Axt
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N-azides (azidamines)
Interesting explosive moitey N-N3 thus the azido analogue of nitramines. I requested the only article I could find on these compounds which details
the synthesis of the azidamine of dimethylamine (CH3)2N-N3. Its in german thus I cant read it, though its formed from nucleophilic substitution
between chloramines with metal azides.
My insane thought is the reaction of hexamine with NaOCl to form the chloramine analogue of RDX (a known reaction) and react this with NaN3 in DCM to
produce Hexahydro-1,3,5-triazido-1,3,5-triazine aka "Azido-RDX".
Wondering if anyone can translate the section regarding the reaction with NaN3 at number 3 on page 243 of the attached article. Also anything
regarding the stability and isolation of the azidamine. I realise its quite probably totally impractical requiring very low temperatures. One part I
did make out was that the author blew his fingers off with the stuff... (#21 in references).
Edit:
Searching google for N-azido finds an article on the azidamine of dibenzylamine, I dont have it but this is the reference. Riaz Ahmed, J.-P. Anselme
"The Interception of N-Dibenzylaminonitrene Generated from N-Azido Dibenzylamine" Canadian Journal of Chemistry 50 pp 1778-1780. <a
href="http://www.chemexplore.net/BookP4s.pdf">This pdf</a> also has some interesting reactions of the azidamines, though mainly specultatory
like reacting TCCA with NaN3.
[Edited on 28-10-2007 by Axt]
Attachment: Nukleophile Substitutionen an N-Chlor-aminen.pdf (499kB)
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Norrys
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Hi
I am from Germany, I could try to translate parts of your article, but my english-level is very low 
Isolation of Dimethyle-amine-azide:
The mixture consisting 250 mMol N-Chloro-dimethylamine (20g), 250 mMol Sodium azide (16g) and 500ml Methylenchloride was stirred for 24 hours at
room-temperature.
After 5 hours, a Formation of Gas occurred, which ended after 12 hours.
The measured amount of gas was 900ml (NPT) = 40mMol nitrogen. The salt-residue contained 66% sodium chloride = 190mMol.
Afer the solvent was removed, they found a an oily residue. Kp =30°C ; 25% of the theoretical yield of Dimethyle-amine-azide.
The product itself and even the solutions were very explosive. An assistent lost a part of a finger, when 50mg of the product exploded. The further
anylyses were done under high vacuum conditions and with very little amounts or low concentrated solutions. The process is very uncertain, so many
other atempts, to produce other azides failed, for exampel, the atempt to produce nitrogen triazide out of nitrogen trichloride produced only nitogen
gas and sodium chloride.
[Bearbeitet am 28-10-2007 von Norrys]
[Bearbeitet am 28-10-2007 von Norrys]
[Bearbeitet am 28-10-2007 von Norrys]
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Mumbles
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The journal you expressed interest in is attached. They use tosyl azide as the agent, and run the reaction at -60C. There isn't anything terribly
useful, but perhaps you will see something I did not.
Attachment: The Interception of N-Dibenzylaminonitrene Generated from N-azido Dibenylamine.pdf (162kB)
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Axt
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Thanks Norrys, I cant fault your english. It seems that the reaction is picky regarding which chloramines will work, lowers my confidence in an RDX
analogue.
I retrieved the citation given in the article Mumbles attached (J. Org. Chem. 35, 960 (1970)). It seems that the dibenzylamine derivative is only
present as a short lived intermediate, although in the discussion it is noted that: "Two N-azidamines have been reported previously: (a) H. Bock and
K.-L. Kompa, Z. Anorg. Allg. Chem., 332, 238 (1964); (b) N. Wyberg and A. Gieren, Angew. Chem., Int. Ed. Engl., 1, 664 (1962)."
