those examples of DDNR (referenced to ring positions for resorcinol) are the ortho structure for the diazo-oxide from what would be position 4 of the diazo to the adjacent 3 position hydroxyl, made into a 3 anhydride.

The DDNR reported by those several authors is

4-diazo-2,6-dinitroresorcinol-(3-anhydride) o-DDNR = HODDNP

I was incorrect in my early impression that the "normal" DDNR diazo-oxide structure would be the para structure that would be from the diazo at 4 to the hydroxyl at 1, forming a 1 anhydride.
That is the exceptional structure obtained by an alternate scheme for diazotization used by Meldola.

The p-DDNR of Meldola would be.

4-diazo-2,6-dinitroresorcinol-(1-anhydride) p-DDNR or iso-DDNR

The name is somewhat misleading for p-DDNR since the compound is not strictly a resorcinol "derivative" but is structurally similar.

That para diazo-oxide iso-DDNR or p-DDNR is the "special case" isomer obtained by a modified diazotization scheme of Meldola, applied to a precursor that is Klapotke's compound [7].

Paracetamol is the starting material for p-DDNP and p-DDNR and each are expected to have enhanced properties over their more commonly known analogous ortho isomers.

[Edited on 2/26/2017 by Rosco Bodine]
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