The first article is that which is attached in my first post, the second which I dont have is:
<b>1,1,-Bis(trimethylsilyl)tetrazadiene</b>
Angewandte Chemie International Edition in English
Volume 1, Issue 12, Date: December 1962, Pages: 664
Nils Wiberg, A. Gieren
http://dx.doi.org/10.1002/anie.196206641
[Edited on 29-10-2007 by Axt]
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The_Davster
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| Quote: | Originally posted by Axt
My insane thought is the reaction of hexamine with NaOCl to form the chloramine analogue of RDX (a known reaction) and react this with NaN3 in DCM to
produce Hexahydro-1,3,5-triazido-1,3,5-triazine aka "Azido-RDX".
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The analagous reaction with silver nitrite and the cyclic chloramine fails to make RDX, and complete destruction of the precursors result, so this
reaction seems a bit improbable
Not that it precludes it, I am just not too hopefull.
[Edited on 29-10-2007 by The_Davster]
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Axt
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Do you know where you saw the attempt at RDX via AgNO2 and its trichloramine?
I never had high hopes, though the azide of cyanuric trichloride is stable where the attempt at its trinitro analogue via AgNO2 fails (you weren't
thinking of that reaction were you?).
(CH2=NCl)3 is the only easily prepared secondary amine that I can think of. Though it itself is only marginally stable.
[Edited on 30-10-2007 by Axt]
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The_Davster
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From memory it is in Urbanski(which volume eludes me), 2 or 3 pages into the section on RDX synthesis, on the right hand side of the page. There is a
molecular structure of the trichloramine drawn there.
(photographic memory is nifty )
Not to get off topic, but the reaction of cyanuric chloride and nitrite was tried and failed?...fascinating, I had always wondered about that
reaction.
EDIT: In keeping with the N-azides stuff, I remember reading that NCl3 and NaN3 were attempted to be reacted to produce a N(N3)3...N10 ...unsucessfully. EDIT: how embarassing..it was in this thread already
Also, potentially very interesting would be the N-chloro-N-nitroamines, and their reaction with azide, followed by heating, perhaps a furoxan type
cyclization could occur?(but making a 4 membered ring? Unlikely I think though...
[Edited on 29-10-2007 by The_Davster]
[Edited on 30-10-2007 by The_Davster]
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Axt
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Thanks I'll check that out. The other possiblility is the chloramine analogue of DPT, which is formed under simular conditions to the RDX analogue,
though in neutral solution (close resemblance to DNPT - r-salt via nitrosation in differing acid conditions). From memory this is more stable then
(CH2=NCl)3. The other alternative would be condensation of ethylenediamine with glyoxal followed by chlorination.
Its mentioned in <a href="http://www.sciencemadness.org/talk/viewthread.php?action=attachment&tid=173&pid=93255">this article</a>
I attached into the trinitromelamine thread about AgNO2 + cyanuric trichloride. But yeh off topic.
Yeh the translation above mentioned that they attempted N10 with failure through that reaction.
Interesting about the chloronitramines, hmm maybe rearangement of the "furoxan" to N,N-dinitrosamine would be prefered in this instance.
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Mumbles
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And the second article you requested. This one is much more promising if I do say so myself.
I'm trying to look up reference #3, but my journal access is being a pain, and not showing the JACS.
Attachment: 1,1-Bis(trimethylsilyl)tetrazadiene.pdf (104kB)
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Axt
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Thanks, interesting stabilty! up to 150°C. Though the reference the cite for this doesnt seem to bare any relevance, it refers only to N4O, nitrosyl
azide, which decomposes <-50°C and is a stronger explosive then NG. I've attached this article previously into the <a
href="http://www.sciencemadness.org/talk/viewthread.php?tid=196&page=1#pid45737">nitrosyl perchlorate thread</a>.
Makes me wonder how they determined its properties. The citation for its explosive properties is:
<b>Covalent Inorganic Azides</b>
Angewandte Chemie International Edition in English
Volume 34, Issue 5, Date: March 20, 1995, Pages: 511-520
Inis C. Tornieporth-Oetting, Thomas M. Klapötke
http://dx.doi.org/10.1002/anie.199505111
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Axt
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I ran across a recent study that I had saved on my computer all along :/ which I planned to bring in and attach but it seems to have been lost in
transit, though some researchers attempted both the above azidamines as reported and failed. Dimethylamine in DCM actually was a complex reaction
which formed methane azides, and the chlorosilazane was unreactive to NaN3.
Another recent article on azidamines (specifically NH(N3)2 and N(N3)3) fails to even mention the above "azidamines" if thats actually what was
obtained. Though they do suggest that they are accessable at least based on their calculations. They suggest reacting (CH3)3SiN3 with halogenated
amines as a possible synthesis route. Article is attached.
Attachment: Theoretical Prediction of the Structures and Stabilities of Azidamines.pdf (1.3MB)
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JohnWW
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With regard to that substituted alkyl N-nitroazidoamine that Axt shows as an intermediate product (before losing N2) in the preparation of an alkyl
N-dinitrosoamine, I observe that it has 5 N atoms in a row. The authors of that article referenced by Axt obviously tried to reduce the -NO2 part of
it to -NH2 or something else more amenable, and then to cyclize it to an alkyl-substituted pentazole, with a ring of 5 N atoms, without success. I
suppose that it shows just how elusive pentazole, or substituted derivatives, is.
However, if NH(N3)2 could be synthesized, 6- or 7-membered all-nitrogen rings may be a possibility. The stability of such all-nitrogen rings would
depend on their having a suitable charge and arrangement of alternating double and single bonds to enable resonance-stabilization. N6 would have to be
neutral (isoelectronic with benzene), N5 with a single negative charge (isoelectronic with cyclopentadienide anion), and N7 with a single positive
charge (isoelectronic with tropylium cation), for that.
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franklyn
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Just a thought
(R)2NCl + NaN3 -> NaCl + (R)2NN3
N2O + (R)2NN3 -> (R)O(R) + N6 . . . 
U P D A T E
Scouted around for N2O and it's readily available and not that expensive
as low as 50 cents U.S. per 8 gram content cylinders.
100 / 8 gram cylinders @ 0.30 £ each delivered , good deal , that's 20
British pounds for the box plus 10 £'s shipping inside U.K.
http://cgi.ebay.com/ws/eBayISAPI.dll?ViewItem&item=17016...
96 / 8 gram cylinders @ 0.50 $ each delivered , very good deal that's $ 48
for a box delivered
http://cgi.ebay.com/ws/eBayISAPI.dll?ViewItem&item=17011...
50 / 8 gram cylinders @ 0.75 $ each delivered ( I'm guessing at shipping cost
you need to start an account and log in to find out. ) they're $ 27.50 the box
http://cookingbuddies.com/osc/product_info.php?cPath=32_55&a...
.
[Edited on 13-11-2007 by franklyn]
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12AX7
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Diazide, or azogen (in analogy to cyanogen)?
Tim
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franklyn
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@ 12AX7
Good point , but who can say , this remains unexplored , yet can be easily attempted
following the synthesis of the Azidamine precursor disclosed in the opening post of this
thread.
Just as Cyanogen Chloride Cl-CN , Chlorine Azide Cl-N3 is a known compound
so this is not such a reach. See page 476 - BRAUER
Along those lines , another aproach could be Cl-N3 + NaN3 -> NaCl + N6
Alternatively
H2NCl + NaN3 -> NaCl + H2NN3
H2NN3 + N2O -> H2O + N6
Related post citing Chloramine
http://www.sciencemadness.org/talk/viewthread.php?tid=6042&a...
.
[Edited on 15-11-2007 by franklyn]
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JohnWW
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It is to be noted that the N3- anion is resonance-stabilized:
N[triplebond]N(+)-N(2-) <----> (2-)N-N(+)[triplebond]N <----> (-)N=N(+)=N(-) .
Such canonical forms are possible with a linear N6 molecule, "azogen":
N[triplebond]N(+)-N=N-N=N(-) <------> (-)N=N-N=N-(+)N[triplebond]N
So it may exist, as another allotrope of nitrogen, although less stable than N3-, and no doubt highly explosive,
I am sure that a cyclic N6 molecule, isoelectronic with benzene, also resonance-stabilized, would be more stable than the linear molecule, because the
N atoms would not bear any charges.
As for the possibility of linear N5, except for the possibility of a free-radical this can exist only as an anion:
N[triplebond]N(+)-N=N-N(2-) <-------> (2-)N-N=N-(+)N[triplebond]N
Similarly to the resonance-stabilized cyclic pentazole anion above which is isoelectronic with the cyclopentadienide anion.
Likewise, linear N7 could exist as a resonance-stabilized cation, similarly to a theoretical cyclic N7+ cation which would be isoelectronic with the
tropylium cation.
[Edited on 11-11-07 by JohnWW]
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franklyn
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On Pentazoles and Tetrazines
For those who really hate Dihydrogen Monoxide
and in the catagory of can you top this allow me to propose
3,6 - Pentazole - 1,2,4,5 - Tetrazine , TA DA
See pretty picture below
References _
Tetrazine Patents
US3244702
US6645325
Pentazole speculations
http://pubs.acs.org/cgi-bin/sample.cgi/joceah/0000/67/i04/ht...
The above in pdf _
http://pubs.acs.org/cgi-bin/sample.cgi/joceah/2002/67/i04/pd...
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Rosco Bodine
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Not wishing to be the devils advocate .........
Of course there is the not so remote possibility that
formation of a whole lot of N2 is what could result , in spite of what might be intended . A whole lot of nitrogen has a way of wanting to be nothing
more than just a whole lot of N2
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franklyn
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3,6-Diazido-1,2,4,5-tetrazine
| Quote: | @ Rosco Bodine
Or worse still , the damn thing could turn out to be an explosive gas. |
U P D A T E
It appears that as of a year ago the diazido variant is a done deal _
Synthesis and Theoretical Studies of 3,6-Diazido-1,2,4,5-tetrazine
*N O T E - This paper written in chinese script , though diagrams are not 
LI Xiao-Tong1, PANG Si-Ping*,2, YU Yong-Zhong1, LUO Yun
(1 School of Material Science & Technology, Beijing Institute of Technology, Beijing 100081)
(2 School of Life Science & Technology, Beijing Institute of Technology, Beijing 100081)
Received 2006-8-4 Revised 2006-11-12 Online 2007-5-18 Accepted 2007-1-10
http://sioc-journal.cn/hxxb/qikan/public/tjdjl_en.asp?id=118...
Abstract
3,6-Diazido-1,2,4,5-tetrazine (DAT) has been synthesized from
3,6-bis(3,5-dimethylpyrazol-l- yl)-1,2,4,5-tetrazine by hydrazinolysis and diazotization.
The molecular geometries, infrared vibrational spectra, and thermodynamic properties of DAT
were calculated using the density functional theory (DFT) method at the B3LYP/6-31G* level.
The investigation into simulation and experiment of IR spectra indicates that there exists no
azido-tetrazole tautomerism in solid DAT. The thermodynamic parameters including heat
capacities, entropies and enthalpies were calculated according to IR spectra, and also the
polynomial functions between thermodynamic parameters and temperature were determined.
The accurate heat of formation 1088 kJ•mol£1 of DAT in gas phase was obtained via
designed isodesmic reaction in which the tetrazine ring and the azide group have been kept.
The data obtained from the present study show a satisfactory detonation performance, with
detonation velocity D of 8.45 km•s£1 and detonation pressure P of 31.3 GPa, both of which
are higher than those of TNT and HMX counterparts.
.
[Edited on 29-12-2007 by franklyn]
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Axt
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The reaction of O2NNCl-C2H4-NClNO2 with NaN3 was found in the abstract of:
N-Halo-N-nitramines. 1. Synthesis and some properties of N-chloro-N-nitramines. Ivshin, V. P.; Fridman, A. L.; Novikov, S. S. Inst. Org.
Khim. im. Zelinskogo, Moscow, USSR. Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya (1970)
The only product mentioned is the parent nitramine in 52% yield, with release of N2.
[Edited on 5-12-2007 by Axt]
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franklyn
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On N-Cl substitutions
http://www.sciencemadness.org/talk/viewthread.php?tid=4282&a...
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